CN111607105B - Bio-based epoxy resin emulsifier, water-based emulsion thereof and preparation method - Google Patents

Bio-based epoxy resin emulsifier, water-based emulsion thereof and preparation method Download PDF

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CN111607105B
CN111607105B CN202010319416.5A CN202010319416A CN111607105B CN 111607105 B CN111607105 B CN 111607105B CN 202010319416 A CN202010319416 A CN 202010319416A CN 111607105 B CN111607105 B CN 111607105B
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gae
pegge
epoxy resin
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CN111607105A (en
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周继亮
张俊珩
张道洪
李廷成
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South Central Minzu University
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    • C—CHEMISTRY; METALLURGY
    • 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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    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Abstract

The invention discloses a bio-based epoxy resin emulsifier. The emulsifier has the structure that the emulsifier has a hydrophobic gallic acid group epoxy resin molecular chain segment, a hydrophilic flexible polyether alcohol amine multi-block chain segment and a phosphorus-containing DOPO molecular chain segment; therefore, the gallic acid-based epoxy resin can be preferably emulsified under aqueous conditions. The invention also discloses an aqueous emulsion obtained by emulsifying gallic acid group epoxy resin by the emulsifier and a preparation method thereof. The prepared water-based emulsion is stable, has fine particle size and has a flame retardant function.

Description

Bio-based epoxy resin emulsifier, water-based emulsion thereof and preparation method
Technical Field
The invention relates to the technical field of epoxy resin, in particular to a bio-based epoxy resin emulsifier, a water-based emulsion thereof and a preparation method thereof.
Background
The epoxy resin material has the advantages of excellent bonding performance, electric insulation performance, low shrinkage rate, high strength and modulus and the like, and plays an important role in the fields of electronics, ships, aerospace, mechanical manufacturing and the like. Conventional petroleum-based derivative type epoxy resins such as bisphenol a type epoxy resins, which require bisphenol a as a raw material for the preparation of petroleum derivatives, require the consumption of a large amount of non-renewable petroleum resources; and bisphenol a is considered a chemical potentially harmful to human health. Due to the increasing shortage of petroleum resources and the increasing awareness of sustainable development, the gradual replacement of petroleum-based derivatives by green bio-based raw materials and derivatives has become an irreversible development trend for the synthesis and preparation of bio-based epoxy resins. In recent years, there is a report in the literature that a gallic acid-based epoxy resin having excellent properties can be prepared by reacting a bio-based gallic acid with epichlorohydrin. In addition, the traditional solvent-based epoxy resin brings harm to ecological environment due to containing a large amount of organic solvent, and is increasingly difficult to meet the requirement of the market on green environmental protection. The waterborne epoxy resin takes water as a dispersion medium instead of an organic solvent, and has the advantages of environmental protection. However, most of the aqueous epoxy resins reported in the prior art are still based on conventional petroleum-based derivative type epoxy resins, such as water-soluble bisphenol A type epoxy resin emulsions or aqueous phenol-formaldehyde epoxy resin emulsions.
Disclosure of Invention
The invention aims to provide a bio-based epoxy resin emulsifier which can well emulsify gallic acid group epoxy resin (GAE) under the aqueous condition.
In order to solve the technical problems, the biological epoxy resin emulsifier provided by the invention is prepared by adopting the following technical scheme:
(1) Preparation of GAE-nDOPO adduct solution
The gallic acid base epoxy resin (GAE) is prepared by the prior technical scheme. For example, the following technical solutions may be adopted: using bio-based Gallic Acid (GA) and Epichlorohydrin (ECH) as raw materials, heating to 100-110 ℃, and carrying out ring-opening reaction under the action of a catalyst (such as tetrabutylammonium bromide) for 4-8 hours; then adding NaOH solution into the reaction solution at room temperature to carry out ring-closure reaction for 2-4 hours, adding water to wash the reaction solution to be neutral, standing and layering the reaction solution, and distilling the oil layer under reduced pressure to obtain the pale yellow semisolid gallic acid base epoxy resin.
Adding GAE, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and a solvent into a reaction device provided with a stirring device, a condensing device and an inert atmosphere (introduced with nitrogen or inert gas), adding triphenylphosphine serving as a catalyst after reactants GAE and DOPO are completely and uniformly dispersed, heating to 120-160 ℃, stirring and reacting for 4-10 hours to completely react to obtain a GAE-nDOPO adduct solution; the size of n is as follows: n is more than or equal to 1 and less than or equal to 3. The reaction equation can be shown as follows:
Figure BDA0002460796910000021
(2) Synthesis of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA)
Firstly, at 40-80 ℃, adding polyether alcohol diglycidyl ether (PEGGE) dropwise into an organic solvent containing ethanolamine (MEA) to carry out chain extension reaction (the molar ratio of the MEA to the added PEGGE is 3-4: 1), removing redundant MEA after the reaction is finished by reduced pressure distillation to obtain an intermediate product MEA-PEGGE-MEA, and dissolving and dispersing the intermediate product MEA-PEGGE-MEA by using the organic solvent to obtain an MEA-PEGGE-MEA solution; and dripping the GAE-nDOPO adduct solution into the MEA-PEGGE-MEA solution at the temperature of between 50 and 80 ℃ for addition reaction to obtain the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct solution. The ratio of the amount of GAE-nDOPO in the GAE-nDOPO adduct solution to the amount of MEA-PEGGE-MEA in the MEA-PEGGE-MEA solution is 1: (4-n). The reaction equation can be shown as follows:
Figure BDA0002460796910000031
(3) Synthesis of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE)
Dropwise adding a GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct solution into the organic solvent containing PEGGE at the temperature of 40-90 ℃, wherein the ratio of the amount of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) to the amount of PEGGE in the organic solvent containing PEGGE is 1: (4-n). The method comprises the steps of carrying out addition reaction on ammonia hydrogen on a GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct solution and an epoxy group at one end of a PEGGE (the epoxy group at the other end is reserved to participate in curing reaction when being applied), synthesizing the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) adduct solution, adjusting the hydrophile-lipophile balance value to be 13.0-16.8 (as known by a person skilled in the art, if the hydrophile-lipophile balance value of the solution is 13.0-16.8, no adjustment is needed, or no adjustment method is needed), and carrying out reduced pressure distillation to remove a solvent, namely preparing the bio-based (i.e. gallic acid group) epoxy resin emulsifier. The reaction equation can be shown as follows:
Figure BDA0002460796910000041
further, in the step (1), the ratio of the DOPO to the epoxy group on the GAE is n:4.
further, in the step (1), the mass of the triphenylphosphine is 7-9% of the sum of the mass of DOPO and the mass of GAE.
Further, in the step (2), the polyether alcohol diglycidyl ether is polyethylene glycol diglycidyl ether.
Further, in the step (2), the organic solvent is propylene glycol methyl ether.
Further, in the step (3), the specific method for adjusting the hydrophilic-lipophilic balance value thereof comprises: after synthesizing the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) adduct solution, dropwise adding a proper amount of glacial acetic acid aqueous solution and amino on the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) adduct at the temperature of 40-60 ℃ for neutralization and salt formation reaction.
The invention also provides a water-based emulsion obtained by emulsifying gallic acid group epoxy resin with the biological epoxy resin emulsifier. The preparation method comprises the following specific steps: according to the weight ratio of 1:3 to 3:2, taking 100 parts by weight of gallic acid base epoxy resin (GAE) and the product obtained by carrying out reduced pressure distillation on the GAE-nDOPO adduct solution prepared in the step (1) as an emulsified substance, adding 15-20 parts by weight of bio-based epoxy resin emulsifier, putting the mixture into a container with a stirring device, uniformly mixing, and heating to 85-90 ℃; under the condition of stirring materials at 900 rpm-950 rpm, 100 parts by weight of deionized water is dripped into the stirred materials, after the water is dripped, the materials are stirred for 50-60 min, and the water-based emulsion with the solid content of 53-55% is obtained after cooling and discharging.
The invention is based on that the gallic acid base epoxy resin is a hydrophobic substance, can not be directly dissolved and dispersed in water, is a semisolid substance with high viscosity at room temperature, and is difficult to be emulsified into a stable emulsion by a common emulsifier. Therefore, the key to the preparation of the gallic acid base epoxy resin water-based emulsion is to synthesize the gallic acid base epoxy resin emulsifier with a special structure. In order to increase the similarity of the emulsifier and an emulsified substance, hydrophobic gallic acid-based epoxy resin molecular chain segments are introduced into the structure of the emulsifier; in order to enhance the water solubility, hydrophilic flexible polyether alcohol amine multi-block segments are introduced; in order to avoid forming a cross-linking structure between the hydrophobic gallic acid group epoxy resin molecular chain segment and the hydrophilic flexible polyether alcohol amine multi-block chain segment, the invention also introduces a phosphorus-containing DOPO molecular chain segment between the hydrophobic gallic acid group epoxy resin molecular chain segment and the hydrophilic flexible polyether alcohol amine multi-block chain segment. The emulsifier prepared in the way has a unique molecular structure, is beneficial to improving the emulsifying performance of the p-gallic acid base epoxy resin and the derivatives thereof, can prepare stable water-based gallic acid base epoxy resin emulsion with small particle size, is green and environment-friendly, and better accords with the sustainable development concept.
Compared with the prior art, the method has the advantages and beneficial effects as follows:
emulsifying the bio-based gallic acid base epoxy resin under the action of a self-made emulsifier with a special structure to prepare a stable waterborne gallic acid base phosphorus-containing epoxy resin emulsion with small particle size, which is relative to a common waterborne petroleum base derivative epoxy resin, such as a waterborne bisphenol A epoxy resin emulsion; has the function of flame retardation, takes the bio-based as the raw material, is more green and environment-friendly, and is more beneficial to sustainable development.
Drawings
FIG. 1 is an IR spectrum of GAE-2DOPO-2 (MEA-PEGGE-MEA-PEGGE).
FIG. 2 is a graph showing the particle size distribution of the emulsion prepared in example 1.
FIG. 3 is a particle size distribution of the emulsion prepared in example 2.
FIG. 4 is a particle size distribution of the emulsion prepared in example 3.
FIG. 5 shows the particle size distribution of a water-soluble bisphenol A epoxy resin emulsion.
FIG. 6 shows the particle size distribution of the aqueous novolac epoxy resin emulsion.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings and specific examples, but the scope of the invention as claimed is not limited to the examples shown.
Example 1
Preparation of emulsifier GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) (n = 2):
(1) Preparation of GAE and GAE-2DOPO adduct solutions: firstly, gallic acid (27.2g, 0.16mol) and epoxy chloropropane (355.2g, 3.84mol) are added into a 1000ml three-neck flask with a stirring device and a reflux condenser tube, stirring and heating are carried out for 30 minutes, 3.84g of tetrabutylammonium bromide (TBAB) is added as a catalyst, the temperature is gradually increased to 105 ℃, after reaction is carried out for 6 hours, reduced pressure distillation is carried out to recover excessive epoxy chloropropane, then 160g of ethyl acetate solvent is added, the temperature is adjusted to 25 ℃, naOH (25.6g, 0.64mol) solution (40% aqueous solution) is added for ring closure reaction for 2 hours, the reaction solution is transferred into a separating funnel, water is added for washing for 3 times until the solution is neutral, standing is carried out, a water layer is separated, an oil layer product is subjected to reduced pressure distillation, and light yellow semisolid epoxy resin (GAE) is obtained (the epoxy value of which is measured to be 0.68). 11.76g of the self-made gallic acid base epoxy resin (GAE) as described above, 8.64g of DOPO, 1.60g of triphenylphosphine as a catalyst and 60g of ethylene glycol monobutyl ether solvent are put into a 250ml three-neck flask provided with a stirring rod and a reflux condenser tube, and the temperature is increased to 150 ℃ for reaction for 5 hours under the protection of nitrogen, thus preparing the GAE-2DOPO adduct solution.
(2) Preparation of MEA-PEGGE-MEA adduct solution: 7.32g (0.12 mol) of ethanolamine was put into a reaction flask containing 50g of propylene glycol methyl ether; a reflux condenser tube, a thermometer and a stirrer are arranged in the reaction bottle. When the temperature in a reaction flask in the constant temperature of a water bath rises to 65 ℃, 22.4g (0.04 mol) of polyethylene glycol diglycidyl ether with the molecular weight of 560 is dropwise added into the reaction flask at a constant speed within 1-2 hours (1 hour and 28 minutes in the embodiment) for chain extension reaction, after the dropwise addition and the heat preservation reaction is carried out for 5 hours, the pressure reduction distillation is carried out to remove the redundant unreacted MEA, and after the MEA-PEGGE-MEA adduct is obtained, the MEA-PEGGE-MEA adduct is dissolved and dispersed in 40 g of propylene glycol methyl ether solvent, and the MEA-PEGGE-MEA adduct solution is prepared.
(3) Preparation of GAE-2DOPO-2 (MEA-PEGGE-MEA-PEGGE): dropwise adding the GAE-2DOPO adduct solution prepared in the step (1) into the MEA-PEGGE-MEA adduct solution at a constant speed within 2-3 hours (2 hours and 42 minutes in the embodiment) at 65 ℃ for reaction, and then carrying out heat preservation reaction for 5 hours to synthesize a GAE-2DOPO-2 (MEA-PEGGE-MEA) adduct; then, dropwise adding the mixture into a propylene glycol methyl ether solution containing 22.4g of polyethylene glycol diglycidyl ether for reaction within 2-3 hours (38 minutes in the embodiment) at the temperature of 65 ℃, keeping the temperature for reaction for 4 hours after the dropwise adding is finished, cooling to 55 ℃, and dropwise adding a mixture of 0.01mol of glacial acetic acid and 8g of water and amino on an addition product of GAE-2DOPO-2 (MEA-PEGGE-MEA-PEGGE) for neutralization and salt formation; then, the solvent is distilled off under reduced pressure to prepare the emulsifier for the epoxy resin without the food acid group. The infrared spectrum is shown in figure 1.
As can be seen from FIG. 1, 1717.3cm -1 The peak appears in the range of 1656.5cm, where the absorption peak of stretching vibration of carbonyl group C =0 in gallic acid chain segment appears -1 、1595.6cm -1 、1459.1cm -1 The absorption peak of the skeleton vibration characteristics of benzene rings on the gallic acid chain segment and the DOPO molecular chain segment is generated and is 1207.4cm -1 A characteristic absorption peak of P = O bond appears at 759.5cm -1 A characteristic absorption peak of a para-disubstituted benzene ring in a gallic acid chain segment appears; at 890.3cm -1 The absorption peak of the out-of-plane bend appears when C-H on the benzene ring in the gallic acid chain segment is substituted by 4-membered. 3443.1cm -1 Is the absorption peak of the tertiary amine formed after the reaction of ethanolamine, 1356.2cm -1 Is located at a C-N telescopic vibration peak of 1118.9cm -1 The peak is the characteristic peak of the polyether chain segment. 2933.9cm -1 、2871.7cm -1 Is represented by-CH in carbon chain 2 -an antisymmetric extensional vibration peak and a symmetric extensional vibration peak.
Preparation of the waterborne epoxy resin emulsion containing the phosphogallate group:
taking 10g of gallic acid base epoxy resin (GAE) prepared according to the step (1), 10g of GAE-2DOPO adduct solution after reduced pressure distillation and 3g of emulsifier GAE-2DOPO-2 (MEA-PEGGE-MEA-PEGGE) to be put into a 250ml three-neck flask with a stirring device to be uniformly mixed, and heating to 90 ℃; under the condition of stirring the materials at 900rpm, 20g of deionized water is dripped into the stirred materials, stirring is carried out for 60min after dripping is finished, and cooling and discharging are carried out to obtain the gallic acid base epoxy resin aqueous emulsion with the solid content of 53%.
The centrifugal stability of the comparative emulsion is measured at normal temperature by adopting a centrifugal sedimentation method, and the classification method comprises the following steps:
level 1: layering at 1500rpm × 20 min; stage 2: layering at 2000rpm × 20 min;
and 3, level: layering at 2500rpm × 20 min; 4, level: layering at 3000rpm × 20 min;
stage 5: layering at 3500rpm × 30 min; stage 6: no separation occurred at 3500rpm X30 min.
The aqueous emulsion prepared in example 1 of the present invention was compared with a conventional petroleum-based epoxy resin aqueous emulsion, wherein a water-soluble bisphenol a-type epoxy resin emulsion (reference (zhanghou, zhonghui, liuna, preparation of water-soluble bisphenol a-type epoxy resin emulsion, adhesion, vol.29 (2): 30-32, 2008) was prepared, and the emulsion particle size distribution thereof is as shown in fig. 5), and an aqueous phenol-formaldehyde epoxy resin emulsion (reference (zhonghui, zhanghou, yangmei, preparation of aqueous phenol-formaldehyde epoxy resin emulsion, chinese coating 2008,23 (4): 41-43) was prepared, and the emulsion particle size distribution thereof is as shown in fig. 6), both of which were conventional petroleum-based epoxy resin aqueous emulsions, and the emulsifier thereof was prepared by using polyethylene glycol and conventional petroleum-based epoxy resin under the action of a strongly corrosive boron trifluoride etherate catalyst, which is toxic. The centrifugal stability and particle size are shown in table 1. The centrifugal stability and particle size of the aqueous emulsion prepared in example 1, the water-soluble bisphenol a epoxy resin emulsion (prepared in reference (zhanghou, zhuang, liuna. Water-soluble bisphenol a epoxy resin emulsion, preparation of adhesive. Vol.29 (2): 30-32, 2008)) and the aqueous novolac epoxy resin emulsion (prepared in reference (zhanghou liang, zhanghou, yangzhou, preparation of yangzhou, aqueous novolac epoxy resin emulsion, chinese coating, 23 (4): 41-43)) are shown in table 1. Emulsion 1 shown in table 1 is a waterborne bisphenol a epoxy resin emulsion; the emulsion 2 is water-based novolac epoxy resin emulsion. Emulsion 3 is the aqueous emulsion prepared in example 1, and the particle size distribution of the emulsion is shown in FIG. 2. The results of the centrifugal stability of the emulsion and the nano-particle size emulsion show that the emulsifier prepared by the invention has excellent performance of emulsifying gallic acid group epoxy resin.
After the GAE-2DOPO adduct solution is prepared according to the step (1) of the example 1, the temperature is reduced to 25 ℃, 7.32g of ethanolamine, 44.8g of polyethylene glycol diglycidyl ether and 50g of propylene glycol methyl ether solvent are all added into the GAE-2DOPO adduct solution at one time to be mixed and stirred, the temperature is increased to 65 ℃, the reaction is kept for 8 hours, the temperature is reduced to 55 ℃, 0.01mol of glacial acetic acid and 8g of water are dropwise added to form salt, and the product in a reaction bottle is subjected to reduced pressure distillation operation to remove the solvent and unreacted MEA, so that the product prepared by the one-pot method is obtained. Taking 3g of the obtained product as an emulsifier, mixing the obtained product with 10g of gallic acid based epoxy resin (GAE) prepared according to the step (1) of the example and 10g of GAE-2DOPO subjected to reduced pressure distillation, putting the mixture into a 250ml three-neck flask with a stirring device, uniformly mixing, and heating to 90 ℃; under the condition of stirring materials at 900rpm, 20g of deionized water is dripped into the stirred materials, after the water dripping is finished, the materials are stirred for 60min, the temperature is reduced and the materials are discharged, the obtained emulsion has slight layering before a centrifugal sedimentation experiment, and has obvious layering and sedimentation when the centrifugal experiment is carried out under the condition of 1500rpm multiplied by 20 min; the emulsifying effect of the emulsifier prepared by the one-pot method is not ideal. The reason is that the gallic acid base epoxy resin and the gallic acid base epoxy resin containing DOPO are both high-viscosity strong hydrophobic substances which are difficult to emulsify, when GAE-2DOPO addition solution, polyethylene glycol diglycidyl ether and ethanolamine are simultaneously mixed together for reaction, the high-efficiency emulsifier which not only contains GAE-2DOPO chain segments but also contains MEA-PEGGE-MEA-PEGGE multi-block structures cannot be controlled and synthesized.
For further comparison, reference is first made to the literature (Zengfeng, chengming, discussion of synthesis of aqueous epoxy emulsifier and preparation of emulsion, chemical reaction engineering and process, 2004 (3): 255-259) to prepare the emulsifier (emulsifier E-20/PEG-1000) from conventional bisphenol A epoxy resin (E-20) and polyethylene glycol (PEG-10000) in the presence of boron trifluoride etherate as catalyst. Then respectively adopting an emulsifier E-20/PEG-1000 and commonly used emulsifiers such as polyoxyethylene sorbitan stearate (Tween-80) and sodium dodecyl benzene sulfonate (ABS) on the market to prepare the gallic acid base aqueous epoxy resin emulsion: taking 10g of gallic acid group epoxy resin (GAE) prepared according to the step (1) and 10g of GAE-2DOPO adduct subjected to reduced pressure distillation as emulsified matters, adding 3g of E-20/PEG-1000 or 3g of polyoxyethylene sorbitan stearate (Tween-80) or 3g of sodium dodecyl benzene sulfonate (ABS) as an emulsifier into a 250ml three-neck flask with a stirring device, heating to 90 ℃, and uniformly mixing; and under the condition of stirring the materials at 900rpm, 20g of deionized water is dripped into the stirred materials, stirring is carried out for 60min after water dripping is finished, cooling and discharging are carried out, and the obtained emulsion has obvious layered precipitation phenomenon before a centrifugal sedimentation experiment. This indicates that the emulsifiers E-20/PEG-1000, tween 80 and ABS can not be emulsified to prepare uniform and stable aqueous emulsion, because the gallic acid base epoxy resin and the gallic acid base epoxy resin containing DOPO are high-viscosity and strong hydrophobic substances, and the emulsifiers have no molecular chain segment which is very similar to that of the emulsified material in the molecular structure, so that the emulsifiers are difficult to emulsify to prepare stable aqueous gallic acid base epoxy resin emulsion.
After the above-mentioned emulsions 1, 2 and 3 were respectively cured with an aqueous epoxy curing agent (prepared according to the literature (Zhoujiliang, duckweed, synthesis and Properties of nonionic self-emulsifying aqueous epoxy curing agent, university chemical engineering report, vol.20 (1): 94-99, 2006)) to form a film on a tin plate cleaned with acetone, the film properties were measured (impact resistance was measured according to GB/T1732-93, and hardness was measured according to GB/T1730-93). The Limit Oxygen Index (LOI) and the UL 94 grade are also an accurate and rapid evaluation method for evaluating the combustion performance and the flame retardant performance of the material. The flame retardant performance Limiting Oxygen Index (LOI) of sample strips prepared by curing different emulsions and the waterborne epoxy curing agent is measured according to GB/T2406; the sample bar size is 130mm multiplied by 6.5mm multiplied by 3mm; the flame retardant property UL-94 vertical burning grade is carried out according to the GB/T2408-2008 standard, and the size of a sample strip is 130mm multiplied by 12.7mm multiplied by 3mm. The film coating performance and the flame retardant performance are shown in Table 1. The results in Table 1 show that the coating film formed by the waterborne phosphoroflavonic acid-group-containing epoxy resin emulsion prepared by the invention is transparent and glossy, and has good impact resistance and pencil hardness. Compared with the traditional aqueous bisphenol A epoxy resin emulsion and aqueous novolac epoxy resin emulsion, the Limiting Oxygen Index (LOI) of the emulsion is greatly improved, and the UL-94 vertical combustion result also shows that the emulsifier prepared by the invention and the introduction of the DOPO containing phosphorus in the gallic acid group epoxy resin play an obvious flame retardant role.
TABLE 1 centrifugal stability, particle size, coating film properties and flame retardancy of the emulsions
Figure BDA0002460796910000121
Example 2
Preparation of emulsifier GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) (n = 3):
(1) Preparation of GAE and GAE-3DOPO adduct solutions: firstly, gallic acid (27.2g, 0.16mol) and epoxy chloropropane (355.2g, 3.84mol) are added into a 1000ml three-neck flask with a stirring device and a reflux condenser tube, stirring and heating are carried out for 30 minutes, 3.84g of tetrabutylammonium bromide (TBAB) is added as a catalyst, the temperature is gradually increased to 105 ℃, after reaction is carried out for 6 hours, reduced pressure distillation is carried out to recover excessive epoxy chloropropane, then 160g of ethyl acetate solvent is added, the temperature is adjusted to 25 ℃, naOH (25.6g, 0.64mol) solution (40% aqueous solution) is added for ring closure reaction for 2 hours, the reaction solution is transferred into a separating funnel, water is added for washing for 3-4 times until the solution is neutral, standing is carried out, a water layer is separated, an oil layer product is subjected to reduced pressure distillation, and light yellow semisolid epoxy resin (GAE is obtained, and the epoxy value of the GAE is measured to be 0.68). 23.52g of the self-made gallic acid base epoxy resin (GAE) as described above, 25.92g of DOPO, 4.20g of triphenylphosphine as a catalyst and 120g of ethylene glycol monobutyl ether solvent are put into a 250ml three-neck flask provided with a stirring rod and a reflux condenser tube, and the temperature is increased to 150 ℃ for reaction for 5 hours under the protection of nitrogen, thus preparing the GAE-3DOPO adduct solution.
(2) Preparation of MEA-PEGGE-MEA adduct solution: 8.54g (0.14 mol) of ethanolamine was charged into a reaction flask containing 50g of propylene glycol methyl ether. The reaction flask is provided with a reflux condenser tube, a thermometer and a stirrer. When the temperature in a reaction flask in the constant temperature of a water bath rises to 65 ℃, 22.4g (0.04 mol) of polyethylene glycol diglycidyl ether with the molecular weight of 560 is dropwise added into the reaction flask at a constant speed within 1-2 hours (35 minutes in the embodiment) for chain extension reaction, after the dropwise addition and the heat preservation reaction for 5 hours, the pressure reduction distillation is carried out to remove the redundant unreacted MEA, and after the MEA-PEGGE-MEA adduct is obtained, the MEA-PEGGE-MEA adduct is dissolved and dispersed in 40 g of propylene glycol methyl ether solvent, and the MEA-PEGGE-MEA adduct solution is prepared.
(3) Preparation of GAE-3DOPO- (MEA-PEGGE-MEA-PEGGE): dropwise adding the GAE-3DOPO adduct solution prepared in the step (1) into the MEA-PEGGE-MEA adduct solution at a constant speed within 2-3 hours (35 minutes in the embodiment) at 65 ℃ to react, and then keeping the temperature to react for 5 hours to synthesize a GAE-3DOPO- (MEA-PEGGE-MEA) adduct; then, dropwise adding the mixture into a propylene glycol methyl ether solution containing 22.4g of polyethylene glycol diglycidyl ether for reaction within 2-3 hours (2 hours and 50 minutes in the embodiment) at the temperature of 65 ℃, keeping the temperature for reaction for 4 hours after the dropwise adding is finished, cooling to 50 ℃, and dropwise adding a mixture of 0.04mol of glacial acetic acid and 10g of water and amino on the GAE-3DOPO- (MEA-PEGGE-MEA-PEGGE) addition product for neutralization and salt formation; then, the solvent is distilled off under reduced pressure to prepare the emulsifier for the epoxy resin without the food acid group.
Preparing the aqueous phosphoribosyl-containing epoxy resin emulsion:
taking 12g of the gallic acid base epoxy resin (GAE) prepared according to the step (1), 8g of GAE-3DOPO adduct solution after reduced pressure distillation and 3.5g of emulsifier GAE-3DOPO- (MEA-PEGGE-MEA-PEGGE) into a 250ml three-neck flask with a stirring device, heating to 90 ℃ and uniformly mixing; and under the condition of stirring the materials at 950rpm, 20g of deionized water is dripped into the stirred materials, stirring is carried out for 60min after dripping is finished, and the water-based epoxy resin emulsion with the solid content of 54 percent is obtained after cooling and discharging.
The centrifugal stability of the comparative emulsion is measured at normal temperature by adopting a centrifugal sedimentation method, and the classification method comprises the following steps:
level 1: layering at 1500rpm × 20 min; stage 2: layering at 2000rpm × 20 min;
and 3, stage: layering at 2500rpm × 20 min; 4, level: layering at 3000rpm × 20 min;
stage 5: layering at 3500rpm × 30 min; and 6, level: no separation occurred at 3500rpm X30 min.
The centrifugal stability and particle size of the emulsion prepared in example 2, the water-soluble bisphenol a-type epoxy resin emulsion (reference (zhanghou, liuna, preparation of water-soluble bisphenol a-type epoxy resin emulsion, adhesion. Vol.29 (2): 30-32, 2008)) and the water-soluble novolac epoxy resin emulsion (reference (zhanghou, yangmei, preparation of water-soluble novolac epoxy resin emulsion, chinese dope.2008, 23 (4): 41-43)) are shown in table 1. Emulsion 1 shown in table 1 is a waterborne bisphenol a epoxy resin emulsion; the emulsion 2 is water-based novolac epoxy resin emulsion. Emulsion 4 was the emulsion prepared in example 2 and the particle size distribution of the emulsion is shown in FIG. 3. The results of the centrifugal stability of the emulsion and the nano-particle size emulsion show that the emulsifier prepared by the invention has excellent performance of emulsifying gallic acid group epoxy resin.
After the above-mentioned emulsions 1, 2 and 4 were respectively cured with an aqueous epoxy hardener (prepared according to the literature (Zhoujiliang, duckweed, non-ionic self-emulsifying aqueous epoxy hardener synthesis and performance, vol.20 (1): 94-99, 2006)) on tin plates cleaned with acetone to form films, the film properties were measured (impact resistance was measured according to GB/T1732-93, and hardness was measured according to GB/T1730-93). The flame retardant performance Limiting Oxygen Index (LOI) of the sample strips prepared by curing different emulsions and the waterborne epoxy curing agent is determined according to GB/T2406; the size of the sample band is 130mm multiplied by 6.5mm multiplied by 3mm; the UL-94 vertical burning grade of the flame retardant property is carried out according to the GB/T2408-2008 standard, and the size of a sample strip is 130mm multiplied by 12.7mm multiplied by 3mm. The film coating performance and the flame retardant performance are shown in Table 1. The results in Table 1 show that the coating film formed by the waterborne phosphoro-gallic acid group-containing epoxy resin emulsion prepared by the invention is transparent and glossy, and has good impact resistance and pencil hardness. Compared with the traditional aqueous bisphenol A epoxy resin emulsion and aqueous novolac epoxy resin emulsion, the Limiting Oxygen Index (LOI) of the emulsion is greatly improved, and the UL-94 vertical combustion result also shows that the emulsifier prepared by the invention and the introduction of the DOPO containing phosphorus in the gallic acid group epoxy resin play an obvious flame retardant role.
Example 3
Preparation of emulsifier GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) (n = 1):
(1) Preparation of GAE and GAE-1DOPO adduct solutions: firstly, gallic acid (27.2g, 0.116mol) and epichlorohydrin (355.2g, 3.84mol) are added into a 1000ml three-neck flask with a stirring device and a reflux condenser tube, stirred and heated for 30 minutes, 3.84g of tetrabutylammonium bromide (TBAB) is added as a catalyst, the temperature is gradually increased to 105 ℃, after 6 hours of reaction, the excessive epichlorohydrin is recovered by reduced pressure distillation, then 160g of ethyl acetate solvent is added, the temperature is adjusted to 25 ℃, naOH (25.6g, 0.64mol) solution (40% by mass of aqueous solution) is added for ring closure reaction for 2 hours, the reaction solution is transferred into a separating funnel, washed for 3 times by adding water to be neutral, and then placed still, a water layer is separated, an oil layer product is distilled under reduced pressure, and light yellow semisolid epoxy resin (GAE, the epoxy value of which is measured is 0.68) is obtained. 11.76g of the self-made gallic acid base epoxy resin (GAE) as described above, 4.32g of DOPO, 1.30g of triphenylphosphine as a catalyst and 60g of ethylene glycol monobutyl ether solvent are put into a 250ml three-neck flask provided with a stirring rod and a reflux condenser tube, and the temperature is increased to 150 ℃ for reaction for 5 hours under the protection of nitrogen, thus preparing the GAE-1DOPO adduct solution.
(2) Preparation of MEA-PEGGE-MEA adduct solution: 14.64g (0.24 mol) of ethanolamine was charged into a reaction flask containing 60g of propylene glycol methyl ether. The reaction flask is provided with a reflux condenser tube, a thermometer and a stirrer. After the temperature in the reaction flask in the constant temperature of water bath is raised to 65 ℃, 33.6g (0.06 mol) of polyethylene glycol diglycidyl ether with the molecular weight of 560 is dropwise added into the reaction flask at a constant speed within 1 to 2 hours (1 hour and 25 minutes in the embodiment) for chain extension reaction, after the dropwise addition and the heat preservation reaction for 5 hours, the pressure reduction distillation is carried out to remove the redundant MEA, the MEA-PEGGE-MEA adduct is obtained, and then the MEA-PEGGE-MEA adduct is dissolved and dispersed in 60 grams of propylene glycol methyl ether solvent, so as to prepare the MEA-PEGGE-MEA adduct solution.
(3) Preparation of GAE-1DOPO-3 (MEA-PEGGE-MEA-PEGGE): dropwise adding the GAE-1DOPO adduct solution prepared in the step (1) into the MEA-PEGGE-MEA adduct solution at a constant speed within 2-3 hours (41 minutes in the embodiment) at 65 ℃ to react, and then keeping the temperature to react for 5 hours to synthesize a GAE-1DOPO-3 (MEA-PEGGE-MEA) adduct; then, dropwise adding the mixture into a propylene glycol methyl ether solution containing 33.6g of polyethylene glycol diglycidyl ether for reaction at 65 ℃ within 2-3 hours (for 2 hours and 48 minutes in the embodiment); then, the solvent is distilled off under reduced pressure to prepare the emulsifier for the epoxy resin without the food acid group.
Preparing the aqueous phosphoribosyl-containing epoxy resin emulsion:
taking 5g of gallic acid base epoxy resin (GAE) prepared according to the step (1), 15g of GAE-1DOPO and 4g of emulsifier GAE-3DOPO- (MEA-PEGGE-MEA-PEGGE) after reduced pressure distillation into a 250ml three-neck flask with a stirring device, heating to 85 ℃ and uniformly mixing; and under the condition of stirring the materials at 900rpm, 20g of deionized water is dripped into the stirred materials, and after the dripping is finished, the materials are stirred for 60min, and then the temperature is reduced and the materials are discharged to obtain the waterborne epoxy resin emulsion with the solid content of 55 percent.
The centrifugal stability of the comparative emulsion is measured at normal temperature by adopting a centrifugal sedimentation method, and the classification method comprises the following steps:
stage 1: layering at 1500rpm × 20 min; and 2, stage: layering at 2000rpm × 20 min;
and 3, stage: layering at 2500rpm × 20 min; 4, level: layering at 3000rpm × 20 min;
stage 5: layering at 3500rpm × 30 min; and 6, level: no separation occurred at 3500 rpm.times.30 min.
The centrifugal stability and particle size of the emulsion prepared in example 3, the water-soluble bisphenol a-type epoxy resin emulsion (reference (zhanghou, liuna, preparation of water-soluble bisphenol a-type epoxy resin emulsion, adhesion. Vol.29 (2): 30-32, 2008)) and the water-soluble novolac epoxy resin emulsion (reference (zhanghou, yangmei, preparation of water-soluble novolac epoxy resin emulsion, chinese dope.2008, 23 (4): 41-43)) are shown in table 1. Emulsion 1 shown in table 1 is a waterborne bisphenol a epoxy resin emulsion; the emulsion 2 is water-based novolac epoxy resin emulsion. Emulsion 5 is the emulsion prepared in example 3 and the particle size distribution of the emulsion is shown in figure 4. The results of the centrifugal stability of the emulsion and the nano-particle size emulsion show that the emulsifier prepared by the invention has excellent performance of emulsifying gallic acid base epoxy resin.
After the above-mentioned emulsions 1, 2 and 5 were respectively cured with an aqueous epoxy hardener (prepared according to the literature (Zhoujiliang, duckweed, non-ionic self-emulsifying aqueous epoxy hardener synthesis and performance, vol.20 (1): 94-99, 2006)) on tin plates cleaned with acetone to form films, the film properties were measured (impact resistance was measured according to GB/T1732-93, and hardness was measured according to GB/T1730-93). The flame retardant performance Limiting Oxygen Index (LOI) of the sample strips prepared by curing different emulsions and the waterborne epoxy curing agent is determined according to GB/T2406; the sample bar size is 130mm multiplied by 6.5mm multiplied by 3mm; the UL-94 vertical burning grade of the flame retardant property is carried out according to the GB/T2408-2008 standard, and the size of a sample strip is 130mm multiplied by 12.7mm multiplied by 3mm. The film coating performance and the flame retardant performance are shown in Table 1. The results in Table 1 show that the coating film formed by the waterborne phosphoro-gallic acid group-containing epoxy resin emulsion prepared by the invention is transparent and glossy, and has good impact resistance and pencil hardness. Compared with the traditional aqueous bisphenol A epoxy resin emulsion and aqueous novolac epoxy resin emulsion, the Limiting Oxygen Index (LOI) of the emulsion is greatly improved, and the UL-94 vertical combustion result also shows that the emulsifier prepared by the invention and the introduction of the DOPO containing phosphorus in the gallic acid group epoxy resin play an obvious flame retardant role.

Claims (9)

1. A preparation method of a bio-based epoxy resin emulsifier is characterized by comprising the following steps: the method comprises the following steps:
1) Preparation of GAE-nDOPO adduct solution:
adding gallic acid base epoxy resin GAE, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO and a solvent into a reaction device provided with a stirring device and a condensing device, adding triphenylphosphine serving as a catalyst after reactants are completely and uniformly dispersed, heating to 120 to 160 ℃, and stirring and reacting for 4 to 10 hours in an inert atmosphere to completely react to obtain a GAE-nDOPO addition solution; the size of n is as follows: n is more than or equal to 1 and less than or equal to 3;
2) Synthesis of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA):
firstly, at 40 to 80 ℃, adding polyether alcohol diglycidyl ether PEGGE dropwise into an organic solvent containing ethanolamine MEA to carry out chain extension reaction to obtain an intermediate product MEA-PEGGE-MEA solution; the molar ratio of the ethanolamine MEA to the polyether alcohol diglycidyl ether PEGGE is 3 to 4:1; dropwise adding the GAE-nDOPO adduct solution into the MEA-PEGGE-MEA solution at 50-80 ℃ for addition reaction to obtain a GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct solution; the ratio of the amount of GAE-nDOPO in the GAE-nDOPO adduct solution to the amount of MEA-PEGGE-MEA in the MEA-PEGGE-MEA solution is 1: (4-n);
3) Synthesis of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE):
dropwise adding a GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct solution into an organic solvent containing polyether alcohol diglycidyl ether PEGGE at the temperature of 40-90 ℃, wherein the ratio of the amount of substances of the polyether alcohol diglycidyl ether PEGGE in the organic solvent containing the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) and the polyether alcohol diglycidyl ether PEGGE is 1: (4-n), performing addition reaction on ammonia hydrogen on the GAE-nDOPO- (4-n) (MEA-PEGGE-MEA) adduct and an epoxy group at one end of polyether alcohol diglycidyl ether PEGGE to synthesize a GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) adduct solution, and adjusting the hydrophilic-lipophilic balance value to be 13.0-16.8; then distilling under reduced pressure to remove the solvent, thus preparing the bio-based epoxy resin emulsifier.
2. The method for preparing bio-based epoxy resin emulsifier according to claim 1, wherein: in the step 1), the mass ratio of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO to the epoxy group on the gallic acid base epoxy resin GAE is n:4.
3. the method for preparing bio-based epoxy resin emulsifier according to claim 1 or 2, wherein: in the step 1), the mass of the triphenylphosphine is 7 to 9 percent of the sum of the mass of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide DOPO and the mass of the gallic acid base epoxy resin GAE.
4. The method for preparing bio-based epoxy resin emulsifier according to claim 1 or 2, wherein: in the step 2), the polyether alcohol diglycidyl ether PEGGE is polyethylene glycol diglycidyl ether.
5. The method for preparing a bio-based epoxy resin emulsifier according to claim 1 or 2, wherein: in the step 2), the organic solvent is propylene glycol methyl ether.
6. The method for preparing bio-based epoxy resin emulsifier according to claim 1 or 2, wherein: in the step 3), the specific method for adjusting the hydrophilic-lipophilic balance value comprises the following steps: synthesizing an additive solution of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE), and then dropwise adding a proper amount of glacial acetic acid aqueous solution and amino groups on the additive solution of GAE-nDOPO- (4-n) (MEA-PEGGE-MEA-PEGGE) at the temperature of 40 to 60 ℃ for neutralization and salt formation.
7. A bio-based epoxy resin emulsifier obtainable by the process of any one of claims 1 to 6.
8. The method of preparing an aqueous emulsion by emulsifying gallic acid based epoxy resin GAE with the bio-based epoxy resin emulsifier as claimed in claim 7, wherein: the method comprises the following steps: carrying out reduced pressure distillation on the GAE-nDOPO addition product solution prepared according to the step 1) to obtain a GAE-nDOPO addition product, wherein the weight ratio of the GAE-nDOPO addition product solution to the GAE-nDOPO addition product solution is 1:3 to 3: taking 100 parts by weight of gallic acid base epoxy resin GAE and GAE-nDOPO addition product as emulsified materials in a proportion of 2, adding 15-20 parts by weight of the bio-based epoxy resin emulsifier, putting the mixture into a container with a stirring device, uniformly mixing, and heating to 85-90 ℃; under the condition of stirring the materials at 900rpm-950 rpm, dropwise adding 100 parts by weight of deionized water into the stirred materials, stirring for 50-60min after water is completely added, and cooling and discharging to obtain the aqueous emulsion with the solid content of 53-55%.
9. An aqueous emulsion prepared by the process of claim 8.
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