CN108503846B - Method for synthesizing nonionic emulsifier by solid acid catalysis and application thereof - Google Patents
Method for synthesizing nonionic emulsifier by solid acid catalysis and application thereof Download PDFInfo
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Abstract
A method for synthesizing a non-ionic emulsifier by solid acid catalysis and application thereof, relating to the field of high polymer materials. The solid acid catalyst is solid in the reaction process all the time, can be completely separated from the product after the reaction is finished, and can be reused after being cleaned, so that the production cost is effectively reduced; the solid acid has higher catalytic efficiency, so that the reaction time is further shortened, and the production efficiency is improved; the solid acid reduces the reaction temperature of the anhydride and the polyethylene glycol, and the reaction can be carried out at low temperature, so that the reaction has selectivity.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to a preparation method and application of a special non-ionic emulsifier for aqueous epoxy resin.
Background
Epoxy resin is a common thermosetting resin, has excellent adhesion, heat resistance, chemical resistance, insulativity, mechanical strength and the like, and is widely applied to the field of coatings. Most of epoxy resins are solid or liquid and have high viscosity and extremely low solubility in water, so that in the use process, organic solvents such as aromatic hydrocarbons, ketones or alcohols need to be added to reduce the viscosity so as to facilitate construction. With the limit of Volatile Organic Compound (VOC) emission, the use of solvent-based epoxy resins in the coating field is limited. The waterborne epoxy resin takes water as a dispersion medium, and the VOC emission is low in the using process, so that the waterborne epoxy resin becomes a new research direction.
Hydrophilic groups need to be introduced in the process of the water-based epoxy resin, and the method for introducing the hydrophilic groups is divided into a self-emulsifying method and an external emulsifying agent method. The self-emulsification method is to link a hydrophilic group to an epoxy resin through a chemical bond, thereby making the epoxy resin itself hydrophilic. The external emulsifier method is to emulsify the epoxy resin by adding an emulsifier. The self-emulsification method can change the structure and functional groups of the epoxy resin, so that the problems of reduced crosslinking density, reduced water resistance, complex reaction process, poor repeatability and the like can be caused. The reverse observation and the addition of the emulsifier have no influence on the structure of the epoxy resin; the universality is strong, and various resin systems can be emulsified; good repeatability and stable performance.
The synthesis of nonionic emulsifiers for emulsifying epoxy resins generally employs condensation of the epoxy resin with other hydrophilic molecules. One end or two ends of the synthesized nonionic emulsifier are provided with epoxy groups, so that the compatibility with epoxy resin can be increased in the process of emulsifying the epoxy resin, and the nonionic emulsifier can participate in curing reaction in the curing process, so that the content of free emulsifier in the cured product is reduced, and the water resistance of the cured product is improved. In the synthesis process, boron trifluoride diethyl etherate, tetrabutyl ammonium bromide, N-dimethylethanolamine, imidazole and the like are generally used as catalysts to accelerate the reaction rate due to the slow reaction speed. These catalysts are effective in increasing the reaction rate and reducing the reaction time, but eventually remain in the product and are not easily separated. In particular, boron trifluoride diethyl etherate generates highly corrosive hydrofluoric acid in water, which is not in accordance with the concept of green chemistry. The solid acid is used as a catalyst in the synthesis process of the non-ionic emulsifier, so that the problems can be effectively avoided: the catalyst is always solid in the reaction process, can be completely separated from the product after the reaction is finished, and can be reused after being cleaned, so that the production cost is effectively reduced; the solid acid has higher catalytic efficiency, so that the reaction time is further shortened, and the production efficiency is improved; the solid acid reduces the reaction temperature of the anhydride and the polyethylene glycol, and the reaction can be carried out at low temperature, so that the reaction has selectivity.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the non-ionic epoxy resin emulsifier is synthesized by using solid acid catalysis, has high selectivity in the reaction process, can be separated from a molecular sieve after the reaction is finished, improves the reaction rate and the utilization rate of a catalyst, avoids the residue of impurities in the emulsifier, and does not need post-treatment.
The invention provides a method for synthesizing a nonionic emulsifier synthesized by solid acid catalysis, which is characterized by comprising the following steps:
(1) under the protection of inert gas, melting 100 parts by mass of polyethylene glycol, adding 1-16 parts by mass of acid anhydride and 0.5-3 parts by mass of solid acid catalyst, carrying out esterification reaction at 50-100 ℃, and reacting for 1-3 hours to obtain an esterified substance solution;
(2) reacting 100 parts by mass of the esterified substance solution obtained in the step (1) with 1-95 parts by mass of epoxy resin at 60-170 ℃, and reacting for 1-4 hours to obtain a mixture of a non-ionic emulsifier and a catalyst;
(3) and (3) filtering the mixture obtained in the step (2) while the mixture is hot, and cooling the filtrate to obtain the nonionic emulsifier.
Preferably, the molecular weight of the polyethylene glycol is 1000-10000.
Preferably, the acid anhydride is one of phthalic anhydride and maleic anhydride.
Preferably, the epoxy resin is liquid epoxy resin with one or more of the trade names E44, E51 and F51.
As a preferable scheme, the catalyst is one or more of a 3A molecular sieve, a 4A molecular sieve and a 5A molecular sieve.
The following formula is a non-ionic emulsifier derived from an epoxy resin other than bisphenol A and maleic anhydride:
Wherein
R1 ═ H or R.
The preparation method of the water-based epoxy resin emulsion, which is provided by the invention, uses the nonionic emulsifier to prepare the water-based epoxy resin emulsion, and comprises the following steps:
uniformly mixing 0.1-20 parts by mass of a non-ionic emulsifier, 100 parts by mass of epoxy resin and 0.1-20 parts by mass of an ionic emulsifier, then dropwise adding 50-100 parts by mass of deionized water, and stirring at 40-80 ℃ to obtain the water-based epoxy resin emulsion.
The component A of the water-based paint prepared by the water-based epoxy resin emulsion comprises the following components in parts by weight: 0.1-1 part of defoaming agent is added into 100 parts of the waterborne epoxy resin emulsion; the component B is a modified aromatic amine waterborne epoxy curing agent; when the epoxy resin is used, the ratio of epoxy equivalent to active hydrogen equivalent of the component A to the component B is 1: (0.8 to 1.2) mixing.
Or the prepared water-based paint, wherein the component A of the prepared colored paint coating consists of the following components in parts by weight: 60-70 parts of water-based epoxy resin emulsion, 8-10 parts of talcum powder, 10-15 parts of iron oxide red, 10-13 parts of zinc phosphate, 0.3-1.2 parts of wetting dispersant and 0.1-1 part of defoaming agent; the component B is a modified aromatic amine waterborne epoxy curing agent; the ratio of epoxy equivalent to active hydrogen equivalent of the component A to the component B is 1: (0.8 to 1.2).
Preferably, the ionic emulsifier is one or a mixture of more of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, allyloxy fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether ammonium sulfate, fatty alcohol polyoxyethylene ether sodium carboxylate, polyaromatic phosphate, sodium dodecyl sulfate, alkylbenzene ethoxylated sulfate and alkyl polyoxyethylene ether ammonium sulfate.
Preferably, the epoxy resin in the aqueous epoxy resin emulsion is one or a mixture of more of E-01, E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51 and E-55.
Preferably, the rotation speed of the stirring is 400-5000 rpm.
The solid content of the water-based epoxy resin emulsion is 30-80%.
The emulsion prepared by the invention can be stored and placed stably for more than half a year. The emulsion is used as a main film forming substance, is compounded with varnish and colored paint prepared from various auxiliary agents and anticorrosive pigment fillers, and is cured to obtain the anticorrosive metal coating, and when the thickness of a paint film taking a steel plate as a base material is 70 mu m, the salt spray resistance time is more than 700 hours.
Detailed description of the invention
The following examples further illustrate the invention without limiting its scope.
Example 1 this example relates to a method for preparing solid acid catalyzed nonionic emulsifier for epoxy resins
250g of polyethylene glycol 6000 is added into a 500ml four-mouth reaction flask, a reflux device is arranged, the mixture is heated and stirred under the nitrogen atmosphere to melt the raw materials, 4.08g of maleic anhydride and 0.8g of 5A molecular sieve are added into the polyethylene glycol 6000 solution, and the constant temperature of 80 ℃ is kept for reaction for 2 hours. Then 16.33g of epoxy resin E-51 is added into the system, and the nonionic emulsifier is obtained after the reaction for 3 hours at the constant temperature of 130 ℃.
Example 2
The procedure of example 1 was repeated except that 16.33g of the epoxy resin E-51 added in the synthesis of the nonionic emulsifier of this embodiment was replaced with 18.94g of the epoxy resin E-44.
Comparative example 3
16.33g of epoxy resin E-51 added in the synthesis of the nonionic emulsifier of this embodiment was replaced with 41.67g of epoxy resin E-20. The rest is the same as in example 1.
Example 4
The synthesis of the nonionic emulsifier of this embodiment is performed by replacing 0.8g of 5A molecular sieve with 0.8g of 4A molecular sieve, and the rest is the same as in example 1.
Example 5
In this embodiment, 0.8g of 5A molecular sieve was replaced with 0.8g of 3A molecular sieve in the synthesis of the nonionic emulsifier, and the reaction times were extended to 3 hours and 4 hours, respectively, as in example 1.
Example 6
The synthesis of the nonionic emulsifier of this embodiment is performed by replacing 0.8g of 5A molecular sieve with 0.8g of an ion exchange membrane, and the rest is the same as in example 1.
Example 7
4.08g of maleic anhydride added in the synthesis of the nonionic emulsifier of this embodiment was replaced with 6.16g of phthalic anhydride, and the procedure was otherwise the same as in example 1.
Example 8
250g of polyethylene glycol 6000 added in the synthesis of the nonionic emulsifier of the present embodiment was replaced with 166.67g of polyethylene glycol 4000, and the rest was the same as in example 1.
Example 9
250g of polyethylene glycol 6000 added in the synthesis of the nonionic emulsifier of this embodiment was replaced with 83.33g of polyethylene glycol 2000, and the rest was the same as in example 1.
Example 10
250g of polyethylene glycol 6000 added in the synthesis of the nonionic emulsifier of the present embodiment is replaced with 125g of polyethylene glycol 6000, and the rest is the same as in example 1.
Example 11
250g of polyethylene glycol 6000 and 16.33g of epoxy resin E-51 added in the synthesis of the nonionic emulsifier of the embodiment are replaced by 83.33g of polyethylene glycol 4000 and 18.94g of epoxy resin E-44, and the rest is the same as that of the embodiment 1.
Example 12
250g of polyethylene glycol 6000 added in the synthesis of the nonionic emulsifier of the present embodiment is replaced with 83.33g of polyethylene glycol 4000, and the rest is the same as in example 1.
Example 13
250g of polyethylene glycol 6000 added in the synthesis of the nonionic emulsifier of this embodiment was replaced with 41.67g of polyethylene glycol 2000, and the rest was the same as in example 1.
Example 14
In the synthesis of the nonionic emulsifier of the embodiment, the reaction time of 2 hours at 80 ℃ and 3 hours at 130 ℃ is respectively changed into the reaction time of 3 hours at 70 ℃ and 2 hours at 110 DEG
Example 15
In the synthesis of the nonionic emulsifier of the embodiment, the reaction time of 2 hours at 80 ℃ and 3 hours at 130 ℃ is respectively changed into the reaction time of 1.5 hours at 80 ℃ and 3 hours at 120 DEG
Example 16
In the synthesis of the nonionic emulsifier of the embodiment, the reaction time of 2 hours at 80 ℃ and 3 hours at 130 ℃ is respectively changed into the reaction time of 2 hours at 90 ℃ and 1.5 hours at 120 DEG
Example 17 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 1, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
EXAMPLE 18 this example relates to the preparation of an aqueous epoxy resin emulsion
4g of the nonionic emulsifier prepared in example 2, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 19 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 2, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 20 this example relates to the preparation of an aqueous epoxy resin emulsion
14g of the nonionic emulsifier prepared in example 2, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 21 this example relates to the preparation of an aqueous epoxy resin emulsion
18g of the nonionic emulsifier prepared in example 2, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
EXAMPLE 22 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 3, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 23 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 4, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
EXAMPLE 24 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 5, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 25 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 6, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 26 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 7, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 27 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 8, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 28 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 8, 200g of epoxy resin E-51 and 2g of ammonium alkyl oxyethylenesulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 29 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 8, 200g of epoxy resin E-51 and 2g of alkyl benzene ethoxylated sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to give an aqueous epoxy resin emulsion.
Comparative example 30 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 8, 200g of epoxy resin E-51 and 2g of BVCONC were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to give an aqueous epoxy resin emulsion.
Example 31 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 9, 200g of epoxy resin E-51 and 2g of ammonium allyloxynonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain an aqueous epoxy resin emulsion.
Example 32 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 10, 200g of epoxy resin E-51 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 33 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 11, 200g of epoxy resin E-44 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 34 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 12, 200g of epoxy resin E-20 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Comparative example 35 this comparative example relates to the preparation of an aqueous epoxy resin emulsion.
10g of the nonionic emulsifier prepared in comparative example 13, 200g of epoxy resin E-51 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
EXAMPLE 36 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 14, 200g of epoxy resin E-51 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 37 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 15, 200g of epoxy resin E-51 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 38 this example relates to the preparation of an aqueous epoxy resin emulsion
10g of the nonionic emulsifier prepared in example 16, 200g of epoxy resin E-51 and 2g of ammonium nonylphenol polyoxyethylene ether sulfate were placed in a 1L beaker, heated to 40 ℃ and 114.15g of deionized water was added dropwise with mechanical stirring (3000rpm) to obtain a water-based epoxy resin emulsion.
Example 39 this example relates to the preparation of an aqueous clear coat coating
0.3g of Additol VXW 6393 was added to 100g of the aqueous epoxy resin emulsion obtained in example 17 under high-speed stirring to give a final aqueous clear coat paint A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
Example 40 this example relates to the preparation of an aqueous clear coat coating
0.3g of Additol VXW 6393 was added to 100g of the aqueous epoxy resin emulsion obtained in example 29 under high-speed stirring to give a final aqueous clear coat paint A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
Example 41 this example relates to the preparation of an aqueous clear coat coating
0.3g of Additol VXW 6393 was added to 100g of the aqueous epoxy resin emulsion obtained in example 32 under high-speed stirring to give a final aqueous clear coat paint A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
Example 42 this example relates to the preparation of an aqueous clear coat coating
0.3g of Additol VXW 6393 was added to 100g of the aqueous epoxy resin emulsion obtained in example 33 under high-speed stirring to give a final aqueous clear coat paint A component. And uniformly stirring 71.58g B component HGF-100 and the prepared A component mixed solution to prepare the varnish.
EXAMPLE 43 this example relates to the preparation of aqueous pigmented paint coatings
0.75g Additol VXW 6208/60, 0.67g Additol VXW 6393, 13.5g iron oxide red, 4.5g talc, 6g barium sulfate, 6g ZAM +, and 0.6g HEUCORIN RZ were added to 100g of the aqueous epoxy resin emulsion obtained in example 17 above with high speed stirring to give the final aqueous pigmented paint coating A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
Example 44 this example relates to the preparation of a waterborne pigmented coating
0.75g Additol VXW 6208/60, 0.67g Additol VXW 6393, 13.5g iron oxide red, 4.5g talc, 6g barium sulfate, 6g ZAM +, and 0.6g HEUCORIN RZ were added to 100g of the aqueous epoxy resin emulsion obtained in example 29 above under high speed stirring to give the final aqueous pigmented paint coating A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
EXAMPLE 45 this example relates to the preparation of a Water-borne color coat coating
0.75g Additol VXW 6208/60, 0.67g Additol VXW 6393, 13.5g iron oxide red, 4.5g talc, 6g barium sulfate, 6g ZAM +, and 0.6g HEUCORIN RZ were added to 100g of the aqueous epoxy resin emulsion obtained in example 32 above with high speed stirring to give the final aqueous pigmented paint coating A component. 82.91g B component HGF-100 and the prepared component A are mixed and stirred evenly to prepare the varnish.
EXAMPLE 46 this example relates to the preparation of aqueous pigmented paint coatings
To 100g of the aqueous epoxy resin emulsion obtained in example 33 above, 0.75g of Additol VXW 6208/60, 0.67g of Additol VXW 6393, 13.5g of iron oxide red, 4.5g of talc, 6g of barium sulfate, 6g of ZAM + and 0.6g of HEUCORIN RZ were added under high-speed stirring to give the final aqueous pigmented paint A component. And uniformly stirring 71.58g B component HGF-100 and the prepared A component mixed solution to prepare the varnish.
The particle size of the aqueous epoxy resin emulsion prepared in examples 17 to 38 is shown in Table 1.
Table 1 example particle size results
The varnish and the colored paint prepared in the embodiments 39 to 46 are cured to obtain a high-performance metal anticorrosive coating, and when the thickness of the coating is about 70 μm, the anticorrosive performance and the mechanical performance are shown in table 2. The thickness of the coating is measured in GB/T6739-2006 and the hardness is measured in GB/T. The adhesion of the coating is determined by a cross-cut method according to GB 9286-1998; the salt spray resistance of the coating is determined according to GB/T1771-1991, wherein the colored paint is tested after scratch treatment; the water resistance of the coating was determined as in GB/T1733-1993; the liquid medium resistance of the coating was determined according to GB/T9274-1988.
TABLE 2 Properties of the clear and pigmented coatings
Claims (7)
1. A method for synthesizing a nonionic emulsifier by solid acid catalysis is characterized by comprising the following steps:
(1) under the protection of inert gas, melting 100 parts by mass of polyethylene glycol, adding 1-16 parts by mass of acid anhydride and 0.5-3 parts by mass of solid acid catalyst, carrying out esterification reaction at 50-100 ℃, and reacting for 1-3 hours to obtain an esterified substance solution;
(2) reacting 100 parts by mass of the esterified substance solution obtained in the step (1) with 1-95 parts by mass of epoxy resin at 60-170 ℃, and reacting for 1-4 hours to obtain a mixture of a non-ionic emulsifier and a catalyst;
(3) filtering the mixture obtained in the step (2) while the mixture is hot, and cooling the filtrate to obtain a nonionic emulsifier;
the catalyst is one or more of a 3A molecular sieve, a 4A molecular sieve and a 5A molecular sieve.
2. The method for synthesizing the nonionic emulsifier by the catalysis of the solid acid according to claim 1, wherein the molecular weight of the polyethylene glycol is 1000-10000.
3. The method for solid acid catalyzed synthesis of nonionic emulsifiers of claim 1 wherein the anhydride is one of phthalic anhydride and maleic anhydride.
4. The method for synthesizing the nonionic emulsifier by the catalysis of the solid acid according to claim 1, wherein the epoxy resin is liquid epoxy resin with one or more of the trade names of E44, E51 and F51.
5. A method for preparing an aqueous epoxy resin emulsion by using the nonionic emulsifier prepared by the method of any one of claims 1 to 4, comprising the steps of:
uniformly mixing 0.1-20 parts by mass of a non-ionic emulsifier, 100 parts by mass of epoxy resin and 0.1-20 parts by mass of an ionic emulsifier, then dropwise adding 50-100 parts by mass of deionized water, and stirring at 40-80 ℃ to obtain the water-based epoxy resin emulsion.
6. The method for preparing an aqueous epoxy resin emulsion according to claim 5, wherein the ionic emulsifier is one or a mixture of more of allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, allyloxy fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether ammonium sulfate, fatty alcohol polyoxyethylene ether carboxylic acid sodium, polyaromatic phosphate, sodium dodecylsulfate, alkyl benzene ethoxylated sulfate, and alkyl polyoxyethylene ether ammonium sulfate; the epoxy resin in the water-based epoxy resin emulsion is one or a mixture of more of E-01, E-03, E-06, E-12, E-14, E-20, E-31, E-35, E-42, E-44, E-51 and E-55.
7. The method for preparing the aqueous epoxy resin emulsion according to claim 6, wherein the stirring speed is 400 to 5000 rpm; the solid content of the water-based epoxy resin emulsion is 30-80%.
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| CN109881486B (en) * | 2019-02-19 | 2020-06-09 | 北京化工大学 | Hyperbranched emulsifier and preparation method thereof |
| CN109868654B (en) * | 2019-02-19 | 2020-06-19 | 北京化工大学 | Water-based epoxy sizing agent and preparation method thereof |
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