CN111116846A - Water-soluble epoxy acrylic resin and preparation method and application thereof - Google Patents
Water-soluble epoxy acrylic resin and preparation method and application thereof Download PDFInfo
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- CN111116846A CN111116846A CN201911367904.7A CN201911367904A CN111116846A CN 111116846 A CN111116846 A CN 111116846A CN 201911367904 A CN201911367904 A CN 201911367904A CN 111116846 A CN111116846 A CN 111116846A
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Abstract
The invention discloses a water-soluble epoxy acrylic resin and a preparation method and application thereof. The method comprises the following steps: bisphenol epoxy resin is grafted to an acrylic resin high molecular chain segment in a free radical graft polymerization mode to prepare epoxy modified acrylic resin, the introduction of the epoxy resin improves the adhesive force of the acrylic resin to a base material, and increases the crosslinking points of the resin, so that the heat resistance and the oil resistance of the resin are improved; and then adding alkali to neutralize with a carboxyl monomer in a resin system, so as to improve the water solubility of the resin and prepare a water-soluble epoxy acrylic resin system. Meanwhile, long-chain alkane monomer of acrylic acid is introduced into an acrylic resin system to improve the toughness of the resin. The prepared ring water-soluble epoxy acrylic resin system can be used as impregnating resin of engine oil filter paper, so that the environment-friendly requirement can be met, and the reinforced filter paper has excellent strength performance, processability and heat-resistant and oil-resistant performance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials and filter materials, and particularly relates to a water-soluble epoxy acrylic resin and a preparation method and application thereof.
Background
The automobile filter paper is also called as 'three filter paper', namely air filter paper, engine oil filter paper and fuel filter paper, and is a filter material for cleaning modern high-speed internal combustion engines. Compared with other filtering materials, the paper filter element has the advantages of low cost, high efficiency, small volume, light weight, simple and convenient use and the like. The automobile filter paper is generally made from wood pulp fiber raw materials, but the raw paper has low tightness, loose paper and low inherent strength, so that the paper must be enhanced by impregnating with reinforced resin to improve the physical strength and structural strength of the filter paper, meet the requirements of product processing and use performance, and ensure the filtering precision and service life of the filter paper. The impregnating resin applied to the three-filter paper mainly comprises phenolic resin, melamine formaldehyde resin, urea resin, amino alkyd resin, epoxy resin, acrylic resin and the like. The most commonly used impregnating resins are mainly solvent-borne phenolic resins and aqueous acrylic resin emulsions.
The alcohol-soluble thermosetting phenolic resin is conventional impregnating resin for engine oil filter paper, the preparation technology of the resin is mature, and the filter element prepared from the treated filter paper is firm and firm, has high rigidity and has excellent oil resistance and temperature resistance. But has the problems that the filter paper lacks flexibility and is easy to crack in the rolling operation; in addition, the resin has the advantages of low curing speed, high temperature and high energy consumption. In order to overcome the defects, the Chinese patent CN107178003A achieves the effect of low-temperature rapid curing by developing a new curing system; chinese patent CN108004840A and Chinese patent CN108035194A propose to solve the problem of rapid curing by adding curing agent and accelerator; chinese patent CN109354660A proposes to improve the toughness by preparing phenolic resin containing unsaturated bond carbon chain structure. Although the above technical method can improve a certain problem, many problems still exist in practical application. In addition, along with the increasing attention of people on environmental protection and energy conservation, the alcohol-soluble phenolic resin has the problems of difficult solvent recovery and potential safety hazard in the process of sizing. For the above reasons, aqueous phenol-formaldehyde impregnating resins are also receiving increasing attention.
The water-soluble phenolic resin applied to the reinforcement of the engine oil filter paper is mainly a thermosetting resol phenolic resin system, and a three-dimensional network phenolic resin crosslinking system is formed after the water-soluble phenolic resin is cured at a high temperature in a later period, so that the filter paper is endowed with excellent strength performance and oil resistance. However, such products often have a series of problems: 1. the free aldehyde and free phenol content of the product are high, so that the use performance and the environmental protection performance of the product are subjected to scaling. 2. The resin shrinkage rate is high in the curing process, so that the filter paper fibers are easy to move, the pore structure of the filter paper is changed, and the filtering performance of the paper is influenced; 3. the preparation process of the water-soluble resol is difficult to control, and the storage time is short; 4. the phenol formaldehyde resin product has darker color by using higher content of strong base as a catalyst. Although some individual problems can be solved by some technical improvements, for example, chinese patent CN103321090A reduces the content of free formaldehyde in the system by modifying with toughening resin and adding formaldehyde scavenger. Chinese patent CN108103848A also proposes the addition of modifiers and plasticizers to improve resin properties. The previous research (Qin Yongsheng, et al. preparation and application of environment-friendly water-soluble phenolic resin for engine oil filter paper. paper science and technology, 2012(3):53-55.) also prepares water-soluble phenolic resin impregnated engine oil filter paper, but the filter paper also has the problems of difficult pleating, wave rolling and the like in the later processing process; in addition, the high amount of strong base catalyst in the resin system results in very dark filter paper color and has negative effects on other properties of the filter element. In the prior art, manufacturers in the industry adopt melamine formaldehyde resin, urea-formaldehyde resin and other resins with light colors, but melamine formaldehyde resin products have large brittleness, and urea-formaldehyde resin has water resistance and high temperature difference resistance; even with the blending method, the color of the phenolic resin cannot be improved, and if an antioxidant is added, the properties of the resin are affected. Therefore, although the application of the water-soluble phenol resin to the engine oil filter paper has many problems, it has not been solved.
The acrylic resin emulsion has the advantages of cohesiveness, film forming property, environmental protection and the like, can greatly improve the strength performance of the air filter paper after being applied to the filter paper, and is widely applied to the reinforcement of the air filter paper at present. However, the water-based acrylic resin emulsion belongs to thermoplastic resin, the resin crosslinking degree is low, and the oil resistance and the high temperature resistance of the resin are not good, so that the water-based acrylic resin emulsion cannot be applied to engine oil filter paper. In fact, the acrylic resin system can also form a water-soluble thermosetting resin system through the regulation and control of the preparation method, so that the heat resistance and the high temperature resistance of the resin system are improved. For example, the previous patent application (CN110066359A) is to prepare a water-soluble acrylic resin and apply the water-soluble acrylic resin to reinforce a glass fiber filter material, and the reinforced glass fiber filter material has excellent oil resistance and high temperature resistance. But the properties of the glass fiber base material and the plant fiber base material are still greatly different, on one hand, the oil resistance and the high temperature resistance of the plant fiber are far lower than those of the glass fiber; on the other hand, the plant fibers have a curled or bent form, and therefore the sheet structure made of the plant fibers is more porous than the glass fiber paper structure. Therefore, the filter paper mainly made of plant fibers is applied to a high-temperature engine oil environment, has higher requirements on enhancing the bonding performance, oil resistance, high temperature resistance and other performances of the resin, and needs to further improve the performance of the acrylic resin.
The epoxy resin is also an excellent thermosetting resin system, the main chain of the most common bisphenol epoxy resin molecular structure contains a nonpolar benzene ring structure, a nonpolar ether bond, a flexible methylene structure and the like, and in addition, the main chain also contains an epoxy group with reactivity and the like, so the epoxy resin has the characteristics of excellent adhesive property, strength property, good chemical resistance, temperature resistance and the like for different substrates, and can meet the application requirements of the engine oil filter paper from the aspect of performance, but the application has two problems: firstly, compared with phenolic resin, epoxy resin is expensive, and the cost of the filter paper reinforced by using the epoxy resin alone is high. In addition, the process of making epoxy resins waterborne also leads to increased costs or reduced performance in order to meet environmental requirements. Thus, the epoxy resin system alone has less application in ordinary filter paper. Although the single epoxy resin or acrylic resin cannot meet all performance requirements of the engine oil filter paper due to the self-reason, the epoxy resin or the acrylic resin is combined by a chemical modification method to prepare a water-soluble epoxy acrylic resin system, so that the advantages of the epoxy resin and the acrylic resin can be combined, the cost of the epoxy resin is effectively reduced, and the environment-friendly requirement is met.
The first method is to use epoxy group of epoxy resin and acrylic monomer with carboxyl, amino or other unsaturated functional monomer to carry out esterification reaction to form epoxy acrylic monomer, then to carry out free radical polymerization, for example, patents CN107118311A, CN103059235A, CN101817930A, CN108559090A all adopt this method to prepare epoxy acrylic resin. The method has the defects that the preparation of the epoxy acrylic monomer is difficult to control, the synthesis of the resin can be influenced by byproducts formed in the process, and the production process is not favorable. The second method is to graft the epoxy resin into an acrylate polymer chain by directly using a free radical graft copolymerization method and carrying out free radical polymerization on methylene with free radical reactivity in the epoxy resin and an acrylate monomer. The method has the greatest advantages of simple process and suitability for industrial production, and has the defect that the epoxy resin cannot be grafted into a resin system one hundred percent. For example, Chinese patents CN104513344A, CN105524231A and the like are the epoxy acrylic resin emulsion prepared by the method. Chinese patent CN109180877A, CN 109293852A and the like prepare epoxy acrylic resin containing carboxyl by the method, and then prepare water-soluble epoxy modified acrylic resin by neutralizing with alkali. However, the benzoyl peroxide with higher initiation temperature and the alcohol ether solvent with high boiling point are adopted as the initiator and the reaction solvent, which has higher requirements on reaction equipment, and in addition, the removal or recycling difficulty of the solvent with high boiling point is high; in addition, these resin systems require the use of melamine formaldehyde resins as crosslinking agents, which results in the introduction of substances containing formaldehyde emissions by the resin system. In addition, as the reinforced resin of the engine oil filter paper, high strength is required, and the reinforced filter paper is required to have excellent processability, and other reported patents are not directed to the engine oil filter paper application, and do not provide a related toughening solution.
Disclosure of Invention
In order to overcome the problems or defects of the application of the existing phenolic resin as an engine oil filter paper reinforced resin system, the invention provides a water-soluble epoxy acrylic resin and a preparation method and application thereof.
The water-soluble epoxy modified acrylic resin provided by the invention is prepared at a lower temperature by a free radical graft polymerization method with an azo initiator with a low initiation temperature and non-toxic ethanol as a solvent, then neutralization reaction is carried out on alkali and carboxyl in an epoxy acrylic resin system to endow the resin with excellent water solubility, the conversion rate of acrylic acid can be further improved by continuously adding a water-soluble epoxy initiator in the later period, and finally, the ethanol can be recovered by a reduced pressure distillation method to inform the water-soluble epoxy acrylic resin system.
According to the invention, the adhesive property, heat resistance and oil resistance of the acrylic resin can be improved by introducing the epoxy resin into the acrylic resin system; and the acrylic acid long-chain alkane monomer is introduced into an acrylic resin system, so that the toughness of the resin can be further improved, and the processability of the resin can be improved. The engine oil filter paper reinforced by the water-soluble epoxy acrylic resin has excellent strength, heat resistance and oil resistance, and can meet the application requirements of the engine oil filter paper. In addition, the resin system does not need to be added with an external cross-linking agent, does not release harmful substances such as formaldehyde and the like, and avoids the inherent problems of the phenolic resin system.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a water-soluble epoxy acrylic resin which comprises the following raw materials: acrylic monomer, epoxy resin, oil-soluble initiator, water-soluble initiator, organic solvent, chain transfer agent, alkali and deionized water;
wherein the acrylic monomer accounts for 75-92 parts, the epoxy resin accounts for 8-25 parts, the mass of the oil-soluble initiator accounts for 1-5% of the mass of the monomer (the mass of the monomer herein refers to the sum of the masses of the acrylic monomer and the epoxy resin) based on the mass of the resin monomer (the sum of the masses of the acrylic monomer and the epoxy resin), the mass of the water-soluble initiator accounts for 0.1-0.4% of the mass of the monomer (the mass of the monomer herein refers to the sum of the masses of the acrylic monomer and the epoxy resin), the mass of the organic solvent accounts for 80-150% of the mass of the monomer (the mass of the monomer herein refers to the sum of the masses of the acrylic monomer and the epoxy resin), and the mass of the chain transfer agent accounts for 0.5-3% of the mass of the monomer (the mass of the monomer herein refers to the sum of the, the mass of the alkali is 4-10% of the mass of the monomer (the mass of the monomer represents the sum of the mass of the acrylic monomer and the mass of the epoxy resin), and the mass of the deionized water is 100-150% of the mass of the monomer (the mass of the monomer represents the sum of the mass of the acrylic monomer and the mass of the epoxy resin);
the invention provides a preparation method of water-soluble epoxy acrylic resin, which comprises the following steps:
(1) mixing an organic solvent and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 73-78 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B, and carrying out heat preservation treatment to obtain a mixed solution C;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution; reducing the temperature of the mixed solution C obtained in the step (3) to 60-65 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60-65 ℃; respectively adding water-soluble initiator solutions into the mixed solution D obtained in the step (4) to carry out redox reaction to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution subjected to oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin.
Further, the water-soluble epoxy acrylic resin comprises the following raw materials in parts by weight:
preferably, the mass portion of the epoxy resin is 10-20.
Preferably, the mass portion of the oil-soluble initiator is 2-3 portions.
Preferably, the mass portion of the water-soluble initiator is 0.2-0.4 portion.
Preferably, the mass part of the chain transfer agent is 1.0-2.5 parts.
Preferably, the alkaline substance is 5-8 parts by mass.
Further, the organic solvent in the step (1) is absolute ethyl alcohol; the epoxy resin in the step (1) is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin; the epoxy value of the epoxy resin in the step (1) is 0.12-0.70;
preferably, the epoxy value of the epoxy resin of step (1) is 0.25 to 0.60.
The chain transfer agent in the step (2) is more than one of dodecyl mercaptan, mercaptoethanol, thioglycolic acid, isooctyl 3-mercaptopropionate, α -methyl styrene linear dimer and 2, 4-diphenyl-4-methyl-1-pentene.
Further, the acrylic monomers in the step (2) comprise carboxyl acrylic monomers, acrylic acid long-chain alkane ester monomers and other acrylic monomers; the carboxyl acrylic monomer is one or more of methacrylic acid, acrylic acid and itaconic acid; the acrylic acid long-chain alkyl ester monomer is dodecyl (methyl) acrylate and tetradecyl (methyl) acrylate; at least one of cetyl (meth) acrylate and stearyl (meth) acrylate; the other acrylic monomers are butyl (meth) acrylate, isooctyl acrylate, ethyl (meth) acrylate, n-octyl acrylate, isooctyl acrylate, methyl (meth) acrylate; one or more of glycidyl (meth) acrylate, isobornyl methacrylate, and isobornyl acrylate; the mass ratio of the carboxyl acrylic monomer to the acrylic acid long-chain alkyl ester monomer is 8-25: 4-12; the mass ratio of the carboxyl acrylic monomer to other acrylic monomers is 8-25: 40-80.
Preferably, the carboxyl acrylic monomer is selected from any one or more of methacrylic acid, acrylic acid and itaconic acid (itaconic acid).
Preferably, the mass ratio of the carboxyl acrylic monomer to the acrylic acid long-chain alkyl ester monomer is 10-20: 4-12.
Further preferably, the mass ratio of the carboxyl acrylic monomer to the acrylic acid long-chain alkyl ester monomer is 10-20: 5-10.
Preferably, the mass ratio of the carboxyl acrylic monomer to other acrylic monomers is 10-20: 40-80.
Further, the oil-soluble initiator in the step (2) and the step (3) is more than one of azobisisobutyronitrile, azobisisoheptonitrile and azobisisobutyronitrile formamide; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 1: 1-1: 3; in the step (3), the time for dripping the mixed solution B is 2-4 hours; the time of the heat preservation treatment in the step (3) is 2-4 hours.
Further, the alkaline substance in the step (4) comprises an inorganic base and an organic base; the mass ratio of the inorganic base to the organic base is 1:2-2: 1; the inorganic alkali is more than one of sodium hydroxide, potassium hydroxide and ammonia water; the mass percentage concentration of the ammonia water is 10-25 wt%; the organic alkali is more than one of diethanolamine, triethanolamine and N, N-dimethylethanolamine. The organic base is a base having a secondary or tertiary amine group.
Preferably, the concentration of the alkaline solution in the step (4) is 10% (mass percentage concentration).
Further, the water-soluble initiator in the step (5) comprises an oxidizing agent and a reducing agent; the oxidant is potassium persulfate or ammonium persulfate, and the reducing agent is sodium bisulfite, sodium bisulfate or sodium thiosulfate; the mass ratio of the oxidant to the reducing agent in the step (5) is 1:2-2: 1; the time of the oxidation-reduction reaction in the step (5) is 0.5-1 hour; the pressure of the reduced pressure distillation in the step (6) is 0.1-0.15Mpa of negative pressure. The water-soluble initiator is a redox initiation system.
The invention provides a water-soluble epoxy acrylic resin prepared by the preparation method, wherein the glass transition temperature (Tg) of the water-soluble epoxy acrylic resin before curing is 25-55 ℃.
The water-soluble epoxy acrylic resin provided by the invention can be applied to preparation of an engine oil filter material.
The invention provides an application method of water-soluble epoxy acrylic resin in preparation of an engine oil filter material, which comprises the following steps:
diluting the water-soluble epoxy acrylic resin to 8-18 wt% (mass concentration) for impregnating the engine oil filter paper, wherein the mass of the water-soluble epoxy acrylic resin is 20-40 wt% of that of the engine oil filter paper; drying, and then performing heating curing treatment at the temperature of 140-170 ℃ for 10-60 min; and obtaining the engine oil filter material.
Preferably, the mass of the water-soluble epoxy acrylic resin is 25-35% of the mass of the engine oil filter paper.
The invention provides an engine oil filter material (engine oil filter paper filter material) prepared by the preparation method.
The invention provides a water-soluble epoxy acrylic resin and a preparation method and application thereof.
According to the invention, bisphenol epoxy resin is grafted to the acrylic resin high molecular chain segment in a free radical graft polymerization manner to prepare the epoxy modified acrylic resin, the introduction of the epoxy resin improves the adhesive force of the acrylic resin to a base material, and increases the crosslinking points of the resin, thereby improving the heat resistance and oil resistance of the resin. And then adding alkali to neutralize with a carboxyl monomer in a resin system, so as to improve the water solubility of the resin and prepare a water-soluble epoxy acrylic resin system. Meanwhile, long-chain alkane monomer of acrylic acid is introduced into an acrylic resin system to improve the toughness of the resin. The prepared ring water-soluble epoxy acrylic resin system can be used as impregnating resin of engine oil filter paper, so that the environment-friendly requirement can be met, and the reinforced filter paper has excellent strength performance, processability and heat-resistant and oil-resistant performance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the preparation method of the water-soluble epoxy acrylic resin, the epoxy acrylic resin system is directly prepared by a free radical graft polymerization method, the grafting rate of the epoxy resin is improved by means of priming of the epoxy resin and dripping of an acrylic monomer, and the process is simple. Azo initiators with low initiation temperature are used as initiators, so that the requirements on the process and equipment are low; adding a redox initiator into the waterborne system to further improve the monomer conversion rate of the acrylic resin system;
(2) according to the preparation method of the water-soluble epoxy acrylic resin, ethanol with no toxicity and low boiling point is used as a reaction solvent, the solvent can be recycled by a reduced pressure distillation method, and the final resin product is a water-based resin system, so that no safety risk exists in the application process;
(3) according to the preparation method of the water-soluble epoxy acrylic resin, the acrylic acid long-chain alkyl ester monomer is introduced into an acrylic resin system to improve the toughness of the resin system and improve the processability of the processed resin; the neutralization system adopts a mode of combining organic alkali and inorganic alkali, the inorganic alkali can greatly improve the water solubility of the resin, and the organic alkali can be used as a catalyst for the crosslinking reaction of an epoxy group and a carboxyl group while improving the water solubility of the resin, so that the curing temperature of the resin is reduced;
(4) according to the water-soluble epoxy acrylic resin provided by the invention, crosslinking agents such as melamine formaldehyde resin and the like are not required to be added, and the resin can be heated to perform self-crosslinking curing, so that toxic substances such as formaldehyde and the like do not exist, and the defect of a phenolic resin system is thoroughly overcome; the developed water-soluble resin reinforced filter paper has excellent strength, processability, heat resistance and oil resistance, can meet the use requirement of the engine oil filter paper, and has wide application prospect.
Drawings
Fig. 1 is a SEM picture (300 x) of filter base paper;
FIG. 2 is an SEM photograph (300 times) of the filter paper after the dipping treatment in example 1;
FIG. 3 is an SEM photograph (300 times) of the filter paper after the dipping treatment in example 2;
FIG. 4 is an SEM photograph (300 times) of the filter paper after the dipping treatment in example 3;
FIG. 5 is an SEM photograph (300 times) of the filter paper after the dipping treatment in example 4;
FIG. 6 is an SEM photograph (300 times) of the filter paper after the dipping treatment of comparative example 1;
FIG. 7 is an SEM photograph (300 times) of the filter paper after the dipping treatment of comparative example 2;
fig. 8 is an SEM picture (300 times) of the filter paper after the dipping treatment of comparative example 4.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
In the following examples and comparative examples, the alkali was used in a solution prepared with deionized water to a concentration of 10% by mass.
Example 1
The composition of the raw materials of the water-soluble thermosetting acrylic resin described in this example is shown in Table 1.
A preparation method of water-soluble epoxy acrylic resin comprises the following steps:
(1) mixing an organic solvent (anhydrous ethanol is selected) and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 75 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B for 3 hours, and carrying out heat preservation treatment for 2 hours to obtain a mixed solution C; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 2: 1;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution (10 wt% solution); reducing the temperature of the mixed solution C obtained in the step (3) to 60 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, wherein the mass of the added water is equal to that of the monomers (the monomers refer to acrylic acid monomers and epoxy resin), and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60 ℃, respectively adding water-soluble initiator solutions into the mixed solution D in the step (4), and carrying out redox reaction for 0.5 hour to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution after oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent under the reduced pressure of-0.15 Mpa, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin. Through tests (the German Nax 204F1 Phoenix differential scanning calorimeter is adopted for testing, the specific test conditions are that the temperature is increased within the range of-50 to 150 ℃ and at the rate of 20 ℃/min under the nitrogen atmosphere), the glass transition temperature of the water-soluble epoxy acrylic resin prepared in the example 1 is 38.6 ℃, and the temperature is shown in the table 1.
The application of the water-soluble epoxy acrylic resin prepared in the embodiment 1 in preparing the engine oil filter material comprises the following steps:
diluting the water-soluble epoxy acrylic resin to 8.0 wt% by adding water to obtain a dispersion of the water-soluble epoxy acrylic resin (the solid content is 8.0%); and (3) dipping the base paper of the filter paper into the dispersion liquid of the water-soluble epoxy acrylic resin through sizing equipment, drying at 100 ℃, and then heating to 170 ℃ for curing for 10min to obtain the engine oil filter paper. The gluing amount of the engine oil filter paper is within the range of 25 +/-1%.
The basic properties of the engine oil filter paper prepared in example 1 using the water-soluble epoxy acrylic resin are shown in Table 2. The shapes of the filter paper after the base paper is filtered and impregnated with resin are shown in figures 1 and 2. As can be seen from comparison of the figures 1 and 2, after the filter base paper is reinforced by the water-soluble epoxy acrylic resin, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and maintain higher air permeability, so that the excellent filtering performance of the base paper is maintained. In addition, the engine oil filter paper has excellent strength performance and oil resistance performance, and meets the application requirements of engine oil filter.
Example 2
The composition of the raw materials of the water-soluble thermosetting acrylic resin described in this example is shown in Table 1.
A preparation method of water-soluble epoxy acrylic resin comprises the following steps:
(1) mixing an organic solvent (anhydrous ethanol is selected) and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 74 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B for 4 hours, and carrying out heat preservation treatment for 2 hours to obtain a mixed solution C; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 1: 1;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution (10 wt% solution); reducing the temperature of the mixed solution C obtained in the step (3) to 65 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, wherein the mass of the added water is equal to that of the monomers (the monomers refer to acrylic acid monomers and epoxy resin), and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60 ℃, respectively adding water-soluble initiator solutions into the mixed solution D in the step (4), and carrying out redox reaction for 0.5 hour to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution after oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent under the reduced pressure of-0.10 Mpa, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin. Through tests (the German Nax 204F1 Phoenix differential scanning calorimeter is adopted for testing, the specific test conditions are that the temperature ranges from-50 ℃ to 150 ℃ under a nitrogen atmosphere and the temperature rise rate is 20 ℃/min.), the glass transition temperature of the water-soluble epoxy acrylic resin prepared in the example 2 is 52.2 ℃, and the temperature is shown in the table 1.
The application of the water-soluble epoxy acrylic resin prepared in the embodiment 2 in preparing the engine oil filter material comprises the following steps:
diluting the water-soluble epoxy acrylic resin to 12.5 wt% by adding water to obtain a dispersion of the water-soluble epoxy acrylic resin (the solid content is 12.5%); and (3) dipping the base paper of the filter paper into the dispersion liquid of the water-soluble epoxy acrylic resin through sizing equipment, drying at 100 ℃, and then heating to 160 ℃ for curing for 30min to obtain the engine oil filter paper. The gluing amount of the engine oil filter paper is within the range of 25 +/-1%.
The basic properties of the engine oil filter paper prepared in example 2 using the water-soluble epoxy acrylic resin are shown in table 2. The shapes of the filter paper after the base paper and the impregnated resin are shown in figures 1 and 3. As can be seen from comparison of the figures 1 and 3, after the filter base paper is reinforced by the water-soluble epoxy acrylic resin, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and maintain higher air permeability, so that the excellent filtering performance of the base paper is maintained. In addition, the engine oil filter paper has excellent strength performance and oil resistance performance, and meets the application requirements of engine oil filter.
Example 3
The composition of the raw materials of the water-soluble thermosetting acrylic resin described in this example is shown in Table 1.
A preparation method of water-soluble epoxy acrylic resin comprises the following steps:
(1) mixing an organic solvent (anhydrous ethanol is selected) and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 76 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B for 3 hours, and carrying out heat preservation treatment for 3 hours to obtain a mixed solution C; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 1: 1;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution (10 wt% solution); reducing the temperature of the mixed solution C obtained in the step (3) to 65 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, wherein the mass of the added water is equal to that of the monomers (the monomers refer to acrylic acid monomers and epoxy resin), and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60 ℃, respectively adding water-soluble initiator solutions into the mixed solution D in the step (4), and carrying out redox reaction for 0.5 hour to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution after oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent under the reduced pressure of-0.10 Mpa, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin. Through tests (the German Nax 204F1 Phoenix differential scanning calorimeter is adopted for testing, the specific test conditions are that the temperature is increased within the range of-50 to 150 ℃ and at the rate of 20 ℃/min under the nitrogen atmosphere), the glass transition temperature of the water-soluble epoxy acrylic resin prepared in the example 3 is 43.7 ℃, and the temperature is shown in the table 1.
The application of the water-soluble epoxy acrylic resin prepared in the embodiment 3 in preparing the engine oil filter material comprises the following steps:
diluting the water-soluble epoxy acrylic resin to 18.0 wt% by adding water to obtain a dispersion of the water-soluble epoxy acrylic resin (the solid content is 18.0 wt%); and (3) dipping the base paper of the filter paper into the dispersion liquid of the water-soluble epoxy acrylic resin through sizing equipment, drying at 100 ℃, and then heating to 170 ℃ for curing for 15min to obtain the engine oil filter paper. The gluing amount of the engine oil filter paper is within the range of 25 +/-1%.
The basic properties of the engine oil filter paper prepared in example 3 using the water-soluble epoxy acrylic resin are shown in Table 2. The shapes of the filter paper after the base paper is filtered and impregnated with resin are shown in figures 1 and 4. As can be seen from comparison of the figures 1 and 4, after the filter base paper is reinforced by the water-soluble epoxy acrylic resin, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and maintain higher air permeability, so that the excellent filtering performance of the base paper is maintained. In addition, the engine oil filter paper has excellent strength performance and oil resistance performance, and meets the application requirements of engine oil filter.
Example 4
The composition of the raw materials of the water-soluble thermosetting acrylic resin described in this example is shown in Table 1.
A preparation method of water-soluble epoxy acrylic resin comprises the following steps:
(1) mixing an organic solvent (anhydrous ethanol is selected) and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 76 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B for 3 hours, and carrying out heat preservation treatment for 3 hours to obtain a mixed solution C; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 1: 1;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution (10 wt% solution); reducing the temperature of the mixed solution C obtained in the step (3) to 65 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, wherein the mass of the added water is equal to that of the monomers (the monomers refer to acrylic acid monomers and epoxy resin), and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60 ℃, respectively adding water-soluble initiator solutions into the mixed solution D in the step (4), and carrying out redox reaction for 1 hour to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution after oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent under the reduced pressure of-0.10 Mpa, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin. Through tests (the test is carried out by using a German Nachi 204F1 Phoenix differential scanning calorimeter, the specific test conditions are that the temperature is increased within the range of-30 to 130 ℃ and 20 ℃/min under the nitrogen atmosphere), the glass transition temperature of the water-soluble epoxy acrylic resin prepared in the example 4 is 31.6 ℃, and the temperature is shown in the table 1.
The application of the water-soluble epoxy acrylic resin prepared in the embodiment 4 in preparing the engine oil filter material comprises the following steps:
diluting the water-soluble epoxy acrylic resin to 12.5 wt% by adding water to obtain a dispersion of the water-soluble epoxy acrylic resin (the solid content is 12.5%); and (3) dipping the base paper of the filter paper into the dispersion liquid of the water-soluble epoxy acrylic resin through sizing equipment, drying at 100 ℃, and then heating to 140 ℃ for curing for 60min to obtain the engine oil filter paper. The gluing amount of the engine oil filter paper is within the range of 25 +/-1%.
The basic properties of the engine oil filter paper prepared in example 4 using the water-soluble epoxy acrylic resin are shown in Table 2. The shapes of the filter paper after the base paper and the impregnated resin are shown in fig. 1 and 5. As can be seen from comparison of the figures 1 and 5, after the filter base paper is reinforced by the water-soluble epoxy acrylic resin, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and maintain higher air permeability, so that the excellent filtering performance of the base paper is maintained. In addition, the engine oil filter paper has excellent strength performance and oil resistance performance, and meets the application requirements of engine oil filter.
Comparative example 1
Preparation and application of water-soluble epoxy acrylic resin
Comparative example 1A water-soluble epoxy acrylic resin having the composition of the raw materials shown in Table 1 was prepared by substantially the same procedure as in example 1.
The basic performance of the prepared water-soluble epoxy acrylic resin applied to reinforced filter paper is shown in table 2, and the shapes of base paper and the filter paper impregnated with the resin are shown in fig. 1 and fig. 6. As can be seen from comparison of the figures 1 and 6, after the water-soluble epoxy acrylic resin is reinforced, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and higher air permeability, so that the excellent filtering performance of the base paper is maintained. However, the resin is sometimes too brittle due to the relatively high glass transition temperature of the resin system. The toughness is too poor and thus the burst strength of the reinforced filter paper is too low. The application requirement of the engine oil filter paper cannot be met, in addition, as the acrylic acid long-chain alkane monomer is not added into the system as a toughening monomer, the processing performance of the resin is poor, and the phenomenon that the pleated part of the filter paper is damaged easily occurs in the processing process.
Comparative example 2
Preparation and application of water-soluble epoxy acrylic resin
Comparative example 2A water-soluble epoxy acrylic resin having the composition of the raw materials shown in Table 1 was prepared by substantially the same procedure as in example 1.
The basic performance of the prepared water-soluble epoxy acrylic resin applied to reinforced filter paper is shown in table 2, and the shapes of base paper and the filter paper impregnated with the resin are shown in fig. 1 and 7. As can be seen from comparison of the figures 1 and 7, after the water-soluble epoxy acrylic resin is reinforced, no obvious hole blocking phenomenon occurs, and the filter paper can maintain the excellent pore structure of the filter paper and higher air permeability, so that the excellent filtering performance of the base paper is maintained. However, the glass transition temperature of the resin system is too low, resulting in too poor stiffness of the resin and thus too low stiffness of the reinforced filter paper. And because the dosage of the epoxy resin in the resin system is less, the crosslinking degree of the cured resin is low, the strength performance and the oil resistance of the resin are poor, and the application requirement of the engine oil filter paper cannot be met.
Comparative example 3
Preparation and application of water-soluble epoxy acrylic resin
Comparative example 3A water-soluble epoxy acrylic resin having the composition of the raw materials shown in Table 1 was prepared by substantially the same procedure as in example 1.
As can be seen from the experimental results, the resin system has higher molecular weight due to no addition of a chain transfer agent, and the water solubility of the resin is poor due to the small dosage of the neutralizing alkali, so that the resin can not be applied due to the phenomenon of separation after water is added.
Comparative example 4
The commercial alcohol-soluble thermosetting phenolic resin (product of Shandong Shengquan company) is adopted, the resin concentration is diluted to 13.5 percent by methanol for sizing, and then the sizing is carried out for 20min at 180 ℃, and the sizing amount of the filter paper is within 25 +/-1 percent. The basic properties after reinforcing the filter paper are shown in comparative example 4 in table 2, and the appearances of the base paper and the filter paper impregnated with the resin are shown in fig. 1 and 8. Comparing fig. 1 and fig. 8, it can be seen that the filter paper reinforced by the thermosetting phenolic resin maintains the excellent pore structure and higher air permeability of the filter paper, thereby maintaining the excellent filtering performance of the base paper. In addition, the filter paper has excellent strength performance and oil resistance performance, and the application requirement of the engine oil filter paper is met.
As can be seen from the performance test results (Table 2) of examples 1-4 and comparative examples 1-4, after the water-soluble epoxy acrylic resin emulsion prepared by the embodiment of the invention is used on the engine oil filter paper, the filter paper has excellent processing performance, and the application performance index can reach the same level of the alcohol-soluble phenolic resin for the engine oil filter paper at present. The water-soluble acrylic acid prepared by the invention can replace alcohol-soluble phenolic resin to be applied to engine oil filter paper.
TABLE 1 data table of the experimental raw material ratios of examples 1-4 and comparative examples 1-3
TABLE 2 results of Performance test of examples 1-4 and comparative examples 1-4
| Sample (I) | Burst (KPa) | Stiffness (mN. m) | Air permeability (mm/s) | Oil resistance (KPa) |
| Filter base paper | 103 | --- | 780 | Below the instrumental test range |
| Example 1 | 401 | 3.12 | 758 | 184 |
| Example 2 | 367 | 3.32 | 763 | 167 |
| Example 3 | 387 | 3.19 | 760 | 179 |
| Example 4 | 406 | 2.97 | 755 | 189 |
| Comparative example 1 | 297 | 3.32 | 753 | 103 |
| Comparative example 2 | 314 | 2.32 | 761 | 83 |
| Comparative example 4 | 411 | 3.26 | 756 | 198 |
Note: the filter base paper is provided for Guangzhou Huachuang chemical material science and technology development company Limited (model OF-3 #);
the bursting strength is measured by adopting an L & W bursting strength tester (Swedish L & W company, model CE180) according to the national standard (GB/T454-2002); the measurement of the stiffness is carried out by adopting a bending stiffness tester (TMI company, USA, model: 79-25-00-0002) according to the national standard (GB/T22364-2018); air permeability was measured using an FX 3300-IV Swiss air permeability apparatus according to the International Standard EN ISO 9.237. The oil resistance test method is detailed below: and (3) placing the filter paper in 160 ℃ engine oil for soaking for 48h, taking out, then, sucking the oil on the filter paper by using the oil absorption paper, and testing the bursting strength of the soaked engine oil filter paper by using the same method.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the water-soluble epoxy acrylic resin is characterized by comprising the following steps:
(1) mixing an organic solvent and epoxy resin, and uniformly stirring to obtain a mixed solution A;
(2) mixing an acrylic monomer, a chain transfer agent and an oil-soluble initiator, and uniformly stirring to obtain a mixed solution B;
(3) heating the mixed solution A to 73-78 ℃, keeping the temperature unchanged, adding an oil-soluble initiator, uniformly stirring, then dropwise adding the mixed solution B, and carrying out heat preservation treatment to obtain a mixed solution C;
(4) adding an alkaline substance into water, and uniformly mixing to obtain an alkaline solution; reducing the temperature of the mixed solution C obtained in the step (3) to 60-65 ℃, adding an alkaline solution under a stirring state for neutralization reaction, then adding water, and uniformly mixing to obtain a mixed solution D;
(5) adding a water-soluble initiator into water, and uniformly mixing to obtain a water-soluble initiator solution; keeping the temperature of the mixed solution D in the step (4) at 60-65 ℃; respectively adding water-soluble initiator solutions into the mixed solution D obtained in the step (4) to carry out redox reaction to obtain a redox mixed solution;
(6) and (3) distilling the mixed solution subjected to oxidation reduction in the step (5) under reduced pressure, recovering the organic solvent, adding water, and uniformly mixing to obtain the water-soluble epoxy acrylic resin.
2. The preparation method of the water-soluble epoxy acrylic resin as claimed in claim 1, wherein the raw materials of the water-soluble epoxy acrylic resin comprise, in parts by mass:
3. the method for preparing the water-soluble epoxy acrylic resin according to claim 1, wherein the organic solvent in the step (1) is absolute ethyl alcohol, the epoxy resin in the step (1) is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin, the epoxy value of the epoxy resin in the step (1) is 0.12-0.70, and the chain transfer agent in the step (2) is one or more of dodecyl mercaptan, mercaptoethanol, thioglycolic acid, isooctyl 3-mercaptopropionate, α -methyl styrene linear dimer and 2, 4-diphenyl-4-methyl-1-pentene.
4. The method for preparing a water-soluble epoxy acrylic resin according to claim 1, wherein the acrylic monomers of the step (2) include carboxyl acrylic monomers, acrylic acid long-chain alkyl ester monomers and other acrylic monomers; the carboxyl acrylic monomer is one or more of methacrylic acid, acrylic acid and itaconic acid; the acrylic acid long-chain alkyl ester monomer is dodecyl (methyl) acrylate and tetradecyl (methyl) acrylate; at least one of cetyl (meth) acrylate and stearyl (meth) acrylate; the other acrylic monomers are butyl (meth) acrylate, isooctyl acrylate, ethyl (meth) acrylate, n-octyl acrylate, isooctyl acrylate, methyl (meth) acrylate; one or more of glycidyl (meth) acrylate, isobornyl methacrylate, and isobornyl acrylate; the mass ratio of the carboxyl acrylic monomer to the acrylic acid long-chain alkyl ester monomer is 8-25: 4-12; the mass ratio of the carboxyl acrylic monomer to other acrylic monomers is 8-25: 40-80.
5. The method for preparing a water-soluble epoxy acrylic resin according to claim 1, wherein the oil-soluble initiator in the steps (2) and (3) is one or more of azobisisobutyronitrile, azobisisoheptonitrile and azobisisobutyronitrile formamide; the mass ratio of the oil-soluble initiator in the step (2) to the oil-soluble initiator in the step (3) is 1: 1-1: 3; in the step (3), the time for dripping the mixed solution B is 2-4 hours; the time of the heat preservation treatment in the step (3) is 2-4 hours.
6. The method for preparing a water-soluble epoxy acrylic resin according to claim 1, wherein the basic substance in the step (4) comprises an inorganic base and an organic base; the mass ratio of the inorganic base to the organic base is 1:2-2: 1; the inorganic alkali is more than one of sodium hydroxide, potassium hydroxide and ammonia water; the mass percentage concentration of the ammonia water is 10-25 wt%; the organic alkali is more than one of diethanolamine, triethanolamine and N, N-dimethylethanolamine.
7. The method for preparing a water-soluble epoxy acrylic resin according to claim 1, wherein the water-soluble initiator of step (5) comprises an oxidizing agent and a reducing agent; the oxidant is potassium persulfate or ammonium persulfate, and the reducing agent is sodium bisulfite, sodium bisulfate or sodium thiosulfate; the mass ratio of the oxidant to the reducing agent is 1:2-2: 1; the time of the oxidation-reduction reaction in the step (5) is 0.5-1 hour; the pressure of the reduced pressure distillation in the step (6) is 0.1-0.15Mpa of negative pressure.
8. A water-soluble epoxy acrylic resin obtained by the production method as set forth in any one of claims 1 to 7, characterized in that the glass transition temperature (Tg) before curing is 25 to 55 ℃.
9. The use of the water-soluble epoxy acrylic resin of claim 8 in the preparation of an engine oil filter.
10. The application of the water-soluble epoxy acrylic resin in preparing the engine oil filter material is characterized by comprising the following steps:
diluting the water-soluble epoxy acrylic resin to 8-18 wt% for impregnating the engine oil filter paper, wherein the mass of the water-soluble epoxy acrylic resin is 20-40 wt% of that of the engine oil filter paper; drying, and then performing heating curing treatment at the temperature of 140-170 ℃ for 10-60 min; and obtaining the engine oil filter material.
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