Copper abietate emulsion in water and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, and particularly discloses a copper abietate emulsion in water and a preparation method thereof. According to the application, the raw material ratio of the copper abietate emulsion in water is optimized, the sulfomethylated alkali lignin and the nanocellulose are jointly used as a first aid component, and the alkyl glycoside and the n-butyl alcohol are jointly used as a second aid component. Under the synergistic effect of various assistants, the copper abietate particles in the emulsion in water are not easy to contact and agglomerate, and are not easy to flocculate and settle in the storage process in a high-temperature environment, so that the uniform dispersion of the copper abietate can be ensured after application, and the control effect of the copper abietate on plant diseases can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pesticides, and more particularly to a copper abietate water emulsion and a preparation method thereof. BACKGROUND

[0002] Among various types of plant diseases, bacterial diseases are an important type next to fungal diseases, and common bacterial diseases include soft rot, bacterial wilt, bacterial spot and bacterial leaf spot. Among various methods for preventing and treating bacterial diseases, chemical pesticide prevention and treatment occupies an extremely important position. In actual agricultural production activities, planters often choose several common pesticides such as antibiotic fungicides, inorganic copper fungicides and organic copper fungicides to deal with the threat of bacterial diseases. Among these pesticides, organic copper fungicides have become a high-cost-performance fungicide for preventing and treating bacterial diseases due to their high copper ion content, good safety and good compatibility with other pesticides.

[0003] Copper abietate is a broad-spectrum and high-efficiency organic copper fungicide, which can effectively inhibit the enzyme activity of pathogenic bacteria by releasing copper ions to destroy the cell membrane structure of pathogenic bacteria, and has a significant effect on crop diseases caused by gram-negative bacteria (such as citrus bacterial wilt, cucumber bacterial angular spot, tomato bacterial wilt, etc.). The mechanism of action of copper abietate has both contact and systemic properties, and has less impact on the environment, so it is favored in organic agriculture and green plant industries.

[0004] According to the related art, the inventors believe that in the traditional preparation of copper abietate, liquid preparations usually have poor stability, especially when stored under high temperature conditions, which can cause flocculation and sedimentation of drug particles, resulting in uneven dispersion of copper abietate after application, which seriously affects the prevention and treatment effect of copper abietate on plant diseases. SUMMARY

[0005] In the related art, the stability of the traditional copper abietate liquid preparation is poor, and flocculation and sedimentation of drug particles can occur when stored under high temperature conditions, which seriously affects the prevention and treatment effect on plant diseases. In order to improve this defect, the present application provides a copper abietate water emulsion and a preparation method thereof.

[0006] In a first aspect, the present application provides a copper abietate water emulsion, which adopts the following technical solution: The copper abietate water emulsion comprises the following components in parts by weight: copper abietate 15-20%, emulsifier 7.2-7.8%, first auxiliary component 5.5-6.2%, thickening agent 0.3-0.5%, second auxiliary component 2.5-2.8%, antifreeze 3.5-4.5%, and the balance is made up with water to 100%; the first auxiliary component comprises sulfomethylated alkali lignin and nanocellulose, the nanocellulose accounts for 30-40% of the total weight of the first auxiliary component, and the second auxiliary component comprises n-butanol and alkyl polyglycoside.

[0007] By adopting the technical scheme, the raw material ratio of the copper abietate water emulsion is preferred, and the sulfomethylated alkali lignin and nanocellulose are selected to be used together as the first auxiliary component, and the alkyl polyglycoside and n-butanol are selected to be used together as the second auxiliary component. The main chain of the sulfomethylated alkali lignin is phenylpropane structure, which has strong hydrophobicity, and the sulfonic acid substituent group on the main chain has strong hydrophilicity, which can be adsorbed on the surface of the copper abietate microparticles, and the contact and agglomeration between different microparticles are limited by the large steric hindrance of the sulfomethylated alkali lignin. In addition to the sulfonic acid substituent group, the sulfomethylated alkali lignin also contains a large amount of alcohol hydroxyl and phenolic hydroxyl, and the nanocellulose is also rich in hydroxyl. The nanocellulose and the sulfomethylated alkali lignin can associate through hydrogen bonds in the water emulsion system, and the network structure formed by the hydrogen bonds and the steric hindance effect of the sulfomethylated alkali lignin produce a synergistic effect, thereby further limiting the contact and agglomeration between different microparticles. The alkyl polyglycoside and n-butanol both have amphiphilic properties, and can also be adsorbed on the surface of the copper abietate microparticles, and the glycoside group in the alkyl polyglycoside is rich in hydroxyl, which can enhance the hydrogen bond association network around the copper abietate microparticles, and produce a good synergistic effect with the first auxiliary component. Under the synergistic effect of various auxiliary agents, the microparticles in the copper abietate water emulsion are not easy to contact and agglomerate, and are not easy to flocculate and settle during storage in a high-temperature environment, so that uniform dispersion of the copper abietate can be ensured after application, which helps to improve the control effect of the copper abietate on plant diseases.

[0008] As preferred, the first auxiliary component further comprises a polyoxyethylene ether comb polymer, and the polyoxyethylene ether comb polymer is prepared by the following method: The sodium hydroxide solution is added to AMPS under ice water bath condition for neutralization, then the acrylamide aqueous solution and the APEG aqueous solution are added, after stirring, the temperature is raised and nitrogen is introduced, then the potassium persulfate and the sodium allylsulfonate are added under nitrogen protection, then the sodium bisulfite is continuously added, and the reaction is waited to end; after the reaction is completed, the product is added to acetone, the obtained precipitate is collected, and after drying and grinding, the polyoxyethylene ether comb polymer is obtained.

[0009] By adopting the technical scheme, the polyoxyethylene ether comb polymer is obtained by using AMPS, acrylamide and APEG as polymerization monomers and using an oxidation-reduction system to initiate polymerization.

[0010] Preferably, the sulfomethylated alkali lignin is prepared by the following method: (1) mixing alkali lignin, water and sodium hydroxide solution to obtain a raw material solution for standby use; weighing sodium sulfite and preparing a formaldehyde aqueous solution for standby use; (2) heating the raw material solution in a water bath, adding sodium sulfite and the formaldehyde aqueous solution in sequence, and then continuing to keep the reaction, after the reaction is completed, waiting for the product to cool down, precipitating the product in ethanol, washing and dialyzing the precipitate to obtain a dialysis solution, and concentrating the dialysis solution by rotary evaporation and freeze-drying to obtain the sulfomethylated alkali lignin.

[0011] By adopting the technical scheme, the sulfomethylated alkali lignin is prepared by using alkali lignin as a raw material and sodium sulfite as a sulfonating agent, and the sulfonation of the alkali lignin is realized under the action of formaldehyde and sodium hydroxide.

[0012] Preferably, in the method for preparing the sulfomethylated alkali lignin, the amount of sodium sulfite is 20-25% of the total weight of the raw material solution.

[0013] By adopting the technical scheme, the amount of sodium sulfite is preferably selected, which helps to fully realize the sulfomethylation of alkali lignin, improves the combination effect of the sulfomethylated alkali lignin and copper abietate particles, helps to reduce the contact and agglomeration between the copper abietate particles, and improves the stability of the copper abietate aqueous emulsion.

[0014] Preferably, the first auxiliary component further comprises a bridged modified sulfomethylated alkali lignin, and the bridged modified sulfomethylated alkali lignin is prepared by the following method: The sulfomethylated alkali lignin is prepared into an aqueous solution, polyether amine and formaldehyde aqueous solution are added in sequence under the condition of water bath heating, and then the reaction is kept, after the reaction is completed, the product is cooled, precipitated in ethanol, the precipitate is washed and dialyzed to obtain a dialysis solution, and the dialysis solution is concentrated by rotary evaporation and freeze-dried to obtain the bridged modified sulfomethylated alkali lignin.

[0015] By adopting the technical scheme, the sulfomethylated alkali lignin is bridged by the polyether amine to obtain the bridged modified sulfomethylated alkali lignin. The bridged modified sulfomethylated alkali lignin has greater steric hindrance compared with the sulfomethylated alkali lignin, which helps to sufficiently reduce the contact and agglomeration between the copper oleate particles and improve the stability of the copper oleate aqueous emulsion.

[0016] Preferably, the bridged modified sulfomethylated alkali lignin accounts for 8-10% of the total weight in the first auxiliary component.

[0017] By adopting the technical scheme, the application preferably uses the bridged modified sulfomethylated alkali lignin, which helps to improve the stability of the copper oleate aqueous emulsion.

[0018] Preferably, the thickening agent includes warm gum.

[0019] By adopting the technical scheme, the warm gum has significant shear thinning characteristics, has high viscosity in a non-shearing state, and the D-glucose units, D-glucuronic acid units, L-rhamnose units on the main chain and L-mannose units and L-rhamnose units on the branched chain can jointly form hydrogen bonds with the first auxiliary component. The hydrogen bond network formed by the rigidity of the warm gum molecules can effectively constrain the copper oleate particles, which can effectively hinder the sedimentation of the copper oleate particles. At the same time, the warm gum is not sensitive to acid, alkali, salt and heat, so it can effectively improve the storage effect of the copper oleate aqueous emulsion under high temperature conditions and reduce the interference of pH value on the stability of the aqueous emulsion.

[0020] Preferably, the thickening agent further includes Dean gum.

[0021] By adopting the technical scheme, the Dean gum is similar to the warm gum and can also jointly form hydrogen bonds with the first auxiliary component and has good heat resistance. The warm gum and the Dean gum can synergistically impart good pseudoplasticity to the aqueous emulsion, effectively hinder the sedimentation of the copper oleate particles, and thus improve the storage stability of the copper oleate aqueous emulsion.

[0022] Preferably, the weight ratio of the warm gum to the Dean gum is (2.5-2.7):1.

[0023] By adopting the technical scheme, the application preferably uses the weight ratio of the warm gum to the Dean gum, which helps to improve the storage stability of the copper oleate aqueous emulsion.

[0024] In a second aspect, the application provides a preparation method of a copper oleate aqueous emulsion, which adopts the following technical scheme.

[0025] A preparation method of a copper oleate aqueous emulsion includes the following steps: (1) mixed copper abietate with part of water, heated to completely dissolved, to obtain copper abietate solution, ready for use; emulsifier, first auxiliary component, thickening agent, second auxiliary component and antifreezing agent were added into the remaining water, after stirring to obtain emulsion; (2) copper abietate solution was added into the emulsion, after stirring to obtain copper abietate water emulsion.

[0026] By adopting the above technical scheme, the present application first prepares copper abietate solution and emulsion respectively, then mixes the two, under the action of various auxiliary agents, copper abietate is dispersed in the system in the form of emulsion particles, thereby obtaining copper abietate water emulsion.

[0027] In summary, the present application has the following beneficial effects: 1. The present application optimizes the raw material ratio of copper abietate water emulsion, and selects sulfomethylized alkali lignin and nanocellulose as the first auxiliary component, and selects alkyl polyglycoside and n-butanol as the second auxiliary component. Under the synergistic action of various auxiliary agents, copper abietate particles in the water emulsion are not easy to contact and agglomerate, and are not easy to flocculate and settle during storage in a high temperature environment, so that uniform dispersion of copper abietate can be ensured after application, which helps to improve the control effect of copper abietate on plant diseases.

[0028] 2. The present application uses polyetheramine to bridge sulfomethylized alkali lignin to obtain bridged modified sulfomethylized alkali lignin. Compared with sulfomethylized alkali lignin, the bridged modified sulfomethylized alkali lignin has greater steric hindrance, which helps to fully reduce the contact and agglomeration between copper abietate particles, and improves the stability of copper abietate water emulsion.

[0029] 3. The present application uses warm and dean gum as a thickening agent, which can impart good pseudoplasticity to the water emulsion within the scope defined in the present application, and can effectively hinder the settlement of copper abietate particles, thereby improving the storage stability of copper abietate water emulsion. DETAILED DESCRIPTION

[0030] The present application will be further described in detail below in combination with examples, preparation examples and comparative examples. The raw materials involved in the present application can be obtained by market purchase.

[0031] Preparation example of polyoxyethylene ether comb polymer The following will be described taking preparation example 1 as an example.

[0032] Preparation example 1 In the present preparation example, the polymerization monomers are composed of AMPS (2-acrylamido-2-methylpropanesulfonic acid), AM (acrylamide) and APEG (allyl polyoxyethylene ether) in a molar ratio of 1:6:4, and the concentration of the polymerization monomers is 30 wt%; the total weight of potassium persulfate and sodium bisulfite is 0.8% of the total weight of the monomers, the molar ratio of potassium persulfate to sodium bisulfite is 1:1.02, and the weight of sodium allyl sulfonate is 1% of the total weight of the monomers.

[0033] In the present preparation example, the polyoxyethylene ether comb polymer is prepared as follows: A 20 wt% sodium hydroxide solution is added to AMPS under ice water bath conditions for neutralization, and after the pH reaches 7, an acrylamide aqueous solution and an APEG aqueous solution are added. After stirring, the temperature is raised to 40°C and nitrogen is introduced. After 10 minutes of nitrogen introduction, potassium persulfate and sodium allyl sulfonate are added, and then a sodium bisulfite solution is added dropwise, and the reaction is continued. After 8 hours of reaction, the product is added to acetone, and the collected precipitate is dried and ground to obtain the polyoxyethylene ether comb polymer.

[0034] Preparation example of sulfomethylated alkali lignin The following is described by taking preparation example 2 as an example.

[0035] Preparation example 2 In the present preparation example, the sulfomethylated alkali lignin is prepared as follows: (1) 200 g of alkali lignin and 600 g of water are mixed, and 30 wt% sodium hydroxide is added dropwise until the alkali lignin is completely dissolved. Then the pH is adjusted to 12 to obtain a raw material solution, which is ready for use. Sodium sulfite is weighed and a 10 wt% formaldehyde aqueous solution is prepared, which is ready for use. In this step, the amount of sodium sulfite is 15% of the total weight of the raw material solution, and the weight of the formaldehyde aqueous solution is 5% of the total weight of the raw material solution. (2) The raw material solution is heated in a water bath at 90°C, and then sodium sulfite and formaldehyde aqueous solution are added successively. The reaction is continued for 3 hours, and then the product is cooled and precipitated in ethanol. The product is dialyzed in a dialysis bag with a molecular weight cutoff of 1000 Da for 7 days to obtain a dialysate. The dialysate is concentrated by rotary evaporation and freeze-dried to obtain the sulfomethylated alkali lignin.

[0036] Preparation example 3 The difference between the present preparation example and preparation example 2 is that the amount of sodium sulfite is 20% of the total weight of the raw material solution.

[0037] Preparation example 4 The difference between the present preparation example and preparation example 2 is that the amount of sodium sulfite is 22% of the total weight of the raw material solution.

[0038] Preparation example 5 The difference between this preparation example and preparation example 2 is that the amount of sodium sulfite is 25% of the total weight of the raw material solution.

[0039] Preparation example of bridged modified sulfomethylated alkali lignin The following is illustrated by taking preparation example 6 as an example.

[0040] Preparation example 6 In this preparation example, the weight of the polyether amine is 12.5% of the weight of the sulfomethylated alkali lignin, and the weight of formaldehyde in the aqueous formaldehyde solution is 2% of the weight of the sulfomethylated alkali lignin.

[0041] In this preparation example, the bridged modified sulfomethylated alkali lignin is prepared as follows: The sulfomethylated alkali lignin is prepared into a 25wt% aqueous solution, and then polyether amine (PEA-400) and 10wt% formaldehyde aqueous solution are added under the condition of 90℃ water bath heating, and then the reaction is continued for 1.5h of incubation. After the reaction is completed, the product is cooled, added into ethanol for precipitation, and then dialyzed in a dialysis bag with a molecular weight cut-off of 1000Da for 7 days to obtain a dialysate. The dialysate is concentrated by rotary evaporation and freeze-dried to obtain the bridged modified sulfomethylated alkali lignin. Example

[0042] Examples 1-5 The following is illustrated by taking example 1 as an example.

[0043] Example 1 In this example, the emulsifier is mixed by agricultural emulsifier 500# emulsifier and agricultural emulsifier 600# emulsifier in a weight ratio of 1:1; the first auxiliary component is composed of sulfomethylated alkali lignin and nanocellulose, wherein the nanocellulose accounts for 40% of the total weight of the first auxiliary component, the sulfomethylated alkali lignin is prepared according to the method of preparation example 2, the average length of the nanocellulose is 60nm, and the average diameter is 5nm; the thickening agent is selected from xanthan gum, the second auxiliary component includes n-butanol and alkyl polyglycoside, and the weight ratio of n-butanol to alkyl polyglycoside is 2:1; the antifreeze agent is selected from urea.

[0044] The present example provides a copper abietate water emulsion, which comprises the following components in parts by weight: copper abietate 15%, emulsifier 7.8%, first auxiliary component 5.5%, thickening agent 0.3%, second auxiliary component 2.8%, antifreeze agent 3.5%, and the balance is made up to 100% by water; The present example provides a preparation method of copper abietate water emulsion, which comprises the following steps: (1) mixed copper abietate with half of the water, heated to copper abietate completely dissolved, to obtain copper abietate solution, ready for use; emulsifier, first auxiliary component, thickening agent, second auxiliary component and antifreeze agent were added into the remaining water, stirred at 3000 rpm for 30 min, to obtain emulsion; (2) copper abietate solution was added into the emulsion, first stirred at 2500 rpm for 15 min, then sheared and dispersed at 13000 rpm for 45 min, to obtain copper abietate water emulsion, the average particle size was 1.06 μm determined by particle size distribution tester.

[0045] As shown in Table 1, the difference between Examples 1-5 mainly lies in that the raw material ratio of copper abietate water emulsion is different.

[0046] Table 1 Raw material ratio of copper abietate water emulsion Example 6 The difference between this example and Example 3 lies in that a part of nanocellulose in the first auxiliary component is replaced by polyoxyethylene ether comb polymer, the polyoxyethylene ether comb polymer is prepared according to the method of Preparation Example 1, and the amount of polyoxyethylene ether comb polymer accounts for 10% of the total weight of the first auxiliary component.

[0047] Example 7 The difference between this example and Example 6 lies in that the sulfomethylated alkali lignin is prepared according to the method of Preparation Example 3.

[0048] Example 8 The difference between this example and Example 6 lies in that the sulfomethylated alkali lignin is prepared according to the method of Preparation Example 4.

[0049] Example 9 The difference between this example and Example 6 lies in that the sulfomethylated alkali lignin is prepared according to the method of Preparation Example 5.

[0050] Example 10 The difference between this example and Example 9 lies in that a part of sulfomethylated alkali lignin in the first auxiliary component is replaced by bridged modified sulfomethylated alkali lignin of Preparation Example 6, and the amount of bridged modified sulfomethylated alkali lignin accounts for 6% of the total weight of the first auxiliary component.

[0051] Example 11 The difference between this example and Example 10 lies in that the amount of bridged modified sulfomethylated alkali lignin accounts for 8% of the total weight of the first auxiliary component.

[0052] Example 12 The difference between this example and Example 10 is that the bridged modified sulfomethylated alkali lignin accounts for 9% of the total weight of the first adjuvant component.

[0053] Example 13 The difference between this example and Example 10 is that the bridged modified sulfomethylated alkali lignin accounts for 10% of the total weight of the first adjuvant component.

[0054] Example 14 The difference between this example and Example 13 is that the thickening agent is xanthan gum.

[0055] Example 15 The difference between this example and Example 14 is that the thickening agent is a mixture of xanthan gum and dean gum in a weight ratio of 3:1.

[0056] Example 16 The difference between this example and Example 15 is that the weight ratio of xanthan gum to dean gum is 2.7:1.

[0057] Example 17 The difference between this example and Example 15 is that the weight ratio of xanthan gum to dean gum is 2.6:1.

[0058] Example 18 The difference between this example and Example 15 is that the weight ratio of xanthan gum to dean gum is 2.5:1.

[0059] Example 19 The difference between this example and Example 18 is that the thickening agent only includes dean gum.

[0060] Comparative Example Comparative Example 1 This comparative example provides a copper abietate water emulsion, which includes the following components in terms of weight percentage: copper abietate 20%, toluene 10%, turpentine 10%, By125 emulsifier 5%, agricultural emulsion 500# emulsifier 5%, OP-8 emulsifier 3%, antifreeze agent propylene glycol 3%, and the balance is made up to 100% by water.

[0061] When preparing the copper abietate water emulsion in this comparative example, first, the copper abietate is dissolved with toluene and turpentine, then the emulsifier is added, and after stirring at 3000 rpm for 15 min, water and antifreeze agent are added, and the stirring is continued at 13000 rpm for 45 min to obtain the copper abietate water emulsion.

[0062] Comparative Example 2 The difference between this comparative example and Example 1 is that the nanocellulose is replaced by the same weight of sulfomethylated alkali lignin.

[0063] Comparative Example 3 The difference between this comparative example and Example 1 is that the sulfomethylated alkali lignin is replaced by the same weight of nanocellulose.

[0064] Comparative Example 4 The difference between this comparative example and Example 1 is that the n-butanol is replaced by the same weight of alkyl polyglycoside.

[0065] Comparative Example 5 The difference between this comparative example and Example 1 is that the alkyl polyglycoside is replaced by the same weight of n-butanol.

[0066] Performance detection test method The copper rosinate aqueous emulsion is sampled, and the LS13320XR laser particle size analyzer is used to detect the D90 particle size of the particles contained in the test aqueous emulsion, which is recorded as the initial particle size. The copper rosinate aqueous emulsion is stored at 55°C for 1 year, and the D90 particle size of the particles contained in the aqueous emulsion is detected again, which is recorded as the particle size over time. The ratio between the particle size over time and the initial particle size is calculated, and the ratio is recorded as the particle size ratio. The detection results of the initial particle size and the particle size ratio are shown in Table 2.

[0067] Table 2 Particle size ratio It can be seen from Examples 1-5 and Comparative Examples 1 in combination with Table 2 that the particle size ratio measured in Examples 1-5 is significantly smaller than that of Comparative Example 1. It can be seen that the particle size of the micro-particles of Examples 1-5 changes less during high-temperature storage. This is because the first and second auxiliary components of the present application hinder the contact and agglomeration between copper rosinate micro-particles through steric hindrance effect and hydrogen bond network, and the thickening agent further prevents the sedimentation of copper rosinate micro-particles on this basis and cooperatively participates in the construction of the hydrogen bond network. Therefore, the copper rosinate aqueous emulsion of the present application is not prone to flocculation and sedimentation during storage in a high-temperature environment, can effectively prolong the shelf life of the product, and can ensure the uniform dispersion of copper rosinate after application, which helps to improve the control effect of copper rosinate on plant diseases.

[0068] In combination with Example 1 and Comparative Examples 2-3 and Table 2, it can be seen that the particle size ratio measured in Comparative Examples 2-3 is relatively large. This is because Comparative Example 2 cannot form a hydrogen bond network in the absence of nanocellulose, and Comparative Example 3 cannot fully combine the first auxiliary component with copper rosinate micro-particles in the absence of sulfomethylated alkali lignin, resulting in poor high-temperature stability of the copper rosinate aqueous emulsion, and a large amount of contact and agglomeration occurs during storage.

[0069] It can be seen from the combination of Example 1 and Comparative Examples 4-5 and Table 2 that the particle size ratio measured in Comparative Examples 4-5 is relatively large because Comparative Examples 4-5 fail to achieve sufficient adsorption of copper gum resin acid microparticles through the synergistic effect of alkyl glycoside and n-butanol, resulting in poor high-temperature stability of the copper gum resin acid water emulsion and a large amount of contact and agglomeration during storage.

[0070] It can be seen from the combination of Example 3 and Example 6 and Table 2 that the particle size ratio measured in Example 6 is relatively small because the addition of polyoxyethylene ether comb polymer can strengthen the hydrogen bond network and provide a certain steric hindrance, reducing the contact and agglomeration between copper gum resin acid microparticles, thereby improving the stability of the copper gum resin acid water emulsion.

[0071] It can be seen from the combination of Example 6, Examples 7-9 and Table 2 that the particle size ratio measured in Examples 7-9 is relatively small because when the amount of sodium sulfite is 20-25% of the total weight of the raw material solution, the sulfonation reaction is relatively complete, improving the combination effect of sulfomethylated alkali lignin and copper gum resin acid microparticles, thereby reducing the contact and agglomeration between copper gum resin acid microparticles and improving the stability of the copper gum resin acid water emulsion.

[0072] It can be seen from the combination of Example 9, Examples 10-13 and Table 2 that the particle size ratio measured in Examples 10-13 is relatively small because the bridged modified sulfomethylated alkali lignin has larger steric hindrance than sulfomethylated alkali lignin, which helps to sufficiently reduce the contact and agglomeration between copper gum resin acid microparticles, thereby improving the stability of the copper gum resin acid water emulsion. When the amount of bridged modified sulfomethylated alkali lignin is 8-10% of the total weight, the stability of the copper gum resin acid water emulsion is better.

[0073] It can be seen from the combination of Example 13, Examples 14-18 and Table 2 that warm rubber and dean gum can synergistically strengthen the constraint of the hydrogen bond network on copper gum resin acid microparticles, and have better thickening effect than xanthan gum, thereby reducing the agglomeration and sedimentation of copper gum resin acid microparticles and effectively improving the stability of the copper gum resin acid water emulsion. When the weight ratio of warm rubber to dean gum is (2.5-2.7):1, the stability of the copper gum resin acid water emulsion is better.

[0074] The above examples are merely an explanation of the present application and are not a limitation of the present application. Those skilled in the art can make modifications to the examples of the present application without creative contribution after reading the present specification, but as long as the modifications are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A copper abietate aqueous emulsion, characterized in that, According to parts by weight, it comprises the following components: copper turpentine acid 15-20%, emulsifier 7.2-7.8%, first auxiliary component 5.5-6.2%, thickening agent 0.3-0.5%, second auxiliary component 2.5-2.8%, antifreeze 3.5-4.5%, the rest is made up to 100% by water; the first auxiliary component includes sulfomethylized alkali lignin and nanocellulose, the nanocellulose accounts for 30-40% of the total weight of the first auxiliary component, and the second auxiliary component includes n-butanol and alkyl glycoside.

2. The copper gum rosin aqueous emulsion according to claim 1, characterized in that, The first auxiliary component further includes a polyoxyethylene ether comb polymer, which is prepared by the following method: Sodium hydroxide solution is added to AMPS under ice water bath conditions for neutralization, then acrylamide aqueous solution and APEG aqueous solution are added, after stirring, heating and nitrogen inlet, potassium persulfate and sodium allylsulfonate are added under nitrogen protection, then sodium bisulfite is continuously added, and the reaction is waited to end; after the reaction is completed, the product is added to acetone, and the obtained precipitate is collected, dried and ground to obtain the polyoxyethylene ether comb polymer.

3. The copper gum rosin aqueous emulsion of claim 1, wherein, The sulfomethylized alkali lignin is prepared by the following method: (1) Mix alkali lignin, water and sodium hydroxide solution to obtain a raw material solution, which is ready for use; weigh sodium sulfite and prepare formaldehyde aqueous solution, which is ready for use; (2) The raw material solution is heated in a water bath, and sodium sulfite and formaldehyde aqueous solution are added in sequence, then the reaction is continued, after the reaction is completed, the product is cooled, added to ethanol for precipitation, and the precipitate is washed and dialyzed to obtain a dialysate, which is concentrated by rotary evaporation and freeze-dried to obtain sulfomethylized alkali lignin.

4. The copper gum rosin aqueous emulsion according to claim 3, characterized in that, In the method for preparing the sulfomethylized alkali lignin, the amount of sodium sulfite is 20-25% of the total weight of the raw material solution.

5. The aqueous copper gum rosin emulsion of claim 3, wherein, The first auxiliary component further includes a bridged modified sulfomethylized alkali lignin, which is prepared by the following method: The sulfomethylized alkali lignin is prepared into an aqueous solution, polyether amine and formaldehyde aqueous solution are added in sequence under water bath heating, then the reaction is continued, after the reaction is completed, the product is cooled, added to ethanol for precipitation, and the precipitate is washed and dialyzed to obtain a dialysate, which is concentrated by rotary evaporation and freeze-dried to obtain the bridged modified sulfomethylized alkali lignin.

6. The copper gum rosin aqueous emulsion according to claim 5, characterized in that, In the first auxiliary component, the bridged modified sulfomethylized alkali lignin accounts for 8-10% of the total weight.

7. The copper gum rosin aqueous emulsion of claim 1, wherein, The thickening agent includes warm rubber.

8. The copper gum rosin aqueous emulsion according to claim 7, characterized in that, The thickening agent further includes Dean gel.

9. The copper gum rosin aqueous emulsion according to claim 8, characterized in that, The weight ratio of the warm rubber to the Dean gel is (2.5-2.7):

1.

10. A process for the preparation of a copper gum rosin aqueous emulsion according to any one of claims 1 to 9, characterized in that, The following steps are included: (1) Mix copper turpentine acid with part of water, heat to complete dissolution to obtain a copper turpentine acid solution, which is ready for use; add the emulsifier, the first auxiliary component, the thickening agent, the second auxiliary component and the antifreeze to the remaining water, stir to obtain an emulsion; (2) Add the copper turpentine acid solution to the emulsion, stir to obtain a copper turpentine acid water emulsion.

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