Suspending agent containing oxine-copper and benziothiazolinone as well as preparation method and application of suspending agent

Abstract

The invention relates to the technical field of suspending agents, in particular to a suspending agent containing oxine-copper and benziothiazolinone as well as a preparation method and application of the suspending agent. The invention relates to a suspending agent containing oxine-copper and benziothiazolinone, which is prepared from the following raw materials in percentage by mass: 28 to 32 percent of oxine-copper, 4 to 8 percent of benziothiazolinone, 1 to 6 percent of dispersing agent, 1 to 6 percent of wetting dispersant, 1 to 1.5 percent of suspending thixotropic agent, 4 to 8 percent of antifreezing agent, 0.05 to 0.5 percent of preservative, 0.05 to 0.5 percent of thickening agent, 0.1 to 0.5 percent of defoaming agent and the balance of water. The dispersing agent comprises polycarboxylic acid ammonium salt; the invention provides the suspending agent containing oxine-copper and benziothiazolinone, which has the advantages of favorable dispersity, favorable stability and favorable control effect. The suspending agent containing oxine-copper and benziothiazolinone provided by the invention has a good control effect on citrus tree canker and cucumber bacterial angular leaf spot.

Description

Technical Field

[0001] The invention relates to the technical field of suspension agents, and in particular to a suspension agent containing quinoline copper and thiamethoxam, and a preparation method and application thereof. Background Art

[0002] In the field of agricultural sterilization technology, the demand for the prevention and control of bacterial diseases such as cucumber bacterial angular leaf spot and citrus canker is increasing. Traditional single-ingredient fungicides will have problems such as decreased prevention and control effects and increased pathogen resistance during long-term use; suspension concentrates will have problems such as poor dispersibility, poor stability, and poor prevention effect.

[0003] Chinese invention patent application CN106417325A discloses a fungicide composition containing thiophanate-methyl and quinoline copper. The fungicide composition is formed by compounding thiophanate-methyl and quinoline copper in a ratio of 80:1 to 80. The fungicide composition is then combined with conventional pesticide auxiliary ingredients to prepare a suspension concentrate, water-dispersible granules, or wettable powder. However, no solution is provided for the dispersibility and stability issues of the suspension concentrate.

[0004] Therefore, providing a suspension concentrate containing quinoline copper and thiophanate-methyl with good dispersibility, stability and preventive effect is the main technical problem that needs to be solved at present. Summary of the Invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a suspension concentrate containing quinoline copper and thiophanate-methyl. The raw materials for its preparation include, by mass percentage, 28-32% quinoline copper, 4-8% thiophanate-methyl, 1-6% dispersant, 1-6% wetting dispersant, 1-1.5% suspension thixotropic agent, 4-8% antifreeze, 0.05-0.5% preservative, 0.05-0.5% thickener, 0.1-0.5% defoaming agent, and the balance water.

[0006] The dispersant includes polycarboxylic acid amino salt;

[0007] In one embodiment, the dispersant is a polycarboxylate amino salt.

[0008] To address the poor dispersibility of suspending agents in water, the inventors discovered during experiments that using polycarboxylic acid ammonium salts as dispersants in combination with quinoline copper, thiamethoxam, a wetting and dispersing agent, and a thixotropic agent can improve the dispersibility of the suspending agent. This is likely due to the polycarboxylic acid ammonium salt forming a strong adsorption layer on the surfaces of quinoline copper and thiamethoxam, significantly reducing the van der Waals forces between the particles, thereby improving the uniformity of the suspending agent's dispersion in water.

[0009] In one embodiment, the CAS number of the copper quinolate is 10380-28-6.

[0010] In one embodiment, the CAS number of the thiophanate-methyl is 2634-33-5.

[0011] In one embodiment, the source of the polycarboxylate amino salt includes ultrasurf 7023A from Wuxi Yijingfeng Technology Co., Ltd.

[0012] In one embodiment, the mass ratio of the dispersant to the wetting dispersant is 1:(0.4-2.5).

[0013] In one embodiment, the wetting and dispersing agent comprises a block polyether mixture.

[0014] In one embodiment, the wetting and dispersing agent is a block polyether mixture.

[0015] In one embodiment, the source of the block polyether mixture includes featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0016] In order to improve the stability of the suspension containing quinoline copper and thiophanate-methyl, the inventors found during the experiment that the use of a dispersant polycarboxylic acid amino salt and a wetting dispersant block polyether mixture in the suspension to cooperate with each other, especially when the mass ratio of the dispersant to the wetting dispersant is 1: (0.4-2.5), has a synergistic effect, which can make the suspension containing quinoline copper and thiophanate-methyl have good stability, and especially avoid the problem of particle size growth when the suspension is dispersed in water. The possible reason is that the polycarboxylic acid amino salt and the block polyether mixture produce a synergistic effect when they cooperate with each other, so that the suspension is quickly dispersed in water, and can avoid the problems of suspension particle agglomeration and particle size growth caused by insufficient wettability.

[0017] In one embodiment, the mass ratio of the suspension thixotropic agent to the dispersant is 1:(2-5).

[0018] In one embodiment, the suspending thixotropic agent comprises a silicate.

[0019] In one embodiment, the silicate comprises magnesium aluminum silicate.

[0020] In one embodiment, the suspending thixotropic agent is a silicate.

[0021] In one embodiment, the silicate is magnesium aluminum silicate.

[0022] In one embodiment, the suspension thixotropic agent is magnesium aluminum silicate.

[0023] In one embodiment, the source of magnesium aluminum silicate includes YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0024] In order to further improve the storage stability of the suspension, the inventors found during the experiment that the use of magnesium aluminum silicate as a suspension thixotropic agent in combination with a mixture of polycarboxylic acid amino salt and block polyether can improve the storage stability of the suspension. The possible reason is that the surface charge of magnesium aluminum silicate and the surface charge of polycarboxylic acid amino salt repel each other, forming a negatively charged adsorption layer on the surface of quinoline copper and thiophanate-methyl particles. The electrostatic repulsion prevents the particles in the suspension from approaching each other and aggregating, thus avoiding flocculation and sedimentation.

[0025] In one embodiment, the preservative comprises a benzisothiazolinone.

[0026] In one embodiment, the preservative is benzisothiazolinone.

[0027] In one embodiment, the CAS number of the benzisothiazolinone is 2634-33-5.

[0028] In one embodiment, the antifreeze agent is propylene glycol.

[0029] In one embodiment, the CAS number of the propylene glycol is 57-55-6.

[0030] In one embodiment, the thickener is xanthan gum.

[0031] In one embodiment, the CAS number of the xanthan gum is 11138-66-2.

[0032] In one embodiment, the defoaming agent is polydimethylsiloxane.

[0033] In one embodiment, the source of the polydimethylsiloxane includes SAG-1511 from Momentive Advanced Materials Co., Ltd.

[0034] In one embodiment, the suspension containing quinoline copper and thiophanate-methyl is prepared from raw materials including, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 2-5% dispersant, 2-5% wetting dispersant, 1-1.5% suspension thixotropic agent, 4-8% antifreeze, 0.05-0.5% preservative, 0.05-0.5% thickener, 0.2-0.3% defoaming agent, and the balance water.

[0035] In order to further improve the fungicidal effect of the suspension containing quinoline copper and thiophanate-methyl in agricultural applications, especially to improve the preventive effect on citrus canker and cucumber bacterial angular spot, the inventors found in the experimental process that by limiting the suspension containing quinoline copper and thiophanate-methyl, the raw materials for its preparation include quinoline copper 30%, thiophanate-methyl 5%, dispersant 2-5%, wetting dispersant 2-5%, suspension thixotropic agent 1-1.5%, antifreeze 4-8%, preservative 0 0.05-0.5%, thickener 0.05-0.5%, defoamer 0.2-0.3%, water as the balance; by adopting the combination of the above raw materials, especially adopting the dispersant as polycarboxylic acid amino salt, the wetting dispersant as block polyether mixture, and the suspending thixotropic agent as magnesium aluminum silicate, the combination of the above raw materials can improve the dispersibility and stability of the suspension agent, and can further improve the prevention effect of the suspension agent containing quinoline copper and thiophanate-methyl on citrus canker and cucumber bacterial angular leaf spot.

[0036] The second aspect of the present invention provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, comprising the following steps:

[0037] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0038] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0039] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0040] In one embodiment, the slurry is sand-milled in S3 to control the volume-weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0041] The third aspect of the present invention provides an application of a suspension concentrate containing quinoline copper and thiophanate-methyl. The suspension concentrate containing quinoline copper and thiophanate-methyl is applied in the field of agricultural sterilization technology.

[0042] Beneficial effects

[0043] 1. The present application provides a suspension containing quinoline copper and thiophanate-methyl with good dispersibility, stability and preventive effect.

[0044] 2. In the present application, by limiting the dispersant to include polycarboxylic acid amino salt, the dispersibility of the suspension containing quinoline copper and thiophanate-methyl in water can be improved.

[0045] 3. In the present application, by limiting the dispersant to include polycarboxylic acid amino salt, limiting the wetting dispersant to include a block polyether mixture, and limiting the mass ratio of the dispersant to the wetting dispersant to 1: (0.4-2.5) for coordination, a synergistic effect is achieved, thereby improving the stability of the suspension containing quinoline copper and thiophanate-methyl.

[0046] 4. In the present application, magnesium aluminum silicate is used as a suspension thixotropic agent in combination with a polycarboxylic acid amino salt and a block polyether mixture to improve the storage stability of a suspension containing copper quinoline and thiophanate-methyl.

[0047] 5. The suspension concentrate containing quinoline copper and thiophanate-methyl provided in this application has a good preventive effect on citrus canker and cucumber bacterial angular spot. DETAILED DESCRIPTION

[0048] Example 1

[0049] In a first aspect of the present embodiment, a suspension concentrate containing quinoline copper and thiophanate-methyl is provided. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 2% dispersant, 2% wetting dispersant, 1% suspension thixotropic agent, 6% antifreeze agent, 0.15% preservative, 0.15% thickener, 0.2% defoaming agent, and the balance water.

[0050] The CAS number of the quinoline copper is 10380-28-6.

[0051] The CAS number of the thiophanate-methyl is 2634-33-5.

[0052] The dispersant is polycarboxylate amino salt.

[0053] The source of the polycarboxylate amino salt is ultrasurf 7023A produced by Wuxi Yijingfeng Technology Co., Ltd.

[0054] The wetting and dispersing agent is a block polyether mixture.

[0055] The source of the block polyether mixture is featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0056] The suspension thixotropic agent is magnesium aluminum silicate.

[0057] The source of the magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0058] The antifreeze agent is propylene glycol.

[0059] The CAS number of the propylene glycol is 57-55-6.

[0060] The preservative is benzisothiazolinone.

[0061] The CAS number of the benzisothiazolinone is 2634-33-5.

[0062] The thickener is xanthan gum.

[0063] The CAS number of the xanthan gum is 11138-66-2.

[0064] The defoaming agent is polydimethylsiloxane.

[0065] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0066] The second aspect of this embodiment provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0067] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0068] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0069] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0070] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0071] The third aspect of this embodiment provides an application of a suspension concentrate containing quinoline copper and thiophanate-methyl. The suspension concentrate containing quinoline copper and thiophanate-methyl is applied in the field of agricultural sterilization technology.

[0072] Example 2

[0073] In a first aspect of the present embodiment, a suspension concentrate containing quinoline copper and thiophanate-methyl is provided. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 3% dispersant, 3% wetting dispersant, 1% suspension thixotropic agent, 6% antifreeze agent, 0.15% preservative, 0.15% thickener, 0.2% defoaming agent, and the balance water.

[0074] The CAS number of the quinoline copper is 10380-28-6.

[0075] The CAS number of the thiophanate-methyl is 2634-33-5.

[0076] The dispersant is polycarboxylate amino salt.

[0077] The source of the polycarboxylate amino salt is ultrasurf 7023A produced by Wuxi Yijingfeng Technology Co., Ltd.

[0078] The wetting and dispersing agent is a block polyether mixture.

[0079] The source of the block polyether mixture is featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0080] The suspension thixotropic agent is magnesium aluminum silicate.

[0081] The source of the magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0082] The antifreeze agent is propylene glycol.

[0083] The CAS number of the propylene glycol is 57-55-6.

[0084] The preservative is benzisothiazolinone.

[0085] The CAS number of the benzisothiazolinone is 2634-33-5.

[0086] The thickener is xanthan gum.

[0087] The CAS number of the xanthan gum is 11138-66-2.

[0088] The defoaming agent is polydimethylsiloxane.

[0089] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0090] The second aspect of this embodiment provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0091] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0092] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0093] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0094] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0095] The third aspect of this embodiment provides an application of a suspension concentrate containing quinoline copper and thiophanate-methyl. The suspension concentrate containing quinoline copper and thiophanate-methyl is applied in the field of agricultural sterilization technology.

[0096] Example 3

[0097] In a first aspect of the present embodiment, a suspension concentrate containing quinoline copper and thiophanate-methyl is provided. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 2% dispersant, 5% wetting dispersant, 1.5% suspension thixotropic agent, 6% antifreeze agent, 0.15% preservative, 0.15% thickener, 0.3% defoaming agent, and the balance water.

[0098] The CAS number of the quinoline copper is 10380-28-6.

[0099] The CAS number of the thiophanate-methyl is 2634-33-5.

[0100] The dispersant is polycarboxylate amino salt.

[0101] The source of the polycarboxylate amino salt is ultrasurf 7023A produced by Wuxi Yijingfeng Technology Co., Ltd.

[0102] The wetting and dispersing agent is a block polyether mixture.

[0103] The source of the block polyether mixture is featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0104] The suspension thixotropic agent is magnesium aluminum silicate.

[0105] The source of the magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0106] The antifreeze agent is propylene glycol.

[0107] The CAS number of the propylene glycol is 57-55-6.

[0108] The preservative is benzisothiazolinone.

[0109] The CAS number of the benzisothiazolinone is 2634-33-5.

[0110] The thickener is xanthan gum.

[0111] The CAS number of the xanthan gum is 11138-66-2.

[0112] The defoaming agent is polydimethylsiloxane.

[0113] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0114] The second aspect of this embodiment provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0115] S1. Stir and mix water, dispersant, wetting dispersant, antifreeze, preservative, defoaming agent and suspension thixotropic agent in sequence to obtain mixture a;

[0116] S2. Add quinoline copper and thiabendazole to mixture a and stir to obtain slurry;

[0117] S3. Sand mill the slurry, then add thickening agent and stir to obtain a suspension containing quinoline copper and thiabendazole.

[0118] In S3, the slurry is sand milled to control the volume-weighted average particle size D[4,3] of the slurry to be less than 2 μm.

[0119] The third aspect of the embodiment provides an application of a suspension containing quinoline copper and thiabendazole, which is applied in the field of agricultural sterilization technology.

[0120] Embodiment 4

[0121] The first aspect of the embodiment provides a suspension containing quinoline copper and thiabendazole, which is prepared from the following raw materials in percentage by mass: quinoline copper 30%, thiabendazole 5%, dispersant 5%, wetting dispersant 2%, suspension thixotropic agent 1.5%, antifreeze 6%, preservative 0.15%, thickening agent 0.15%, defoaming agent 0.2%, and water in balance.

[0122] The CAS number of the quinoline copper is 10380-28-6.

[0123] The CAS number of the thiabendazole is 2634-33-5.

[0124] The dispersant is polycarboxylic acid ammonium salt.

[0125] The polycarboxylic acid ammonium salt is ultrasurf 7023A from Wuxi Yijingfeng Technology Co., Ltd.

[0126] The wetting dispersant is block polyether mixture.

[0127] The block polyether mixture is featdis 894D from Shanghai Xuezhu Fine Chemical Co., Ltd.

[0128] The suspension thixotropic agent is magnesium aluminum silicate.

[0129] The magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Material Co., Ltd.

[0130] The antifreeze is propylene glycol.

[0131] The CAS number of the propylene glycol is 57-55-6.

[0132] The preservative is benzisothiazolinone.

[0133] The CAS number of the benzisothiazolinone is 2634-33-5.

[0134] The thickener is xanthan gum.

[0135] The CAS number of the xanthan gum is 11138-66-2.

[0136] The defoaming agent is polydimethylsiloxane.

[0137] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0138] The second aspect of this embodiment provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0139] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0140] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0141] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0142] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0143] The third aspect of this embodiment provides an application of a suspension concentrate containing quinoline copper and thiophanate-methyl. The suspension concentrate containing quinoline copper and thiophanate-methyl is applied in the field of agricultural sterilization technology.

[0144] Comparative Example 1

[0145] The first aspect of this comparative example provides a suspension containing quinoline copper and thiophanate-methyl. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 2% dispersant, 2% wetting dispersant, 6% antifreeze, 0.15% preservative, 0.15% thickener, 0.2% defoamer, and the balance water.

[0146] The CAS number of the quinoline copper is 10380-28-6.

[0147] The CAS number of the thiophanate-methyl is 2634-33-5.

[0148] The dispersant is polycarboxylate amino salt.

[0149] The source of the polycarboxylate amino salt is ultrasurf 7023A produced by Wuxi Yijingfeng Technology Co., Ltd.

[0150] The wetting and dispersing agent is a block polyether mixture.

[0151] The source of the block polyether mixture is featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0152] The antifreeze agent is propylene glycol.

[0153] The CAS number of the propylene glycol is 57-55-6.

[0154] The preservative is benzisothiazolinone.

[0155] The CAS number of the benzisothiazolinone is 2634-33-5.

[0156] The thickener is xanthan gum.

[0157] The CAS number of the xanthan gum is 11138-66-2.

[0158] The defoaming agent is polydimethylsiloxane.

[0159] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0160] The second aspect of this comparative example provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0161] S1. Water, dispersant, wetting dispersant, antifreeze, preservative, and defoaming agent were stirred and mixed in sequence to obtain a mixture a;

[0162] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0163] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0164] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0165] Comparative Example 2

[0166] The first aspect of this comparative example provides a suspension containing quinoline copper and thiophanate-methyl. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 3% dispersant, 2% wetting dispersant, 1% suspension thixotropic agent, 6% antifreeze agent, 0.15% preservative, 0.15% thickener, 0.2% defoaming agent, and the balance water.

[0167] The CAS number of the quinoline copper is 10380-28-6.

[0168] The CAS number of the thiophanate-methyl is 2634-33-5.

[0169] The dispersant is naphthalenesulfonate formaldehyde condensate.

[0170] The source of the naphthalenesulfonate formaldehyde condensate is 1608 powder from Suzhou Sihang Daneng New Materials Co., Ltd.

[0171] The wetting and dispersing agent is a block polyether mixture.

[0172] The source of the block polyether mixture is featdis 894D from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0173] The suspension thixotropic agent is magnesium aluminum silicate.

[0174] The source of the magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0175] The antifreeze agent is propylene glycol.

[0176] The CAS number of the propylene glycol is 57-55-6.

[0177] The preservative is benzisothiazolinone.

[0178] The CAS number of the benzisothiazolinone is 2634-33-5.

[0179] The thickener is xanthan gum.

[0180] The CAS number of the xanthan gum is 11138-66-2.

[0181] The defoaming agent is polydimethylsiloxane.

[0182] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0183] The second aspect of this comparative example provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0184] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0185] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0186] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0187] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0188] Comparative Example 3

[0189] The first aspect of this comparative example provides a suspension containing quinoline copper and thiophanate-methyl. The raw materials for its preparation are, by mass percentage, 30% quinoline copper, 5% thiophanate-methyl, 3% dispersant, 3% wetting dispersant, 1% suspension thixotropic agent, 6% antifreeze agent, 0.15% preservative, 0.15% thickener, 0.2% defoaming agent, and the balance water.

[0190] The CAS number of the quinoline copper is 10380-28-6.

[0191] The CAS number of the thiophanate-methyl is 2634-33-5.

[0192] The dispersant is sodium polycarboxylate.

[0193] The source of the sodium polycarboxylate is SP-27001 from Jiangsu Qingyu Chemical Technology Co., Ltd.

[0194] The wetting and dispersing agent is an alkyl sulfonate mixture.

[0195] The source of the alkyl sulfonate mixture is SP-SC29 from Jiangsu Qingyu Chemical Technology Co., Ltd.

[0196] The suspension thixotropic agent is magnesium aluminum silicate.

[0197] The source of the magnesium aluminum silicate is YH-ED from Zhejiang Yuheng New Materials Co., Ltd.

[0198] The antifreeze agent is propylene glycol.

[0199] The CAS number of the propylene glycol is 57-55-6.

[0200] The preservative is benzisothiazolinone.

[0201] The CAS number of the benzisothiazolinone is 2634-33-5.

[0202] The thickener is xanthan gum.

[0203] The CAS number of the xanthan gum is 11138-66-2.

[0204] The defoaming agent is polydimethylsiloxane.

[0205] The source of the polydimethylsiloxane is SAG-1511 from Maitu Advanced Materials Co., Ltd.

[0206] The second aspect of this comparative example provides a method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl, which comprises the following steps:

[0207] S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a;

[0208] S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry;

[0209] S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

[0210] In the above-mentioned S3, the slurry is sand-milled to control the volume weighted average particle size D[4, 3] of the slurry to be less than 2 μm.

[0211] Performance Testing

[0212] 1. Dispersion test:

[0213] The suspension containing quinoline copper and thiophanate-methyl provided in Examples 1-4 and Comparative Examples 1-3 was prepared according to

[0214] The test was conducted in accordance with GBT 32775-2016 Pesticide Dispersion Determination Method. The test results are shown in Table 1. The results were considered qualified if the dispersion was uniform, there was no particle size growth, and there was no water precipitation after hot storage. The results were considered unqualified if there was uneven dispersion, particle size growth, or a lot of water precipitation after hot storage.

[0215] Table 1

[0216]

[0217] The test results in Table 1 show that the suspension concentrates containing copper quinoline and thiophanate-methyl provided in Examples 1-4 have good dispersion uniformity, no particle size growth, and no water precipitation after hot storage, thus reaching a qualified state.

[0218] 2. Storage test:

[0219] The suspension containing quinoline copper and thiophanate-methyl provided in Example 1 and Comparative Example 2 was placed at 23°C.

[0220] After being stored at 54°C for 14 days, the appearance of the suspension concentrate containing quinoline copper and thiophanate-methyl was observed, and the suspension rate, foaming property, pH and particle size were tested. The test results are shown in Table 2. The suspension rate test was carried out using the GBT

[0221] 14825-2023 Determination of Suspension Rate of Pesticides”; for foaming test, GBT 28137-2011 Determination of Persistent Foaming of Pesticides was used.

[0222] Table 2

[0223]

[0224] For particle size stability during high-temperature storage, the change rate of the volume-weighted average particle size D[4,3] needs to be less than 10%. The test results in Table 2 show that the change rate of the volume-weighted average particle size D[4,3] of the suspension concentrate provided in Example 1 during hot storage is less than 10%; the change rate of the volume-weighted average particle size D[4,3] of the suspension concentrate provided in Comparative Example 2 during hot storage is greater than 10%. When the change rate of the volume-weighted average particle size D[4,3] of the suspension concentrate during hot storage is greater than 10%, the volume particle size increases after hot storage, and the product will have the risk of sedimentation during the shelf life, thereby reducing the storage stability of the suspension concentrate.

[0225] 2. Field application experiment on citrus canker:

[0226] Ⅰ. The contents of the field application experiment on citrus canker in Ziyun Village, Qingxi Town, Qianwei County, Leshan City, Sichuan Province are as follows:

[0227] Environment and facility cultivation conditions:

[0228] 3.1 Test site location:

[0229] Group 2, Ziyun Village, Qingxi Town, Qianwei County, Leshan City, Sichuan Province (104°E, 29°N).

[0230] 3.2 Test target situation:

[0231] Target: Canker [Xanthomonas campestris], no canker developed at the time of application.

[0232] 3.3 Test crops, growth period and growth conditions:

[0233] Citrus tree variety: Wogan, about 7 years old, about 55 trees planted per mu, conventional open-field cultivation, the first application of pesticides was at the early stage of summer shoot emergence of the citrus trees, and the second application was at the end of physiological fruit drop.

[0234] 3.4 Soil data of the test site:

[0235] Sandy loam, pH 5.2, organic matter content 23.2g / kg.

[0236] 3.5 Agricultural operations in the experimental site:

[0237] No other pesticides were applied before the experiment, and routine fertilizer and water management was used.

[0238] 3.6 Meteorological data:

[0239] Weather conditions at the test site on the days of application: On May 22, 2022, the first application, there was rain in the early morning. The weather was sunny at the time of application, with a temperature of 21.1°C, a relative humidity of 79.0%, and a precipitation of 0.4 mm, which did not affect the test. On June 1, 2022, the second application, there was rain in the early morning. The weather was cloudy at the time of application, with a temperature of 23.7°C, a relative humidity of 91.3%, and a precipitation of 20.3 mm, which did not affect the test. On June 11, 2022, the third application, there was rain in the early morning. The weather was cloudy at the time of application, with a temperature of 22.4°C, a relative humidity of 93.5%, and a precipitation of 5.0 mm, which did not affect the test. Weather conditions at the test site during the test period are shown in the table.

[0240] 3.7 Information on pesticides for controlling other diseases and pests:

[0241] On June 6, 2022, 4000 times of 33% spiroworm·thiazolinone was applied to control citrus scale insects.

[0242] Application method:

[0243] Period and method: Crop: citrus trees, variety: Wogan. The first application of pesticide is at the early stage of summer shoot growth of citrus trees, at the end of the second physiological fruit drop, and before ulcer disease occurs. Use the secondary dilution method to prepare the solution, and spray evenly with a sprayer.

[0244] Application equipment: Linong HD400 sprayer with conical nozzle, spray pressure 0.2-0.4 MPa, nozzle diameter 1 mm, flow rate 710 ml / min, and the error after calibration is within 10%.

[0245] Application time and frequency: May 22, 2022, first spray; June 1, 2022, second spray; June 11, 2022, third spray; a total of 3 applications, and a control experiment using clean water, the test results are shown in Table 3. The amount of each suspension containing quinoline copper and thiophanate-methyl provided in Examples 1-4 was 3.6 ml, and the suspension was diluted 1500 times with water before application.

[0246] Usage capacity: Each tree consumes about 1.8 liters of water, and the water consumption per hectare is about 1,485 liters.

[0247] Survey method, time, and frequency: Survey once every 20 days after three doses of the drug to evaluate the efficacy of the drug. Specific time: July 1, 2022.

[0248] The calculation formula of the disease index in Table 3 is:

[0249] The disease index is the disease index;

[0250]

[0251] Table 3

[0252] Example % Control Significance Disease Index Example 1 77 aA 4 Example 2 76.04 aA 9.42 Example 3 67.32 cdBC 12.99 Example 4 66.05 dBC 13.42 Water 17.4

[0253] The test results in Table 3 show that the suspension concentrates containing quinoline copper and thiophanate-methyl provided in Examples 1 and 2 have a protective effect of more than 75% 10 days after administration, and have a good protective effect against citrus canker.

[0254] II. The contents of the field application experiment on citrus canker in Xinjian Village, Huangxing Town, Changsha County, Hunan Province are as follows:

[0255] Environment and facility cultivation conditions:

[0256] 3.1 Test site location:

[0257] The experimental site was set up in a citrus orchard at the Xinjian Village Experimental Base in Huangxing Town, Changsha County.

[0258] 3.2 Test target situation:

[0259] Canker disease (Xanthomonas campestris); the pesticide is applied at the early stage of the disease.

[0260] 3.3 Test crops, varieties and growth conditions:

[0261] Citrus, variety: Langfeng navel orange. Six-year-old trees, in their spring shoot growth phase at the time of the experiment, exhibited uniform growth.

[0262] 3.4 Soil type of the test site:

[0263] The soil is lime mud field soil, which is relatively fertile, has good fertility, and is easy to drain and irrigate.

[0264] 3.5 Water and fertilizer management in the experimental site:

[0265] Field water and fertilizer management was carried out as usual.

[0266] 3.6 Meteorological data:

[0267] On March 28, at the time of application, the temperature was measured at 20.6°C and the humidity was 62.4%. Weather data for the test site that day was sunny, with a temperature of 11-23°C and a northwest wind of Force 1. On April 6, at the time of application, the temperature was measured at 23.4°C and the humidity was 58.6%. Weather data for the test site that day was cloudy, with a temperature of 25-36°C and a northwest wind of Force 1. On April 13, at the time of application, the temperature was measured at 15.9°C and the humidity was 63.6%. Weather data for the test site that day was overcast, with a temperature of 12-17°C and a northwest wind of Force 1. Cloudy and rainy weather dominated the test period. See the meteorological data tables (Appendixes 4 and 5) for details.

[0268] 3.7 Information on pesticides for controlling other diseases and pests:

[0269] No other fungicides were sprayed during the trial period.

[0270] Application method:

[0271] Period and method of use:

[0272] Apply the pesticide before or at the early stages of citrus canker. Weigh the required dosage for each treatment, dilute with water, and spray uniformly, avoiding any overlap or omissions. A blank control was sprayed with water. The test results are shown in Table 4. The suspension concentrates containing quinoline copper and thiamethoxam provided in Examples 1-4 were applied in a dosage of 3.6 ml each, diluted 1500-fold with water.

[0273] Application equipment: YQ-16 electric sprayer.

[0274] Application time and number of times: The pesticide was applied three times in total, on March 28, 2022, April 6, 2022 and April 13, 2022 respectively.

[0275] Usage capacity: The application rate is 2 liters per tree, and spray until the liquid wets the leaves but does not drip.

[0276] Investigation method, time and frequency: The disease occurrence after pesticide treatment was investigated on the 23rd day after the last application of pesticide (May 6).

[0277] Table 4

[0278] Example % Control Significance Disease Index Example 1 80.47 aA 2.11 Example 2 84.45 Aa 2.11 Example 3 75.77 BCbc 6.04 Example 4 77.55 BCb 5.64 Water 10.83

[0279] The test results in Table 4 show that the suspension concentrates containing quinoline copper and thiophanate-methyl provided in Examples 1 and 2 have a protective effect of more than 80% 10 days after administration, and have a good protective effect against citrus canker.

[0280] 3. Field application experiment on bacterial angular leaf spot of cucumber:

[0281] I. Application testing against bacterial angular leaf spot of cucumbers was conducted at the Ecological Research Institute's dedicated base at Zhuanghang Comprehensive Experimental Station, Shanghai Academy of Agricultural Sciences, 888 Yezhuang Road, Fengxian District, Shanghai. The test results are shown in Table 5. Environmental and Facility Cultivation Conditions: Site Location: The test site is located at the Ecological Research Institute's dedicated base at Zhuanghang Comprehensive Experimental Station, Shanghai Academy of Agricultural Sciences, 888 Yezhuang Road, Fengxian District, Shanghai. The terrain is flat and the irrigation and drainage facilities are well-established. Target Conditions: At the start of the test, bacterial angular leaf spot (Pseudomonas syringae) was sporadically occurring on individual cucumber plants, indicating an early stage of disease.

[0282] Test crop, variety and growing conditions: The test crop was cucumber, and the variety was Shengqing No. 1. Cucumber, greenhouse cultivation, good growth, all test plots had uniform cultivation conditions (soil type, water and fertilizer management, transplanting period, planting density, growth period, etc.), and met the local scientific agricultural practices. The first time of spraying, the cucumber was in the flowering and fruiting period.

[0283] Test site soil type: The soil in this area is Qinghuang soil, with medium soil fertility and medium organic matter content. Test site water and fertilizer management: base fertilizer of test site is 1 ton of commercial organic fertilizer and 50 kg of compound fertilizer (15-10-17) per mu, drip irrigation is used for fertilizer and water management during growth, and other field management is carried out according to the conventional method.

[0284] Weather data: May 15, 2020, first time of spraying: southwest wind, 1.5 m / s, temperature 21.3-29.8℃, relative humidity 68%-99%; May 22, 2020, second time of spraying: southeast wind 2.3 m / s, temperature

[0285] 19.4-25.9℃, relative humidity 61%-89%. Weather data during the test period: During the test period, there were 4 rainy days, the total rainfall was 16.5 mm, the daily average temperature was between 16.5-26.0℃, and the daily average relative humidity was between 54.2%-90.8%.

[0286] Data of other pesticides for controlling other pests and diseases: No other pesticides were used during the test.

[0287] Spraying method: The first time of spraying was started when the cucumber bacterial angular spot disease occurred sporadically. When preparing the pesticide, first measure the water quantity in the control area, then put the pesticide in a little clean water, mix it, then dilute it with water to the water quantity in the test area, and then carry out leaf spraying; the amount of each use of the suspension concentrate containing oxine-copper and thiabendazole provided in Examples 1-4 is 3.6 ml, which is diluted with water at a ratio of 1500:1 before spraying.

[0288] Spraying equipment: Singapore Linnong PJB-16 sprayer, single conical spray head, working pressure 2

[0289] kgf / cm 2 .

[0290] Spraying time and frequency: The first time of spraying was May 15, 2020, and the second time of spraying was May 22, 2020. The first time of spraying was during the flowering and fruiting period of cucumber, and the cucumber bacterial angular spot disease occurred sporadically. There were several rainfall processes during the test period.

[0291] Usage capacity: 30 liters of pesticide solution per mu.

[0292] Investigation method, time and frequency: the control effect was investigated 7 days after the 2nd application (May 22, 2020), a total of 1 time.

[0293] Table 5

[0294]

[0295] As can be seen from the test results in Table 5, the control effect of the suspensions containing quinolate copper and thiabendazole provided by Examples 1 and 2 is more than 80% 10 days after application, and has good control effect on cucumber bacterial angular spot.

[0296] II. Application test on cucumber bacterial angular spot in Caomiao Village, Heilong Town, Qingshen County, Sichuan Province, and the test results are shown in Table 6.

[0297] 1. Test conditions:

[0298] 1.1 Crop and target: crop / cucumber / eggplant, target / bacterial angular spot [Pseudomonas syringae].

[0299] 1.2 Test conditions: The test was conducted in cucumber field in Caomiao Village, Heilong Town, Qingshen County, Sichuan Province from July 3, 2020 to July 31, 2020. Cucumber variety: eggplant, seedling on May 13, 2020, transplanting on May 22, 2020, about 2000 plants / acre. The previous crop was pepper, and the field was brown-gray semi-sandy soil with medium fertility level, pH 5.9, and organic matter content about 1.8%. No other fungicides were applied before the test.

[0300] 2. Test design and arrangement:

[0301] 2.2.2 Plot area and repetition: 4 repetitions, plot area 15 m 2 , and a protective row was set between plots.

[0302] 2.3 Application method:

[0303] 2.3.1 Application time and frequency: during the flowering and fruiting period of cucumber, spraying was started before the occurrence of bacterial angular spot, with an interval of 7 days, and 3 times of continuous application. Specific time: July 3, 2020, July 10, 2020, and July 17, 2020; the use amount of the suspensions containing quinolate copper and thiabendazole provided by Examples 1-4 was 3.6 ml each time, and all were diluted with water at 1500 times to spray.

[0304] 2.3.2 Use equipment and application method: the pesticide solution was prepared by twice dilution method, and the main preparation tools were balance, graduated cylinder, pipette, glass rod, etc. PB-16 type sprayer was used for spraying, the spraying pressure was 0.2-0.3 Mpa, the nozzle diameter was 1 mm, and the water consumption per plot was about 1-1.35 liters.

[0305] 2.3.3 Meteorological Data: July 3, 2020, the first application, sunny weather. July 10, 2020, the second application, rain fell in the early morning, but it was cloudy at the time of application, which did not affect the test. July 17, 2020, the third application, rain fell in the early morning, but it was cloudy at the time of application, which did not affect the test. Detailed data is shown in the attached table.

[0306] 2.3.4 Soil data: Brown-gray semi-sandy soil, medium fertility, pH 5.9, organic matter content

[0307] About 1.8%.

[0308] 2.3.5 Prevention and control of non-target organisms: No other pesticides were applied during the trial.

[0309] 3 Investigation and Results

[0310] 3.1 Survey Method: Samples were collected at five diagonal points in each plot, and all leaves of three plants were inspected at each point. Grading: Grade 0: No lesions; Grade 1: Lesions account for less than 5% of the total leaf area; Grade 3: Lesions account for 6%-10% of the total leaf area; Grade 5: Lesions account for 11%-20% of the total leaf area; Grade 7: Lesions account for 21%-50% of the total leaf area; Grade 9: Lesions account for more than 51% of the total leaf area.

[0311] 3.2 Survey Time and Frequency: One survey will be conducted 14 days after the third dose, for a total of two surveys. Specific time: July 31, 2020.

[0312] Table 6

[0313] Example Disease Index % Control Significance Example 1 5.5 68.2 aA Example 2 8.76 66.49 aA Example 3 1.81 56.61 Bb Example 4 9.4 45.7 dD

[0314] The test results in Table 6 show that the suspension concentrates containing quinoline copper and thiophanate-methyl provided in Examples 1 and 2 have a protective effect of more than 66% 10 days after administration, and have a good protective effect against bacterial angular leaf spot of cucumber.

Claims

1. A suspension concentrate containing quinoline copper and thiophanate-methyl, characterized in that: The raw materials for its preparation include, by mass percentage, 28-32% of quinoline copper, 4-8% of thiamethoxam, 1-6% of dispersant, 1-6% of wetting and dispersing agent, 1-1.5% of suspension thixotropic agent, 4-8% of antifreeze agent, 0.05-0.5% of preservative, 0.05-0.5% of thickener, 0.1-0.5% of defoaming agent, and the balance of water; The dispersant includes polycarboxylic acid amino salt.

2. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 1, wherein The mass ratio of the dispersant to the wetting dispersant is 1:(0.4-2.5).

3. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 1, wherein The wetting and dispersing agent includes a block polyether mixture.

4. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 1, wherein The mass ratio of the suspension thixotropic agent to the dispersant is 1:(2-5).

5. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 1, wherein The suspending thixotropic agent includes a silicate.

6. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 5, characterized in that The silicate includes magnesium aluminum silicate.

7. The suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 1, wherein The preservatives include benzisothiazolinone.

8. A method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: S1. The water, dispersant, wetting dispersant, antifreeze, preservative, defoamer and suspension thixotropic agent were stirred and mixed in sequence to obtain a mixture a; S2. Copper quinoline and thiophanate-methyl were added to the mixture a and stirred to obtain a slurry; S3. The slurry is sand-milled, and a thickener is added and stirred to obtain a suspension containing quinoline copper and thiophanate-methyl.

9. The method for preparing a suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in claim 8, wherein: In the step S3 , the slurry is sand-milled to control the volume-weighted average particle size of the slurry to be less than 2 μm.

10. Use of the suspension concentrate containing quinoline copper and thiophanate-methyl as claimed in any one of claims 1 to 7, characterized in that: The suspension containing quinoline copper and thiophanate-methyl is used in the technical field of agricultural sterilization.

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