Crystalline form C of shuangzuocaotong, preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of herbicide crystallization process, particularly to Crystalline form C of shuangzuocaotong, and a preparation method therefor and use thereof. The Crystalline form C of shuangzuocaotong has an X-ray powder diffraction pattern having characteristic absorption peaks at the following 2θ positions: 10.159, 10.658, 13.318, 14.579, 16.096, 18.061, 19.322, 19.68, 20.04, 20.659, 21.281, 23, 24.16, 24.619, 26.101, 26.74, 30.359, 31.018, 32.378, 35.398 and 38.26 degrees, wherein 2θ has an error range within ±0.2°. The Crystalline form C of shuangzuocaotong has good stability, and its compounded composition with additional active ingredient(s) has a good control effect to broadleaf weeds and some gramineous weeds in wheat, significantly better than that of Crystalline form A of shuangzuocaotong.

Claims

1. Crystalline form C of shuangzuocaotong, characterized in that the Crystalline form C has an X-ray powder diffraction pattern having characteristic absorption peaks at the following 20 positions: 10.159, 10.658, 13.318, 14.579, 16.096, 18.061, 19.322, 19.68, 20.04, 20.659, 21.281, 23, 24.16, 24.619, 26.101, 26.74, 30.359, 31.018, 32.378, 35.398 and 38.26 degrees, wherein the 2θ has an error range within ±0.2°.

2. The Crystalline form C of shuangzuocaotong according to claim 1, characterized in that the characteristic absorption peaks have the following Ho values: 22, 22.9, 18.9, 28.7, 100, 21.5, 17.6, 35, 10.7, 18.3, 11.1, 55.4, 61.3, 28.1, 12.2, 7.6, 10.1, 6.1, 9.4, 8.2 and 7.6, respectively.

3. The Crystalline form C of shuangzuocaotong according to claim 1, characterized in that the X-ray powder diffraction pattern is basically the same as shown in FIG. 2.

4. A method for preparing the Crystalline form C of shuangzuocaotong according to claim 1, comprising the following steps: shuangzuocaotong is dissolved in a solvent which is selected from a group consisting of: absolute ethyl alcohol, n-propyl alcohol, isobutyl alcohol, absolute ethyl ether, methyl tertiary butyl ether, butyl acetate, methyl benzene and isopropyl benzene, and then heated to complete dissolution; the solvent is removed by natural volatilization, and the Crystalline form C is obtained.

5. A herbicidal compounded composition, comprising the Crystalline form C of shuangzuocaotong according to claim 1 and an adjuvant.

6. The herbicidal compounded composition according to claim 5, wherein the composition further comprises additional active ingredients.

7. The herbicidal compounded composition according to claim 6, wherein the composition has a total mass content of active ingredients within 75%.

8. The herbicidal compounded composition according claim 5, wherein the composition has a formulation selected from a group consisting of: suspension concentrate, oil dispersion, emulsifiable concentrate, microemulsion, granule, suspoemulsion or water-dispersible granule.

9. A method for controlling broadleaf weeds or some gramineous weeds in wheat, the method comprising a step of administrating the Crystalline form C of shuangzuocaotong according to claim 1 or the herbicidal compounded composition comprising the Crystalline form C of shuangzuocaotong according to claim 1 to the broadleaf weeds or gramineous weeds.

10. The herbicidal compounded composition according to claim 5, wherein the adjuvant is one or more selected from a group consisting of: solvents, solid diluents, emulsifiers, humectants, dispersants, antifreezes, defoamers and thickeners.

11. The herbicidal compounded composition according to claim 6, wherein the active ingredient is selected from a group consisting of: MCPA-Na, MCPA-isooctyl ester, 2,4-D butyl ester, 2,4-D isooctyl ester, MCPA-dimethylamine salt, fluroxypyr, fluroxypyr-mepthyl, halauxifen-methyl, dicamba, isoproturon, chlorotoluron, diflufenican, picolinafen, carfentrazone-ethyl, fluoroglycofen-ethyl, fenoxaprop-P-ethyl, clodinafop-propargyl (acid), tralkoxydim, pinoxaden, halosulfuron-methyl, mesosulfuron-methyl, flucarbazone-sodium, florasulam, pyroxsulam, metribuzin, prometryn, terbutryn, bentazone, bromoxynil, bromoxynil octanoate, flufenacet and any combination thereof.

12. The herbicidal compounded composition according to claim 6, wherein the composition has a total mass content of active ingredients within 50%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the XRPD pattern of Crystalline form A of shuangzuocaotong in Example 1 of the present invention.

(2) FIG. 2 is the XRPD pattern of Crystalline form C of shuangzuocaotong in Example 2 of the present invention.

SPECIFIC MODELS FOR CARRYING OUT THE INVENTION

(3) The above contents of the present invention will be described in detail with reference to the following examples. However, it should not be understood that the scope of the above described subject of the present invention is limited to the following examples. All the techniques realized on the strength of the above described contents of the present invention is within the scope of the present invention.

Determination Method of XRPD

(4) Instrument model: Bruker D8 advance, target: Cu Kα (40 kV, 40 mA), distance between sample and detector: 30 cm, scanned area 3°-45° (2θ value), scan path: 0.05 s

Example 1

(5) The method in CN 103980202 B was taken as reference to obtain the technical material of shuangzuocaotong, which was in the form of Crystalline form A.

Example 2

(6) 3000 g of Crystalline form A of shuangzuocaotong technical material was placed into a 10 L flask. 6 L of absolute ethyl alcohol, n-propyl alcohol, isobutanol, absolute ethyl ether, methyl tert-butyl ether, butyl acetate, methyl benzene or isopropyl benzene was added. The materials were dissolved completely upon heating and stirring, and then was leaved for volatilizing naturally at or below 25° C. until the absolute ethyl alcohol, n-propyl alcohol, isobutanol, absolute ethyl ether, methyl tert-butyl ether, butyl acetate, methyl benzene or isopropyl benzene as volatilized completely to obtain the powder of Crystalline form C of shuangzuocaotong.

(7) Physicochemical Stability Test

(8) The Crystalline form A of shuangzuocaotong obtained from Example 1 and the Crystalline form C of shuangzuocaotong obtained from Example 2 were subjected to HPLC and the contents of Crystalline form A and Crystalline form C were about 96.0% by actual measurement. Thereafter, technical materials of the two crystalline forms were placed into ovens with temperatures of 25° C., 40° C., 55° C. and 70° C. respectively and left there for 2 months for thermal storage test. Then the type of crystalline form and the purity were determined and results were listed below in Table 1.

(9) TABLE-US-00001 TABLE 1 Stability test of different crystalline forms of shuangzuocaotong Crystalline form A Crystalline form C of shuangzuocaotong of shuangzuocaotong of Example 1 of Example 2 Sample Crystalline form Purity Crystalline form Purity 25° C. Crystalline form A 96.0% Crystalline form C 96.0% 40° C. Crystalline form A 95.5% Crystalline form C 95.8% 55° C. Crystalline form A 95.1% Crystalline form C 95.7% 70° C. Crystalline form A 94.2% Crystalline form C 95.2%

(10) It is shown in table 1 that both Crystalline forms A and C of shuangzuocaotong are in good stability at different temperatures. Particularly, even at the high temperature of 70° C., the crystalline forms maintain good physicochemical stability and the crystalline forms are unchanged. The purity of Crystalline form C is better than that of Crystalline form A, which indicates Crystalline form C is of high application potential.

(11) Preparation Process and in-Door Bioassay Test

(12) The Crystalline form A of shuangzuocaotong obtained from Example 1 and the Crystalline form C of shuangzuocaotong obtained from Example 2 were processed to preparations according to the following formulations. Detailed formulations are as the following:

(13) 5% Shuangzuocaotong OD

(14) 5% shuangzuocaotong+5% emulsifier calcium dodecyl benzene sulfonate+8% emulsifier phenethyl phenol polyoxyethylene ether+4% emulsifier castor oil polyoxyethylene ether+2.5% thickener organobentonite+2% thickener silicon dioxide by gas phase method+20% dispersion medium soybean oil+balance of dispersion medium methyl oleate.

(15) 8% Shuangzuocaotong SC

(16) 8% shuangzuocaotong+4% dispersant polycarboxylate+2% humenctant fatty alcohol polyoxyethylene ether+0.25% thickener xanthan gum+0.5% thickener carboxymethyl cellulose+5% antifreezer glycerol+0.1% defoamer silicone oil+balance of water

(17) 40% Shuangzuocaotong⋅MCPA-Na WP

(18) 5% shuangzuocaotong+35% MCPA-Na+6% polycarboxylates dispersant+5% fatty alcohol polyoxyethylene ether+5% white carbon black by precipitation method+balance of calcined kaolin

(19) 27% Shuangzuocaotong⋅MCPA-isooctyl Ester EW

(20) 2.5% shuangzuocaotong+24.5% MCPA-isooctyl ester+5% cyclohexanone+3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt+2% phenethyl phenol polyoxyethylene ether+3% castol oil polyoxyethylene ether+3% ethylene glycol+balance of water

(21) 25% Shuangzuocaotong⋅2,4-D butyl Ester EC

(22) 2.5% shuangzuocaotong+22.5% 2,4-D butyl ester+10% isopropanol+4% calcium dodecyl benzene sulfonate+6% castol oil polyoxyethylene ether+balance of No. 150 aromatic solvent oil

(23) 27% Shuangzuocaotong⋅2,4-D Isooctyl Ester EC

(24) 2.5% shuangzuocaotong+24.5% 2,4-D isooctyl ester+5% cyclohexanone+4% calcium dodecylbenzene sulfonate+6% nonyl phenol polyoxyethylene ether+balance of No. 100 aromatic solvent oil

(25) 17% Shuangzuocaotong⋅Fluroxypyr ME

(26) 5% shuangzuocaotong+12% fluroxypyr+10% cyclohexanone+10% ethyl alcohol+8% sodium di-sec-octyl maleate sulfonate+8% phenethyl phenol polyoxyethylene ether+3% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate+balance of water

(27) 3% Shuangzuocaotong⋅Halauxifen-methyl EW

(28) 2.5% shuangzuocaotong+0.5% halauxifen-methyl+10% cyclohexanone+10% No. 150 solvent oil+3% nonylphenol polyoxyethylene ether phosphate triethanolamine salt+2% phenethyl phenol polyoxyethylene ether+3% castor oil polyoxyethylene ether+3% ethylene glycol+balance of water

(29) 30% Shuangzuocaotong⋅Dicamba WP

(30) 5% shuangzuocaotong+25% dicamba+6% polycarboxylates dispersant+5% fatty alcohol polyoxyethylene ether+5% white carbon black by precipitation method+balance of calcined kaolin

(31) 20% Shuangzuocaotong⋅Bromoxynil EC

(32) 2.5% shuangzuocaotong+17.5% bromoxynil+5% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt+5% fatty acid polyoxyethylene ester+8% castor oil polyoxyethylene ether+2% organobentonite+balance of methyl oleate

(33) 27% Shuangzuocaotong⋅Bromoxynil Octanoate EC

(34) 2.5% shuangzuocaotong+24.5% bromoxynil octanoate+5% N-methyl pyrrolidone+4% calcium dodecylbenzene sulfonate+5% fatty alcohol polyoxyethylene ether+balance of No. 100 aromatic solvent oil

(35) 35% Shuangzuocaotong⋅Isoproturon SC

(36) 1.5% shuangzuocaotong+33.5% isoproturon+5% sodium lignin sulfonate+2% nekal+0.2% xanthan gum+5% glycerol+balance of water

(37) 50% Shuangzuocaotong⋅Terbutryn SC

(38) 2.5% shuangzuocaotong+47.5% terbutryn+5% naphthalene sulfonate+2% fatty alcohol polyoxyethylene ether+0.1% xanthan gum+5% glycerol+balance of water

(39) 35% Shuangzuocaotong⋅Diflufenican SC

(40) 5% shuangzuocaotong+30% diflufenican+5% nonylphenol polyoxyethylene ether phosphate triethanolamine salt+2% fatty alcohol polyoxyethylene ether+0.15% xanthan gum+5% glycerol+balance of water

(41) 40% Shuangzuocaotong⋅Picolinafen SC

(42) 25% shuangzuocaotong+15% picolinafen+5% polycarboxylates dispersant+2% nonylphenol polyoxyethylene ether+0.2% xanthan gum+5% glycerol+balance of water

(43) 12% Shuangzuocaotong⋅Flufenacet SC

(44) 2% shuangzuocaotong+10% flufenacet+5% polycarboxylates dispersant+2% nonylphenol polyoxyethylene ether+0.2% xanthan gum+5% glycerol+balance of water

(45) 22% Shuangzuocaotong⋅MCPA-Dimethylamine Salt SC

(46) 2.5% shuangzuocaotong+19.5% MCPA-dimethylamine salt+5% polycarboxylates dispersant+2% fatty alcohol polyoxyethylene ether+0.3% xanthan gum+5% glycerol+balance of water

(47) 50% Shuangzuocaotong⋅Chlortoluron WP

(48) 1.5% shuangzuocaotong+48.5% chlortoluron+10% sodium lignin sulfonate+5% nekal+5% white carbon black by precipitation method+balance of diatomite

(49) 33% Shuangzuocaotong⋅Prometryn WP

(50) 3% shuangzuocaotong+30% prometryn+8% naphthalene sulfonate+5% fatty alcohol polyoxyethylene ether+5% white carbon black by precipitation method+balance of calcined kaolin

(51) 3% Shuangzuocaotong⋅Carfentrazone-Ethyl WDG

(52) 2.5% shuangzuocaotong+0.5% carfentrazone-ethyl+10% naphthalene sulfonates+5% nekal+1% disintegrant polyvinyl alcohol+balance of filler diatomite

(53) 14% Shuangzuocaotong⋅Metribuzin WDG

(54) 2.5% shuangzuocaotong+11.5% metribuzin+10% polycarboxylates+5% polyethylene glycol+1% disintegrant polyvinyl alcohol+balance of filler diatomite

(55) 3% Shuangzuocaotong⋅Fluoroglycofen-Ethyl EC

(56) 2.5% shuangzuocaotong+0.5% fluoroglycofen-ethyl+5% cyclohexanone+5% calcium dodecyl benzene sulfonate+5% phenethyl phenol polyoxyethylene ether+balance of No. 100 aromatic solvent oil

(57) 9% Shuangzuocaotong⋅Fenoxaprop-P-Ethyl EW

(58) 2.5% shuangzuocaotong+6.5% fenoxaprop-P-ethyl+6% cyclohexanone+6% No. 150 solvent oil+10% ethyl alcohol+8% calcium dodecyl benzene sulfonate+8% nonyl phenol polyoxyethylene ether+5% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate+balance of water

(59) 14% Shuangzuocaotong.Clodinafop-Propargyl EW

(60) 4% shuangzuocaotong+10% clodinafop-propargyl+10% cyclohexanone+10% ethylene glycol butyl ether+8% calcium dodecyl benzene sulfonate+8% castor oil polyoxyethylene ether+5% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate+balance of water

(61) 17% Shuangzuocaotong⋅Pinoxaden EW

(62) 5% shuangzuocaotong+12% pinoxaden+10% cyclohexanone+5% No. 150 solvent oil+10% ethylene glycol butyl ether+8% calcium dodecyl benzene sulfonate+8% fatty alcohol polyoxyethylene ether+5% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate+balance of water

(63) 65% Shuangzuocaotong⋅Tralkoxydim WDG

(64) 5% shuangzuocaotong+60% tralkoxydim+15% polycarboxylates+5% nekal+1% disintegrant polyvinyl alcohol+balance of filler bentonite

(65) 39% Shuangzuocaotong⋅Halosulfuron-Methyl WDG

(66) 15% shuangzuocaotong+24% halosulfuron-methyl+20% polycarboxylates+5% polyethylene glycol+1% disintegrant polyvinyl alcohol+balance of filler diatomite

(67) 7% Shuangzuocaotong⋅Mesosulfuron-Methyl OD

(68) 5.2% shuangzuocaotong+1.8% mesosulfuron-methyl+5% sodium di-sec-octyl maleate sulfonate+5% dehydrated sorbitol fatty acid polyoxyethylene ester+6% castor oil polyoxyethylene ether+3% organobentonite+3% white carbon black by gas phase method+20% soybean oil+balance of methyl oleate

(69) 11% Shuangzuocaotong⋅Flucarbazone-Sodium OD

(70) 5% shuangzuocaotong+6% flucarbazone-sodium+5% fatty alcohol polyoxyethylene ether phosphate triethanolamine salt+5% fatty alcohol polyoxyethylene ether+4% castor oil polyoxyethylene ether+3% organobentonite+20% soybean oil+balance of methyl oleate

(71) 6% Shuangzuocaotong⋅Florasulam OD

(72) 5% shuangzuocaotong+1% florasulam+5% sodium di-sec-octyl maleate sulfonate+5% dehydrated sorbitol fatty acid polyoxyethylene ester+4% nonylphenol polyoxyethylene ether+2.6% organobentonite+25% soybean oil+balance of methyl oleate

(73) 7% Shuangzuocaotong⋅Pyroxsulam OD

(74) 5% shuangzuocaotong+2% pyroxsulam+5% fatty alcohol polyoxyethylene ether phosphate triethanolamine salt+5% dehydrated sorbitol fatty acid polyoxyethylene ester+6% nonylphenol polyoxyethylene ether+3% organobentonite+25% soybean oil+balance of methyl oleate

(75) 38% Shuangzuocaotong⋅Bentazone OD

(76) 1.5% shuangzuocaotong+36.5% bentazone+5% sodium di-sec-octyl maleate sulfonate+5% nonylphenol polyoxyethylene ether+8% castor oil polyoxyethylene ether+0.5% organobentonite+balance of methyl oleate

(77) Determination using Greenhouse pot-cultured method: bamyardgrass (Echinochloa crusgalli) at 3-4 leaf stage (from the corn field of test site in Huangdao District, Shandong Province); Crickweed (Malachium aquaticum) at 3-5 leaf stage (seeds collected from Siyang county, Suqian city, Jiangsu Province); 3WP-2000 type travelling spray tower (Nanjing Research Institute for Agricultural Mechanization, Ministry of Agriculture) was used to conduct uniform stem and leaf spray with 4 replicates for each treatment, and the average plant control (visual) 30 days after the application (30 DAA) are as follows (see Table 2).

(78) TABLE-US-00002 TABLE 2 Control effect (%) of preparations with different crystalline forms of shuangzuocaotong (30 DAA). Applica- Barnyard- Applica- Barnyard- tion rate grass Crickweed tion rate grass Crickweed Preparation g/hm.sup.2 control effect % Preparation g/hm.sup.2 control effect % 5% Crystalline form 15.0 77.3 87.4 5% Crystalline form 15.0 50.9 57.4 C of A of shuangzuocaotong shuangzuocaotong OD OD 8% Crystalline form 22.5 91.8 92.2 8% Crystalline form 22.5 43.8 51.4 C of A of shuangzuocaotong shuangzuocaotong SC SC 40% Crystalline form 90.0 82.5 94.7 40% Crystalline form 90.0 50.4 68.5 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ MCPA-Na WP MCPA-Na WP 27% Crystalline form 121.5 83.4 96.4 27% Crystalline form 121.5 52.7 65.4 C of A of shuangzuocaotong .Math.+ shuangzuocaotong + MCPA-isooctyl ester MCPA-isooctyl ester EW EW 25% Crystalline form 112.5 81.2 97.5 25% Crystalline form 112.5 51.2 74.1 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ 2,4-D butyl ester EC 2,4-D butyl ester EC 27% Crystalline form 121.5 82.5 97.2 27% Crystalline form 121.5 55.6 67.7 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ 2,4-D-isooctyl ester 2,4-D-isooctyl ester EC EC 17% Crystalline form 38.3 82.1 100.0 17% Crystalline form 38.3 55.6 70.4 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ fluroxypyr ME fluroxypyr ME 3% Crystalline form 13.5 81.4 95.3 3% Crystalline form 13.5 53.2 50.7 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ halauxifen-methyl halauxifen-methyl EW EW 30% Crystalline form 67.5 82.3 97.3 30% Crystalline form 67.5 57.4 61.7 C of A of shuangzuocaotong + shuangzuocaotong .Math.+ dicamba WP dicamba WP 20% Crystalline form 90.0 83.2 100.0 20% Crystalline form 90.0 50.6 65.8 C of A of shuangzuocaotong + shuangzuocaotong .Math.+ bromoxynil EC bromoxynil EC 27% Crystalline form 121.5 81.2 100.0 27% Crystalline form 121.5 51.3 79.2 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ bromoxynil octanoate bromoxynil octanoate EC EC 35% Crystalline form 262.5 90.8 100.0 35% Crystalline form 262.5 60.7 75.2 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ isoproturon SC isoproturon SC 50% Crystalline form 225.0 92.4 98.3 50% Crystalline form 225.0 66.7 65.6 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ terbutryn SC terbutryn SC 35% Crystalline form 78.8 92.8 99.7 35% Crystalline form 78.8 65.2 70.3 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ diflufenican SC diflufenican SC 40% Crystalline form 18.0 94.7 97.3 40% Crystalline form 18.0 67.9 70.4 C of A of shuangzuocaotong + shuangzuocaotong .Math.+ picolinafen SC picolinafen SC 12% Crystalline form 67.5 89.5 97.4 12% Crystalline form 67.5 55.4 46.8 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ flufenacet SC flufenacet SC 22% Crystalline form 99.0 84.6 96.3 22% Crystalline form 99.0 58.2 64.1 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ MCPA-dimethylamine MCPA-dimethylamine salt SC salt SC 50% Crystalline form 375.0 86.9 94.6 50% Crystalline form 375.0 57.4 60.3 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ chlortoluron WP chlortoluron WP 33% Crystalline form 123.8 85.3 94.1 33% Crystalline form 123.8 52.8 65.4 C of A of shuangzuocaotong .Math.+ shuangzuocaotong+ prometryn WP prometryn WP 3% Crystalline form 13.5 82.2 93.2 3% Crystalline form 13.5 50.6 72.9 C of A of shuangzuocaotong + shuangzuocaotong .Math.+ carfentrazone-ethyl carfentrazone-ethyl WDG WDG 14% Crystalline form 63.0 97.3 97.2 14% Crystalline form 63.0 50.5 65.2 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ metribuzin WDG metribuzin WDG 3% Crystalline form 13.5 95.3 96.2 3% Crystalline form 13.5 55.9 70.3 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ fluoroglycofen-ethyl fluoroglycofen-ethyl EC EC 9% Crystalline form 54.0 97.1 85.3 9% Crystalline form 54.0 55.6 51.3 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ fenoxaprop-P-ethyl fenoxaprop-P-ethyl EW EW 14% Crystalline form 52.5 94.2 84.3 14% Crystalline form 52.5 63.8 55.6 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ clodinafop-propargyl clodinafop-propargyl EW EW 17% Crystalline form 51.0 94.9 86.2 17% Crystalline form 51.0 63.6 52.7 C of A of shuangzuocaotong .Math.+ shuangzuocaotong + pinoxaden EW pinoxaden EW 65% Crystalline form 195.0 93.7 87.4 65% Crystalline form 195.0 62.1 50.6 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ tralkoxydim WDG tralkoxydim WDG 39% Crystalline form 29.3 96.2 95.2 39% Crystalline form 29.3 52.3 67.8 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ halosulfuron-methyl halosulfuron-methyl WDG WDG 7% Crystalline form 15.1 95.9 96.4 7% Crystalline form 15.1 50.2 73.5 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ mesosulfuron-methyl mesosulfuron-methyl OD OD 11% Crystalline form 24.8 94.2 96.8 11% Crystalline form 24.8 65.3 62.9 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ flucarbazone-sodium flucarbazone-sodium OD OD 6% Crystalline form 13.5 82.1 98.2 6% Crystalline form 13.5 59.6 51.3 C of A of shuangzuocaotong + shuangzuocaotong .Math.+ florasulam OD florasulam OD 7% Crystalline form 15.8 95.2 99.3 7% Crystalline form 15.8 50.7 72.6 C of A of shuangzuocaotong .Math.+ shuangzuocaotong .Math.+ pyroxsulam OD pyroxsulam OD 38% Crystalline form 285.0 84.3 100.0 38% Crystalline form 285.0 52.4 70.5 C of A of shuangzuocaotong .Math.+ shuangzuocaotong + bentazone OD bentazone OD

(79) The above examples give description to the basic principles, main characteristics and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above examples. The aforementioned examples and the descriptions in the specification is only for explanation of the present invention. Changes and modifications can be made for the present invention within the range of the principles of the present invention. All these changes and modifications are in the protection scope of the present invention.