CN103109802A - Preparation method and application of 1,3-dichloropropene solid slow-release preparation - Google Patents
Preparation method and application of 1,3-dichloropropene solid slow-release preparation Download PDFInfo
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- CN103109802A CN103109802A CN2013100626311A CN201310062631A CN103109802A CN 103109802 A CN103109802 A CN 103109802A CN 2013100626311 A CN2013100626311 A CN 2013100626311A CN 201310062631 A CN201310062631 A CN 201310062631A CN 103109802 A CN103109802 A CN 103109802A
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- dichloropropylene
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- dichloro
- keeping agent
- dichloropropene
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- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007787 solid Substances 0.000 title claims abstract description 19
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000002689 soil Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 238000009834 vaporization Methods 0.000 claims description 15
- 230000008016 vaporization Effects 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 11
- 230000000844 anti-bacterial effect Effects 0.000 claims description 9
- 239000003899 bactericide agent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000004659 sterilization and disinfection Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003795 desorption Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract 5
- 230000002745 absorbent Effects 0.000 abstract 5
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000004927 clay Substances 0.000 abstract 1
- 239000011550 stock solution Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 201000010099 disease Diseases 0.000 description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 6
- 244000241257 Cucumis melo Species 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009313 farming Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UHPMCKVQTMMPCG-UHFFFAOYSA-N 5,8-dihydroxy-2-methoxy-6-methyl-7-(2-oxopropyl)naphthalene-1,4-dione Chemical compound CC1=C(CC(C)=O)C(O)=C2C(=O)C(OC)=CC(=O)C2=C1O UHPMCKVQTMMPCG-UHFFFAOYSA-N 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 244000003416 Asparagus officinalis Species 0.000 description 1
- 235000005340 Asparagus officinalis Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000009847 Cucumis melo var cantalupensis Nutrition 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 241000223218 Fusarium Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 241000243785 Meloidogyne javanica Species 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 241000233639 Pythium Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 244000000034 soilborne pathogen Species 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a preparation method and application of a 1, 3-dichloropropene solid slow-release preparation. The preparation process is specifically as follows: the slow-release preparation is prepared by using an adsorption method of separation, that is, an absorbent carrier which has high absorption performance and desorption performance is adopted and used for absorbing the gasified 1,3-dichloropropene for 3 to 4 hours, thus obtaining different soil sanitizers with the content of 1,3-dichloropropene ranging from 5 to 40wt%, wherein the absorbent carrier comprises at least one of activated carbon, activated clay and a polymeric absorbent, and preferably, the absorbent carrier is the activated carbon; and the grain weight of the absorbent carrier is 0.5 to 10g. By adopting the product prepared by the method disclosed by the invention, the control effect the same as that of the stock solution can be gained, and the product is even wider in broad spectrum; specific experimental conditions can be saved; and the operation process is simple, the repeatability is great, and the effect of the soil sanitizer can be efficiently realized along with high quality. The method is wide in applicable scope and application prospect.
Description
Technical field
The invention belongs to solid dosage forms agricultural chemicals manufacturing technology field, be specifically related to 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent its preparation method and application.
Background technology
Soil-borne disease is that the pathogen of surviving in soil infects, a caused class disease, on vegetables, melon and fruit, ornamental plants, forest development serious, especially harm is outstanding heavy on protection ground crop.The situation of China recent years is: along with agricultural production and economic development, the chamber crop cultivated area grows with each passing day, and has become the important means that the peasant increases income, and is also the important measures that traditional farming changes to modern agriculture.And the development of green house also provides adapt circumstance for generation, the development of soil-borne disease.Usually after cultivation 3-5, crop yield and quality are had a strong impact on, and generally want the underproduction 20% ~ 40%, even total crop failure more than Severe Reduction to 60%, along with the green house cultivation continues the cultivation year after year of expansion and high added value crop, the problem of soil-borne disease is more and more serious.Therefore China area out of the ordinary as Qingzhou in Shandong, Shouguang and other places, begins with having played 1, and the 3-dichloropropylene is prevented and treated crop pest.
1,3-dichloropropylene (general 1,3-dichloropropene by name, chemical formula C
3H
4Cl
2) to root-knot nematode and other soil nematodes on the protection such as control vegetables, strawberry, flowers, melon, asparagus, celery, carrot, sweet potato, soybean, fruit tree, grape, Chinese herbal medicine ground crop, fine control efficiency is arranged all.All have to soil-borne pathogen sickle-like bacteria (Fusarium spp), to corruption mould (Pythium spp), epidemic disease mould (Phytophthoro spp) with fashion and well press down anti-effect.Therefore western developed country is as Australia, Spain and the U.S. etc., and after Celfume forbidding in 2005, just use 1, the 3-dichloropropylene is widely used as the soil disinfection bactericide, and using method is for irrigating and the machinery injection.
1, to prevent and treat the crop pest effect fine although the 3-dichloropropylene is used for the farmland, and liquor uses and has following disadvantage: as ground temperature during lower than 15 ℃, more than the processing time needed for three weeks, mostly very cold area easy mistake farming season, can't use.In addition, water insoluble because of it, seriously polluted to underground water.So Environmental Protection in America law regulation, farmland are used 1,3-dichloropropylene stoste, no matter irrigate or injection, need to the population residence, certain buffer zone is arranged.
Summary of the invention
For 1,3-dichloropropylene stoste is used for the existing disadvantage in farmland as bactericide, the present invention is to provide a kind of novel form, system utilizes the property of medicament characteristics and carrier, changes the primary liquid formulation into the gas slow release formulation, takes adsorption method of separation with 1, the gas of 3-dichloropropylene heating vaporization passes in the retort that adsorbing agent carrier is housed, in end-product 1, the rare content of 3-dichloro third is that 5 ~ 40wt% namely gets semi-finished product, finally coated, the packing.Product is with plastic bottle or pack packing, and ditch spread or spread manuer in holes all can; Available gas begins to discharge in 10 ~ 15 ℃ of low temperature, and increases with Rise of Geotemperature, and final desorption is in zero.Control efficiency is the same with stoste, and wide spectrum more, and the longevity of residure is long, can reach more than 3 ~ 4 months.Utilization ratio of drug can improve 3 ~ 4 times.Safe, economic, as to play lastingly protective plant root system effect.Concrete technical scheme is:
An aspect of of the present present invention is: a kind of 1, and 3-dichloropropylene Solid Releasing Fresh-keeping Agent, it is by 1, rare and the adsorbing agent carrier of 3-dichloro third forms, and is described 1, and the rare content of 3-dichloro third is 5 ~ 40wt%, described adsorbing agent carrier is active carbon, atlapulgite, at least a composition in polymeric adsorbent.
For the described adsorbing agent carrier of technique scheme, described 1 in better situation, the rare content of 3-dichloro third is 20 ~ 40wt%.
For the described adsorbing agent carrier of technique scheme, in better situation, described adsorbing agent carrier is that particle diameter is 0.3 ~ 0.5cm, and grain is heavily the polymeric adsorbent particle of 0.5 ~ 10g.
For the described adsorbing agent carrier of technique scheme, in better situation, described adsorbing agent carrier is: 100 ~ 200 purpose atlapulgites particle diameter after the granulation oven dry is 0.3 ~ 0.5cm, and grain is heavily 0.5 ~ 10g.
For the described adsorbing agent carrier of technique scheme, in better situation, described adsorbing agent carrier is heavily 0.5 ~ 10g active carbon for grain.
Another aspect of the present invention is: a kind of 1, the preparation method of 3-dichloropropylene Solid Releasing Fresh-keeping Agent, it comprises step: the gas of 1,3-dichloropropylene heating vaporization is passed in the retort that adsorbing agent carrier is housed, make 1 in end-product, the rare content of 3-dichloro third is 5 ~ 40wt%.
For the described adsorbing agent carrier preparation method of technique scheme, in better situation, the temperature of described heating vaporization is 80 ℃ ~ boiling point.
Another aspect of the present invention is: technique scheme is described 1, the application of 3-dichloropropylene Solid Releasing Fresh-keeping Agent in preparation soil disinfection bactericide.
Described 1 for technique scheme, the application of 3-dichloropropylene Solid Releasing Fresh-keeping Agent in preparation soil disinfection bactericide, concrete grammar is: use mentioned above 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent, according to the usage amount of 30kg/ mu, soil layer 15 ~ 20cm is imbedded in ditch spread or spread manuer in holes.
Character of innovation of the present invention is:
A) product of the present invention is solid low content slow release formulation, uses with the fortune storage and does not have potential safety hazard.
B) easy to use, be with a wide range of applications and application prospect.
C) need not special experiment condition, simple to operate, good reproducibility, former survival dose is little, and cost is low.
D) active ingredient slowly discharges the drug effect phase that increased.Be so far the world unique 1, the granular preparation that 3-dichloro third is rare.
E) prepare this slow release formulation with adsorption method of separation, technique is reasonable, and method is easy, and three-waste free discharge has no adverse effects to environment.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.The solution that relates in method described in the embodiment of the present invention if no special instructions, obtains or the preparation of conventional method method by commercial sources.
Embodiment 1
20wt% contains the preparation of volume preparation: the adsorbent dried particles active carbon 80g that packs in the glass adsorption tower, and the suitable for reading of glass adsorption tower is the tail gas outlet, the tail gas outlet connects the decomposed solution bottle.The end opening of glass adsorption tower is air inlet, joins with the vaporization bottle, packs 1 in the vaporization bottle, the rare raw material of 3-dichloro third, in vaporization bottle 1,3-dichloro third is rare when being heated to 80 ℃ ~ boiling point, keeps 3-4h, along with 1, the rare continuous vaporization of 3-dichloro third reduces, and the adsorption temp of glass adsorption tower is 4 ~ 10 ℃, when decrement reaches 20g, take out the active carbon of packing in the glass adsorption tower, be weighed as 100g and namely obtain finished product.
Wherein, the grain of described adsorbent is heavily 0.5 ~ 10g.
Embodiment 2
40wt% contains the preparation of volume preparation: device is as embodiment 1, atlapulgite particle 60g packs in adsorption tower, in vaporization bottle 1,3-dichloro third is rare when being heated to 80 ℃ ~ boiling point, keeps 4h, along with 1, the rare continuous vaporization of 3-dichloro third reduces, and the adsorption temp of glass adsorption tower is 4 ~ 10 ℃, when decrement reaches 40g, take out adsorbed product in the glass adsorption tower, be weighed as 100g and namely obtain finished product.
Wherein, the atlapulgite commercially available product is approximately 100 ~ 200 orders of powdery fineness, needs can use through the granulation oven dry.Particle diameter 0.3 ~ 0.5cm, grain is heavily 0.5 ~ 10g.
Embodiment 3
40wt% contains the preparation of volume preparation: device is as embodiment 1; adsorbent dried particles active carbon 60g packs in adsorption tower; in vaporization bottle 1,3-dichloro third is rare when being heated to 80 ℃ ~ boiling point, keeps 4h; along with 1; the rare continuous vaporization of 3-dichloro third reduces, and the adsorption temp of glass adsorption tower is 4 ~ 10 ℃, when decrement reaches 40g; take out adsorbed product in the glass adsorption tower, be weighed as 100g and namely obtain finished product.
Wherein, the grain of described adsorbent dried particles active carbon is heavily 0.5 ~ 10g.
Embodiment 4
5wt% contains the preparation of volume preparation: device is as embodiment 1, polymeric adsorbent particle 95g packs in adsorption tower, in vaporization bottle 1,3-dichloro third is rare when being heated to 80 ℃ ~ boiling point, keeps 4h, along with 1, the rare continuous vaporization of 3-dichloro third reduces, and the adsorption temp of glass adsorption tower is 4 ~ 10 ℃, when decrement reaches 5g, take out adsorbed product in the glass adsorption tower, be weighed as 100g and namely obtain finished product.
Wherein, described adsorbent polymeric adsorbent grain diameter 0.3 ~ 0.5cm, grain is heavily 0.5 ~ 10g.
Embodiment 5
Take Melon as example, detect the soil disinfection bactericide as a comparison, product is with plastic bottle or pack packing, every mu of consumption is 30kg, ditch spread or spread manuer in holes all can, imbed soil layer 15 ~ 20cm; Observed result after 60 days:
1. use liquid 1, the rare stoste of 3-dichloro third is as the soil disinfection bactericide;
2. use the product soil disinfection bactericide of the described method preparation of the embodiment of the present invention 3;
Available gas begins to discharge in 10-15 ℃ of low temperature, and increases with Rise of Geotemperature, and final desorption is in zero.
The disease-free generation of the equal well developed root system of the muskmelon of two experimental group, control efficiency reaches more than 98%; As seen the 2. group actual use 1, the rare stoste of 3-dichloro third is only 9kg, less than the 1. group 1/3rd, avoid the groundwater contamination problem, therefore adopted the product of the method for the invention preparation, on the basis of conservation, control efficiency is the same with stoste, and wide spectrum more, the longevity of residure is long, can reach more than 3 ~ 4 months.Utilization ratio of drug can improve 3 ~ 4 times.Safe, economic, as to play lastingly protective plant root system effect.Need not special experiment condition, operating procedure is simple, and good reproducibility can high-quality reaches the effect of soil disinfection bactericide efficiently, and the method is with a wide range of applications and application prospect.
Claims (9)
1. one kind 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: by 1, rare and the adsorbing agent carrier of 3-dichloro third forms, and is described 1, and the rare content of 3-dichloro third is 5 ~ 40wt%, described adsorbing agent carrier is active carbon, atlapulgite, at least a composition in polymeric adsorbent.
2. according to claim 1 a kind of 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: described 1, the rare content of 3-dichloro third is 20 ~ 40wt%.
3. according to claim 1 a kind of 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: described adsorbing agent carrier is that particle diameter is 0.3 ~ 0.5cm, and grain is heavily the polymeric adsorbent particle of 0.5 ~ 10g.
4. according to claim 1 a kind of 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: described adsorbing agent carrier is: 100 ~ 200 purpose atlapulgites particle diameter after the granulation oven dry is 0.3 ~ 0.5cm, and grain is heavily 0.5 ~ 10g.
5. according to claim 1 a kind of 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: described adsorbing agent carrier is heavily 0.5 ~ 10g active carbon for grain.
6. as claimed in claim 1 a kind of 1, the preparation method of 3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: comprise that the gas with 1,3-dichloropropylene heating vaporization passes in the retort that adsorbing agent carrier is housed, make 1 in end-product, the rare content of 3-dichloro third is 5 ~ 40wt%.
7. according to claim 4 a kind of 1, the preparation method of 3-dichloropropylene Solid Releasing Fresh-keeping Agent is characterized in that: the temperature of described heating vaporization is 80 ℃ ~ boiling point.
8. as claimed in claim 11, the application of 3-dichloropropylene Solid Releasing Fresh-keeping Agent in preparation soil disinfection bactericide.
9. application as claimed in claim 8 is characterized in that: right to use requires 1 described 1,3-dichloropropylene Solid Releasing Fresh-keeping Agent, and according to the usage amount of 30kg/ mu, soil layer 15 ~ 20cm is imbedded in ditch spread or spread manuer in holes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100626311A CN103109802A (en) | 2013-02-26 | 2013-02-26 | Preparation method and application of 1,3-dichloropropene solid slow-release preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100626311A CN103109802A (en) | 2013-02-26 | 2013-02-26 | Preparation method and application of 1,3-dichloropropene solid slow-release preparation |
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| CN103109802A true CN103109802A (en) | 2013-05-22 |
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| CN2013100626311A Pending CN103109802A (en) | 2013-02-26 | 2013-02-26 | Preparation method and application of 1,3-dichloropropene solid slow-release preparation |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454682A (en) * | 1966-01-21 | 1969-07-08 | Shell Oil Co | Phosphorodiamidothioates |
| CN101480178A (en) * | 2008-01-11 | 2009-07-15 | 中国农业科学院植物保护研究所 | Mixed pesticide capsule preparation for preventing and treating nematode and soil-borne disease |
| CN101627755A (en) * | 2009-08-13 | 2010-01-20 | 郑百祥 | Solid preparation of 1.3-dichloropropylene and preparation method thereof |
| CN101627754A (en) * | 2009-08-13 | 2010-01-20 | 郑百祥 | Mixed solid preparation of chloropicrin and 1.3-dichloropropylene and manufacturing technology thereof |
| CN102246792A (en) * | 2010-11-30 | 2011-11-23 | 杨银洲 | Agricultural broad spectrum bactericide |
| EP1601250B1 (en) * | 2003-03-05 | 2012-05-23 | Kanesho Soil Treatment Bvba | Compositions for controlling plant-injurious organisms |
| CN102919270A (en) * | 2012-11-23 | 2013-02-13 | 董德华 | Soil disinfectant composition |
-
2013
- 2013-02-26 CN CN2013100626311A patent/CN103109802A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454682A (en) * | 1966-01-21 | 1969-07-08 | Shell Oil Co | Phosphorodiamidothioates |
| EP1601250B1 (en) * | 2003-03-05 | 2012-05-23 | Kanesho Soil Treatment Bvba | Compositions for controlling plant-injurious organisms |
| CN101480178A (en) * | 2008-01-11 | 2009-07-15 | 中国农业科学院植物保护研究所 | Mixed pesticide capsule preparation for preventing and treating nematode and soil-borne disease |
| CN101627755A (en) * | 2009-08-13 | 2010-01-20 | 郑百祥 | Solid preparation of 1.3-dichloropropylene and preparation method thereof |
| CN101627754A (en) * | 2009-08-13 | 2010-01-20 | 郑百祥 | Mixed solid preparation of chloropicrin and 1.3-dichloropropylene and manufacturing technology thereof |
| CN102246792A (en) * | 2010-11-30 | 2011-11-23 | 杨银洲 | Agricultural broad spectrum bactericide |
| CN102919270A (en) * | 2012-11-23 | 2013-02-13 | 董德华 | Soil disinfectant composition |
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Application publication date: 20130522 |