CN1220577A - 杀虫性硅氧烷弹性体 - Google Patents
杀虫性硅氧烷弹性体 Download PDFInfo
- Publication number
- CN1220577A CN1220577A CN97195084.9A CN97195084A CN1220577A CN 1220577 A CN1220577 A CN 1220577A CN 97195084 A CN97195084 A CN 97195084A CN 1220577 A CN1220577 A CN 1220577A
- Authority
- CN
- China
- Prior art keywords
- methyl
- oil
- chrysanthemum monocarboxylate
- dimethyl
- ketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 15
- 229920001971 elastomer Polymers 0.000 title claims description 16
- 239000000806 elastomer Substances 0.000 title claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims description 11
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000002917 insecticide Substances 0.000 claims abstract description 10
- -1 3-benzyloxy phenoxy Chemical group 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- DDVNRFNDOPPVQJ-HQJQHLMTSA-N transfluthrin Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@H]1C(=O)OCC1=C(F)C(F)=CC(F)=C1F DDVNRFNDOPPVQJ-HQJQHLMTSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- RLLPVAHGXHCWKJ-UHFFFAOYSA-N permethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-UHFFFAOYSA-N 0.000 claims description 4
- 229960003536 phenothrin Drugs 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003381 stabilizer Substances 0.000 claims description 4
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- ZCVAOQKBXKSDMS-OIISXLGYSA-N (+)-trans-(R)-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@H]1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-OIISXLGYSA-N 0.000 claims description 2
- ZCVAOQKBXKSDMS-PVAVHDDUSA-N (+)-trans-(S)-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-PVAVHDDUSA-N 0.000 claims description 2
- CXBMCYHAMVGWJQ-CABCVRRESA-N (1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)methyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 claims description 2
- SBNFWQZLDJGRLK-RTWAWAEBSA-N (1R)-trans-phenothrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-RTWAWAEBSA-N 0.000 claims description 2
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 claims description 2
- FSYXMFXBRJFYBS-UHFFFAOYSA-N Furamethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=CC=C(CC#C)O1 FSYXMFXBRJFYBS-UHFFFAOYSA-N 0.000 claims description 2
- 241000256626 Pterygota <winged insects> Species 0.000 claims description 2
- 240000004460 Tanacetum coccineum Species 0.000 claims description 2
- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 claims description 2
- ZCVAOQKBXKSDMS-UHFFFAOYSA-N allethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-UHFFFAOYSA-N 0.000 claims description 2
- 229940024113 allethrin Drugs 0.000 claims description 2
- 229960001901 bioallethrin Drugs 0.000 claims description 2
- 150000001718 carbodiimides Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- NYPJDWWKZLNGGM-UHFFFAOYSA-N fenvalerate Chemical compound C=1C=C(Cl)C=CC=1C(C(C)C)C(=O)OC(C#N)C(C=1)=CC=CC=1OC1=CC=CC=C1 NYPJDWWKZLNGGM-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
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- SBNFWQZLDJGRLK-UHFFFAOYSA-N phenothrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 SBNFWQZLDJGRLK-UHFFFAOYSA-N 0.000 claims description 2
- 125000005544 phthalimido group Chemical group 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- SMKRKQBMYOFFMU-UHFFFAOYSA-N prallethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OC1C(C)=C(CC#C)C(=O)C1 SMKRKQBMYOFFMU-UHFFFAOYSA-N 0.000 claims description 2
- 229940015367 pyrethrum Drugs 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000006884 silylation reaction Methods 0.000 claims description 2
- CXBMCYHAMVGWJQ-UHFFFAOYSA-N tetramethrin Chemical compound CC1(C)C(C=C(C)C)C1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960005199 tetramethrin Drugs 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 241000723353 Chrysanthemum Species 0.000 claims 2
- 239000002728 pyrethroid Substances 0.000 abstract description 4
- 241000238631 Hexapoda Species 0.000 abstract description 3
- 230000001846 repelling effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 29
- 235000019198 oils Nutrition 0.000 description 29
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 9
- 241000255925 Diptera Species 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000000361 pesticidal effect Effects 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- 229920005573 silicon-containing polymer Polymers 0.000 description 5
- 239000005792 Geraniol Substances 0.000 description 4
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 4
- 235000010654 Melissa officinalis Nutrition 0.000 description 4
- 244000062730 Melissa officinalis Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
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- 239000000975 dye Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 229940113087 geraniol Drugs 0.000 description 4
- 239000000865 liniment Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
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- 125000005375 organosiloxane group Chemical group 0.000 description 3
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
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- XKWSWANXMRXDES-UHFFFAOYSA-N 3-methylbutyl octanoate Chemical compound CCCCCCCC(=O)OCCC(C)C XKWSWANXMRXDES-UHFFFAOYSA-N 0.000 description 2
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 239000001585 thymus vulgaris Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/18—Vapour or smoke emitting compositions with delayed or sustained release
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及杀虫性硅氧烷弹性体、其制备方法及其在控制或驱除昆虫,特别是在内部空间控制或驱除昆虫方面的应用,其特征在于,它们包含至少一类掺在适当硅氧烷弹性体中的拟除虫菊酯杀虫剂。
Description
本发明涉及杀虫性硅氧烷弹性体、其制备方法及其在控制或驱除昆虫,特别是在内部空间控制或驱除昆虫方面的应用。这些新型组合物的特征在于,它们包括至少一种掺在适当硅氧烷弹性体中的杀虫剂。
本发明的硅氧烷弹性体的特征在于,在加热或不加热条件下它们能释放包含于其中的杀虫剂,而在此过程中不改变它们的形状。这样,获得了最佳的作用效率和持久性而保持了低的能量输入。这个新型的杀虫剂制剂可任选在适当的加热装置中将适当的含有杀虫剂的硅氧烷弹性体温热用来对付所有的飞虫,特别是蚊子、刺螫蝇等,而不用任何形状的容器。
在例如使用电加热装置,即所谓的药片蒸发器杀死蚊子的情况下,已知将适当的材料如纸浆或棉板、石棉或陶瓷用拟除虫菊酯杀虫剂浸渍以获得杀虫剂药片。通过能产生120-190℃的加热装置蒸发该杀虫剂。凝胶蒸发器基于相似的原理,杀虫剂掺在凝胶制剂中。
控制例如蚊子的另一个方法是使用所谓的液体蒸发器,其中杀虫性液体制剂通过温热灯芯体系而连续蒸发。
所有这些现有技术蒸发原理的一个重大缺点还在于这样的事实:使用者可能会接触到活性化合物或活性化合物制剂,例如通过液体蒸发器中液体制剂的泄漏或通过小孩咀嚼和吞食药片蒸发器的纸药片。
所提到的现有技术蒸发器体系的另一个缺点是活性化合物的不均匀释放。
此外,药片蒸发器的作用持续时间限制在最多12小时。
本发明涉及基于硅氧烷的杀虫性弹性体,该弹性体没有上述缺点而且易于使用,例如作为聚合物块掺入已知的铝盘中(EP 0321279)或作为直接在已知的蒸发器装置的加热器表面上的聚合物块,像用于凝胶蒸发器中的那种(EP 0321279)。这样,获得了在低工作温度60-150℃,优选80-120℃下连续的释放速率。
本发明的具有杀虫作用的硅氧烷弹性体包括包含至少一种硅氧烷弹性体和至少一种类型的活性拟除虫菊酯化合物的混合物。
适宜的硅氧烷弹性体及这些适宜的硅氧烷弹性体的制备公开于德国专利申请DE-A-4014310中,该弹性体可以通过在铂催化剂存在或不存在下用含乙烯基的硅氧烷的羟甲硅烷基化反应或者通过在锡化合物存在或不存在下使用烷氧基硅烷使有机聚硅氧烷材料交联而制备。
适宜的硅氧烷弹性体及其制备代表现有技术,参见US 3261801,US 3468838和US 3865778,该硅氧烷弹性体基于使用有机过氧化物化合物可交联成弹性体的有机硅氧烷材料。
适宜的硅氧烷弹性体公开于德国专利申请DE-A-2911352中,该硅氧烷弹性体基于使用至少一种碱性无机固体可交联的有机硅氧烷材料。
适宜的硅氧烷弹性体公开于欧洲专利申请EP-A-0010708中,该硅氧烷弹性体基于通过加入聚碳二亚胺聚硅氧烷共聚物交联的有机硅氧烷材料。
下面是优选的活性拟除虫菊酯化合物:
1)天然除虫菊,
2)3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d/l-顺/反-菊酸酯(丙烯除虫菊酯,Pynamin),
3)3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-顺/反-菊酸酯(Pynamin forte),
4)d-3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-反-菊酸酯(Exrin),
5)3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-反-菊酸酯(Bioallethrin),
6)N-(3,4,5,6-四氢苯二甲酰亚氨基)-甲基dl-顺/反-菊酸酯(似虫菊,Neopynamin),
7)5-苄基-3-呋喃甲基d-顺/反-菊酸酯(灭虫菊,Chrysronforte),
8)5-(2-炔丙基)-3-呋喃甲基菊酸酯(Furamethrin),
9)3-苯氧苄基-2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸酯(苄氯菊酯,Exmin),
10)苯氧苄基d-顺/反-菊酸酯(醚虫菊,Sumithrin),
11)α-氰基苯氧基苄基异丙基-4-氯苯基乙酸酯(腈氯苯苯醚菊酯,Sumicidin),
12)(S)-α-氰基-3-苯氧基苄基(1R,顺)-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
13)(R,S)-α-氰基-3-苯氧基苄基(1R,1S)-顺/反-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
14)α-氰基-3-苯氧基苄基d-顺/反-菊酸酯,
15)1-乙炔基-2-甲基-2-戊烯基顺/反-菊酸酯,
16)1-乙炔基-2-甲基-2-戊烯基2,2-二甲基-3-(2-甲基-1-丙烯基)-环丙烷-1-羧酸酯,
17)1-乙炔基-2-甲基-2-戊烯基2,2,3,3-四甲基环丙烷羧酸酯,
18)1-乙炔基-2-甲基-2-戊烯基2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷-1-羧酸酯,
19)(1R)-3-炔丙基-2-甲基-环戊-2-烯-4-酮-1-基顺/反-菊酸酯(prallethrin),
20)2,3,5,6-四氟苄基(+)-1R-反-2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸酯(transfluthrin,Bayothrin),
或这些活性化合物的混合物。
活性化合物3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-顺/反-菊酸酯(Pynamin forte)和2,3,5,6-四氟苄基(+)-1R-反-2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸酯(transfluthrin)是特别优选的。
本发明的化合物的适宜填料为例如BET表面积为50-500m2/g的细碎的热解或沉淀硅石。这种填料可以是表面改性的,例如通过有机硅化合物。改性也可在混入聚合物期间通过加入例如六甲基二硅氮烷或1,3-二乙烯基-1,1,3,3-四甲基二硅氮烷来实现。
另外,像例如硅藻土、细碎的石英粉、非晶硅石或碳黑这样的物质也可混入作填料。
此外,像例如有机或无机助剂这样的添加剂可混入本发明的混合物中作例如稳定剂、着色剂或香料。
适宜的有机和无机助剂为:
铵盐和磨碎的天然岩石如高岭土、粘土、滑石粉、白垩、石英、绿坡缕石、蒙脱土或硅藻土及磨碎的合成矿石如细碎的硅石、矾土、二氧化钛和硅酸盐;作为颗粒的固体载体适宜的有:
例如碾碎并分级的天然岩石如方解石、大理石、浮石、海泡石、白云石和合成的无机和有机矿石颗粒以及有机材料颗粒如锯屑、椰子壳、玉米芯和烟草茎;作为乳化剂或发泡剂适宜的有:
例如非离子和阴离子乳化剂如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚如烷基芳基聚乙二醇醚、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐和蛋白水解产物;作为分散剂适宜的有:
例如木素-亚硫酸盐废液和甲基纤维素。
粘着剂如羧甲基纤维素及粉末、颗粒或胶乳形式的天然和合成聚合物如阿拉伯树胶、聚乙烯醇、聚乙酸乙烯酯以及天然磷脂如脑磷脂和卵磷脂及合成磷脂可用于本发明的含有杀虫剂的硅氧烷弹性体中。其它添加剂可以是矿物油和植物油。
可以使用着色剂例如无机颜料如氧化铁、氧化钛和普鲁士蓝,及有机染料如茜素染料、偶氮染料和金属酞菁染料,以及痕量的营养素如铁、锰、硼、铜、钴、钼和锌的盐。
除臭剂例如甲基丙烯酸月桂酯、牻牛儿醇巴豆酸酯、乙酰苯肉豆蔻酸酯、对甲基乙酰苯苯甲醛、乙酸苄酯、丙酸苄酯、戊基肉桂醛、茴香醛、苯醚、苯甲酸甲酯、苯甲酸乙酯、苯乙酸甲酯、苯乙酸乙酯、尼奥灵、黄樟脑等可加到本发明的制剂中。
可进一步加到本发明的制剂中的其它物质为天然香料例如麝香、灵猫香、龙涎香、海狸香及类似的香料;香汗芹油、杏仁油、琥珀子净油、当归根油、茴香子油、罗勒油、月桂油、安息香香膏、香柠檬精油、桦木油、蔷薇木油、普通染料木净油、白千层油、依兰油、辣椒油、
嵩子油、小豆蔻油、胡萝卜子油、山扁豆油、雪松油、芹菜子油、肉桂皮油、香茅油、鼠尾草油、丁子香油、庚酸乙酯、芫荽油、荜澄茄油、樟脑油、莳萝油、taragon油、桉树油、甜小茴香油、古蓬香脂香膏、蒜油、老鹳草油、姜油、柚油、酒花油、风信子净油、茉莉净油、刺柏油、岩蔷薇油、桂叶油、熏衣草油、柠檬油、柠檬草油、圆叶当归根油、肉豆蔻油、橘子油、含羞草净油、没药净油、芥子油、水仙净油、苦橙花油、肉豆蔻油、栎藓净油、乳香香膏、洋葱油、红没药香膏、橙油、橙花油、固结鸢尾油、胡椒油、秘鲁香脂、橙叶油、松针油、玫瑰净油、玫瑰油、迷迭香油、檀香油、鼠尾草油、薄荷油、苏合香油、百里香油、塔鲁香脂、香豆净油、晚香玉净油、松节油、香草荚净油、韦惕蔚油、紫罗兰叶净油、衣兰油及类似的植物油等。
可加入到本发明的硅氧烷制剂中的合成香料为:
蒎烯、苎烯和类似的烃;3,3,5-三甲基环己醇、里哪醇、牻牛儿醇、橙花醇、香茅醇、薄荷醇、冰片、冰片基甲氧基环己醇、苄醇、茴香醇、肉桂醇、β-苯乙醇、顺-3-己醇、萜品醇和类似的醇;茴香脑、二甲苯麝香、异丁子香酚、甲基丁子香酚和类似的酚;α-戊基肉桂醛、茴香醛、正丁醛、枯茗醛、仙客来醛、癸醛、异丁醛、己醛、庚醛、正壬醛壬二烯醇、柠檬醛、香茅醛、羟基香茅醛、苯甲醛、甲基壬基乙醛、肉桂醛、十二醛、α-己基肉桂醛、十一醛、天芥菜精、香草醛、乙基香草醛和类似的醛;甲基戊基酮、甲基β-萘基酮、甲基壬基酮、麝香酮、丁二酮、2,3-戊二酮、2,3-己二酮、香芹酮、双甲酮、樟脑、苯乙酮、对甲基苯乙酮、芷香酮、甲基芷香酮和类似的酮;戊基丁内酯、苯醚、甲基苯基缩水甘油酯、壬基丙酮、香豆素、桉树脑、乙基甲基苯基缩水甘油酯和类似的内酯或氧化物;甲酸甲酯、甲酸异丙酯、甲酸里哪酯、乙酸乙酯、乙酸辛酯、乙酸甲酯、乙酸苄酯、乙酸肉桂酯、丙酸丁酯、乙酸异戊酯、异丁酸异丙酯、牻牛儿醇异戊酸酯、己酸烯丙酯、庚酸丁酯、辛酸辛酯、庚炔酸甲酯、辛炔酸甲酯、辛酸异戊酯、月桂酸甲酯、肉豆蔻酸乙酯、肉豆蔻酸甲酯、苯甲酸乙酯、苯甲酸苯甲酯、甲基苯乙酸甲酯、苯乙酸异丁酯、肉桂酸甲酯、苯丙烯酸苯丙烯酯、水杨酸甲酯、茴香酸乙酯、氨茴酸甲酯、丙酮酸乙酯、α-丁基丁酸乙酯、丙酸苯甲酯、乙酸丁酯、丁酸丁酯、乙酸对叔丁基环己基酯、乙酸柏木酯、香茅醇乙酸酯、香茅醇甲酸酯、乙酸对甲苯酯、丁酸乙酯、己酸乙酯、肉桂酸乙酯、乙酸乙基苯基酯、巴西基酸亚乙基酯、牻牛儿醇乙酸酯、牻牛儿醇甲酸酯、水杨酸异戊酯、戊酸异戊酯、乙酸异冰片酯、乙酸里哪酯、氨茴酸甲酯、二氢茉莉酸甲酯、乙酸壬酯、β-苯乙基乙酸酯、三氯亚甲基苯基甲基乙酸酯、萜品基乙酸酯、韦惕蔚基乙酸酯和类似的酯。
这些可以单独使用,或者可以使用其至少两种的相互混合物。如果适当,除了香料,本发明的制剂还可包括香料工业中惯用的添加剂,例如绿叶油或类似的挥发抑制剂,如丁子香酚或类似的粘度调节剂。
除了杀虫性活性化合物,本发明的硅氧烷弹性体还可包括工业杀菌剂和杀真菌剂,例如
2,4,4-三氯-2’-羟苯基醚、2,3,5,6-四氯-4-(甲基磺酰基)-吡啶、烷基苄基二甲基氯化铵、苄基二甲基-(2-(2-(对-1,1,3,3-四甲基丁基苯氧基)乙氧基)乙基)氯化铵、4-异丙基环庚三烯酚酮N-二甲基-N-苯基-N’-(氟二氯甲硫基)磺酰胺、2-(4’-噻唑基)-苯并咪唑、N-(氟二氯甲硫基)苯邻二甲酰亚胺、6-乙酸基-2,4-二甲基-间二噁英等,
和用于农业的杀菌剂和杀真菌剂,例如
亚乙基双二硫代氨基甲酸锌、亚乙基双硫代氨基甲酸锰、锌代森锰复合物、双二甲基二硫代氨基甲酰基亚乙基双二硫代氨基甲酸锌、双(二甲基硫代氨基甲酰基)二硫化物、2,6-二硝基-4-辛基苯基巴豆酸酯等,
或驱避剂,例如
苯二甲酸二甲酯、2,3,4,5-双(Δ2-亚丁基)四氢呋喃、2,3,4,5-双(Δ2-亚丁基)四氢糠醇、N,N-二乙基-间甲苯甲酰胺(以下称作“DEET”)、辛酸、二乙酰胺、2,3,4,5-双(Δ2-亚丁基)四氢糠醛、异辛可部酸二正丙酯、仲丁基苯乙烯基酮、壬基苯乙烯基酮、正丙基N-乙酰苯胺、2-乙基-1,3-己二醇、丁二酸二正丁酯、2-丁氧乙基-2-亚糠基乙酸酯、苯二甲酸二丁酯、四氢噻吩、β-萘酚、二烯丙基硫化物、双(二甲基硫代氨基甲酰基)二硫化物等。
本发明的杀虫性弹性体可以通过混入紫外吸收剂作为添加剂借助抗氧化剂得以稳定。适宜的紫外吸收剂为已知的紫外吸收剂。
优选使用苯酚衍生物例如丁羟基甲苯(BHT)、丁羟基茴香醚(BHA),双酚衍生物,芳基胺例如苯基-α-萘胺、苯基-β-萘胺,对氨基苯乙醚和丙酮或类似物的缩合物或二苯酮。
本发明的组合物-般包括0.1-80重量%,优选0.2-40重量%,更优选0.5-20重量%的活性化合物。
本发明还提供了制备本发明的杀虫性硅氧烷弹性体的方法,即通过以很高的剪切速度将含有OH-封端的聚二烷基硅氧烷和填料的碱性混合物与另一个OH-封端的聚二烷基硅氧烷、所需量的活性化合物及适宜的稳定剂混合。加入适宜的交联催化剂之后,将所得的组合物压成药片并在适当温度熟化。
根据以下实施例说明本发明的杀虫性弹性体的制备及应用。
实施例
实施例1:
杀虫性弹性体的制备,活性化合物含量1.5%:
在容量为1升的行星式混合器中以很高的剪切速度(最少80rpm)于30分钟内将含有平均粘度为18Pa.s的OH-封端的聚二甲基硅氧烷和表面积约为300m2/g的细碎热解硅石的碱性混合物(例如Silopren碱性混合物P490,Bayer AG(75%的聚二甲基硅氧烷CAS#70-131-67-8;25%的热解硅酸CAS#76-31-86-9))200g与分三份每份40g的120g平均粘度为2Pa.s的OH-封端的聚二甲基硅氧烷(例如Silopren C2,Bayer AG CAS#70-131-67-8)混合。加入聚合物后,在10分钟内混合4.88g transfluthrin和3.28g丁羟基甲苯(BHT)。最后在减压下将整个混合物脱气2分钟。
为了交联,将100g预混料与4g交联剂例如Silopren C Vernetzer5,Bayer AG(由40.0重量%的四乙氧基硅烷、32.5重量%的乙基聚硅酸盐和27.5重量%的二丁基二月桂酸锡搅拌直至获得均匀材料。减压下再将整个混合物脱气2分钟。
用浓度为1%的洗涤剂水溶液作为脱模剂对模具进行预处理并在室温熟化72小时。
实施例2:
杀虫性弹性体的制备,活性化合物含量10%:
在容量为1升的行星式混合器中以很高的剪切速度(最少80rpm)于30分钟内将含有平均粘度为18Pa.s的OH-封端的聚二甲基硅氧烷和表面积约为300m2/g的细碎热解硅石的碱性混合物200g与分三份每份40g的120g平均粘度为2Pa.s的OH-封端的聚二甲基硅氧烷混合。加入聚合物后,在10分钟内混合35.56g transfluthrin和3.6g丁羟基甲苯(BHT)。最后在减压下将整个混合物脱气2分钟。
为了交联,将100g预混料与4g交联剂例如Silopren C Vernetzer5,Bayer AG(由40.0重量%的四乙氧基硅烷(CAS#78-10-4)、32.5重量%的乙基聚硅酸盐(CAS#68-412-37-3)和27.5重量%的二丁基二月桂酸锡(CAS#77-58-7)组成)组成)搅拌直至获得均匀材料。减压下再将整个混合物再脱气2分钟。
用浓度为1%的洗涤剂水溶液作为脱模剂对模具进行预处理并在室温熟化72小时。
实施例3:
释放速率的测定:
用通过实施例1的方法制备的活性化合物含量为1.5%的硅氧烷弹性体测定释放速率。将弹性体在尺寸为25mm×40mm×4mm的模具中于室温熟化72小时。将用这种方法获得的硅氧烷药片在Steinel公司的MV-1型加热仪上加热至100-110℃,经过7次循环,每次8小时。
用实施例1的方法制备的硅氧烷弹性体的蒸发速率[mg/h] | ||
循环 | 蒸发炉A | 蒸发炉B |
1 | 6.4 | 7.0 |
3 | 2.5 | 2.8 |
4 | 1.4 | 1.6 |
5 | 1.3 | 1.5 |
6 | 1.2 | 1.0 |
7 | 1.5 | 1.5 |
所获得的蒸发速率显示了预期的典型过程,其中在开始的循环中蒸发量较大并且在后来的循环中蒸发速率平衡在约1-2mg/h的水平。
实施例4
生物活性
本发明的含有杀虫剂的硅氧烷弹性体在蒸发体系中的杀虫作用:
蚊子种类:埃及伊蚊
房间尺寸:34m3
房间类型:打开1扇窗子
温度:23-30℃
相对湿度:23-34%
加热温度:100-110℃
制剂用量:3.5g
活性化合物含量:1.6%
运行时间/经过一定时间(天)后试验 | 经过一定时间(小时)后引入蚊子 | 一定分钟或小时后击倒率 | 下列时间后的死亡% | ||
50% | 100% | 9h | 24h | ||
1天8小时 | 012345678 | 47′10′11′19′10′8′9′8′6′ | 59′24′19′56′15′45′40′16′12′ | 100100100100100100100100100 | 100100100100100100100100100 |
2天16小时 | 012345678 | 46′21′25′23′23′23′22′17′20′ | 1h08′45′49′36′44′42′38′26′35′ | 100100100100100100100100100 | 100100100100100100100100100 |
3天24小时 | 012345678 | 50′35′40′39′34′35′24′19′16′ | 59′58′1h26′1h16′1h07′1h07′1h02′48′40′ | 100100100100100100100100100 | 100100100100100100100100100 |
运行时间/经过一定时间(天)后试验 | 经过一定时间(小时)后引入蚊子 | 一定分钟或小时后击倒率 | 下列时间后的死亡% | ||
50% | 100% | 9h | 24h | ||
4天32小时 | 012345678 | 1h01′31′33′52′1h45′44′1h12′25′>1h | 1h31′1h04′1h11′2h20′2h34′1h28′1h43′41′>1h | 10010010010010010010010055 | 10010010010010010010010098 |
5天40小时 | 012345678 | 1h04′29′36′41′41′31′22′19′>1h | 2h40′2h23′1h47′1h10′1h24′1h01′59′36′>1h | 10010010010010010010010033 | 10010010010010010010010098 |
6天48小时 | 012345678 | 1h10′37′57′47′38′57′50′50′20′ | 1h50′1h17′1h23′1h52′1h41′1h38′1h10′1h02′>1h | 10010010010010010010010083 | 10010010010010010010010086 |
运行时间/经过一定时间(天)后试验 | 经过一定时间(小时)后引入蚊子 | 一定分钟或小时后击倒率 | 下列时间后的死亡% | ||
50% | 100% | 9h | 24h | ||
7天56小时 | 012345678 | 1h02′1h10′1h20′1h03′44′45′48′53′22′ | 2h08′1h59′2h54′2h03′1h20′1h47′1h26′>2h>1h | 1001001001001001001009078 | 10010010010010010010010095 |
Claims (8)
1.包含杀虫活性化合物的硅氧烷弹性体。
2.根据权利要求1的硅氧烷弹性体,其特征在于,它们在加热或不加热情况下释放包含于其中的杀虫剂,而在此过程中不改变其形状。
3.根据权利要求1的杀虫性硅氧烷弹性体,其特征在于,它们包含天然除虫菊,
3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d/l-顺/反-菊酸酯(丙烯除虫菊酯,Pynamin),
3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-顺/反-菊酸酯(Pynamin forte),
d-3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-反-菊酸酯(Exrin),
3-烯丙基-2-甲基-环戊-2-烯-4-酮-1-基d-反-菊酸酯(Bioallethrin),
N-(3,4,5,6-四氢苯二甲酰亚氨基)-甲基dl-顺/反-菊酸酯(似虫菊,Neopynamin),
5-苄基-3-呋喃甲基d-顺/反-菊酸酯(灭虫菊,Chrysronforte),
5-(2-炔丙基)-3-呋喃甲基菊酸酯(Furamethrin),
3-苯氧苄基2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸酯(苄氯菊酯,Exmin),
苯氧苄基d-顺/反-菊酸酯(醚虫菊,Sumithrin),
α-氰基苯氧基苄基异丙基-4-氯苯基乙酸酯(腈氯苯苯醚菊酯,Sumicidin),
(S)-α-氰基-3-苯氧基苄基(1R,顺)-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
(R,S)-α-氰基-3-苯氧基苄基(1R,1S)-顺/反-3-(2,2-二氯乙烯基)-2,2-二甲基环丙烷羧酸酯,
α-氰基-3-苯氧基苄基d-顺/反-菊酸酯,
1-乙炔基-2-甲基-2-戊烯基顺/反-菊酸酯,
1-乙炔基-2-甲基-2-戊烯基2,2-二甲基-3-(2-甲基-1-丙烯基)-环丙烷-1-羧酸酯,
1-乙炔基-2-甲基-2-戊烯基2,2,3,3-四甲基环丙烷羧酸酯,
1-乙炔基-2-甲基-2-戊烯基2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷-1-羧酸酯,
(1R)-3-炔丙基-2-甲基-环戊-2-烯-4-酮-1-基顺/反-菊酸酯(prallethrin),
2,3,5,6-四氟苄基(+)-1R-反-2,2-二甲基-3-(2,2-二氯乙烯基)-环丙烷羧酸酯(transfluthrin,Bayothrin),
或这些活性化合物的混合物作为杀虫活性化合物。
4.根据权利要求1的杀虫性硅氧烷弹性体,其特征在于,它们包含至少一种通过下列方法制备的硅氧烷弹性体:
通过在铂催化剂存在或不存在下使用含乙烯基的硅氧烷的羟甲硅烷基化反应,或者
在锡化合物存在或不存在下使用烷氧基硅烷,或者
使用有机过氧化物化合物,或者
使用至少一种碱性无机固体,或者
通过加入聚碳二亚胺聚硅氧烷共聚物,使有机聚硅氧烷材料交联。
5.根据权利要求1-4的杀虫性硅氧烷弹性体,其特征在于,它们包含0.1-80重量%的活性化合物。
6.根据权利要求1-5的杀虫性硅氧烷弹性体,其特征在于,它们包含BET表面积为50-500m2/g的细碎的热解或沉淀硅石、硅藻土、细碎的石英粉、非晶硅石或碳黑和稳定剂、着色剂或香料作为填料。
7.使用权利要求1-6的杀虫性硅氧烷弹性体控制或驱除飞虫的应用。
8.制备权利要求1-6的杀虫性硅氧烷弹性体的方法,其特征在于,以很高的剪切速度将含有OH-封端的聚二烷基硅氧烷和填料的碱性混合物与另一种OH-封端的聚二烷基硅氧烷、所需量的活性化合物及适宜的稳定剂混合,加入适宜的交联催化剂之后,将所得的组合物压成药片并在适当温度熟化。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19621304A DE19621304A1 (de) | 1996-05-28 | 1996-05-28 | Siliconelastomere mit insektizider Wirkung |
DE19621304.5 | 1996-05-28 |
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CN1220577A true CN1220577A (zh) | 1999-06-23 |
Family
ID=7795445
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---|---|---|---|
CN97195084.9A Pending CN1220577A (zh) | 1996-05-28 | 1997-05-15 | 杀虫性硅氧烷弹性体 |
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Country | Link |
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US (1) | US6183765B1 (zh) |
EP (1) | EP0906013A1 (zh) |
JP (1) | JP2000511165A (zh) |
CN (1) | CN1220577A (zh) |
AR (1) | AR007300A1 (zh) |
AU (1) | AU2955697A (zh) |
BR (1) | BR9709468A (zh) |
DE (1) | DE19621304A1 (zh) |
ID (1) | ID16893A (zh) |
TR (1) | TR199802469T2 (zh) |
WO (1) | WO1997045011A1 (zh) |
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CN102771518A (zh) * | 2012-08-14 | 2012-11-14 | 安徽巨地农业科技有限公司 | 嗅觉型鸟类翅目昆虫的驱避颗粒剂和微乳剂及其制备方法 |
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DE20011294U1 (de) * | 2000-07-03 | 2001-08-16 | Prokscha, Ingrid, 87719 Mindelheim | Kunststoffelement für ein Telefon |
WO2003090530A1 (en) * | 2002-04-24 | 2003-11-06 | Bayer Cropscience S.A. | Composition for luring and controlling arthropods comprising synthetic silicic acid and protein autolysate |
MXPA04012032A (es) * | 2002-07-08 | 2005-03-07 | Basf Ag | Mezclas fungicidas a base de dithianon. |
US7341736B2 (en) * | 2004-01-30 | 2008-03-11 | S.C. Johnson & Son, Inc. | Aerosol spray resistant to discoloration |
BE1016051A5 (nl) * | 2004-05-18 | 2006-02-07 | Utexbel Nv | Insectenwerende behandeling van textiel. |
EP2077123A1 (en) * | 2008-01-04 | 2009-07-08 | V. Mane Fils | Transparent anhydrous gel comprising perfume |
JP5571265B1 (ja) * | 2013-02-28 | 2014-08-13 | 大日本除蟲菊株式会社 | 香り付き防虫剤、香り付き防虫器、及び香り付き防虫剤の製造方法 |
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US3261801A (en) | 1962-08-22 | 1966-07-19 | Gen Electric | Reversion resistant organopolysiloxane containing barium oxide or barium peroxide |
GB1154727A (en) | 1965-09-17 | 1969-06-11 | Angus George Co Ltd | Improvements relating to Silicone Rubber Oil Seals |
US3865778A (en) | 1974-02-07 | 1975-02-11 | Gen Electric | Heat vulcanizable silicone rubber compositions resistant to oil degradation |
US4172904A (en) * | 1976-06-15 | 1979-10-30 | Young, Prussin, Mgk, J.V. | Case IV (D) adherent controlled release pesticide |
DE2847481A1 (de) | 1978-11-02 | 1980-05-14 | Bayer Ag | Verfahren zur herstellung von zu elastomeren haertbaren organosiloxanmassen mit vermindertem druckverformungsrest |
US4548999A (en) | 1978-11-02 | 1985-10-22 | Bayer Aktiengesellschaft | Elastomeric organopolysiloxanes containing polycarbodiimide-polysiloxane copolymers |
DE2911352A1 (de) | 1979-03-22 | 1980-10-02 | Wacker Chemie Gmbh | Zu elastomeren vernetzbare massen |
DE2919338A1 (de) | 1979-05-14 | 1980-11-20 | Wacker Chemie Gmbh | Verwendung von organopolysiloxanelastomer |
US4823990A (en) | 1987-12-18 | 1989-04-25 | Essex Chemical Corporation | Dispensing device |
US4908208A (en) | 1988-04-22 | 1990-03-13 | Dow Corning Corporation | Matrix for release of active ingredients |
FR2635640B1 (fr) | 1988-08-24 | 1993-04-23 | Rhone Poulenc Agrochimie | Compositions solides silicones a action biologique agricole |
FR2661683A1 (fr) | 1990-05-02 | 1991-11-08 | Rhone Poulenc Chimie | Systeme matriciel de liberation controlee comportant un principe actif hydrosoluble disperse dans une matrice constituee d'un copolymere silicone thermoplastique. |
DE4014310A1 (de) | 1990-05-04 | 1991-11-07 | Bayer Ag | Siliconelastomere mit vermindertem druckverformungsrest sowie verfahren zu deren herstellung |
DE4424786A1 (de) | 1994-07-14 | 1996-01-18 | Bayer Ag | Insektizid-enthaltende Gelformulierungen für Verdampfersysteme |
US5856271A (en) * | 1995-06-07 | 1999-01-05 | Battelle Memorial Institute | Method of making controlled released devices |
US5705175A (en) * | 1996-02-29 | 1998-01-06 | Pennzoil Products Company | Non-aqueous controlled release insect repellent and insecticide gels |
-
1996
- 1996-05-28 DE DE19621304A patent/DE19621304A1/de not_active Withdrawn
-
1997
- 1997-05-15 US US09/194,092 patent/US6183765B1/en not_active Expired - Lifetime
- 1997-05-15 AU AU29556/97A patent/AU2955697A/en not_active Abandoned
- 1997-05-15 BR BR9709468A patent/BR9709468A/pt not_active IP Right Cessation
- 1997-05-15 JP JP09541497A patent/JP2000511165A/ja active Pending
- 1997-05-15 EP EP97923908A patent/EP0906013A1/de not_active Withdrawn
- 1997-05-15 TR TR1998/02469T patent/TR199802469T2/xx unknown
- 1997-05-15 WO PCT/EP1997/002490 patent/WO1997045011A1/de not_active Application Discontinuation
- 1997-05-15 CN CN97195084.9A patent/CN1220577A/zh active Pending
- 1997-05-26 ID IDP971754A patent/ID16893A/id unknown
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102771518A (zh) * | 2012-08-14 | 2012-11-14 | 安徽巨地农业科技有限公司 | 嗅觉型鸟类翅目昆虫的驱避颗粒剂和微乳剂及其制备方法 |
CN102771518B (zh) * | 2012-08-14 | 2014-07-23 | 安徽巨地农业科技有限公司 | 嗅觉型鸟类翅目昆虫的驱避颗粒剂和微乳剂及其制备方法 |
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TR199802469T2 (xx) | 1999-03-22 |
EP0906013A1 (de) | 1999-04-07 |
BR9709468A (pt) | 1999-08-10 |
US6183765B1 (en) | 2001-02-06 |
ID16893A (id) | 1997-11-20 |
AR007300A1 (es) | 1999-10-27 |
AU2955697A (en) | 1998-01-05 |
WO1997045011A1 (de) | 1997-12-04 |
JP2000511165A (ja) | 2000-08-29 |
DE19621304A1 (de) | 1997-12-04 |
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