CN1319456C - Novel copper and triazole antiseptics for wood - Google Patents
Novel copper and triazole antiseptics for wood Download PDFInfo
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- CN1319456C CN1319456C CNB2003101241539A CN200310124153A CN1319456C CN 1319456 C CN1319456 C CN 1319456C CN B2003101241539 A CNB2003101241539 A CN B2003101241539A CN 200310124153 A CN200310124153 A CN 200310124153A CN 1319456 C CN1319456 C CN 1319456C
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- copper
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- triazole
- wood
- wood preservative
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- 239000010949 copper Substances 0.000 title claims abstract description 57
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 18
- 239000002023 wood Substances 0.000 title claims abstract description 14
- 230000002421 anti-septic effect Effects 0.000 title abstract description 5
- 229940064004 antiseptic throat preparations Drugs 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- -1 aminoethyl alcohol Chemical compound 0.000 claims abstract description 32
- 239000005822 Propiconazole Substances 0.000 claims abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 claims abstract description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005839 Tebuconazole Substances 0.000 claims abstract description 11
- UFNOUKDBUJZYDE-UHFFFAOYSA-N 2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol Chemical compound C1=NC=NN1CC(O)(C=1C=CC(Cl)=CC=1)C(C)C1CC1 UFNOUKDBUJZYDE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- 239000003171 wood protecting agent Substances 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000003755 preservative agent Substances 0.000 claims description 10
- 239000005757 Cyproconazole Substances 0.000 claims description 9
- 230000002335 preservative effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- ZXBVATFSHBMXOL-UHFFFAOYSA-N copper;2h-triazole Chemical compound [Cu].C=1C=NNN=1 ZXBVATFSHBMXOL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 241001330002 Bambuseae Species 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000000843 anti-fungal effect Effects 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical group [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- YCLLJOTVFONODL-UHFFFAOYSA-N boric acid;copper Chemical compound [Cu].OB(O)O YCLLJOTVFONODL-UHFFFAOYSA-N 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 67
- 239000004094 surface-active agent Substances 0.000 abstract description 12
- 238000012360 testing method Methods 0.000 abstract description 7
- 150000001875 compounds Chemical group 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- BESJRHHIPGWPTC-UHFFFAOYSA-N azane;copper Chemical group N.[Cu] BESJRHHIPGWPTC-UHFFFAOYSA-N 0.000 abstract 1
- 229960002645 boric acid Drugs 0.000 abstract 1
- 235000010338 boric acid Nutrition 0.000 abstract 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000004321 preservation Methods 0.000 description 5
- 241000233866 Fungi Species 0.000 description 4
- 241000256602 Isoptera Species 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000249899 Populus tomentosa Species 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241001492489 Postia placenta Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- XGIKILRODBEJIL-UHFFFAOYSA-N 1-(ethylamino)ethanol Chemical compound CCNC(C)O XGIKILRODBEJIL-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920002531 Rubberwood Polymers 0.000 description 1
- OUFJROAVKKYZEN-UHFFFAOYSA-N [Cr].[Cu].[As] Chemical compound [Cr].[Cu].[As] OUFJROAVKKYZEN-UHFFFAOYSA-N 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- SBFUAYPDMPMYBP-ATMONBRVSA-L copper (Z)-cyclohexyl-oxido-oxidoiminoazanium Chemical compound [Cu++].[O-]\N=[N+](/[O-])C1CCCCC1.[O-]\N=[N+](/[O-])C1CCCCC1 SBFUAYPDMPMYBP-ATMONBRVSA-L 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- AYWHENVLARCQQQ-UHFFFAOYSA-N copper;1h-pyrrole Chemical class [Cu].C=1C=CNC=1 AYWHENVLARCQQQ-UHFFFAOYSA-N 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The present invention relates to novel copper and triazole antiseptic for wood. The corresponding content of all the component comprises 16 to 31% of copper, 0.7 to 6% of triazole, 0 to 26% of boride (calculated by boracic acid), 4 to 6% of alcohol, 0 to 47% of ammonia, 6 to 60% of aminoethyl alcohol, 1 to 4% of quaternary surfactant and 0 to 1% of phosphate. The copper in a preparation is combined with the ammonia in a complex compound form, and the cost is lower than that of aminoethyl alcohol; when the preparation comprises a copper-ammonia complex compound, the stability and the copper sessile rate after the wood is processed are equivalent to those of a copper-ammonia group ethanol complex compound preparation, the triazole comprises propiconazole except for tebuconazole and cyproconazol, and boride and a small amount of phosphate can be contained in the preparation. A test result with durability in the field indicates that the preparation has the effects of good corrosion resistance, and fine white ant resistance.
Description
Technical field the present invention relates to the composition of the new copper triazole wood preservative of a class, and the application in the preservative treatment of wood (bamboo) material.
Background technology timber is bioabsorbable polymer material, be subjected to the harm of biotic factors such as bacterium worm easily and be degraded, as rotten, damage by worms, wood preservation can overcome this defective.Compare with developed countries, preserving timber application quantity at home is less, and its development potentiality is bigger.In recent years, domestic wood preservation industry is very fast in southern area development, mainly handles a spot of agricultural material, gardens with material and rubber wood timber wood for furniture, wherein section port.The preservative of domestic present use mainly is a copper chromium arsenic (CCA), and quaternary ammonium copper (ACQ) is used with material in a small amount of gardens.CCA once at home and abroad is extensive use of, and after the timber of handling because of CCA surpassed its service life, waste wood was handled relatively difficulty, as adopt burn and the recovery of heavy metal, microbial decomposition after the absorption recovery etc. of heavy metal.Chromium, arsenic are heavy metal among the CCA, have greater environmental impacts, and it uses in the strict restriction of some countries, as forbids using in the place that contacts with the people, and its consumption descends year by year, has not for example had CCA among the wood preservative standard JIS 1570 of Japan in 2004.The research of the substitute of CCA is very urgent.In recent years, some with copper (Cu) be basic Chrome-free, no arsenic waterborne-type preservation as: ACQ, copper azoles (CuAz), Cu-HDO, two Methyl disulfide just worldwide are used widely for acyl copper (CDDC).
Gareth Williams has introduced the preparation that consists of copper, Tebuconazole, amido alcohol in 2000 and has been used for wood preservative in United States Patent (USP) RE36798, copper combines with the form of amido alcohol with complex compound in the preparation.Reimer Goettsche has introduced copper, Cyproconazole, amido alcohol, surfactant/contain phosphonium compounds in United States Patent (USP) 6441016B2 in 2002 preparation is used for wood preservation, wherein copper 2.5-45%, Cyproconazole 0.5-15%, amido alcohol 5-50%, surfactant 0.5-30%.In the copper triazole preparation, the solvability of triazole in water is minimum, and precipitation generally should be added ionic surface active agent easily.Amido alcohol amount can partly overcome the lability of preparation in the increase preparation, but uses amido alcohol higher with the cost of copper formation complex compound.
The fixation performance of its active ingredient in timber is the key factor, the particularly timber that uses under outdoor conditions of its antiseptic effect quality of decision behind the copper preservative processing timber.CCA in timber anchorage research and report morely, wherein the copper chromate of Sheng Chenging etc. helps the set in timber, and the anchorage of some other copper preservative report is less.JiangM-L, et al report that at IRG/WP03-30316 indoor current lose result of experiment and show, the fixation rate of the timber copper that the preparation of organic acid mantoquitas such as copper citrate is handled is not as ACQ.
The maximum difference of report is in summary of the invention the present invention and the foreign patents: copper can combine with the form of ammonia with complex compound in the preparation, and the cost of its preparation is low with the cost of the preparation of the pure complexing of amido than copper; Triazole has propiconazole in the preparation except that Tebuconazole, Cyproconazole; Boride, carbamate additives for low phosphorus hydrochlorate can be arranged in the preparation, also can not have boride, carbamate additives for low phosphorus hydrochlorate; A small amount of quaternary cationics and amido ethanol have been added in the preparation.
The weight of copper triazole wood preservative of the present invention is composed as follows: copper 16-31%, triazole 0.7-6%, boride (calculating with boric acid) 0-26%, alcohols 4-6%, ammonia 0-47%, amido ethanol 6-60%, quaternary surfactant 1-4%, phosphate 0-1%, wherein ammonia and phosphatic content are not 0 simultaneously.
Copper in the preservative of the present invention is bivalent cupric ion, comprising: copper sulphate, verdigris, copper chloride, copper oxide or Kocide SD.When the triazole in the preparation was Tebuconazole (tebuconazole), the ratio of copper and Tebuconazole was comparatively suitable between 25: 1 and 10: 1, and the ratio of copper and ammonia is comparatively suitable between 1: 1.3 and 1: 0.6.
When the triazole in the preparation was Cyproconazole (cyproconazole), the ratio of copper and Cyproconazole was comparatively suitable between 100: 1 and 50: 1, and the ratio of copper and ammonia is comparatively suitable between 1: 1.3 and 1: 0.6.
When the triazole in the preparation was propiconazole (propiconazole), the ratio of copper and propiconazole was comparatively suitable between 25: 1 and 5: 1, and the too low propiconazole of ratio precipitates easily, and the increase of the amount of propiconazole can improve the cost of preparation; The preparation that the ratio of copper and propiconazole is too high is relatively poor to the inhibition effect of some rot fungis.When using propiconazole, can make part with ammonia in the preparation, add a small amount of amido ethanol, the amount of amido ethanol is not more than 1/8 of ammonia, also can use amido ethanol to make part, adds a spot of ammonia or does not add ammonia.
When the preparation preparation, need triazole be dissolved with organic solvents such as a small amount of alcohols, acetone, DMF, alcohols comprises ethanol, propyl alcohol, isopropyl alcohol.Indoor current lose result of experiment and show, the fixation rate that uses ammoniacal liquor to make copper in the preparation of part among the present invention is higher than or is equivalent to do with amido ethanol the preparation of part.
Add quaternary cationics in the preparation, can improve the stability of formulation energy, triazole can not precipitate.The ratio of the amount of copper and quaternary cationics is comparatively suitable between 16: 1 to 6: 1.In addition, quaternary cationics itself also has certain antifungal activity, and price comparison is suitable.Quaternary surfactant comprises that the anion in two ten alkyl-dimethyl ammonium chlorides (DDAC), dodecylbenzyl alkyl dimethyl ammonium chloride (BAC), two eight alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, eight alkyl, ten alkyl-dimethyl ammonium chlorides, cocoyl trimethyl ammonium chloride (coco trimethyl ammonium chloride) or the above quarternary ammonium salt compound is a bromine.
In the preparation boride can be arranged,, also can not have boride as boric acid or sodium tetraborate (borax).Do not reduce the stability of formulation energy after adding boride, do not cause the precipitation of copper or triazole active ingredient.When boride is arranged, the ratio of copper and boride (in boric acid) is more suitable between 2: 1 and 1: 2, when the outdoor timber that uses down with the ground contact conditions uses preparation of the present invention to carry out preservative treatment, can reduce the usage amount of boride or not use boride.When the indoor timber that does not use down with the ground contact conditions does not use preparation of the present invention to carry out preservative treatment, can not add boride in the preparation.
Preparation during long preservation, in the time of ammonia and most copper complexing, added a spot of amido ethanol and can improve stability of formulation more than 6 months, and copper can not precipitate.
Phosphate is significantly improved to the fixation rate of some copper agent copper, but phosphatic amount should not be bigger, with the ratio of copper below 10: 1, it is bigger to add phosphatic amount, stability of formulation is poor more.Phosphate comprises diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP).
Preparation 1-7 and example 1-4 can be more detailed to the present invention explanation, but content of the present invention just preparation 1-7 and example 1-4.
Embodiment preparation 1 bronze medal 16%, boric acid 16%, propiconazole 0.7%, ethanol 5%, amido ethanol 60%, two ten alkyl-dimethyl ammonium chloride surfactants 1%, phosphate 1%.
Preparation 2
Copper 16%, boric acid 16%, Tebuconazole 0.7%, ethanol 5%, amido ethanol 60%, two ten alkyl-dimethyl ammonium chloride surfactants 1%, phosphate 1%.
Preparation 3
Copper 25%, boric acid 25%, Tebuconazole 1%, ammoniacal liquor 31%, ethanol 6%, amido ethanol 8%, two ten alkyl-dimethyl ammonium chloride surfactants 4%.
Preparation 4
Copper 25%, boric acid 25%, propiconazole 1%, ammoniacal liquor 31%, ethanol 6%, amido ethanol 8%, two ten alkyl-dimethyl ammonium chloride surfactants 4%.
Preparation 5
Copper 37%, Tebuconazole 1.5%, ammoniacal liquor 47%, ethanol 6%, amido ethanol 6%, two ten alkyl-dimethyl ammonium chloride surfactants 2.5%.
Preparation 6
Copper 37%, propiconazole 13%, ammoniacal liquor 47%, ethanol 6%, amido ethanol 6%, dodecylbenzyl alkyl dimethyl ammonium chloride 2.5%.
Preparation 7
Copper 37%, Cyproconazole 0.6%, ammoniacal liquor 47%, ethanol 6%, amido ethanol 6%, dodecylbenzyl alkyl dimethyl ammonium chloride 2.5%.
The preparation of example 1 preparation 4
1.2g propiconazole is dissolved in the 10g ethanol, add 10g amido ethanol and 70% couple ten alkyl-dimethyl ammonium chloride surfactant 6.9g, make solution A: 115.5g copper sulphate (containing 5 water of crystallization), after adding that 357g is water-soluble and separating, add 25% ammoniacal liquor 147g, add 5.5% boric acid 528g dissolving again, mix, promptly make the preparation 4 of 5.1% (in copper, propiconazole, boric acid sum) with the above-mentioned solution A that makes.
The preparation method of other preparations is with example 1.
Example 2 some preparations are handled the resistance leachability energy behind the timber
With reference to the method for AWPA E11-97, the different preparations of inhaling doses are handled timber, and gas was done after 21 days, carry out indoor current and lose test, and the sample grouping with distilled water immersion 14 days, is refreshed the water periodically and collected leachate.With the concentration of copper in the Atomic Absorption Spectrometer measurement leachate, calculate the fixation rate of medicament again according to AWPA E11-97 standard.The results are shown in Table 1.
In the table 1, ammoniacal liquor or ethylaminoethanol are little to the fixation rate influence of copper in the preparation; When copper suction dose was suitable, the fixation rate of copper was suitable behind the examination material that preparation 2,3,5 and ACQ-B handle.The fixation rate of copper generally was higher than the fixation rate that hangs down when inhaling dose when preparation was inhaled dose at height.
The fixation rate of some preparations of table 1 copper in wet-land pine tree
| Preparation | Inhale dose * (kg/m 3) | Fixation rate (%) |
| 2 | 2.19 7.15 | 85.4 86.0 |
| 3 | 2.18 7.30 | 83.4 88.4 |
| 5 | 1.14 3.69 | 85.4 89.2 |
| ACQ-B | 2.35 6.56 | 83.7 89.4 |
*Annotate: preparation 2,3,5 is inhaled dose and is calculated with copper, triazole, boric acid sum,
ACQ-B inhales dose with CuO, and the DDAC sum is calculated.
Example 3 some preparations are handled the indoor corrosion resistant performance behind the bamboo wood
Corrosion resistant test method: adopt GB/T 13942.1-92 method, bacterial classification: Corious versicolor (C.v), Poria placenta (P.p); The examination material is a mao bamboon, size: 20mm (L) * 20mm (T) * 5mm (R).
Preparation 1-4 is inhaling dose 1.8-7.6kg/m
3The time, whiterot fungi Corilus versicolor Quel. (Corious versicolor) and the continuous skin transverse hole fungus of brown rot fungus (Poria placenta) there are certain inhibition effect.The natural decay resistance of the mao bamboon of adopting in this test is corrosion resistant grade slightly, and contrast tries the loss in weight of material between 10-20%.
Indoor corrosion resistant result of the test behind the table 2 part preparation processing bamboo wood
| Preparation | Inhale dose (Kg/M 3) | Rate of weight loss %C.v | Inhale dose (Kg/M 3) | Rate of weight loss %P.p |
| Contrast | 0 | 12.8 | 0 | 11.9 |
| 1 | 2.1 4.7 7.3 | 0.3 0.3 0.7 | 1.8 4.6 6.6 | 2.0 1.0 1.6 |
| 2 | 2.2 4.6 7.2 | 1.9 1.0 1.2 | 1.9 4.5 6.9 | 2.0 1.8 1.4 |
| 3 | 2.1 4.9 7.6 | 0.9 0.7 1.0 | 1.8 4.2 7.1 | 1.5 1.4 1.3 |
| 4 | 2.1 4.9 6.9 | 1.2 0.5 0.2 | 2.2 4.4 7.2 | 1.7 1.2 1.4 |
Example 4 some preparations are handled the open-air endurance quality behind the timber
Open-air long duration test method: adopt ASTM D 1758-96, Chinese white poplar examination material size: 20mm * 20mm * 300mm (L), mao bamboon examination material size: 30mm (T) * 5-7mm (R) * 300mm (L), the thickness (R) that keeps mao bamboon examination material is processed, test site: Shahe, Guangzhou, Guangdong, test period: December.
Preparation 1-7 has in various degree antiseptic effect to Chinese white poplar, and control sample is rotten fully or termite food empty (table 3).In the table 4, the part preparation is better to the antiseptic effect of mao bamboon, and after 18 months test periods, the contrast mao bamboon is rotten, the classification of termite durability is 0.
Table 3 preparation is handled the open-air endurance quality (December) behind the Chinese white poplar
| Preparation | Inhale dose (Kg/M 3) | The durability classification | |
| Rotten | Termite | ||
| Contrast | 0 | 0 | 0 |
| 1 | 2.70 6.34 11.4 | 8.2 9.6 9.6 | 10 10 10 |
| 2 | 1.91 4.03 5.19 | 7.2 8 8.8 | 8.4 8.6 9.6 |
| 3 | 1.69 4.27 6.80 | 6.6 9 9.2 | 5.2 9 9 |
| 4 | 1.47 4.40 6.17 | 7.6 7.8 9.2 | 6.4 8.6 8.6 |
| 5 | 1.90 2.98 | 9.2 10 | 9.2 10 |
| 6.12 10.5 | 9.6 10 | 10 10 | |
| 6 | 2.29 5.29 11.1 | 9.8 9.4 10 | 10 10 10 |
| 7 | 2.00 | 9.8 | 10 |
Table 4 preparation is handled the open-air endurance quality (December) behind the mao bamboon
| Preparation | Inhale dose (Kg/M 3) | The durability classification | |
| Rotten | Termite | ||
| Contrast | 0 | 5.2 | 2 |
| 2 | 1.32 4.34 5.42 | 9 8.8 9.6 | 10 10 10 |
| 5 | 1.84 3.30 | 10 10 | 10 10 |
| 6 | 2.35 3.40 | 10 10 | 10 10 |
Claims (14)
1. copper triazole wood preservative, the weight of this preservative is composed as follows: copper 16-31%, triazole 0.7-6%, boride (calculating with boric acid) 0-26%, alcohols 4-6%, ammonia 0-47%, amido ethanol 6-60%, the quaternary cationics 1-4% with antifungal activity and phosphate 0-1%, condition is that ammonia and phosphatic content are not 0 simultaneously.
2. according to the wood preservative of claim 1, wherein said copper is the bivalent cupric ion compound that is selected from copper sulphate, verdigris, copper chloride, copper oxide or Kocide SD.
3. according to the wood preservative of claim 1, wherein said triazole is a propiconazole.
4. according to the wood preservative of claim 3, wherein the ratio of copper and propiconazole is between 25: 1 and 5: 1.
5 wood preservatives according to claim 1, wherein said triazole is a Tebuconazole.
6. according to the wood preservative of claim 5, wherein the ratio of copper and Tebuconazole is between 25: 1 and 10: 1, and the ratio of copper and ammonia is between 1: 1.3 and 1: 0.6.
7. according to the wood preservative of claim 1, wherein said triazole is a Cyproconazole.
8. according to the wood preservative of claim 7, wherein the ratio of copper and Cyproconazole is between 100: 1 and 50: 1, and the ratio of copper and ammonia is between 1: 1.3 and 1: 0.6.
9. according to the wood preservative of claim 1, wherein said boride is sodium tetraborate, boric acid or their mixture.
10. according to the wood preservative of claim 9, wherein when described wood preservative contains boride, be between 2: 1 and 1: 2 in the ratio of boric acid copper and boride.
11. according to the wood preservative of claim 1, wherein said alcohols is ethanol, propyl alcohol or isopropyl alcohol.
12. wood preservative according to claim 1, wherein said quaternary cationics is two ten alkyl-dimethyl ammonium chlorides (DDAC), dodecylbenzyl alkyl dimethyl ammonium chloride (BAC), two eight alkyl-dimethyl ammonium chlorides, two dodecyl dimethyl ammonium chloride, eight alkyl, ten alkyl-dimethyl ammonium chlorides or cocoyl trimethyl ammonium chloride, or anion is the above-mentioned quarternary ammonium salt compound of bromide ion.
13. according to the wood preservative of claim 1, wherein said phosphate is diammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP).
14. the application of copper triazole wood preservative in timber, bamboo wood or wood materials preservative treatment that claim 1-13 is any.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9961895B2 (en) | 2011-11-04 | 2018-05-08 | Arch Timber Protection Limited | Additives for use in wood preservation |
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| US9961895B2 (en) | 2011-11-04 | 2018-05-08 | Arch Timber Protection Limited | Additives for use in wood preservation |
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