CN1709868B - Dithio dipropyl acidamide, and its preparing method and use - Google Patents
Dithio dipropyl acidamide, and its preparing method and use Download PDFInfo
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- CN1709868B CN1709868B CN 200510081681 CN200510081681A CN1709868B CN 1709868 B CN1709868 B CN 1709868B CN 200510081681 CN200510081681 CN 200510081681 CN 200510081681 A CN200510081681 A CN 200510081681A CN 1709868 B CN1709868 B CN 1709868B
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- China
- Prior art keywords
- ammonia
- propyl
- dithio
- dipropyl acidamide
- acid amides
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Links
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 title claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 title claims description 28
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 title claims description 25
- 238000000034 method Methods 0.000 title description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- -1 alkyl ammonia Chemical compound 0.000 claims description 62
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 41
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 17
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 16
- 230000003115 biocidal effect Effects 0.000 claims description 15
- 239000003139 biocide Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000003373 anti-fouling effect Effects 0.000 claims description 14
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 10
- 229960001826 dimethylphthalate Drugs 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000007098 aminolysis reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000251557 Ascidiacea Species 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 241000228153 Penicillium citrinum Species 0.000 description 1
- 241001339782 Scapharca broughtonii Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000009313 farming Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
This invention is a N, N'-dialkyldithiodipropionamide, which character is that its molecular formula is (C3H4NOSRR1)2, thereinto, R is CnHn+1(n=1-8),(CH2)3OCH3, (CH2)3OCH2CH3, (CH2)3OCH(CH3) 2, (CH2)3OCH2CH2CH2CH3, (CH2)3O(CH2)5CH(CH3) 2, (CH2)3OCH2CH2OCH3 or (CH2)3OCH2CH2OC6H5; R1 is hydrogen or methyl. This N, N'-dialkyldithiodipropionamide can be used for preparing coating, this compound has high-efficient , low-toxicity characteristics, can be turned into the degradable compound in the environment, it is a kind of effective sterilization agent that defends the mildew.
Description
Technical field
The present invention relates to a kind of dithio dipropyl acidamide, particularly relate to a kind of N, N '-dialkyl dithio dipropyl acidamide and preparation method thereof and the application in preparation marine antifouling coating and mould-repellant coating.
Background technology
The biocide mildewcide of Shi Yonging is of a great variety in the market, mainly can be divided into several big classes such as chloride class biocide mildewcide, triazole species biocide mildewcide.These biocide mildewcides in use all exist some problems, and the price height of quaternary ammonium salt biocide mildewcide for example if long-term use separately also can be developed immunity to drugs, and easily spumes, and uses under water hardness condition with higher and can reduce fungicidal effectiveness etc.; Chloride in addition biocide mildewcide has the shortcoming of high poison, high residue.Organo-tin compound is commonly used for marine antifoulant, promptly the multipolymer of methacrylic acid tributyl tin ester and methyl methacrylate and Red copper oxide (Cu
2O) composition is as a kind of antifouling paint, be coated on surfaces such as hull bottom, constantly discharge poison material tributyltin oxide (TBT) and Red copper oxide owing to the effect of seawater, harmful dirt settling (barnacle, Ascidian, marine alga etc.) that commute is attached to hull, maritime facilities surface has lethal effect, thereby plays antifouling effect.But simultaneously, TBT can cause gender variation and housing distortion, the serious harm marine eco-environment and the sea farming industry of oyster, blood clam and mussel.That the fungus and mildew resistance coating biocide mildewcide that is used for occasions such as various public places, household, office exists is volatile, timeliness short, narrow antimicrobial spectrum and defective such as harmful, and it can not be applied on a large scale.Taked various active measures to forbid or restrict sales and high malicious, the high residue biocide mildewcide of use at present.Therefore be badly in need of that exploitation is efficient, the biocide mildewcide of low toxicity, low residue.
Summary of the invention
The purpose of this invention is to provide a kind of N, N '-dialkyl dithio dipropyl acidamide and preparation method thereof, and it is used to prepare marine antifouling coating and mould-repellant coating as biocide mildewcide, to remedy the demand of prior art.
A kind of N, N '-dialkyl dithio dipropyl acidamide is characterized in that its molecular formula is (C
3H
4NOSRR
1)
2, structural formula is:
In the formula, R=C
nH
N+1(n=1-8), (CH
2)
3OCH
3, (CH
2)
3OCH
2CH
3, (CH
2)
3OCH (CH
3)
2, (CH
2)
3OCH
2CH
2CH
2CH
3, (CH
2)
3O (CH
2)
5CH (CH
3)
2, (CH
2)
3OCH
2CH
2OCH
3Or (CH
2)
3OCH
2CH
2OC
6H
5R
1=H or CH
3
Above-mentioned N, the preparation method of N '-dialkyl dithio dipropyl acidamide is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and methyl acrylate reaction, and the latter generates N, N '-dialkyl dithio dipropyl acidamide with alkyl ammonia generation aminolysis reaction again; The temperature of reaction of above-mentioned generation dithio dipropyl dimethyl phthalate reaction is 0～50 ℃, 2～12 hours reaction times; The mol ratio of described dithio dipropyl dimethyl phthalate and alkyl ammonia react is 1: 1～5,0～50 ℃ of temperature of reaction, 4～24 hours reaction times.
Above-mentioned N, N '-dialkyl dithio dipropyl acidamide is as the application of biocide mildewcide in the preparation marine antifouling coating.
Above-mentioned N, N '-dialkyl dithio dipropyl acidamide is as the application of biocide mildewcide in the preparation mould-repellant coating.
N of the present invention, N '-dialkyl dithio dipropyl acidamide can be used for preparing coating, and this compound has efficiently, the characteristics of low toxicity, can be converted into biodegradable compounds in environment, is a kind of effective biocide mildewcide.
Embodiment
1, the preparation of sodium polysulphide
In the beaker of 250ml, add 45.0g Na
2S.9H
2O and 8.8g sulphur powder are heated to boiling, and until whole dissolvings, cooling back suction filtration obtains red clarifying sodium polysulfide solution, be chilled to 0～5 ℃ standby.
2, the preparation of β-dithio dipropyl dimethyl phthalate
In the there-necked flask of the 500ml that whipping appts, condenser, thermometer are housed, add 200ml 10% (weight percentage) NaHCO successively
3Solution, 21.7g methyl acrylate are cooled to 0～5 ℃, drip the good sodium polysulfide solution of above-mentioned cooling in 1.5 hours.Remove ice-water bath then, at room temperature continue reaction 5～6h.Reaction finishes standing demix, branch vibration layer, the Na of adding 120ml 1mol/L in oil reservoir
2SO
3The aqueous solution continues reaction 3h down at 50 ℃ then, and reaction finishes.Standing demix again, branch vibration layer, oil reservoir obtains pure flaxen oily product β-dithio dipropyl dimethyl phthalate 26.8g through underpressure distillation, and productive rate is 89.3%.
Aforesaid propylene acid methyl esters is replaced with methyl methacrylate, can obtain β-dithio dimethyl propylene dimethyl phthalate by same procedure operation.
3, N, N '-dimethoxy propyl disulfide is synthetic for dipropyl acidamide
Add 26.7g γ-methoxy propyl ammonia, 2.5ml triethylamine in the 500ml there-necked flask of whipping appts, condenser, thermometer is housed successively, control reaction temperature is 0～5 ℃, drips the β-dithio dipropyl dimethyl phthalate 23.8g for preparing in 1.5 hours.Remove ice-water bath then, at room temperature continue reaction 24 hours, reaction finishes, and obtains the faint yellow solid product through suction filtration, and the dehydrated alcohol recrystallization is used in dry back, obtains white plates crystal 2 4.1g, and productive rate is 68.4%.
Above-mentioned γ-methoxy propyl ammonia is replaced with γ-ethoxy-c ammonia, γ-isopropoxy third ammonia, γ-butoxy third ammonia, γ-different octyloxy third ammonia, γ-methoxyethoxy third ammonia, γ-benzene oxygen ethoxy-c ammonia, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, ethamine, heptyl amice or octylame can obtain N respectively, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide, N, N '-dibutoxy propyl disulfide is for dipropyl acidamide, N, the different octyloxy propyl disulfide of N '-two is for dipropyl acidamide, N, N '-dimethoxy ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-hexichol oxygen ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-dibutoxy propyl disulfide is for dipropyl acidamide, N, N '-Methyl disulfide is for dipropyl acidamide, N, N '-diethyl-dithio dipropyl acidamide, N, N '-dipropyl dithio dipropyl acidamide, N, N '-dibutyl dithio dipropyl acidamide, N, N '-diamyl disulfide is for dipropyl acidamide, N, N '-dihexyl dithio dipropyl acidamide, N, N '-diheptyl dithio dipropyl acidamide or N, N '-dioctyl dithio dipropyl acidamide.
If above-mentioned β-dithio dipropyl dimethyl phthalate replaces with β-dithio dimethyl propylene dimethyl phthalate, then can get N, N '-dimethoxy propyl disulfide is for the dimethyl propylene acid amides, if again γ-methoxy propyl ammonia is replaced with γ-ethoxy-c ammonia, γ-isopropoxy third ammonia, γ-butoxy third ammonia, γ-different octyloxy third ammonia, γ-methoxyethoxy third ammonia, γ-benzene oxygen ethoxy-c ammonia, methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, ethamine, heptyl amice or octylame can obtain N respectively, N '-diethoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-diisopropoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-dibutoxy propyl disulfide is for the dimethyl propylene acid amides, N, the different octyloxy propyl disulfide of N '-two is for the dimethyl propylene acid amides, N, N '-dimethoxy ethoxycarbonyl propyl dithio dimethyl propylene acid amides, N, N '-hexichol oxygen ethoxycarbonyl propyl dithio dimethyl propylene acid amides, N, N '-dibutoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-Methyl disulfide is for the dimethyl propylene acid amides, N, N '-diethyl-dithio dimethyl propylene acid amides, N, N '-dipropyl dithio dimethyl propylene acid amides, N, N '-dibutyl dithio dimethyl propylene acid amides, N, N '-diamyl disulfide is for the dimethyl propylene acid amides, N, N '-dihexyl dithio dimethyl propylene acid amides, N, N '-diheptyl dithio dimethyl propylene acid amides or N, N '-dioctyl dithio dimethyl propylene acid amides.
With products therefrom with infrared spectra (IR), nucleus magnetic resonance (
1H NMR) method characterizes, and has proved that the compound of gained is compound of the present invention.
4, the application of compound of the present invention in the preparation marine antifouling coating
Marine antifouling coating of the present invention is made up of resin solution, softening agent, one or more stopping composition and one or more compounds of the present invention, and their weight percentage scope is 20～60,1～20,1～30 and 1～50.During preparation, with concentration is butylacetate solution, 2.5g clorafin, 12g red iron oxide, the aerosil of 2.5g, the 33g N of the 50g acrylic resin of 40% (concentration expressed in percentage by weight), N '-diethoxy propyl disulfide filters with 100 purpose strainers then for the vibration 2 hours in a paint shaker that contains granulated glass sphere of the mixture of dipropyl acidamide.The antifouling property of the antifouling paint that obtains for test, with reference to national standard " antifouling varnish model shallow sea soak test method " (GB 5370-85), with above-mentioned antifouling paint brushing plate long for 250mm, wide be that the experiment model adopts use iron bolt in the rectangular batten of trough of belt two to fix on 150mm, the thick soft steel experiment model for 2mm.Should test model and hang over Deep sea net cage culture zone, Xun Shan town, Rongcheng City (2 years) and obtained goodish experimental result, as shown in the table.
| 6 months | 12 months | 24 months | |
| Blank model | 20 | 40 | 100 |
| Soaked the model of antifouling paint | 0 | 0 | 8 |
Annotate: 0,8,20,40,100 is the bond area percentage ratios of marine organisms on model.
During the preparation marine antifouling coating, can also be with above-mentioned N, N '-diethoxy propyl disulfide is used N of the present invention instead for dipropyl acidamide, N '-dimethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide, N, N '-dibutoxy propyl disulfide is for dipropyl acidamide, N, N '-dimethoxy ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-hexichol oxygen ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-Methyl disulfide is for dipropyl acidamide, N, N '-diethyl-dithio dipropyl acidamide; Used organic solvent ethyl acetate can be used butylacetate, dimethylbenzene, toluene or butanols instead; Used softening agent Vaseline can be used clorafin, dibutyl phthalate or dioctyl phthalate (DOP) instead; Used stopping composition red iron oxide can be used talcum powder, titanium dioxide, aerosil or zinc oxide instead, all can obtain obvious effects.
5, the application of The compounds of this invention in the preparation mould-repellant coating
Preparation during mould-repellant coating with 25 parts of water, 0.4 part of sodium polyphosphate, 36 parts of titanium dioxide, 3.6 parts of N, N '-diethoxy propyl disulfide is for dipropyl acidamide, the vibration 2 hours in a paint shaker that contains granulated glass sphere of the mixture of 35 parts of ACRYLIC EMULSION, transfer pH=8～9 to filter with 100 purpose strainers then and be product. in order to test its performance, with reference to the experimental situation standard this coating is applied to be equipped with 6 kinds of mould aspergillus nigers, flavus in the test block, wood is mould, the bud branch is mould, in the test block of Penicillium citrinum, bread mould, humidity 96% temperature 26-28 ℃. the result is as shown in the table
| 1 month | 6 months | 12 months | 24 months | |
| Blank model | 20 | 40 | 80 | 100 |
| Scribble the test block of this coating | 0 | 0 | 0 | 5 |
Annotate: 0,5,20,40,80,100 is the bond area percentage ratio of mould in test block.With N, N '-diethoxy propyl disulfide changes other compound of the present invention for dipropyl acidamide also can obtain similar effects.
Claims (5)
1. N, N '-dialkyl dithio dipropyl acidamide is characterized in that its molecular formula is (C
3H
4NOSRR
1)
2, structural formula is:
In the formula, R=(CH
2)
3OCH
3, (CH
2)
3OCH
2CH
3, (CH
2)
3OCH (CH
3)
2, (CH
2)
3OCH
2CH
2CH
2CH
3, (CH
2)
3O (CH
2)
5CH (CH
3)
2, (CH
2)
3OCH
2CH
2OCH
3Or (CH
2)
3OCH
2CH
2OC
6H
5R
1=H or CH
3
2. the described N of claim 1, the preparation method of N '-dialkyl dithio dipropyl acidamide, it is characterized in that generating the dithio dipropyl dimethyl phthalate with sodium polysulphide and corresponding methyl acrylate reaction, the latter generates N, N '-dialkyl dithio dipropyl acidamide with alkyl ammonia generation aminolysis reaction again; The temperature of reaction of above-mentioned generation dithio dipropyl dimethyl phthalate reaction is 0～50 ℃, 2～12 hours reaction times; The mol ratio of described dithio dipropyl dimethyl phthalate and alkyl ammonia react is 1: 1～5,0～50 ℃ of temperature of reaction, 5～24 hours reaction times; Described alkyl ammonia is γ-methoxy propyl ammonia, γ-ethoxy-c ammonia, γ-isopropoxy third ammonia, γ-butoxy third ammonia, γ-different octyloxy third ammonia, γ-methoxyethoxy third ammonia or γ-benzene oxygen ethoxy-c ammonia.
3. preparation method as claimed in claim 2, it is characterized in that described N, N '-dialkyl dithio dipropyl acidamide is N, N '-dimethoxy propyl disulfide is for dipropyl acidamide, N, N '-diethoxy propyl disulfide is for dipropyl acidamide, N, N '-diisopropoxy propyl disulfide is for dipropyl acidamide, N, N '-dibutoxy propyl disulfide is for dipropyl acidamide, N, the different octyloxy propyl disulfide of N '-two is for dipropyl acidamide, N, N '-dimethoxy ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-hexichol oxygen ethoxycarbonyl propyl dithio dipropyl acidamide, N, N '-dimethoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-diethoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-diisopropoxy propyl disulfide is for the dimethyl propylene acid amides, N, N '-dibutoxy propyl disulfide is for the dimethyl propylene acid amides, N, the different octyloxy propyl disulfide of N '-two is for the dimethyl propylene acid amides, N, N '-dimethoxy ethoxycarbonyl propyl dithio dimethyl propylene acid amides, N, N '-hexichol oxygen ethoxycarbonyl propyl dithio dimethyl propylene acid amides or N, N '-dibutoxy propyl disulfide is for the dimethyl propylene acid amides.
4. the described N of claim 1, N '-dialkyl dithio dipropyl acidamide is as the application of biocide mildewcide in the preparation marine antifouling coating.
5. the described N of claim 1, N '-dialkyl dithio dipropyl acidamide is as the application of biocide mildewcide in the preparation mould-repellant coating.
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| CN 200510081681 CN1709868B (en) | 2005-04-18 | 2005-07-04 | Dithio dipropyl acidamide, and its preparing method and use |
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|---|---|---|---|
| CN200510043361.5 | 2005-04-18 | ||
| CN200510043361 | 2005-04-18 | ||
| CN 200510081681 CN1709868B (en) | 2005-04-18 | 2005-07-04 | Dithio dipropyl acidamide, and its preparing method and use |
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| CN107628977B (en) * | 2017-09-27 | 2019-09-17 | 浙江海洋大学 | The preparation of one type allicin compound and should be in the application in marine antifouling coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169949A (en) * | 1973-02-28 | 1979-10-02 | Rohm And Haas Company | Isothiazolidin-3-ones |
| CN1042350A (en) * | 1988-10-31 | 1990-05-23 | 北京市营养源研究所 | N, the preparation method of N '-dimethyl-3,3 '-dithio dipropyl acidamide |
-
2005
- 2005-07-04 CN CN 200510081681 patent/CN1709868B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169949A (en) * | 1973-02-28 | 1979-10-02 | Rohm And Haas Company | Isothiazolidin-3-ones |
| CN1042350A (en) * | 1988-10-31 | 1990-05-23 | 北京市营养源研究所 | N, the preparation method of N '-dimethyl-3,3 '-dithio dipropyl acidamide |
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