CN104725637B - Polythioether-base polymercaptan, and synthesis method and application thereof - Google Patents
Polythioether-base polymercaptan, and synthesis method and application thereof Download PDFInfo
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- CN104725637B CN104725637B CN201310719492.5A CN201310719492A CN104725637B CN 104725637 B CN104725637 B CN 104725637B CN 201310719492 A CN201310719492 A CN 201310719492A CN 104725637 B CN104725637 B CN 104725637B
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- polymercaptan
- polysulfide ether
- copper
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- 238000001308 synthesis method Methods 0.000 title 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 19
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 164
- 229920001021 polysulfide Polymers 0.000 claims description 83
- 239000005077 polysulfide Substances 0.000 claims description 83
- 150000008117 polysulfides Polymers 0.000 claims description 83
- 239000000047 product Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- -1 azo dicyano valeric acid Chemical compound 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 5
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical group COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 238000007171 acid catalysis Methods 0.000 claims 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000007888 film coating Substances 0.000 abstract description 17
- 238000009501 film coating Methods 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 2
- 238000012644 addition polymerization Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229920006295 polythiol Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 238000000280 densification Methods 0.000 description 16
- 238000001556 precipitation Methods 0.000 description 16
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 15
- 238000001704 evaporation Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000008020 evaporation Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- HMPSOEYFMTWOFC-UHFFFAOYSA-N propane-2,2-dithiol Chemical compound CC(C)(S)S HMPSOEYFMTWOFC-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical group CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UZASMYQTKALYAA-UHFFFAOYSA-N 1-benzothiophene 1H-pyrrole Chemical class N1C=CC=C1.S1C=CC2=C1C=CC=C2 UZASMYQTKALYAA-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a polythioether-base compound, of which the side chain structure contains abundant mercapto group, thereby forming the polythioether-base polymercaptan. The invention also provides a method for synthesizing the polythioether-base polymercaptan, which comprises the following steps: carrying out mercapto-alkyne addition polymerization reaction to obtain polythioether, and carrying out acidic hydrolysis. The method has the advantages of high speed, high efficiency, simple technique and high yield. The mercapto group in the polythioether-base polymercaptan molecular chain can form a sulfur-copper bond with copper, the mercaptan bond can be self-condensed to form a compact thick-film coating, and thus, the polythioether-base polymercaptan can be used as a copper corrosion inhibitor. The slow-release film formed by the polythioether-base polymercaptan on the copper surface has the advantages of high adhesion, high compactness and high thickness, satisfies the performance requirements on the copper corrosion inhibition film at present, and effectively protects the copper base from external corrosion.
Description
Technical field
The present invention relates to polysulfide based compound is and in particular to a kind of polysulfide ether polymercaptan, its synthetic method and application.
Background technology
Copper has excellent intensity, machining property, electric conductivity, heat conductivity, is widely used in electric, light industry, machine
The fields such as tool manufacture, building industry, national defense industry.However, copper is in air, oxygenated water, oxidizing acid and electrolyte solution
Can corrode.Therefore, one of key factor of its stable performance is to maintain to the anti-corrosion protection of copper material.
Anticorrosion technique has multiple, such as: cathodic protection, organic coating protection, corrosion inhibiter etc..Wherein, corrosion inhibiter refers to
Add micro in medium or this kind of chemical substance can be so that metal corrosion rate in the medium be greatly reduced on a small quantity.It has
Have the characteristics that the simple to operate, engineering time is short, easy reparation.Unlike cathodic protection need build complexity Circuits System, also unlike
Coating protection needs the brushing of specification, and some operating modes are not suitable for brushing organic coating.So, it is in Chemical cleaning, antifreeze
The places such as liquid, circulating cooling liquid, air storage are widely used.
At present, can have a lot as the product of copper material corrosion inhibitor, for example: chromate, BTA, sulfydryl benzo thiophene
Azoles, small molecule mercaptan etc., these corrosion inhibiter are broadly divided into three classes: passivation membranous type, precipitation membranous type and adsorbed film type, are become to delay
The adhesive force of erosion film is all preferable with compactness.But, the thickness of these three films is generally relatively low, is below 100nm, causes its obstruct
Corrosive medium limited in one's ability.In order to improve the performance of corrosion inhibiter it is necessary to while taking into account adhesive force and compactness, further
Raising corrosion inhibition film thickness.
Content of the invention
The present invention provides a kind of polysulfide based compound of new structure, contains a large amount of sulfydryls in its side-chain structure, is formed
Polysulfide ether polymercaptan, structural formula is as follows:
Wherein, n is the integer between 5～100, including 5 and 100；
R1 is-(ch2)n1-、-ch2ch2(xch2ch2)n2-、-ch2-c6h4-ch2-、-ch2chch2Oh- or-ch2(choh)n3ch2-, wherein n1 is the integer between 2～10, including 2 and 10；N2, n3 are the integer between 1～5, including 1 with 5:x be o or
S atom；
R2 is-(ch2)n4-, wherein n4 is the integer between 1～9, including 1 and 9.
Substantial amounts of sulfydryl is contained such that it is able to form sulfur copper key with copper in the molecular side chain of above-mentioned polysulfide ether polymercaptan,
Thiol bond in strand passes through to self condense the thick film coating that can form densification simultaneously, and therefore this polysulfide ether polymercaptan can
Apply as copper inhibitor, the release membranes that it forms on copper surface have the advantages that adhesive force is strong, compactness is high, thickness is high,
Meet the performance requirement at present to copper corrosion inhibition film, be effectively protected Copper substrate from extraneous corrosion.
Present invention also offers a kind of synthetic method synthesizing above-mentioned polysulfide ether polymercaptan, the method is initially with mercapto
Base-alkynes click chemistry polymerization obtains polythiaether, is then passed through acid hydrolysis and obtains polysulfide ether polymercaptan, has quick height
Effect, simple process, the advantage of high income.The method specifically includes following steps:
Step 1: sequentially add two mercaptan, alkynyl carbothioic acid ester, initiator in the reactor, enter under initiating accident sequence effect
Row sulfydryl-alkynes polyaddition reaction；
Step 2: under inert gas shielding, step 1 products therefrom is dissolved in solvent, with the thio carboxylic of the alkynyl in step 1
The addition of acid esters is to calculate equivalent, sequentially adds water, alcohol or its mixture of 0.01～1 equivalent, 0.01～0.1 equivalent
Acid catalyst, be hydrolyzed under 50-120c reaction；
Step 3: the solvent in step 2 products therefrom is removed, then precipitates, be dried, obtain polysulfide ether polymercaptan.
Two described mercaptan compounds are to have end sulfenyl dithiol compound, and its molecular structural formula is hs-r1-sh, r1
Selected from-(ch2)n1-、-ch2ch2(xch2ch2)n2-、-ch2-c6h4-ch2-、-ch2chch2Oh- or-ch2(choh)n3ch2-, its
Middle n1 is the integer between 2～10, including 2 and 10；N2, n3 are the integer between 1～5, including 1 and 5；X is o or s atom.Bag
Include but be not limited to dithioglycol, dimercaptopropane, succinimide mercaptans, pentane disulfide thioalcohol, ethanthiol, mercaptan in heptan two, pungent two mercaptan, second two
Diethylene glycol diethyl ether base two mercaptan, diethyl thioether group two mercaptan, xylol base two mercaptan etc..
The molecular structural formula of described alkynyl carbothioic acid ester is ch ≡ c-r2-s-co-r3, and wherein r2 is-(ch2)n4-,
N4 is the integer between 1～9, is alkyl or phenyl including 1 and 9, r3.This alkynyl carbothioic acid ester includes but is not limited to propinyl
Thiacetate, butynyl thiacetate, pentynyl thiacetate, hexin base thiacetate, propinyl propane thioic acid
Ester, propinyl Thiobenzoate etc..
Described initiator type is different according to initiating accident sequence difference, is caused from temperature-sensitive free radical when initiating accident sequence is heat
Agent, selects photosensitive free radical initiator when initiating accident sequence is for radiation energy.Described temperature-sensitive radical initiator includes but does not limit to
In azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, 2, the double (4- of 2 '-azo
Methoxy -2,4- methyl pentane nitrile), benzoyl peroxide, potassium peroxydisulfate or Ammonium persulfate. etc..Described photosensitive free radical initiator
Including but not limited to dimethoxybenzoin, 1- hydroxycyclohexyl phenyl ketone or methyl benzoylformate etc..
Preferably, in described step 1, two mercaptan, alkynyl carbothioic acid ester, initiator are with mol ratio 1: (0.9～1)
: (0.01～0.1) mixing.
Preferably, in described step 1, polyaddition reaction 0.5-24 hour.
In described step 2, solvent is selected from, but not limited to, water, methanol, ethanol, isopropanol, toluene, benzene, chloroform, dichloromethane
Alkane, oxolane, dioxane, hexane, ether, ethyl acetate, n, n- dimethylformamide, n, n- dimethyl acetylamide or n- first
One of base ketopyrrolidine or several mixture.
In described step 2, acid catalyst includes but is not limited to hydrochloric acid, sulphuric acid or p-methyl benzenesulfonic acid.
In described step 2, alcohol is selected from but not limited to methanol, ethanol, propanol or isopropanol.
Preferably, in described step 2, hydrolysis 1-24 hour.
Brief description
Fig. 1 be the embodiment of the present invention 1 step (1) in obtained with propinyl thiacetic acid. polyisocyanate polyaddition using dithioglycol
Product1H nmr spectrum；
Fig. 2 is the polythiaether being obtained with propinyl thiacetate with dithioglycol in the step (3) of the embodiment of the present invention 1
Base polymercaptan product1H nmr spectrum；
Fig. 3 is the polythiaether being obtained with propinyl thiacetate with dithioglycol in the step (3) of the embodiment of the present invention 1
The AC impedance spectroscopy of base polymercaptan product.
Specific embodiment
Embodiment is described in further detail to the present invention it should be pointed out that described below is implemented below in conjunction with the accompanying drawings
Example is intended to be easy to the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.9 molar part propinyl thiacetate,
0.01 molar part azodiisobutyronitrile, at 70 DEG C, carries out sulfydryl-alkynes polyaddition reaction 0.5 hour；
(2), under nitrogen protection, step (1) products therefrom is dissolved in 0.25 molar part ethanol, sequentially adds 0.01 mole
The water of part, 0.01 molar part hydrochloric acid, hydrolysis 24 hours at 50 DEG C；
(3) by step (2) products therefrom evaporating ethanol, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Fig. 1 is to obtain products therefrom in above-mentioned steps (1)1H nmr spectrum.Fig. 2 is the polysulfide that step (3) obtains
Ether polymercaptan1H nmr spectrum, which show the proton signal (1.8ppm) of obvious sulfydryl.Fig. 3 is step
(3) the polysulfide ether polymercaptan product electrochemical alternate impedance spectrum figure obtaining.
Substantial amounts of sulfydryl is contained such that it is able to form sulfur with copper in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan
Copper key, the thiol bond in strand, therefore can be used as copper inhibitor by self condensing the thick film coating that can form densification simultaneously
And apply.
Embodiment 2:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) dithioglycol compound containing 1 molar part, 1 molar part propinyl thiacetic acid. are sequentially added in the reactor
Ester, 0.1 molar part azo dicyano valeric acid, at 50 DEG C, carry out sulfydryl-alkynes polyaddition reaction 24 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 10 molar part toluene, sequentially adds the first of 1 molar part
Alcohol, 0.1 molar part p-methyl benzenesulfonic acid, reacts 1 hour at 120 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 3:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dimercaptopropane containing 1 molar part, 0.95 molar part butynyl thiacetate,
0.05 molar part azodiisobutyronitrile, at 65 DEG C, carries out sulfydryl-alkynes polyaddition reaction 12 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 1 molar part oxolane, sequentially adds 0.1 molar part
Water, 0.02 molar part hydrochloric acid, at 65 DEG C react 12 hours；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 4:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) ethylene glycol diethyl ether base two mercaptan containing 1 molar part, 0.95 molar part propinyl are sequentially added in the reactor
Thiobenzoate, 0.02 molar part 2,2'-Azobis(2,4-dimethylvaleronitrile), at 70 DEG C, carry out sulfydryl-alkynes polyaddition reaction 0.5-24 is little
When；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 2 molar part n, in n- dimethylformamide, sequentially adds
0.2 molar part water, 0.05 molar part sulphuric acid, reacts 10 hours at 100 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 5:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor ethanthiol containing 1 molar part, 0.98 molar part propinyl thiopropionate,
0.05 molar part benzoyl peroxide, at 70 DEG C, carries out sulfydryl-alkynes polyaddition reaction 24 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 5 molar part benzene, sequentially adds the second of 0.4 molar part
Alcohol, 0.06 molar part p-methyl benzenesulfonic acid, reacts 18 hours at 90 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 6:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor pungent two mercaptan containing 1 molar part, 0.98 molar part propinyl thiacetate,
0.03 molar part azo-bis-iso-dimethyl, at 70 DEG C, carries out sulfydryl-alkynes polyaddition reaction 10 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 3 molar part isopropanols, sequentially adds 0.1 molar part
Water, 0.05 molar part hydrochloric acid, reacts 12 hours at 80 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 7:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) diethyl thioether group two mercaptan containing 1 molar part, the thio second of 1 molar part propinyl are sequentially added in the reactor
Acid esters, 0.04 molar part azodiisobutyronitrile, at 70 DEG C, carry out sulfydryl-alkynes polyaddition reaction 20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 5 molar part toluene, sequentially adds the second of 0.1 molar part
Alcohol, 0.05 molar part p-methyl benzenesulfonic acid, reacts 10 hours at 100 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 8:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.9 molar part butynyl thiacetate,
0.1 molar part azodiisobutyronitrile, at 70 DEG C, carries out sulfydryl-alkynes polyaddition reaction 12 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 2 molar part chloroforms, sequentially adds the second of 0.1 molar part
Alcohol, 0.1 molar part p-methyl benzenesulfonic acid, reacts 24 hours at 70 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 9:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dimercaptopropane containing 1 molar part, 0.95 molar part propinyl thiacetate,
0.03 molar part dimethoxybenzoin, under ultraviolet light irradiation, carries out sulfydryl-alkynes polyaddition reaction 24 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 5 molar part toluene, sequentially adds 0.1 molar part
Water, 0.05 molar part hydrochloric acid, reacts 5 hours at 100 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 10:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.95 molar part propinyl thiacetate,
0.02 molar part 1- hydroxycyclohexyl phenyl ketone, under ultraviolet light irradiation, carries out sulfydryl-alkynes polyaddition reaction 20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 5 molar part ethanol, and 0.03 molar part hydrochloric acid, in 70 DEG C
Lower reaction 12 hours；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 11:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.95 molar part propinyl thiacetate,
0.02 molar part 1- hydroxycyclohexyl phenyl ketone, under ultraviolet light irradiation, carries out sulfydryl-alkynes polyaddition reaction 20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 5 molar part ethanol, and 0.03 molar part hydrochloric acid, in 70 DEG C
Lower reaction 12 hours；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 12:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.95 molar part propinyl thiacetate,
0.04 molar part dimethoxybenzoin, under ultraviolet light irradiation, carries out sulfydryl-alkynes polyaddition reaction 24 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 3 molar part solvents, sequentially adds 0.01-1 molar part
Water or alcohol, 0.01-0.1 molar part acid catalyst, at 50-120 DEG C react 1-24 hour；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 13:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) sequentially add in the reactor dithioglycol containing 1 molar part, 0.9-1 molar part butynyl thiacetate,
0.02 molar part 2,2 '-azo is double (4- methoxy -2,4- methyl pentane nitrile), at 60 DEG C, carries out sulfydryl-alkynes polyaddition reaction
20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 3 molar part isopropanols, sequentially adds 0.3 molar part
Water, 0.01-0.1 molar part hydrochloric acid, reacts 12 hours at 80 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 14:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) Isosorbide-5-Nitrae-dithiothreitol dithio containing 1 molar part, 0.9-1 molar part propinyl sulfur are sequentially added in the reactor
For acetass, 0.02 molar part 2,2 '-azo is double (4- methoxy -2,4- methyl pentane nitrile), at 60 DEG C, carries out sulfydryl-alkynes and adds
Become polyreaction 20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 3 molar part isopropanols, sequentially adds 0.3 molar part
Water, 0.01-0.1 molar part hydrochloric acid, reacts 12 hours at 80 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment 15:
In the present embodiment, the structural formula of polysulfide ether polymercaptan is:
The preparation method of above-mentioned polysulfide ether polymercaptan comprises the steps:
(1) dimercaptopropanol, BAL containing 1 molar part, 0.9-1 molar part propinyl thiacetic acid. are sequentially added in the reactor
Ester, 0.02 molar part 2,2 '-azo is double (4- methoxy -2,4- methyl pentane nitrile), at 60 DEG C, carries out sulfydryl-alkynes addition polymerization
Reaction 20 hours；
(2) under nitrogen protection, by step 1) products therefrom is dissolved in 3 molar part isopropanols, sequentially adds 0.3 molar part
Water, 0.01-0.1 molar part hydrochloric acid, reacts 12 hours at 80 DEG C；
(3) by step (2) products therefrom evaporation of solvent, through precipitation, it is dried to obtain polysulfide ether polymercaptan.
Same as Example 1, contain substantial amounts of sulfydryl in the above-mentioned prepared molecular side chain of polysulfide ether polymercaptan, thus
Sulfur copper key can be formed with copper, the thiol bond in strand passes through to self condense the thick film coating that can form densification, therefore simultaneously
Can apply as copper inhibitor.
Embodiment described above technical scheme has been described in detail it should be understood that the above only
For the specific embodiment of the present invention, it is not limited to the present invention, all any modifications made in the spirit of the present invention,
Supplement or similar fashion replacement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of polysulfide ether polymercaptan is it is characterised in that have following structural formula:
Wherein, n is the integer between 5～100, including 5 and 100；
R1 is-(ch2)n1-、-ch2ch2(xch2ch2)n2-、-ch2-c6h4-ch2-、-ch2ch(ch2Oh)-or-ch2(choh)n3ch2-, wherein n1 is the integer between 2～10, including 2 and 10；N2, n3 are the integer between 1～5, including 1 and 5；X be o or
S atom；R2 is-(ch2)n4-, wherein n4 is the integer between 1～9, including 1 and 9.
2. the synthetic method of polysulfide ether polymercaptan according to claim 1 is it is characterised in that comprise the following steps:
(1) sequentially add two mercaptan, alkynyl carbothioic acid ester, initiator in the reactor, under initiating accident sequence effect, carry out mercapto
Base-alkynes polyaddition reaction；
(2) under inert gas shielding, step (1) products therefrom is dissolved in solvent, with the alkynyl carbothioic acid ester in step 1
Addition is to calculate equivalent, sequentially adds water, alcohol or its mixture of 0.01～1 equivalent, the acid catalysiss of 0.01～0.1 equivalent
Agent, be hydrolyzed at 50-120 DEG C reaction；
(3) solvent in step (2) products therefrom is removed, then precipitate, be dried, obtain polysulfide ether polymercaptan.
3. the synthetic method of polysulfide ether polymercaptan according to claim 2 is it is characterised in that described two mercaptan chemical combination
Thing molecular structural formula is hs-r1-sh, and r1 is selected from-(ch2)n1-、-ch2ch2(xch2ch2)n2-、-ch2-c6h4-ch2-、-ch2ch
(ch2Oh)-, or-ch2(choh)n3ch2-, wherein n1 is the integer between 2～10, including 2 and 10；N2, n3 are between 1～5
Integer, including 1 and 5；X is o or s atom.
4. the synthetic method of polysulfide ether polymercaptan according to claim 2 is it is characterised in that the thio carboxylic of described alkynyl
The molecular structural formula of acid esters is ch ≡ c-r2-s-co-r3, and wherein r2 is-(ch2)n4-, n4 is the integer between 1～9, including 1
It is selected from alkyl or phenyl with 9, r3.
5. the synthetic method of polysulfide ether polymercaptan according to claim 2 is it is characterised in that in described step (1),
Two mercaptan, alkynyl carbothioic acid ester, the mol ratio of initiator are 1:(0.9～1): (0.01～0.1).
6. the synthetic method of the polysulfide ether polymercaptan according to claim 2,3 or 4 is it is characterised in that described step
(1), in, initiator is temperature-sensitive radical initiator or photosensitive free radical initiator.
7. the synthetic method of polysulfide ether polymercaptan according to claim 6 is it is characterised in that described temperature-sensitive free radical
Initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2 '-azo
Double (4- methoxy -2,4- methyl pentane nitriles), benzoyl peroxide, potassium peroxydisulfate or Ammonium persulfate.；Described photosensitive free radical draws
Sending out agent is dimethoxybenzoin, 1- hydroxycyclohexyl phenyl ketone or methyl benzoylformate.
8. the synthetic method of the polysulfide ether polymercaptan according to claim 2,3 or 4 is it is characterised in that described acid is urged
Agent is hydrochloric acid, sulphuric acid or p-methyl benzenesulfonic acid.
9. the synthetic method of the polysulfide ether polymercaptan according to claim 2,3 or 4 is it is characterised in that described alcohol is
Methanol, ethanol, propanol or isopropanol.
10. the polysulfide ether polymercaptan described in claim 1 is as the application of copper inhibitor.
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| JP2009074024A (en) * | 2007-08-30 | 2009-04-09 | Nikon-Essilor Co Ltd | Composition for optical material, optical material, base material for lens for glasses, and lens for glasses |
| US8552143B2 (en) * | 2010-03-04 | 2013-10-08 | The University Of Akron | Method for the preparation of poly (disulfide) polymers and gels |
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| CN100545195C (en) * | 2001-11-14 | 2009-09-30 | 埃西勒国际通用光学公司 | High index and high impact poly thiourethane/urea material, its manufacture method and the purposes in optical field |
| CN100519612C (en) * | 2002-12-20 | 2009-07-29 | Ppg工业俄亥俄公司 | High impact poly (urethane urea) polysulfides |
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Denomination of invention: A polysulfide based thiol, its synthesis method and application Effective date of registration: 20231024 Granted publication date: 20170125 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Ningbo Yuyao sub branch Pledgor: Ningbo Haiqiang Equipment Technology Co.,Ltd. Registration number: Y2023980062389 |