CN101100461A - Thiadiazoles derivative for halopolymer vulcanization crosslinking and synthetic method for the same - Google Patents
Thiadiazoles derivative for halopolymer vulcanization crosslinking and synthetic method for the same Download PDFInfo
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- CN101100461A CN101100461A CNA200710016228XA CN200710016228A CN101100461A CN 101100461 A CN101100461 A CN 101100461A CN A200710016228X A CNA200710016228X A CN A200710016228XA CN 200710016228 A CN200710016228 A CN 200710016228A CN 101100461 A CN101100461 A CN 101100461A
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- 238000004132 cross linking Methods 0.000 title claims abstract description 23
- 150000004867 thiadiazoles Chemical class 0.000 title claims description 69
- 238000004073 vulcanization Methods 0.000 title claims description 44
- 238000010189 synthetic method Methods 0.000 title claims description 24
- 238000000034 method Methods 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 150
- 239000000243 solution Substances 0.000 claims description 98
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 44
- 239000012065 filter cake Substances 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 38
- 238000010992 reflux Methods 0.000 claims description 35
- 239000005457 ice water Substances 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- 150000001263 acyl chlorides Chemical class 0.000 claims description 25
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 25
- -1 alkali metal salt Chemical class 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 12
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 claims description 9
- 229960004756 ethanol Drugs 0.000 claims description 9
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 9
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 7
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 claims description 7
- YOSVFFVBSPQTTP-UHFFFAOYSA-N hexadecane-1-sulfonyl chloride Chemical compound CCCCCCCCCCCCCCCCS(Cl)(=O)=O YOSVFFVBSPQTTP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 235000010755 mineral Nutrition 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims description 7
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical class S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 claims description 2
- OWNSZSBRIOHAAJ-UHFFFAOYSA-N 1-chlorosulfonyloxybutane Chemical class CCCCOS(Cl)(=O)=O OWNSZSBRIOHAAJ-UHFFFAOYSA-N 0.000 claims description 2
- BALPWYNKTYFBPB-UHFFFAOYSA-N 2-(3-methylphenyl)-2-oxoacetyl chloride Chemical compound CC=1C=C(C(=O)C(=O)Cl)C=CC1 BALPWYNKTYFBPB-UHFFFAOYSA-N 0.000 claims description 2
- KMVZDSQHLDGKGV-UHFFFAOYSA-N 2-chlorobenzenesulfonyl chloride Chemical group ClC1=CC=CC=C1S(Cl)(=O)=O KMVZDSQHLDGKGV-UHFFFAOYSA-N 0.000 claims description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 2
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 claims description 2
- YOQOZEWAUBOAPW-UHFFFAOYSA-N CCCCl=S(=O)=O Chemical compound CCCCl=S(=O)=O YOQOZEWAUBOAPW-UHFFFAOYSA-N 0.000 claims description 2
- IXWUPTJSAZCADA-UHFFFAOYSA-N S(=O)(=O)(C1=CC=CC=C1)ClC Chemical compound S(=O)(=O)(C1=CC=CC=C1)ClC IXWUPTJSAZCADA-UHFFFAOYSA-N 0.000 claims description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012346 acetyl chloride Substances 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 2
- RRIJYVGANIXLNL-UHFFFAOYSA-N anisole;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.COC1=CC=CC=C1 RRIJYVGANIXLNL-UHFFFAOYSA-N 0.000 claims description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- CEMUQLXAOCBFNV-UHFFFAOYSA-N ethylbenzene;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.CCC1=CC=CC=C1 CEMUQLXAOCBFNV-UHFFFAOYSA-N 0.000 claims description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 2
- LUXWSKCGUPBKBG-UHFFFAOYSA-N formyl chloride propylbenzene Chemical compound C(=O)Cl.C(CC)C1=CC=CC=C1 LUXWSKCGUPBKBG-UHFFFAOYSA-N 0.000 claims description 2
- OKHSVCZDYHBEKX-UHFFFAOYSA-N formyl chloride toluene Chemical compound C(=O)Cl.CC1=CC=CC=C1 OKHSVCZDYHBEKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- VDRWNKIQBYUKGD-UHFFFAOYSA-N octadecane-1-sulfonyl chloride Chemical compound CCCCCCCCCCCCCCCCCCS(Cl)(=O)=O VDRWNKIQBYUKGD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 claims description 2
- KFQWKJJWUWTIRL-UHFFFAOYSA-N propylbenzene;sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O.CCCC1=CC=CC=C1 KFQWKJJWUWTIRL-UHFFFAOYSA-N 0.000 claims description 2
- SNHOURMNEXCAJV-UHFFFAOYSA-N sulfuryl dichloride;toluene Chemical compound ClS(Cl)(=O)=O.CC1=CC=CC=C1 SNHOURMNEXCAJV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 28
- 229910052736 halogen Inorganic materials 0.000 abstract description 25
- 150000002367 halogens Chemical class 0.000 abstract description 25
- 239000002904 solvent Substances 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 150000001266 acyl halides Chemical class 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000003795 chemical substances by application Substances 0.000 description 26
- 229920001971 elastomer Polymers 0.000 description 22
- 229910000474 mercury oxide Inorganic materials 0.000 description 22
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical class [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 22
- 239000004709 Chlorinated polyethylene Substances 0.000 description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- 238000009835 boiling Methods 0.000 description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 7
- 229910052728 basic metal Inorganic materials 0.000 description 7
- 150000003818 basic metals Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229910017053 inorganic salt Inorganic materials 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 229920001084 poly(chloroprene) Polymers 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 6
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000002826 coolant Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- MFZUXRKTKZKWSS-UHFFFAOYSA-N benzene;sulfuryl dichloride Chemical class ClS(Cl)(=O)=O.C1=CC=CC=C1 MFZUXRKTKZKWSS-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WZSQETZUXVEWOP-UHFFFAOYSA-N N1N=NC=C2C1=CC=N2.S2SSC=C2 Chemical class N1N=NC=C2C1=CC=N2.S2SSC=C2 WZSQETZUXVEWOP-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000907903 Shorea Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005559 polyacrylic rubber Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- QZQIWEZRSIPYCU-UHFFFAOYSA-N trithiole Chemical compound S1SC=CS1 QZQIWEZRSIPYCU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
A thiobiazole derivative containing halogen polymer for vulcanized cross-linking and its synthesis are disclosed. The process is carried out by taking DMTD, metal strong alkaline and acyl halide as raw materials, taking ethanol solution as composite solvent, taking concentrated inorganic acid as acidifying reagent, and synthesizing selectively to obtain final product. It costs low and is simple, convenient, and controllable. It has less consumption, short flow path and no use for oxidant.
Description
Technical field
The present invention relates to thiadiazoles derivative and synthetic method thereof, relate in particular to and to be used for particularly crosslinked thiadiazoles derivative and the synthetic method thereof of the Halogen vulcanization of rubber of halogen containing polymers as structural formula (1) or (2).
Wherein: the R group in the said structure formula is: aromatic base or C
1-17Alkyl.
Background technology
Halogen containing polymers comprises Halogen rubber, Halogen plastics, rubble thermoplastics blend etc., wherein Halogen rubber has as the main kind of the important component part of specialty elastomer: and chlorinated polyethylene rubber (CPE, CM), chloroprene rubber (CR), epichlorohydrin rubber (CO), table epichlorohydrin rubber (ECO), chlorosulfonated polyethylene rubber (CSM), polyvinyl chloride (PVC), neoprene, CPE/PVC, IIR (brominated butyl rubber), polyacrylic rubber etc.Thereby make rubber show outstanding weathering resistance, ozone resistance, resistant to chemical media owing to contain halogen in the Halogen rubber, fire-retardant, heat-proof aging, many characteristics such as oil resistant and electrical property are good, the utilization of Halogen rubber is very extensive in rigorous environment, is subject to people's attention day by day.
Up to the present domestic and international sulfuration about halogen containing polymers has had the multidigit expert to do commentary, in recent years for the toxicity problem that solves vulcanizing agent with give high molecular polymer new function, several high-molecular weight vulcanizing agents have been developed both at home and abroad successively, but for the smaller halogen containing polymers of reactive behavior especially Halogen vulcanization of rubber effect is not very good, domestic present sulfuration for Halogen rubber mainly contains two kinds of vulcanization systems: peroxide cure and thiourea cure system, when adopting peroxide cure, be easy to generate bubble and very big smell, can not open vulcanization, mechanical properties of vulcanizate is bad, adopt thiourea cure system vulcanization rate too slow, the resistance toheat of cross-linked rubber is bad.Rubber processing enterprise wishes to find the good vulcanizing agent of the good scorching quality of a kind of curability especially.Abroad also begun very early the Halogen vulcanization of rubber is studied, the conspicuous Chris company of the U.S. has developed the dimercaptothiodiazole compound, people such as village develops the tri-thiol pyrrolotriazine derivatives and is used for the crosslinked of Halogen rubber in the Japan, but these two kinds of vulcanizing agents all have shortcoming: though the fast scorching quality of the vulcanization rate of dimercaptothiodiazole compound is bad, the vulcanization rate of tri-thiol triaizine compounds is slow excessively.
There is following deficiency about the domestic and international prior art of the synthesis technique of vulcanizing agent:
1,, several synthetic methods that can be used as the Halogen vulcanizer have been introduced in 696 in U.S. Pat 6,635.For example: formula (3) compound
Wherein: R
2, R
2Represent C
2-5Alkyl.
This patent is introduced (3) compound and be can be used as for example efficient vulcanization crosslinking agent of Halogen rubber such as chlorinated polyethylene rubber, neoprene, epichlorohydrin rubber of halogen containing polymers.But produce such vulcanizing agent and will use the feasible danger increase in process of production of oxygenant (hydrogen peroxide), and owing to use oxygenant to make 2,5-dimercapto-1,3, the sulfydryl of 4-thiadiazoles (DMTD) is easy to be oxidized into dimer or polymer compounds, the very big product separation that is unfavorable for of the viscosity of product is purified when aftertreatment, the yield of resultant is very low even can not get target product, conditional request strictness during reaction, technology is variant slightly will to generate a large amount of resinous, make that the post-processing difficulty of product is very big, be unfavorable for realizing industrialization.
2, in U.S. Pat 5, the compound of having introduced a kind of structural formula (4) in 849,925 also can be used for the vulcanization crosslinking of Halogen rubber, but this compounds also will use oxygenant when producing, control to reaction conditions also is that requirement is relatively stricter, is unfavorable for realizing industrialization.
3, in Chinese patent 200610004725.3, introduced the novel cpd of a kind of structural formula (5): two-DMTD, it is the derivative of a kind of DMTD, can be used for lubricating oil, be used as extreme-pressure anti-friction additive, can be used for the report that Halogen rubber is used as vulcanizing agent but yet there are no two-DMTD.In patent, introduced and utilized the sulfhydryl protected reagent of basic metal, made oxygenant with hydrogen peroxide under suitable condition, made the DMTD autohemagglutination be combined into dimer, obtained two-DMTD, also will use oxygenant equally in the method as DMTD.
4, open clear 61-238 the Japanese Patent spy, reported the compound of structural formula (6) in 838 (1986): poly-2,5-dimercapto-1,3, the 4-thiadiazoles, it can be used to vulcanize Halogen rubber, for example chlorinated polyethylene rubber (CPE, CM), chloroprene rubber (CR), it is fine to be used as the vulcanizing agent effect in the table epichlorohydrin rubber (EGO), gathers 2,5-dimercapto-1 but introduce to produce in this patent, 3, to select oxygenant (hydrogen peroxide) during the 4-thiadiazoles for use, if in hydrogen peroxide dropping process excessive velocities, the fierce and very exothermic of reaction, the bad control of temperature of reaction, be easy to generate a large amount of yellow flosss, influence the yield of product, so this method also be unfavorable for realizing industrialization.
5, open clear 54-58 the Japanese Patent spy, 750 (1979) had once mentioned 2, and it is crosslinked that 5-dimercapto-1,3,4-thiadiazoles can be used for chlorinatedpolyethylene (CPE) vulcanization of rubber, but the over-all properties of rubber item is relatively poor.
6, Eurpat Appl.Ep78,155 (1983) have reported many sulfhydryl compound-thiadiazoles, can be used for the vulcanization crosslinking of chlorinated polyethylene rubber (CPE), but do not introduce the production method of sulfydryl-thiadiazole compound.
7, at Ger.offer DE3, reported with 2 in 336,753 (1985), 5-dimercapto-1,3,4 thiadiazoles acid amides can vulcanize chlorinatedpolyethylene (CPE).But but this kind vulcanizing agent is easy to generate toxic gas and limits its application in sulfidation.
8, domestic expert once reported the applied research of the crosslinked CPE of thiadiazoles derivative, the little refined people such as grade of Lee has introduced " applied research of the crosslinked CPE of thiadiazoles derivative " on the academic free paper sessions of 2005 national polymers, the little refined grade of Lee ECHO-A class vulcanization system that foreign country is commonly used in this paper, peroxide vulcanizing system has carried out the sulfuration over-all properties relatively with the thiadiazoles derivative vulcanization system, the result shows that Thiadiazole Curing System has tangible advantage than other two vulcanization systems, can replace peroxide vulcanizing system fully, but this paper is not introduced the structure of thiadiazoles derivative and concrete production method.
9, on the academic free paper session of national polymer in 2005, people such as Li Wenjie have delivered two kinds of vulcanization systems, peroxide systems and the thiadiazoles system of having introduced in " dynamic vulcanization prepares the CPE/PCV thermoplastic elastomer " paper the CPE/PVC dynamic vulcanization.In the paper result show thiadiazoles curability and peroxide cure performance near but do not introduce structure and the preparation method that thiophene two is done oxazole derivatives equally.
10, the Xie Zhonglin of Beijing Research ﹠ Design Institute of Rubber Industry professor mentions in to " China's chlorinatedpolyethylene market requirement and suggestion for investment " and is used for the novel vulcanization system-Thiadiazole Curing System of chlorinated polyethylene rubber and has the two advantage of superoxide and thiourea cure system, therefore the welcome of being processed the boundary is not deeply produced but this kind vulcanizing agent is at present domestic.
In a word, up to the present domestic by retrieval report and the research of not seeing the thiadiazoles derivative suitability for industrialized production that is useful on the polymer containing halogen vulcanization crosslinking.
Summary of the invention
Deficiency at vulcanizing agent production existence in the existing technology, the purpose of this invention is to provide a kind of with industry 2,5-dimercapto-1,3,4-thiadiazoles (DMTD), metal overbase (sodium hydroxide), acyl chlorides is a raw material, is double solvents with the ethanolic soln, is acidizing reagent with the concentrated hydrochloric acid, under the situation that does not have oxygenant to exist, high yield, highly selective synthesize the method as the thiadiazoles derivative of structural formula (1) or (2).
Wherein: the R group in the said structure formula is: aromatic base or C
1-17Alkyl.
One of preferred following group of above-mentioned aromatic base:
One of preferred following group of abovementioned alkyl:
CH
3-，C
2H
5-，C
3H
7-，C
4H
9-，C
5H
11-，C
7H
15-，C
8H
17-，
C
16H
33-，C
15H
31-，C
17H
35-。
It is simple that the present invention has synthetic method, and flow process is short, the yield height, advantages such as the three wastes are few have been avoided the use oxygenant than the present invention of existing technical matters flow process, make the technology controlling and process ratio be easier to, post-processing operation is simplified, and energy consumption reduces, and the cost of product obviously reduces.The inventive method synthetic thiadiazoles derivative is used for the sulfuration test of Halogen rubber, the result shows that thiadiazoles derivative has the advantage of peroxide cure and thiourea cure system concurrently, the vulcanization rate of Thiadiazole Curing System can not produce the incipient scorch phenomenon again soon, mechanical properties of vulcanizate is good, and Thiadiazole Curing System can be at 150 ℃ of following open vulcanizations, this be described two kinds of vulcanization systems can not than, thiadiazoles vulcanizing agent sulfidation does not have irritating smell, compliance with environmental protection requirements has solved the above vulcanizing agent and has had the big problem of toxicity in use.
The synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking of the present invention, realized by following steps:
(1) in reactor, adds the water of metal base and proportional quantity, stir, be made into mass percent concentration and be 25%～35% the metal base aqueous solution, lower the temperature to alkali lye simultaneously and with ice-water bath, make temperature to 5 ℃～10 ℃;
(2) with mass ratio be 1: 3.5～4.5 amount with 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) joins in the ethanolic soln, stirring and dissolving becomes yellow clear solution, simultaneously to the solution cooling, makes temperature to 5 ℃～10 ℃;
(3) with DMTD: alkali-metal mol ratio is that 1: 1 amount is added drop-wise to the described DMTD ethanolic soln of step (2) in the described metal base aqueous solution of step (1), ceaselessly stirring therebetween makes the temperature of mixed solution be no more than 10 ℃, solution only becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein, get light yellow transparent mixture solution;
(4) the described mixture solution of step (3) is remained on 20 ℃～30 ℃ by water-bath with its temperature, then to wherein dripping acyl chlorides or SULPHURYL CHLORIDE, make acyl chlorides or SULPHURYL CHLORIDE and 2,5-dimercapto-1,3,4-thiadiazoles (DMTD) an alkali metal salt carries out nucleophilic substitution reaction in ethanolic soln, form 2,5-dimercapto-1,3, the acyl group list substitution compound of 4-thiadiazoles (DMTD), wherein acyl chlorides or SULPHURYL CHLORIDE dripping quantity are acyl chlorides or SULPHURYL CHLORIDE with molar ratio computing: an alkali metal salt of DMTD=1～2 in the mixture solution: 1; After acyl chlorides or SULPHURYL CHLORIDE drip, mixture solution is warming up to reflux temperature, and under reflux temperature, reacted 2-5 hour, get white or yellow grume mixture with water-bath;
(5) give step (4) described mixture cooling with ice-water bath, make its temperature to 0 ℃～5 ℃, then to wherein dripping dense mineral acid, stir simultaneously, when mixture pH=2～3, stop to drip acid (not needing to add acid) if the pH value of mixture has reached this numerical value, under the ice-water bath cooling conditions mixture is left standstill 4hr～5hr and make its layering, the upper strata is faint yellow settled solution, and lower floor is white or yellow powder product, filters by the suction filtration groove, get filter cake, filtrate is recycled;
(6) filter cake uses deionized water wash earlier till washings pH=7; And then become white or yellow powder precipitation with cold washing with alcohol to filter cake;
(7) filter cake that obtains is placed in baking oven or the vacuum drier, 60 ℃～70 ℃ dryings 12～15 hours, white or yellow thiadiazoles derivative.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: preferred NaOH of described metal base or KOH.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: the concentration of described ethanolic soln preferred 70%.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: described acyl chlorides is aromatic series acyl chlorides or aliphatics acyl chlorides.
Wherein: described aromatic series acyl chlorides is a Benzoyl chloride, Butyltriphenylphosphonium chloride, parachlorobenzoyl chloride, o-chlorobenzoyl chloride, the o-methyl-benzene formyl chloride, m-methyl benzoyl formyl chloride, anisoyl chloride, to the ethylamino benzonitrile acyl chlorides, to the propylbenzene formyl chloride, to one of tert.-butylbenzene formyl chloride; Described aliphatics acyl chlorides is an Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, capryl(yl)chloride, valeryl chloride, n-Hexadecane acyl chlorides, one of stearyl chloride.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: described SULPHURYL CHLORIDE is aromatic sulfonyl or aliphatics SULPHURYL CHLORIDE.
Wherein: described aromatic sulfonyl is a benzene sulfonyl chloride, Tosyl chloride, parachloroben-zenesulfonyl chloride, adjacent chlorobenzene sulfonyl chloride, the o-methyl-benzene SULPHURYL CHLORIDE, a Methyl benzenesulfonyl chlorine is to the anisole SULPHURYL CHLORIDE, to the ethylbenzene SULPHURYL CHLORIDE, to the propylbenzene SULPHURYL CHLORIDE, to one of tert.-butylbenzene SULPHURYL CHLORIDE; Described aliphatics SULPHURYL CHLORIDE is an ethyl chloride, sulfonyl propyl chlorine, butyl sulfochlorides, octyl group SULPHURYL CHLORIDE, amyl group SULPHURYL CHLORIDE, hexadecyl SULPHURYL CHLORIDE, one of octadecyl SULPHURYL CHLORIDE.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: preferred 70 ℃～80 ℃ of described reflux temperature.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: the preferred concentrated hydrochloric acid of described dense mineral acid or the vitriol oil; Most preferable concentrations is 36.5% concentrated hydrochloric acid.
In the synthetic method of above-mentioned thiadiazoles derivative for halopolymer vulcanization crosslinking: the dehydrated alcohol that described cold ethanol is preferably 0 ℃～4 ℃.
Aforesaid method synthetic thiadiazoles derivative is characterized in that: described thiadiazoles derivative is preferably as the compound of one of structural formula (9), (11), (12):
In the building-up reactions of carrying out with the inventive method optimal way, the reaction equation that relates generally to is:
(1) sulfhydryl protected reaction:
(2) nucleophilic substitution reaction:
(3) acidifying reduction reaction:
The sulphur atom of basic metal being protected with dense mineral acid is reduced to sulfydryl again, to obtain target product.
Below in conjunction with reaction conditions, proportioning raw materials, describe above-mentioned technical process in detail by four key steps:
The first step: sulfhydryl protected reaction
Utilize the sulfydryl of basic metal protection DMTD; under the situation that does not have oxygenant to exist with industry 2; 5-dimercapto-1; 3; 4-thiadiazoles (DMTD), NaOH is a raw material, is double solvents with the ethanolic soln; the water stirring and dissolving that adds sodium hydroxide and proportional quantity in reactor earlier becomes water white solution, cools to about 5 ℃ to alkali lye with ice-water bath.Then slowly to the ethanolic soln that wherein adds DMTD and constantly stir, the temperature that will guarantee mixed solution in the dropping process is no more than 10 ℃, after the ethanolic soln of DMTD drips fully, mixture becomes a kind of lurid clear solution, requires DMTD: NaOH=1: 1 (mol ratio).
The amount of the double solvents of using by quality ratio, alcohol solvent: DMTD=3.5～4.5: 1, the concentration of ethanolic soln preferred 70%.
Second step: nucleophilic substitution reaction
After the ethanolic soln of DMTD drips fully, by water-bath mixture temperature is remained on 20 ℃～30 ℃, in reactor, drip acyl chlorides with dropping funnel, there is a large amount of white precipitates to generate in the mixture, the precipitation that generates in the polyhybrid thing more along with the acyl chlorides dripping quantity is also many more, drip the stopping property that to note keeping equipment in the process of acyl chlorides because acyl chlorides can hydrolysis in water, in air, volatilize than being easier to, so it is excessive requiring the amount of acyl chlorides in reaction process, to improve the yield of product.Real reaction requires acyl chlorides: DMTD=1～2: 1 (mol ratio), is raised to reflux temperature with the water-bath intensification to mixture slowly again after acyl chlorides drips always, and 70 ℃～80 ℃ of preferred reflux temperatures keep reaction 2～5 hours under this temperature.
The 3rd step: acidifying reduction reaction:
Since in the sulfhydryl protected reaction of the first step, used highly basic, part is sulfhydryl protected.Require later on the sulphur atom of basic metal protection is reduced to sulfydryl again finishing nucleophilic substitution reaction, to obtain target product.Because sulfydryl heat release when acidifying of protection; in order to prevent that sulfydryl from coming off; in actually operating, can cool to 0 ℃～5 ℃ to mixture with ice-water bath; to wherein slowly dripping concentrated hydrochloric acid; in concentrated hydrochloric acid dropping process, when the pH=2 of mixed solution～3, stop to dripping hydrochloric acid (if the pH of mixture has reached requirement, mineral acid can not add) wherein; at this moment mixture almost becomes the immobilising mixture of a kind of congee shape, places it in then and leaves standstill 4～5 hours in the ice-water bath.
The 4th step: washing is dry
Mixture leaves standstill 4～5 hours in ice-water bath after, demixing, lower floor is white or xanchromatic throw out, and the upper strata is flaxen liquid, filters in the suction filtration groove then, and filtrate can be recycled.Filter cake earlier with deionized water wash till the pH=7 of washings, and then with cold absolute ethanol washing filter cake, the filter cake that obtains is placed on drying in baking oven or the vacuum drier, promptly gets white or the xanchromatic target product: thiadiazoles derivative.
The technical characterstic of the inventive method is:
1) recently make one of them sulfydryl highly selective generation substitution reaction of DMTD by the batching of control basic metal and DMTD, thus the target product in the formula of formation (1) or (2), and this also is the advantage place of this invention.
2) in the process of manufacturing objective product, react the monomeric compound that generates as shown in the formula (7) by basic metal and DMTD:
Wherein: X represents blocking group, preferably sodium Metal 99.5;
X group in the formula in the compound reacts with at least a acylting agent respectively; surprisingly acylting agent highly selective and protected-S-X especially-single substitution reaction taken place in S-Na; formed the compound that contains formula (1) or (2); and do not have protected-SH not participate in reaction; the acyl substitution reaction has taken place in the single sulfydryl that shows as DMTD; and with high purity, high yield has obtained the compound of formula (1) or (2).
3) acylting agent selected for use of the present invention is an acyl chlorides; SULPHURYL CHLORIDE; preferably aromatic series acyl chlorides, aromatic sulfonyl chloride; because contain high reactivity chlorine in the acylting agent of selecting for use; therefore help that S-X carries out nucleophilic reaction among acyl chlorides and the DMTD, this also is the smooth key point of preparation formula of the present invention (1) (2) compound.
4) the sulfhydryl protected reagent of selecting for use among the present invention is saturated or near saturated NaOH, the KOH aqueous solution; when reacting, make every effort to as much as possible sulfhydryl protected with DMTD with DMTD; the Another reason of selecting NaOH or KOH saturated solution for use is to contain a spot of water in the saturated solution; can prevent acyl chlorides, SULPHURYL CHLORIDE generation hydrolysis reaction as much as possible; the consumption of acylting agent will guarantee in reaction process simultaneously; generally be acylting agent :-S-X=1～2: 1 (mol ratio), this is the key of the complete nucleophilic substitution reaction of protection sulfydryl.
5) the present invention does not select any oxygenant for use than being also advantageous in that of conventional DMTD derivative preparation method, only adopts basic metal to replace the sulphur atom on the sulfydryl among the DMTD, uses acylting agent to incite somebody to action with high selectivity ground then
In X base replace, and finally form compound in formula (1) and (2).
6) technical problem that solves of the present invention be the ratio of components of the acylting agent by control DMTD and alkali make among the DMTD-SH is with high selectivity and acyl group generation nucleophilic substitution reaction; in preparation process, at first allow DMTD and NaOH saturated solution react; sulfhydryl protected formation (7) compound with DMTD; under the condition of control reaction temperature, allow then the acylting agent attack protected-the S atom; thereby formed the single substituted radical of DMTD; the compound solubleness in ethanolic soln that forms is very little, thereby target product crystallization in mixed solution is separated out.The result shows as long as DMTD is controlled in strictness in reaction process: alkali: the ratio of components of acyl group reagent, just can realize the single substitution compound with the synthetic DMTD of high selectivity, just target product.
Among the present invention as long as DMTD: NaOH=1: 1 just can especially effectively protect among the DMTD-SH, and the compound that is used for introducing blocking group is a mineral alkali, preferred NaOH, as long as protect about 1: 1 of mol ratio, just can highly selective protection (7) compound.
On technical scale can by simple potential measurement method measure feeding quantity and this chemistry amount ratio near value.
The beneficial effect of the inventive method:
The industrial raw material DMTD of the present invention to be easy to get, industrial soda (NaOH, KOH), acyl chlorides, technical hydrochloric acid is a raw material, avoids using oxygenant, has synthesized thiadiazoles derivative.It is simple to have synthetic method, and flow process is short, the yield height, and advantage such as the three wastes are few, than existing technical matters flow process, emergence has been avoided the use oxygenant now, makes the technology controlling and process ratio be easier to, and post-processing operation is simplified, and energy consumption reduces, and the cost of product reduces.Generally speaking, advantage of the present invention is mainly reflected in the following aspects:
(1) avoid using the oxygenant of high corrosion danger among the present invention, the reaction process operational safety, easy control of reaction conditions, the requirement of processing condition is not strict, and is beneficial to the realization suitability for industrialized production.
(2) sulfydryl among the protection DMTD of employing metal overbase elder generation among the present invention prevents oxidized productive rate and the purity of influencing of sulfydryl in reaction process.The yield of product reaches 93%, and purity reaches more than 99%
(3) industry 2 is adopted in invention, 5-dimercapto-1,3, and 4-thiadiazoles (DMTD), NaOH, acyl chlorides are raw material, the source abundance of raw material is cheap.Reduced the raw materials for production cost.
(4) gentle of reaction conditions needs back flow reaction in water-bath, and processing condition control easily.Reaction times is short, and it is just passable only need under refluxad to react several hrs.
(5) ratio of components just can be with high yield accurately as long as control in the reaction process material in the invention well, the synthetic target product of highly selective.The yield of product can reach 90%.
(6) postprocessing working procedures of product is simple to operate, just can finish by the simple filtering washing operation, and solvent can be recycled
Conclusion:
With the inventive method synthetic thiadiazoles derivative, the yield of product can reach more than 90%, purity can reach more than 99%, at Halogen rubber (CPE, CR, ECO) done the simultaneous test of comprehensive curability in, the curability of the synthetic thiadiazoles derivative of curability demonstration is suitable with the similar vulcanizing agent effect of U.S.'s import.
Embodiment
Embodiment 1: thiadiazoles derivative (8) synthesis technique
(1) agitator is being housed, thermometer, the condensing reflux pipe, adding 20gNaOH (0.5mol) and 70ml water in the four-hole boiling flask of the 1L of constant pressure funnel are made into the NaOH aqueous solution, stirring and dissolving back fully drops to 7 ℃～10 ℃ by ice-water bath to solution temperature, becomes a kind of clear solution.76 gram DMTD (0.5mol) are joined in the 300ml ethanol (70%) stirring and dissolving to be become yellow clear solution and cools to 10 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with 76 gram DMTD to flask by dropping funnel then, liberated heat is spread timely, solution becomes yellow clear solution in four-hole boiling flask, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off).
(2) mixture that obtains in (1) is placed in the water-bath, by water-bath its temperature is remained on 20 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, restrain Benzoyl chlorides (0.75mol) by constant pressure funnel to wherein dripping 106, the color of mixture is become yellow muddy by clear when Benzoyl chloride begins to drip inwards, there are a large amount of yellow mercury oxides to generate, exothermic heat of reaction in the process that Benzoyl chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with Benzoyl chloride generate a large amount of yellow mercury oxides, when the amount of Benzoyl chloride is added to a half mixture by the yellow mercury oxide last white precipitate (powder) that generates that shoals, the throw out of the white powder of generation becomes a kind of white grume thing in flask.
(3) slowly the temperature of water-bath is raised to 80 ℃, allows mixture begin to reflux, when mixture temperature reaches 70 ℃, begin to occur a large amount of backflows in the flask, keep reflux state 2-3hr, mixture is a white paste in the bottle.
(4) mixture temperature is dropped to 5 ℃ by ice-water bath, when wherein to drip concentration be the stirring that do not stop of 36.5% concentrated hydrochloric acid until the pH=2-3 of mixture, stop dripping hydrochloric acid by dropping funnel.Mixture is placed on ice-water bath leaves standstill 4hr and make its layering, the upper strata is yellow settled solution, and lower floor is the white powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with cold absolute ethanol washing filter cake, last filter cake becomes the white powder precipitation, be placed in the vacuum drying oven 60 ℃ of dryings 12 hours white powder product 118 grams, yield 93%.
Embodiment 2: thiadiazoles linking agent (9) synthesis technique
(1) agitator is being housed, thermometer, the condensing reflux pipe, adding 28g KOH (0.5mol) and 75ml water in the four-hole boiling flask of the 1L of constant pressure funnel are made into the KOH aqueous solution, stirring and dissolving back fully drops to about 10 ℃ to solution temperature by ice-water bath, becomes a kind of clear solution.76 gram DMTD (0.5mol) are joined in the 300ml ethanol stirring and dissolving to be become yellow clear solution and cools to about 10 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with 76 gram DMTD to flask by dropping funnel then, liberated heat is spread timely, solution becomes yellow clear solution in four-hole boiling flask, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off).
(2) mixture that obtains in (1) is placed in the water-bath, by water-bath its temperature is remained on 30 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, restrain benzene sulfonyl chlorides (0.75mol) by constant pressure funnel to wherein dripping 132, the color of mixture is become yellow muddy by clear when benzene sulfonyl chloride begins to drip inwards, there are a large amount of yellow mercury oxides to generate, exothermic heat of reaction in the process that benzene sulfonyl chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with benzene sulfonyl chloride generate a large amount of yellow mercury oxides, when the amount of benzene sulfonyl chloride is added to a half mixture by the yellow mercury oxide last light-yellow precipitate (powder) that generates that shoals, the throw out of the yellow powder powder of generation becomes a kind of yellow grume thing in flask.
(3) slowly the temperature of water-bath is raised to 80 ℃, allows mixture begin to reflux, when mixture temperature reaches 70 ℃, begin to occur a large amount of backflows in the flask, keep reflux state 4-5hr, mixture is a white paste in the bottle.
(4) mixture temperature is dropped to 5 ℃ by ice-water bath, when wherein dripping stirring that the vitriol oil do not stop, stop to drip sulfuric acid until the pH=2-3 of mixture by dropping funnel.Mixture is placed on ice-water bath leaves standstill the 5hr layering, the upper strata is yellow settled solution, and lower floor is the yellow powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with 2 ℃ of absolute ethanol washing filter cakes, last filter cake becomes the yellow powder precipitation, be placed in the vacuum drying oven 65 ℃ of dryings 12 hours yellow powder shape product 120 grams, yield 83%.
Embodiment 3; Thiadiazoles derivative (10) synthesis technique
(1) agitator is being housed, thermometer, the condensing reflux pipe, adding 20gNaOH (0.5mol) and 70ml water in the four-hole boiling flask of the 1L of constant pressure funnel are made into the NaOH aqueous solution, stirring and dissolving back fully drops to about 7 ℃ to solution temperature by ice-water bath, becomes a kind of clear solution.76 gram DMTD (0.5mol) are joined in the 300ml ethanol stirring and dissolving to be become yellow clear solution and cools to 10 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with 76 gram DMTD to flask by dropping funnel then, liberated heat is spread timely, solution becomes yellow clear solution in four-hole boiling flask, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off).
(2) mixture that obtains in (1) is placed in the water-bath, by water-bath its temperature is remained on 25 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, by constant pressure funnel to the 5 gram propionyl chlorides (0.6mol) of Dropwise 5 wherein, the color of mixture is become yellow muddy by clear when propionyl chloride begins to drip inwards, there are a large amount of yellow mercury oxides to generate, exothermic heat of reaction in the process that propionyl chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with propionyl chloride generate a large amount of yellow mercury oxides, when the amount of propionyl chloride is added to a half mixture by the yellow mercury oxide last white precipitate (powder) that generates that shoals, the throw out of the white powder of generation becomes a kind of white grume thing in flask.
(3) slowly the temperature of water-bath is raised to 80 ℃, allows mixture begin to reflux, when mixture temperature reaches 70 ℃, begin to occur a large amount of backflows in the flask, keep reflux state 2-3hr, mixture is a white paste in the bottle.
(4) mixture temperature is dropped to 5 ℃ by ice-water bath, when wherein dripping stirring that concentrated hydrochloric acid do not stop, stop dripping hydrochloric acid until the pH=2-3 of mixture by dropping funnel.Mixture is placed on ice-water bath leaves standstill the 4hr layering, the upper strata is yellow settled solution, and lower floor is the white powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with 4 ℃ of washing with alcohol filter cakes, last filter cake becomes the white powder precipitation, be placed in the vacuum drying oven 60 ℃ of dryings 15 hours white powder product 92 grams, yield 90%.
Embodiment 4: thiadiazoles derivative (11) synthesis technique:
(1) agitator is housed, thermometer, the condensing reflux pipe, adding 20gNaOH (0.5mol) and 60ml water in the four-hole boiling flask of the 1L of constant pressure funnel are made into the NaOH aqueous solution, stirring and dissolving back fully drops to about 10 ℃ to solution temperature by ice-water bath, becomes a kind of clear solution.76 gram DMTD (0.5mol) are joined in the 300ml ethanol (70%) stirring and dissolving to be become yellow clear solution and cools to about 10 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with 76 gram DMTD to flask by dropping funnel then, liberated heat is spread timely, solution becomes yellow clear solution in four-hole boiling flask, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off).
(2) mixture that obtains in (1) is placed in the water-bath, by water-bath its temperature is remained on 20 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, restrain Butyltriphenylphosphonium chlorides (0.5mol) by constant pressure funnel to wherein dripping 77.5, the color of mixture is become yellow muddy by clear when Butyltriphenylphosphonium chloride begins to drip inwards, there are a large amount of yellow mercury oxides to generate, exothermic heat of reaction in the process that Butyltriphenylphosphonium chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with Butyltriphenylphosphonium chloride generate a large amount of yellow mercury oxides, when the amount of Butyltriphenylphosphonium chloride is added to a half mixture by the yellow mercury oxide last white precipitate (powder) that generates that shoals, the throw out of the white powder of generation becomes a kind of white grume thing in flask.
(3) slowly the temperature of water-bath is raised to 80 ℃, allows mixture begin to reflux, when mixture temperature reaches 70 ℃, begin to occur a large amount of backflows in the flask, keep reflux state 3-4hr, mixture is a white paste in the bottle.
(4) mixture temperature is dropped to 5 ℃ by ice-water bath, when wherein dripping stirring that concentrated hydrochloric acid do not stop, stop dripping hydrochloric acid until the pH=2-3 of mixture by dropping funnel.Mixture is placed on ice-water bath leaves standstill 4hr, layering occurs, the upper strata is yellow settled solution, and lower floor is the white powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with cold washing with alcohol filter cake, last filter cake becomes the white powder precipitation, be placed in the vacuum drying oven 70 ℃ of dryings 12 hours white powder product 120 grams, yield 90%.
Embodiment 5: thiadiazoles linking agent (12) synthesis technique
(1) agitator is being housed, thermometer, the condensing reflux pipe, adding 20gNaOH (0.5mol) and 65ml water in the four-hole boiling flask of the 1L of constant pressure funnel are made into the NaOH aqueous solution, stirring and dissolving back fully drops to about 6 ℃ to solution temperature by ice-water bath, becomes a kind of clear solution.76 gram DMTD (0.5mol) are joined in the 300ml ethanol stirring and dissolving to be become yellow clear solution and cools to about 8 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with 76 gram DMTD to flask by dropping funnel then, liberated heat is spread timely, solution becomes yellow clear solution in four-hole boiling flask, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off).
(2) mixture that obtains in (1) is placed in the water-bath, by water-bath its temperature is remained on 26 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, restrain Tosyl chlorides (0.6mol) by constant pressure funnel to wherein dripping 114, the color of mixture is become yellow muddy by clear when Butyltriphenylphosphonium chloride begins to drip inwards, there are a large amount of yellow mercury oxides to generate, exothermic heat of reaction in the process that Butyltriphenylphosphonium chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with Tosyl chloride generate a large amount of yellow mercury oxides, when the amount of Tosyl chloride is added to a half mixture by the yellow mercury oxide last light-yellow precipitate (powder) that generates that shoals, the throw out of the yellow powder powder of generation becomes a kind of yellow grume thing in flask.
(3) slowly the temperature of water-bath is raised to 80 ℃, allows mixture begin to reflux, when mixture temperature reaches 70 ℃, begin to occur a large amount of backflows in the flask, keep reflux state 3-5hr, mixture is yellow mashed prod in the bottle.
(4) mixture temperature is dropped to 5 ℃ by ice-water bath, when wherein dripping stirring that concentrated hydrochloric acid do not stop, stop dripping hydrochloric acid until the pH=2-3 of mixture by dropping funnel.Mixture is placed on ice-water bath leaves standstill 5hr, layering occurs, the upper strata is yellow settled solution, and lower floor is the yellow powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with cold absolute ethanol washing filter cake, last filter cake becomes the yellow powder precipitation, be placed in the vacuum drying oven 65 ℃ of dryings 14 hours yellow powder shape product 150 grams, yield 83%.
Embodiment 6: thiadiazoles derivative (8) preparation
(1) agitator is being housed, thermometer, adding 40KG NaOH and 150L water in the enamel reaction still of the 2000L of condensing reflux pipe are made into the NaOH aqueous solution, and stirring and dissolving back fully drops to about 8 ℃ to solution temperature by refrigerant, and mixture becomes a kind of clear solution.150KG DMTD joined in the 650L ethanol (70%) becomes yellow clear solution in the dissolution kettle stirring and dissolving, cool to about 8 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with DMTD to reactor by under meter control then, liberated heat is spread timely, solution becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off, by chuck cooling water control temperature of reaction).
(2) by controlling the temperature of reacting kettle jacketing water coolant, keep mixture temperature at 20 ℃-30 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, by under meter to wherein adding 170 kilograms of Benzoyl chlorides, the color of mixture is become yellow muddy by clear when Benzoyl chloride begins to drip inwards, there is yellow mercury oxide to generate, exothermic heat of reaction in the process that Benzoyl chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with Benzoyl chloride generate a large amount of yellow mercury oxides, when the amount of Benzoyl chloride is added to a half mixture by the yellow mercury oxide last white precipitate (powder) that generates that shoals, the throw out of the white powder of generation becomes a kind of white grume thing in flask.
(3) temperature to the reflux temperature of control reacting kettle jacketing water makes mixture begin to reflux, and when mixture temperature reaches 70 ℃, begins to occur a large amount of backflows in the reactor, keeps reflux state 4-5hr, and mixture is a white paste in the reactor.
(4) temperature by control chuck water coolant drops to 5 ℃ with mixture temperature, stops dripping hydrochloric acid by dropping funnel when wherein dripping stirring that concentrated hydrochloric acid (36.5%) do not stop until the pH=2-3 of mixture.Mixture is placed on ice-water bath leaves standstill 4hr～5hr, layering occurs, the upper strata is yellow settled solution, and lower floor is the white powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with 3 ℃ of absolute ethanol washing filter cakes, last filter cake becomes the white powder precipitation, be placed in the vacuum drying oven 60 ℃ of dryings 15 hours, 220 kilograms of white powder products, yield 90%.
Embodiment 7: thiadiazoles linking agent (9) synthesis technique
(1) agitator is being housed, thermometer, adding 40KG NaOH and 140L water in the enamel reaction still of the 2000L of condensing reflux pipe are made into the NaOH aqueous solution, and stirring and dissolving back fully drops to about 9 ℃ to solution temperature by refrigerant, and mixture becomes a kind of clear solution.150KG DMTD joined to be become yellow clear solution in the dissolution kettle stirring and dissolving in the 650L ethanol (70%) and cools to about 8 ℃, slowly add ethanolic soln and the ceaselessly stirring that is dissolved with DMTD to reactor by under meter control then, liberated heat is spread timely, solution becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein.(DMTD is dissolved in heat release in the process of alkaline solution, and mixture temperature raises, and will notice in reaction process guaranteeing that mixture temperature can not surpass 30 ℃ of sulfydryls that prevent DMTD and come off, by chuck cooling water control temperature of reaction).
(2) by controlling the temperature of reacting kettle jacketing water coolant, keep mixture temperature at 20 ℃-30 ℃, at this moment the color of mixture becomes light brown viscous solution by yellow, by under meter to wherein adding 264 kilograms of benzene sulfonyl chlorides, the color of mixture is become yellow muddy by clear when benzene sulfonyl chloride begins to drip inwards, there is yellow mercury oxide to generate, exothermic heat of reaction in the process that benzene sulfonyl chloride drips inwards, temperature rises to 30 ℃ by 20 ℃, to be no more than 30 ℃ by the temperature that mixture is controlled in water-bath, the more and more mixtures that drip inward along with benzene sulfonyl chloride generate a large amount of yellow mercury oxides, when the amount of benzene sulfonyl chloride is added to a half mixture by the yellow mercury oxide last yellow mercury oxide that generates that shoals, the throw out of the yellow powder shape of generation becomes a kind of yellow grume thing in flask.
(3) temperature of control reacting kettle jacketing water makes mixture begin to reflux to reflux temperature, when mixture temperature reaches 70 ℃, begins to occur a large amount of backflows in the reactor, keeps reflux state 2-4hr, and mixture is yellow mashed prod in the reactor.
(4) temperature by control chuck water coolant drops to 5 ℃ with mixture temperature, stops to drip sulfuric acid by dropping funnel when wherein dripping stirring that the vitriol oil (98%) do not stop until the pH=2 of mixture.Mixture is placed on ice-water bath leaves standstill 5hr, layering occurs, the upper strata is yellow settled solution, and lower floor is the yellow powder product, by the suction filtration groove sedimentation and filtration in the mixture is come out, and containing etoh solvent and water in the filtrate can be recycled by water distilling apparatus.Filter cake earlier with deionized water wash remove wherein inorganic salt NaCl and residual HCl, till the pH=7 of the filtrate of washing.And then with 1 ℃ of absolute ethanol washing filter cake, last filter cake becomes the yellow powder precipitation, be placed in the vacuum drying oven 62 ℃ of dryings 13 hours, 236 kilograms of yellow powder shape products, yield 83%.
Embodiment 8: the thiadiazoles derivative preparation
(1) in reactor, adds the water of NaOH and proportional quantity, stir, be made into mass percent concentration and be 30% the NaOH aqueous solution, lower the temperature to alkali lye simultaneously and with ice-water bath, make temperature to 5 ℃～8 ℃;
(2) with mass ratio be 1: 3.5 amount with 2,5-dimercapto-1,3,4-thiadiazoles are that DMTD joins in 70% ethanolic soln, stirring and dissolving becomes yellow clear solution, simultaneously to the solution cooling, makes temperature to 5 ℃～8 ℃;
(3) with DMTD: the mol ratio of NaOH is that 1: 1 amount is added drop-wise to the described DMTD ethanolic soln of step (2) in the described NaOH aqueous solution of step (1), ceaselessly stirring therebetween makes the temperature of mixed solution be no more than 10 ℃, solution only becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein, get light yellow transparent mixture solution;
(4) the described mixture solution of step (3) is remained on 20 ℃～30 ℃ by water-bath with its temperature, then to wherein dripping anisoyl chloride, make anisoyl chloride and 2,5-dimercapto-1,3,4-thiadiazoles sodium salt carries out nucleophilic substitution reaction in ethanolic soln, form 2,5-dimercapto-1,3, the acyl group list substitution compound of 4-thiadiazoles, wherein the anisoyl chloride dripping quantity is anisoyl chloride with molar ratio computing: the sodium salt of DMTD in the mixture solution=1.5: 1; After anisoyl chloride drips, mixture solution is warming up to reflux temperature, and under reflux temperature, reacted 4-5 hour, get white pasty mixture with water-bath;
(5) give step (4) described mixture cooling with ice-water bath, make its temperature to 0 ℃～5 ℃, then to wherein dripping concentrated hydrochloric acid, stir simultaneously, when mixture pH=2～3, stop to drip acid, under the ice-water bath condition mixture is left standstill 4hr～5hr and make its layering, the upper strata is faint yellow settled solution, and lower floor is white or yellow powder product, filters by the suction filtration groove, get filter cake, filtrate is recycled;
(6) filter cake uses deionized water wash earlier till washings pH=7; And then become white or yellow powder precipitation with 2 ℃ of absolute ethanol washing to filter cakes;
(7) filter cake that obtains is placed in the vacuum drier, 60 ℃ of dryings 14 hours, white or yellow thiadiazoles derivative.
Embodiment 9: the thiadiazoles derivative preparation
(1) in reactor, adds the water of KOH and proportional quantity, stir, be made into mass percent concentration and be 33% the KOH aqueous solution, lower the temperature to alkali lye simultaneously and with ice-water bath, make temperature to 8 ℃～10 ℃;
(2) with mass ratio be 1: 4 amount with 2,5-dimercapto-1,3,4-thiadiazoles are that DMTD joins in 70% ethanolic soln, stirring and dissolving becomes yellow clear solution, simultaneously to the solution cooling, makes temperature to 5 ℃～10 ℃;
(3) with DMTD: the mol ratio of KOH is that 1: 1 amount is added drop-wise to the described DMTD ethanolic soln of step (2) in the described KOH aqueous solution of step (1), ceaselessly stirring therebetween makes the temperature of mixed solution be no more than 10 ℃, solution only becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein, get light yellow transparent mixture solution;
(4) the described mixture solution of step (3) is remained on 20 ℃～30 ℃ by water-bath with its temperature, to wherein dripping the hexadecyl SULPHURYL CHLORIDE, make hexadecyl SULPHURYL CHLORIDE and 2 then, 5-dimercapto-1,3,4-thiadiazoles sylvite carries out nucleophilic substitution reaction in ethanolic soln, form 2,5-dimercapto-1,3, the acyl group list substitution compound of 4-thiadiazoles, wherein hexadecyl SULPHURYL CHLORIDE dripping quantity is the hexadecyl SULPHURYL CHLORIDE with molar ratio computing: the sylvite of DMTD in the mixture solution=2: 1; After the hexadecyl SULPHURYL CHLORIDE drips, mixture solution is warming up to reflux temperature, and under reflux temperature, reacted 3-5 hour, get white pasty mixture with water-bath;
(5) give step (4) described mixture cooling with ice-water bath, make its temperature to 0 ℃～5 ℃, then to wherein dripping the vitriol oil, stir simultaneously, when mixture pH=2～3, stop to drip acid, under the ice-water bath condition mixture is left standstill 4hr～5hr and make its layering, the upper strata is faint yellow settled solution, and lower floor is white or yellow powder product, filters by the suction filtration groove, get filter cake, filtrate is recycled;
(6) filter cake uses deionized water wash earlier till washings pH=7; And then become white or yellow powder precipitation with 0 ℃ of absolute ethanol washing to filter cake;
(7) filter cake that obtains is placed in the baking oven, 70 ℃ of dryings 12 hours, white or yellow thiadiazoles derivative.
Embodiment 10:
Application Example 1～5 synthetic formula (8), (9), (10), (11), (12) thiadiazoles derivative carry out curability research
Experimental data sees Table 1, table 2:
Table 1 vulcanization characteristics curve data
| The sizing material numbering | MH | ML | t10 | t50 | t90 | |
| T-01 T-02 T-03 T-04 T-05 | Vanax808/ thiadiazoles derivative (8) Vanax808/ thiadiazoles derivative (9) Vanax808/ thiadiazoles derivative (10) Vanax808/ thiadiazoles derivative (11) Vanax808/ thiadiazoles derivative (12) | 2.38 2.33 2.20 2.18 2.29 | 0.41 0.42 0.42 0.41 0.42 | 0:01:46 0:02:16 0:02:18 0:02:52 0:01:54 | 0:03:42 0:04:42 0:05:14 0:05:40 0:04:00 | 0:08:32 0:09:40 0:11:03 0:12:19 0:09:40 |
Table 2 cured properties data
| Project | T-01 | T-02 | T-03 | T-04 | T-05 |
| Hardness ShoreA 100% stretches % hot strength MPa elongation at break % firmness change hot strength rate of change % elongation at break rate of change % surely | 87 4.89 12.77 254 +5 +6.7 -23 | Physical property 88 4.62 12.76 272+4+7.2-24 | 83 4.44 12.72 282 120 ℃ * 72H of conditions of vulcanization+6+8.1-25 | 160℃×12min 89 3.55 11.54 260 +4 +7 -26 | 87 4.65 12.75 255 +5 +7.3 -24 |
Annotate: 1. curability testing tool: vulkameter tension tester hardness tester ageing oven.
2. test recipe: CM352 100; MgO 10; CaSt 2; N550 25; White carbon black 15;
CaCO
3 20； DOP 20；sundex790 15；
Thiadiazoles derivative 2.5; Vanax808 0.8.
Claims (10)
1. the synthetic method of a thiadiazoles derivative for halopolymer vulcanization crosslinking, realized by following steps:
(1) in reactor, adds the water of metal base and proportional quantity, stir, be made into mass percent concentration and be 25%～35% the metal base aqueous solution, lower the temperature to alkali lye simultaneously and with ice-water bath, make temperature to 5 ℃～10 ℃;
(2) with mass ratio be 1: 3.5～4.5 amount with 2,5-dimercapto-1,3,4-thiadiazoles are that DMTD joins in the ethanolic soln, stirring and dissolving becomes yellow clear solution, simultaneously to the solution cooling, makes temperature to 5 ℃～10 ℃;
(3) with DMTD: alkali-metal mol ratio is that 1: 1 amount is added drop-wise to the described DMTD ethanolic soln of step (2) in the described metal base aqueous solution of step (1), ceaselessly stirring therebetween makes the temperature of mixed solution be no more than 10 ℃, solution only becomes yellow clear solution in reactor, then solution is removed by filter insolubles wherein, get light yellow transparent mixture solution;
(4) the described mixture solution of step (3) is remained on 20 ℃～30 ℃ by water-bath with its temperature, to wherein dripping acyl chlorides or SULPHURYL CHLORIDE, make acyl chlorides or SULPHURYL CHLORIDE and 2 then, 5-dimercapto-1,3,4-thiadiazoles an alkali metal salt carries out nucleophilic substitution reaction in ethanolic soln, form 2,5-dimercapto-1,3, the acyl group list substitution compound of 4-thiadiazoles, wherein acyl chlorides or SULPHURYL CHLORIDE dripping quantity are acyl chlorides or SULPHURYL CHLORIDE with molar ratio computing: an alkali metal salt of DMTD=1～2 in the mixture solution: 1; After acyl chlorides or SULPHURYL CHLORIDE drip, mixture solution is warming up to reflux temperature, and under reflux temperature, reacted 2-5 hour, get white or yellow grume mixture with water-bath;
(5) give step (4) described mixture cooling with ice-water bath, make its temperature to 0 ℃～5 ℃, then to wherein dripping dense mineral acid, stir simultaneously, when mixture pH=2～3, stop to drip acid, under the ice-water bath cooling conditions mixture is left standstill 4hr～5hr and make its layering, the upper strata is faint yellow settled solution, and lower floor is white or yellow powder product, filters by the suction filtration groove, get filter cake, filtrate is recycled;
(6) filter cake uses deionized water wash earlier till washings pH=7; And then become white or yellow powder precipitation with cold washing with alcohol to filter cake;
(7) filter cake that obtains is placed in baking oven or the vacuum drier, 60 ℃～70 ℃ dryings 12～15 hours, white or yellow thiadiazoles derivative.
2. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: described metal base is NaOH or KOH.
3. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: the concentration of described ethanolic soln is 70%.
4. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: described acyl chlorides is aromatic series acyl chlorides or aliphatics acyl chlorides.
5. as the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking as described in the claim 4, it is characterized in that: described aromatic series acyl chlorides is a Benzoyl chloride, Butyltriphenylphosphonium chloride, parachlorobenzoyl chloride, o-chlorobenzoyl chloride, the o-methyl-benzene formyl chloride, m-methyl benzoyl formyl chloride, anisoyl chloride is to the ethylamino benzonitrile acyl chlorides, to the propylbenzene formyl chloride, to one of tert.-butylbenzene formyl chloride; Described aliphatics acyl chlorides is an Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, capryl(yl)chloride, valeryl chloride, n-Hexadecane acyl chlorides, one of stearyl chloride.
6. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: described SULPHURYL CHLORIDE is aromatic sulfonyl or aliphatics SULPHURYL CHLORIDE.
7. as the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking as described in the claim 6, it is characterized in that: described aromatic sulfonyl is a benzene sulfonyl chloride, Tosyl chloride, parachloroben-zenesulfonyl chloride, adjacent chlorobenzene sulfonyl chloride, the o-methyl-benzene SULPHURYL CHLORIDE, between Methyl benzenesulfonyl chlorine, to the anisole SULPHURYL CHLORIDE, to the ethylbenzene SULPHURYL CHLORIDE, to the propylbenzene SULPHURYL CHLORIDE, to one of tert.-butylbenzene SULPHURYL CHLORIDE; Described aliphatics SULPHURYL CHLORIDE is an ethyl chloride, sulfonyl propyl chlorine, butyl sulfochlorides, octyl group SULPHURYL CHLORIDE, amyl group SULPHURYL CHLORIDE, hexadecyl SULPHURYL CHLORIDE, one of octadecyl SULPHURYL CHLORIDE.
8. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: described reflux temperature is 70 ℃～80 ℃.
9. the synthetic method of thiadiazoles derivative for halopolymer vulcanization crosslinking according to claim 1, it is characterized in that: described dense mineral acid is the concentrated hydrochloric acid or the vitriol oil; Described cold ethanol is 0 ℃～4 ℃ dehydrated alcohol.
10. the described method synthetic of claim 1 thiadiazoles derivative, it is characterized in that: described thiadiazoles derivative is the compound as one of structural formula (9), (11), (12):
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102574826A (en) * | 2009-10-08 | 2012-07-11 | 米其林技术公司 | Thiadiazole which can be used as a vulcanization accelerator and method for obtaining same |
| CN102702130A (en) * | 2012-03-28 | 2012-10-03 | 南开大学 | Heterocyclic asymmetric aromatic dithioether compound and synthesis method and application thereof |
| CN103613868A (en) * | 2013-05-22 | 2014-03-05 | 烟台恒鑫化工科技有限公司 | Novel vulcanization system-containing chlorinated polyethylene mixed rubber and processing technology |
| CN105061361A (en) * | 2015-08-03 | 2015-11-18 | 烟台恒诺化工科技有限公司 | Nanometer anti-wear particle formed through reaction of thiadiazole derivative and rare earth element, and preparation method and application thereof |
| CN115989222A (en) * | 2020-08-26 | 2023-04-18 | 路博润公司 | 2,5-dimercapto-1,3,4-thiadiazole ("DMTD") zinc salt derivative |
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| ATE169654T1 (en) * | 1993-09-10 | 1998-08-15 | Vanderbilt Co R T | HARDENING SYSTEM FOR HALOGENATED ELASTOMERS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102574826A (en) * | 2009-10-08 | 2012-07-11 | 米其林技术公司 | Thiadiazole which can be used as a vulcanization accelerator and method for obtaining same |
| CN102574826B (en) * | 2009-10-08 | 2015-11-25 | 米其林集团总公司 | Thiazole that can be used as vulcanization accelerator and preparation method thereof |
| CN102702130A (en) * | 2012-03-28 | 2012-10-03 | 南开大学 | Heterocyclic asymmetric aromatic dithioether compound and synthesis method and application thereof |
| CN103613868A (en) * | 2013-05-22 | 2014-03-05 | 烟台恒鑫化工科技有限公司 | Novel vulcanization system-containing chlorinated polyethylene mixed rubber and processing technology |
| CN105061361A (en) * | 2015-08-03 | 2015-11-18 | 烟台恒诺化工科技有限公司 | Nanometer anti-wear particle formed through reaction of thiadiazole derivative and rare earth element, and preparation method and application thereof |
| CN115989222A (en) * | 2020-08-26 | 2023-04-18 | 路博润公司 | 2,5-dimercapto-1,3,4-thiadiazole ("DMTD") zinc salt derivative |
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