CN106633183B - Polythiaether PVC co-stabilizers and the preparation method and application thereof - Google Patents
Polythiaether PVC co-stabilizers and the preparation method and application thereof Download PDFInfo
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- CN106633183B CN106633183B CN201610905347.XA CN201610905347A CN106633183B CN 106633183 B CN106633183 B CN 106633183B CN 201610905347 A CN201610905347 A CN 201610905347A CN 106633183 B CN106633183 B CN 106633183B
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- pvc
- polythiaether
- ethyl ester
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- stabilizers
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- -1 Sulfhydryl compound Chemical class 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000012760 heat stabilizer Substances 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 17
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 16
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 15
- 239000008158 vegetable oil Substances 0.000 claims description 15
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 14
- 239000005639 Lauric acid Substances 0.000 claims description 12
- 239000003017 thermal stabilizer Substances 0.000 claims description 12
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229940047889 isobutyramide Drugs 0.000 claims description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical class CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 claims description 3
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 230000006872 improvement Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- NEJMTSWXTZREOC-UHFFFAOYSA-N 4-sulfanylbutan-1-ol Chemical class OCCCCS NEJMTSWXTZREOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N ethyl stearic acid Natural products CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims 1
- QNNVICQPXUUBSN-UHFFFAOYSA-N 2-sulfanylpropan-1-ol Chemical compound CC(S)CO QNNVICQPXUUBSN-UHFFFAOYSA-N 0.000 claims 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims 1
- 239000005642 Oleic acid Substances 0.000 claims 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims 1
- 229940093471 ethyl oleate Drugs 0.000 claims 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 5
- 230000001988 toxicity Effects 0.000 abstract description 4
- 231100000419 toxicity Toxicity 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 239000004800 polyvinyl chloride Substances 0.000 description 38
- 229920000915 polyvinyl chloride Polymers 0.000 description 37
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- NRFGDNQTKLWDIH-UPHRSURJSA-N bis(sulfanyl) (z)-but-2-enedioate Chemical compound SOC(=O)\C=C/C(=O)OS NRFGDNQTKLWDIH-UPHRSURJSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465805 Nymphalidae Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 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 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
- C07C319/24—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides by reactions involving the formation of sulfur-to-sulfur bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of polythiaether PVC co-stabilizers and the preparation method and application thereof, and the preparation method comprises the following steps：Sulfhydryl compound, oxidant and reflux solvent are mixed, the molar ratio of the sulfhydryl compound, oxidant and reflux solvent is 1~2：1：1~2, and the catalyst of the sulfhydryl compound weight 0.01%~3% is added, after reacting 1~10h at a temperature of 60~200 DEG C, it is dry steam solvent to get.The polythiaether PVC co-stabilizers that the present invention obtains overcome the defect that existing preparation method generates a large amount of violent in toxicity hydrogen sulfide, and higher product yield has outstanding performance.
Description
Technical field
The present invention relates to chemical technology field, more particularly to a kind of polythiaether PVC co-stabilizers and preparation method thereof with
Using.
Background technology
Polyvinyl chloride (PVC) is one of the thermoplastic developed earliest in the world, it is because having excellent acid and alkali-resistance
Property, wearability, electrical insulating property be good, flame retardancy, and mature production technology, it is at low cost, be easier to the characteristics of machine-shaping, become only
Inferior to polyethylene, polyacrylic the third-largest synthetic resin.
However, when PVC is processed at high temperature, it may occur that elimination hydrogen chloride, key break and the crosslinking of macromolecular, and makes PVC
Degradation coloring occurs, mechanical performance declines, therefore heat stabilizer must be used in processing PVC.
By years development, a great variety of PVC heat stabilizer can be divided into one-component heat by the difference of complicated components
Stabilizer and composite thermal stabilizer two major classes.One-component heat stabilizer includes mainly metal soap, lead heat stabilizer, has
Machine tin heat stabilizer, organic antimomy stabilizer, hydrotalcite heat stabilizer and without metal heat stabilizer.And by two kinds or two kinds with
Upper one pack system heat stabilizer is made of mixed more than one one pack system heat stabilizer and more than one co-stabilizers (auxiliary agent)
Mould assembly stabilizer is known as composite thermal stabilizer.Composite thermal stabilizer can be divided into following six major class because of the difference of its main effect component：Lead
Based composite heat stabilizer, zinc-base composite thermal stabilizer, cadmium based composite heat stabilizer, organotin based composite heat stabilizer, antimony base are multiple
Close heat stabilizer and organic based composite heat stabilizer.Composite thermal stabilizer with its comprehensive performance balance, high performance-price ratio the characteristics of at
For the main body of commodity heat stabilizer.
Currently, PVC heat stabilizer new product development is concentrated mainly on research and development and the compound thermal of novel one pack system heat stabilizer
In the design of stabilizer.There is technology to disclose a kind of novel latent mercaptan PVC heat stabilizer.This novel heat stabilizer is not only
Being used alone has good thermal stability, and is greatly carried with the thermostable effect after Ca-Zn composite heat stabilizer compounding
It is high.Also technology discloses the method using maleic anhydride and mercaptoethanol reaction synthesis dimercapto maleate PVC heat stabilizer,
The dimercapto maleate synthesized in this way can be while keeping thermal stability and the transparency with organo-tin het stabilizer compounding, drop
Low tin content reduces cost.Also technology describes what catechol and its derivative were compounded with organic antimomy stabilizer
Antimony base compound stabilizer not only has good heat stabilizer, but also improves the storage performance of heat stabilizer.Also technology
It is steady with preferable ultraviolet light to disclose Cosan, mercaptan acid and the compound obtained antimony base compound stabilizer of organic antimomy stabilizer
Qualitative energy and storage performance.
There is technology to describe and disulfide be made by isooctyl thioglycolate and sulfur reaction, as PVC co-stabilizers with
Organo-tin het stabilizer is used in compounding, and can improve thermal stability.But the shortcomings that preparation method of the technology is to generate largely
Violent in toxicity hydrogen sulfide.
Invention content
Based on this, it is necessary in view of the above-mentioned problems, providing a kind of polythiaether PVC co-stabilizers and preparation method thereof and answering
With.The preparation method of the present invention uses the oxidant of environment-friendly type, the shortcomings that overcoming existing preparation method.The present invention is also to more sulphur
Ether is used in compounding with Ca-Zn composite heat stabilizer, organic antimomy stabilizer as PVC co-stabilizers and is studied.
Specific technical solution is as follows：
The invention discloses a kind of preparation methods of polythiaether PVC co-stabilizers, and the preparation method comprises the following steps：
Sulfhydryl compound, oxidant and reflux solvent are mixed, the molar ratio of the sulfhydryl compound, oxidant and reflux solvent is
1~2：1：1~2, and the catalyst of the sulfhydryl compound weight 0.01%~3% is added, it is anti-at a temperature of 60~200 DEG C
After answering 1~10h, it is dry steam solvent to get；
The polythiaether PVC co-stabilizers have following structure shown in formula I：
R1—Sn—R2(I),
In formula I, S is element sulphur, the integer that n is 1~6；R1And R2It is identical or differ, R1And R2Selected from alkyl, R3OH、
R4-COOR5And R6-OOCR7；
R3、R4、R5、R6And R7Selected from alkyl, alkenyl, alkynyl, aryl, naphthenic base, cycloalkenyl group；
The alkyl is alkyl, alkenyl, alkynyl, aryl, naphthenic base or cycloalkenyl group.
In wherein some embodiments, the sulfhydryl compound is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 2- methyl -2-
At least one in mercaptoethanol, 4- Mercaptobutanols, lauryl mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester
Kind；The aliphatic acid mercapto ethyl ester is selected from sad mercapto ethyl ester, capric acid mercapto ethyl ester, lauric acid mercapto ethyl ester, cocinic acid mercapto
Base ethyl ester, palmitic acid mercapto ethyl ester, stearic acid mercapto ethyl ester, vegetable oil acid mercapto ethyl ester, arachidic acid mercapto ethyl ester；
The reflux solvent is one kind in dimethylbenzene, toluene and hexamethylene；
The oxidant is at least one of bis- bromo- 5,5- Dimethyl Hydan of hydrogen peroxide and 1,3-；
The catalyst is at least one of triethylamine, formamide and isobutyramide.
In wherein some embodiments, the sulfhydryl compound is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, dodecyl
At least one of mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester；The aliphatic acid mercapto ethyl ester is selected from bay
Sour mercapto ethyl ester, cocinic acid mercapto ethyl ester, vegetable oil acid mercapto ethyl ester；
The reflux solvent is at least one of toluene and dimethylbenzene；
The oxidant is hydrogen peroxide；
The catalyst is at least one of triethylamine and isobutyramide.
Above-mentioned sulfhydryl compound is more preferably 2 mercapto ethanol, isooctyl thioglycolate, lauric acid mercapto ethyl ester, vegetable oil
Sour mercapto ethyl ester.
In wherein some embodiments, the dosage of the catalyst be the sulfhydryl compound weight 0.9%~
1.5%.
In wherein some embodiments, the reaction temperature is 80~160 DEG C, and the reaction time is 1~3h.
In wherein some embodiments, the polythiaether PVC co-stabilizers are 2,2- dihydroxy diethyl disulphides, diethyl
The different monooctyl ester disulfide of acid, tin dilaurate ethyl ester disulfide or two vegetable oil acid ethyl ester disulfides.
Invention additionally discloses a kind of above-mentioned preparation-obtained polythiaether PVC co-stabilizers of preparation method.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers to compound preparation increase PVC heat with organo-tin het stabilizer
Application in the composite thermal stabilizer of stability.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers to prevent PVC zinc from burning with calcium zinc heat stabilizer compounding preparation
Application in the composite thermal stabilizer of phenomenon.
Invention additionally discloses above-mentioned polythiaether PVC co-stabilizers to compound preparation improvement PVC purples with organic antimomy stabilizer
Application in the composite thermal stabilizer of outer photostability and storage stability.
The present invention provides a kind of novel polythiaether PVC co-stabilizers and preparation method thereof, and existing preparation method is overcome to produce
The shortcomings that raw a large amount of violent in toxicity hydrogen sulfide, while the co-stabilizer being expanded and is applied to hard transparent PVC product, have splendid
Compatibility, help stability, the transparency and ultraviolet light stability.The present invention is easily contracted by oxidation using the mercapto groups of thiol molecule
Polythiaether is synthesized, and then substantially increases the molecular chain length of sulfhydryl compound, molecular mass is increased, makes it as co-stabilizer
When significantly improved with the compatibilities of PVC molecules, there is lubrication property in preferably, be not easy to be precipitated in process.
The present invention compared with the prior art the advantages of and have the beneficial effect that：
(1) Optimization of preparation：Generation without violent in toxicity hydrogen sulfide, oxidation product are water, and reaction yield is high, uses
Solvent boiling point is higher, is easy recycling；
(2) help stability good：Polythiaether co-stabilizer synthesized by the present invention has preferable with organo-tin het stabilizer
Compatibility and synergistic effect are a kind of preferable auxiliary heat stabilizers, and can be prevented with calcium zinc heat stabilizer with the use of playing
The effect of " zinc burning "；
(3) greasy property is good：Polythiaether co-stabilizer synthesized by the present invention possesses larger molecular weight, with PVC molecules
Compatibility it is preferable, fabulous lubricating action can be played, and be not easy to be precipitated in process；
(4) ultraviolet light stabilized performance is good：Polythiaether co-stabilizer synthesized by the present invention has preferable ultraviolet light stabilized
Performance.
Specific implementation mode
To be best understood from the present invention, further detailed description done to the present invention with reference to embodiment, but the present invention
Embodiment is without being limited thereto.
Supplier or the preparation method for occurring raw material and equipment in embodiment are as follows：
2 mercapto ethanol is the product that China Petroleum ＆ Chemical Co., Ltd. Maoming Branch provides, technical grade；
30% hydrogen peroxide is the product that Guangzhou Chemical Reagent Factory provides, and analysis is pure；
Hexamethylene is the product that Guangzhou Chemical Reagent Factory provides, and analysis is pure；
Triethylamine is the product that Chengdu Kingsoft chemical reagent Co., Ltd provides, and analysis is pure；
Isobutyramide is the product that Hubei Ju Sheng Science and Technology Ltd.s provide, SILVER REAGENT；
Isooctyl thioglycolate is the product that Sanmenxia Aoke Chemical Industry Co., Ltd. provides, technical grade；
Toluene is the product that Maoming Hao Jie chemical industry Co., Ltd provides, technical grade；
Dimethylbenzene is the product that Guangzhou Chemical Reagent Factory provides, and analysis is pure；
Lauric acid is the product that Guangzhou Fu Rui Chemical Co., Ltd.s provide, technical grade；
Vegetable oil acid is the product that big western general chemical (Sichuan) Co., Ltd of standing grain provides, technical grade；
The preparation method of lauric acid mercapto ethyl ester and vegetable oil acid mercapto ethyl ester：
Lauric acid or vegetable oil acid carry out esterification with mercaptoethanol respectively, wherein lauric acid or vegetable oil acid can be by
Acid value calculates the amount of the substance of its carboxyl, for calculation in the molar ratio, the carboxyl and sulfydryl in lauric acid or vegetable oil acid in raw material
The molar ratio of ethyl alcohol is 1:1.2, the catalyst p-methyl benzenesulfonic acid of reaction-ure mixture 1 ‰ is added, in 50-70 DEG C of progress ester of vacuum
Change reaction, until the acid value of reaction solution is less than 20mgKOH/g, is considered as esterification terminal, lauric acid mercapto ethyl ester is obtained by filtration
Or vegetable oil acid mercapto ethyl ester.
Embodiment 1
A kind of preparation method of polythiaether PVC co-stabilizers, includes the following steps：
Equipped with blender, thermometer, water cooling condensate liquid water knockout drum four-hole boiling flask in, be added 156.24g2- sulfydryls
(molar ratio between above-mentioned 2 mercapto ethanol, 30% hydrogen peroxide, toluene is 2 for ethyl alcohol, 30% hydrogen peroxide 113.4g, 185g toluene:
1:2), 1.6g catalyst of triethylamine is stirred to react 1.5h at 80 DEG C, and then distillation removing organic solvent obtains 151.3g 2,
2- dihydroxy diethyl disulphides, yield 98.09%.
Product structure formula is：HOCH2-CH2-S-S-CH2-CH2OH。
Embodiment 2
A kind of preparation method of polythiaether PVC co-stabilizers, includes the following steps：
Equipped with blender, thermometer, water cooling condensate liquid water knockout drum four-hole boiling flask in, be added 408.4g thioacetic acid
Different monooctyl ester, 30% hydrogen peroxide 113.4g, 185g toluene (mole between above-mentioned isooctyl thioglycolate, 30% hydrogen peroxide, toluene
Than being 2:1:2), 4.05g catalyst of triethylamine is stirred to react 2h at 110 DEG C, and then distillation removing organic solvent obtains
The different monooctyl ester disulfide of 398.4g oxalic acid, yield 97.6%.
Product structure formula is：(CH3)2CH(CH2)5OCOC-S-S-COCO(CH2)5CH(CH3)2。
Embodiment 3
A kind of preparation method of polythiaether PVC co-stabilizers, includes the following steps：
Equipped with blender, thermometer, water cooling condensate liquid water knockout drum four-hole boiling flask in, be added 520.88g lauric acid
Mercapto ethyl ester, 30% hydrogen peroxide 113.4g, 212g dimethylbenzene are (between above-mentioned lauric acid mercapto ethyl ester, 30% hydrogen peroxide, dimethylbenzene
Molar ratio be 2:1:2), 5.2g catalyst isobutyramide is stirred to react 3h at 140 DEG C, then distillation removing organic solvent
Obtain 508.8g tin dilaurate ethyl ester disulfides, yield 98.06%.
Product structure formula is：C11H23COOCHCH-S-S-CHCHOOCC11H23。
Embodiment 4
A kind of preparation method of polythiaether PVC co-stabilizers, includes the following steps：
Equipped with blender, thermometer, water cooling condensate liquid water knockout drum four-hole boiling flask in, be added 684.24g vegetable oil
Sour mercapto ethyl ester, 30% hydrogen peroxide 113.4g, 212g dimethylbenzene (above-mentioned vegetable oil acid mercapto ethyl ester, 30% hydrogen peroxide, dimethylbenzene
Between molar ratio be 2:1:2), 6.85g catalyst isobutyramide is stirred to react 3h at 140 DEG C, and then distillation removing is organic
Solvent obtains bis- vegetable oil acid ethyl ester disulfides of 669.1g, yield 98.07%.
Product structure formula：
CH3(CH2)7CH=CH (CH2)7COOCHCH-S-S-CHCHOOC(CH2)7CH=CH (CH2)7CH3。
Comparative example 1
A kind of preparation method of polythiaether PVC co-stabilizers, reaction product is substantially the same manner as Example 2, and difference lies in it
Oxidant uses sulphur, and byproduct of reaction is hydrogen sulfide.
Equipped with blender, thermometer, water cooling condensate liquid water knockout drum four-hole boiling flask in, be added 408.4g thioacetic acid
Different monooctyl ester, Cosan 32.06g, 2.45g organic amine catalyst, are stirred to react 2h at 80 DEG C, and reaction end gas uses sodium hydroxide
Aqueous solution absorbs.The different monooctyl ester disulfide of 386.2g oxalic acid, yield 95.03% most is obtained by filtration through filter paper afterwards.
Product structure formula is：(CH3)2CH(CH2)5OCOC-S-S-COCO(CH2)5CH(CH3)2。
Application experiment example 1
5 kinds obtained different polythiaethers, which are synthesized, with a kind of Commercial epoxy soybean oil and Examples 1 to 4, comparative example 1 helps stabilization
Agent is made into the Methyltin composite heat stabilizer that Theil indices are 16% with commercially available methyl tin heat stabilizer T181 respectively, is denoted as respectively
1#、2#、3#、4#、5#、6#.And obtained Methyltin composite heat stabilizer is applied to PVC transparent sheet formulation double roller and is plasticated examination
In testing, additive amount is 1.2%, and after polyvinyl chloride resin powder, heat stabilizer and other auxiliary agents are mixed, high temperature carries out twin-roll machine
It plasticates test, it is primary at interval of sampling in 2 minutes at 194 DEG C, until all sheet materials turn yellow.Double roller is measured to plasticate the color of sample
Product index b value, in this way can the effectively thermostable effect for compareing stabilizer.It is more yellow that b values are more just showing as color, more it is negative then
It shows as more blue.Test result is as follows for it：
Table one：The PVC transparent sheet formulation double roller of Methyltin composite heat stabilizer is plasticated test
From table one it is found that dosage under the same conditions, in terms of thermal stability and the transparency, the embodiment of the present invention synthesis
Obtained polythiaether co-stabilizer is better than the maximum auxiliary heat stabilizer epoxidized soybean oil of dosage and existing preparation method in industry
The obtained different monooctyl ester disulfide of oxalic acid.
Application experiment example 2
The 5 kinds of different polythiaethers obtained with a kind of commercially available phosphite ester 1500N and the synthesis of Examples 1 to 4 and comparative example 1
Co-stabilizer respectively with calcium zinc heat stabilizer compound, additive amount be compound stabilizer total amount 40%, be denoted as respectively 7#, 8#, 9#,
10#、11#、12#.The double roller that obtained Ca-Zn composite heat stabilizer is applied to PVC profile formula is plasticated in experiment, additive amount
It is 1.2%, after polyvinyl chloride resin powder, heat stabilizer and other auxiliary agents are mixed, high temperature carries out twin-roll machine and plasticates test,
It is primary at interval of sampling in 3 minutes at 194 DEG C, until all sheet materials turn yellow.Double roller is measured to plasticate the chromaticity index b value of sample,
It in this way can the effectively thermostable effect for compareing stabilizer.It is more yellow that b values are more just showing as color.Test result is as follows for it：
Table two：The PVC profile formula double roller of calcium-zinc composite stabilizing agent is plasticated test
From table two it is found that in terms of thermal stability, polythiaether co-stabilizer and industry that the embodiment of the present invention synthesizes
Commonly anti-" zinc burning " organic auxiliary heat stabilizer phosphite ester 1500N equally has good thermal stability；In dosage phase
With under conditions of, tin dilaurate ethyl ester disulfide and the two commercially available phosphite esters of vegetable oil acid ethyl ester disulfide ratio and existing preparation
The different monooctyl ester disulfide of oxalic acid that method obtains possesses better long-term thermal stability performance, has better anti-zinc burning effect.
Application experiment example 3
Synthesized with Examples 1 to 4 and comparative example 1 the different polythiaether co-stabilizers of 5 kinds obtained respectively with commercially available mercaptan
Antimony heat stabilizer compounds, and additive amount is the 2% of compound stabilizer, is denoted as 13#, 14#, 15#, 16#, 17# respectively, and not add
The mercaptans type heat stabilizer of polythiaether does reference, is denoted as 18#.Obtained mercaptans type composite thermal stabilizer is placed in ultraviolet-visible
It irradiates in case, observes by the naked eye and record the time of heat stabilizer blackening, the ultraviolet light stabilized performance of stabilizer is compareed with this.
Experimental result is as follows：
Table three：The ultraviolet light stabilized performance of mercaptans type compound stabilizer is tested
From table three it is found that the polythiaether heat stabilizer of synthesis of the embodiment of the present invention is a kind of fabulous UV light stabilizing agent,
The ultraviolet light stabilized performance and storage performance of raising mercaptans type heat stabilizer that can be by a relatively large margin.In the identical condition of dosage
Under, the polythiaether heat stabilizer monooctyl ester disulfide more different than the oxalic acid that existing preparation method obtains of synthesis of the embodiment of the present invention possesses
Better ultraviolet light stability.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of preparation method of polythiaether PVC co-stabilizers, which is characterized in that the preparation method comprises the following steps：It will
The molar ratio of sulfhydryl compound, oxidant and reflux solvent mixing, the sulfhydryl compound, oxidant and reflux solvent is 1
~2：1：1~2, and the catalyst of the sulfhydryl compound weight 0.01%~3% is added, it is anti-at a temperature of 60~200 DEG C
After answering 1~10h, it is dry steam solvent to get；
The polythiaether PVC co-stabilizers have following structure shown in formula I：
R1—Sn—R2(I),
In formula I, S is element sulphur, the integer that n is 1~6；R1And R2It is identical or differ, R1And R2Selected from alkyl, R3OH、R4-
COOR5And R6-OOCR7；
R3、R4、R5、R6And R7Selected from alkyl, alkenyl, alkynyl, aryl, naphthenic base, cycloalkenyl group；
The alkyl is alkyl, alkenyl, alkynyl, aryl, naphthenic base or cycloalkenyl group；
The sulfhydryl compound is 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, 2- methyl -2 mercapto ethanol, 4- Mercaptobutanols, ten
At least one of dialkyl group mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester；The aliphatic acid mercapto ethyl ester choosing
From sad mercapto ethyl ester, capric acid mercapto ethyl ester, lauric acid mercapto ethyl ester, palmitic acid mercapto ethyl ester, stearic acid mercapto ethyl ester, plant
Oleic acid mercapto ethyl ester, arachidic acid mercapto ethyl ester；
The reflux solvent is one kind in dimethylbenzene, toluene and hexamethylene；
The oxidant is hydrogen peroxide；
The catalyst is at least one of triethylamine, formamide and isobutyramide.
2. the preparation method of polythiaether PVC co-stabilizers according to claim 1, which is characterized in that the sulfhydryl compound
For in 2 mercapto ethanol, 3- sulfydryl -1- propyl alcohol, lauryl mercaptan, isooctyl thioglycolate and aliphatic acid mercapto ethyl ester
It is at least one；The aliphatic acid mercapto ethyl ester is selected from lauric acid mercapto ethyl ester, cocinic acid mercapto ethyl ester, vegetable oil acid sulfydryl second
Ester；
The reflux solvent is at least one of toluene and dimethylbenzene；
The catalyst is at least one of triethylamine and isobutyramide.
3. according to the preparation method of any one of the claim 1~2 polythiaether PVC co-stabilizers, which is characterized in that described to urge
The dosage of agent is the 0.9%~1.5% of the sulfhydryl compound weight.
4. according to the preparation method of any one of the claim 1~2 polythiaether PVC co-stabilizers, which is characterized in that described anti-
It is 80~160 DEG C to answer temperature, and the reaction time is 1~3h.
5. the preparation method of polythiaether PVC co-stabilizers according to claim 1, which is characterized in that the polythiaether PVC is helped
Stabilizer is 2,2- dihydroxy diethyl disulphides, the different monooctyl ester disulfide of oxalic acid, tin dilaurate ethyl ester disulfide or two plants
Ethyl oleate disulfide.
6. a kind of preparation-obtained polythiaether PVC co-stabilizers of any one of Claims 1 to 5 preparation method.
7. polythiaether PVC co-stabilizers described in claim 6 are compounding preparation increase PVC thermal stability with organo-tin het stabilizer
Composite thermal stabilizer in application.
8. polythiaether PVC co-stabilizers described in claim 6 are preventing PVC zinc from burning phenomenon with calcium zinc heat stabilizer compounding preparation
Application in composite thermal stabilizer.
9. polythiaether PVC co-stabilizers described in claim 6 are steady with organic antimomy stabilizer compounding preparation improvement PVC ultraviolet lights
Application in qualitative and storage stability composite thermal stabilizer.
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| CN103435845A (en) * | 2013-08-30 | 2013-12-11 | 淮安飞翔液晶材料有限公司 | Auxiliary heat stabilizer of organic tin |
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