CN111440258B - A kind of polyvinyl ether compound and preparation method thereof - Google Patents
A kind of polyvinyl ether compound and preparation method thereof Download PDFInfo
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- CN111440258B CN111440258B CN202010359649.8A CN202010359649A CN111440258B CN 111440258 B CN111440258 B CN 111440258B CN 202010359649 A CN202010359649 A CN 202010359649A CN 111440258 B CN111440258 B CN 111440258B
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- polyvinyl
- ether
- acid
- polyvinyl ether
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- 229920001289 polyvinyl ether Polymers 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229920000098 polyolefin Polymers 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 4
- 229940069096 dodecene Drugs 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229940095068 tetradecene Drugs 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 3
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 2
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 2
- 239000000047 product Substances 0.000 description 15
- 150000001241 acetals Chemical class 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 150000002373 hemiacetals Chemical group 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种聚乙烯基醚化合物，该化合物中烯烃聚合物以共价键接于聚乙烯基醚中，其结构式如下：；其中：n1≥1，n2≥2，R1和R4均为碳原子数为1~6的烃基，R2和R3均为芳基、碳原子数为1~13的烃基或氢原子中的一种。本发明还公开了该化合物的制备方法。本发明不含缩醛结构、化学稳定性良好，且生产成本低。The present invention relates to a kind of polyvinyl ether compound, in which olefin polymer is covalently bonded to polyvinyl ether, and its structural formula is as follows: 
; where: n 1 ≥1, n 2 ≥2, R 1 and R 4 are both hydrocarbon groups with 1 to 6 carbon atoms, R 2 and R 3 are both aryl groups, hydrocarbon groups with 1 to 13 carbon atoms or A type of hydrogen atom. The invention also discloses a preparation method of the compound. The invention has no acetal structure, good chemical stability and low production cost.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a polyvinyl ether compound and a preparation method thereof.
Background
The polyvinyl ether lubricating oil has excellent lubricating property and good compatibility, and compared with lubricating oil such as poly-alpha olefin (PAO) lubricating oil and mineral oil, the polyvinyl ether lubricating oil has the advantages of large usable viscosity range, low pour point, high maximum non-seizure load and the like, thereby becoming an oil product with wide application background and being widely applied to lubricating oil viscosity index improvers, pour point depressants, refrigeration industry and other mechanical fields. However, the polyvinyl ether prepared at present has the defects of poor chemical stability, easy decomposition and discoloration when meeting acid and the like.
Polyvinyl ethers are generally obtained by cationic polymerization, and in order to control the molecular weight of the polyvinyl ether, compounds such as alcohol, water, acetal, etc. are generally added during the preparation process, so that the final product contains acetal structures, and the acetal and hemiacetal structures belong to unstable structures: under acidic conditions, the aldehyde is converted to the carboxylic acid. Therefore, in order to eliminate the acetal or hemiacetal structure in polyvinyl ether, it is common to obtain a stable compound by subjecting polyvinyl ether to a hydrogenation reaction at a high temperature (90 to 240 ℃) and a high pressure (5 to 15 MPa) under the catalysis of a catalyst such as a noble metal to eliminate the acetal or hemiacetal structure therein. The patent CN107216926A discloses a preparation method of polyvinyl ether lubricant base oil, which is to prepare polyvinyl ether by taking vinyl methyl ether and vinyl ethyl ether as raw materials under the conditions of 5-15 MPa of pressure and 100-200 ℃ of temperature and nickelThe hydrogenation reaction is completed under the catalysis of a catalyst of a series or noble metal, and finally, the product is obtained by distillation. Patent CN1182414A discloses a method for producing ether compounds, which adopts a catalyst containing nickel and inorganic oxides such as silicon oxide, magnesium oxide and the like at a temperature of 90-190 ℃ and a pressure of 3kg/cm2To 60kg/cm2Preparing the end ether polyvinyl ether by hydrogenolysis of the end acetal polyvinyl ether under the condition of (1), and finally obtaining the product by precipitation or filtration.
The method has the defects of expensive catalyst, harsh hydrogenation condition, high energy consumption, complex process and easy corrosion of equipment under high-temperature and high-pressure conditions.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyvinyl ether compound which does not contain an acetal structure and has good chemical stability and is terminated by an olefin polymer.
Another technical problem to be solved by the present invention is to provide a method for preparing the polyvinyl ether compound.
In order to solve the above problems, the present invention provides a polyvinyl ether compound, which is characterized in that: the olefin polymer in the compound is covalently bonded in polyvinyl ether, and the structural formula is as follows:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Both are aryl, alkyl with 1-13 carbon atoms or one of hydrogen atoms.
The process for producing a polyvinyl ether compound as described above is characterized in that: uniformly mixing an organic solvent, acetal-terminated polyvinyl ether and a cationic initiator, slowly adding olefin at the temperature of 0-25 ℃ under the condition of continuous stirring, reacting for 1-2 h, washing with water, and distilling to obtain an olefin polymer terminated polyvinyl ether compound; the adding amount of the organic solvent is 5-30% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the cationic initiator is 0.3-10% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the olefin is 0.8-27.8% of the mass of the polyvinyl ether containing acetal terminated end.
The acetal-terminated polyvinyl ether is one of polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl n-propyl ether, polyvinyl isopropyl ether, polyvinyl n-butyl ether, polyvinyl isobutyl ether, polyvinyl sec-butyl ether, polyvinyl tert-butyl ether, polyvinyl n-pentyl ether and polyvinyl n-hexyl ether, and the molecular weight of the acetal-terminated polyvinyl ether is 800-3000.
The cationic initiator is protonic acid or Lewis acid.
The protonic acid is concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid (HSO)3Cl), fluorosulfonic acid (HSO)3F) Trichloroacetic acid (CCl)3COOH), trifluoroacetic acid (CF)3COOH), trifluoromethanesulfonic acid (CF)3SO3H) One kind of (1).
The Lewis acid is boron trifluoride (BF)3) Aluminum trichloride (AlCl)3) Titanium tetrachloride (TiCl)4) Tin tetrachloride (SnCl)4) Zinc chloride (ZnCl)2) Antimony pentachloride (SbCl)5) One kind of (1).
The organic solvent is one of n-hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane and carbon tetrachloride.
The olefin is one of ethylene, propylene, 1-butene, 2-butene, isobutene, styrene, alpha-methyl styrene, butadiene, isoprene, hexene, 1-octene, 1-decene, dodecene and tetradecene.
Compared with the prior art, the invention has the following advantages:
1. the invention converts the polyvinyl ether terminated by acetal structure into olefin terminated polyvinyl ether, and improves the chemical stability of the polyvinyl ether.
2. The preparation method is simple and mild in condition, the synthesized polyvinyl ether does not need hydrogenation, the defects of expensive catalyst, harsh condition, high energy consumption, dangerous operation and the like in the traditional polyvinyl ether lubricating oil hydrogenation process are overcome, the production cost is effectively reduced, and the method can be widely applied to the field of refrigeration systems and other machinery.
Detailed Description
A polyvinyl ether compound in which an olefin polymer is covalently bonded to a polyvinyl ether, having the formula:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Both are aryl, alkyl with 1-13 carbon atoms or one of hydrogen atoms.
Example 1
Into a three-necked flask were charged 24g of n-hexane as a solvent, 80g (0.1 mol) of absolute ethanol-terminated polyvinyl methyl ether (M n= 800) and 8g of phosphoric acid, stirring and mixing uniformly, slowly introducing 1-butene, stirring at 0-25 ℃ for 1h, stopping, weighing to obtain 16g of introduced 1-butene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 2
A three-necked flask was charged with 20g of solvent n-hexane, 100g (0.1 mol) of methanol-terminated polyvinyl ethyl etherM n= 1000) and 1.5 g of boron trifluoride, stirring and mixing uniformly, slowly introducing isobutene, stirring for 1h at 0-25 ℃, stopping, weighing to obtain 27.8g of introduced isobutene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 3
In a three-neck flask were charged 20g of chloroform as a solvent, 120g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-propyl etherM n= 1200) and 0.9 g of aluminum trichloride, stirring and mixing uniformly, slowly introducing isoprene, stirring at 0-25 ℃ for 2h, stopping, and weighing to obtain introduced isopreneThe diene is 18.48g, and the product is obtained after water washing and rotary evaporation are carried out to remove impurities and unreacted substances.
Example 4
Into a three-necked flask were charged 27g of n-hexane as a solvent, 150g (0.1 mol) of anhydrous ethanol-terminated polyvinyl isopropyl etherM n= 1500) and 0.75 g sulfuric acid, stirring and mixing uniformly, slowly adding 1-octene, stirring at 0-25 ℃ for 2h, stopping, weighing to obtain 26.1g of added 1-octene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 5
Into a three-necked flask were charged 27g of chloroform as a solvent, 180g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-butyl etherM n= 1800) and 2.9 g of aluminum trichloride, stirring and mixing uniformly, slowly adding 1-decene, mechanically stirring at 0-25 ℃ for 1h, stopping, weighing to obtain 19.8g of added 1-decene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 6
Into a three-necked flask were charged 28g of n-hexane as a solvent, 200 g (0.1 mol) of anhydrous ethanol-terminated polyvinyl isobutyl etherM n= 2000) and 5.0 g of aluminum trichloride, stirring and mixing uniformly, slowly adding the dodecene, stirring for 2 hours at the temperature of 0-25 ℃, stopping, weighing to obtain 24.6g of added dodecene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 7
A three-necked flask was charged with 22g of n-hexane as a solvent, 220g (0.1 mol) of absolute ethanol-terminated polyvinyl sec-butyl ether (M n= 2200) and 0.66 g of boron trifluoride, stirring and mixing uniformly, slowly adding tetradecene, stirring for 2h at 0-25 ℃, stopping, weighing to obtain 28.38g of the added tetradecene, washing with water, and removing impurities and unreacted substances by rotary evaporation to obtain the product.
Example 8
Into a three-necked flask were charged 25g of n-hexane as a solvent, 250g (0.1 mol) of anhydrous ethanol-terminated poly (vinyl t-butyl ether) ((M n= 2500) and 5.25 g phosphoric acid, stirring and mixing evenlySlowly introducing 2-butene, stirring for 1.5h at 0-25 ℃, stopping, weighing to obtain 12.25g of introduced 2-butene, and washing with water and performing rotary evaporation to remove impurities and unreacted substances to obtain the product.
Example 9
Into a three-necked flask were charged 28g of chloroform as a solvent, 280g (0.1 mol) of anhydrous ethanol-terminated polyvinyl n-amyl etherM n= 2800) and 3.4 g of aluminum trichloride, stirring and mixing uniformly, slowly introducing ethylene, stirring at 0-25 ℃ for 2 hours, stopping, weighing to obtain 2.24g of introduced ethylene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
Example 10
In a three-neck flask were charged 15g of solvent n-hexane, 300g (0.1 mol) of absolute ethanol-terminated polyvinyl n-hexyl ether (M n= 3000) and 5.5 g phosphoric acid, stirring and mixing uniformly, then slowly introducing propylene, stirring for 2h at 0-25 ℃, stopping, weighing to obtain 5.7g of introduced propylene, and removing impurities and unreacted substances through water washing and rotary evaporation to obtain the product.
In the above examples 1 to 10, the protonic acid may be concentrated sulfuric acid, perchloric acid, or chlorosulfonic acid (HSO)3Cl), fluorosulfonic acid (HSO)3F) Trichloroacetic acid (CCl)3COOH), trifluoroacetic acid (CF)3COOH), trifluoromethanesulfonic acid (CF)3SO3H) One kind of (1).
The Lewis acid may also be titanium tetrachloride (TiCl)4) Tin tetrachloride (SnCl)4) Zinc chloride (ZnCl)2) Antimony pentachloride (SbCl)5) One kind of (1).
The organic solvent can also adopt one of cyclohexane, dichloromethane, dichloroethane and carbon tetrachloride.
The olefin can also be one of styrene, alpha-methyl styrene, butadiene and hexene.
The product performances obtained in the above examples 1 to 10 are shown in table 1, and it can be seen that the examples 1 to 10 all have very low pour points and good compatibility.
Table 1 results of product performance tests obtained in examples 1 to 10
Although particular embodiments of the invention have been described and illustrated in detail, it should be understood that various equivalent changes and modifications could be made to the above-described embodiments in accordance with the present invention, and its functional effects could be achieved without departing from the spirit of the present invention.
Claims (7)
1. A polyvinyl ether compound characterized in that: the olefin polymer in the compound is covalently bonded in polyvinyl ether, and the structural formula is as follows:
wherein: n is1≥1，n2≥2，R1And R4All are C1-6 alkyl, R2And R3Are one of aryl, alkyl with 1-13 carbon atoms or hydrogen atoms;
the preparation method comprises the following steps: uniformly mixing an organic solvent, acetal-terminated polyvinyl ether and a cationic initiator, slowly adding olefin at the temperature of 0-25 ℃ under the condition of continuous stirring, reacting for 1-2 h, washing with water, and distilling to obtain an olefin polymer terminated polyvinyl ether compound; the adding amount of the organic solvent is 5-30% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the cationic initiator is 0.3-10% of the mass of the polyvinyl ether containing acetal terminated end; the addition amount of the olefin is 0.8-27.8% of the mass of the polyvinyl ether containing acetal terminated end.
2. The polyvinyl ether compound according to claim 1, wherein: the acetal-terminated polyvinyl ether is one of polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl n-propyl ether, polyvinyl isopropyl ether, polyvinyl n-butyl ether, polyvinyl isobutyl ether, polyvinyl sec-butyl ether, polyvinyl tert-butyl ether, polyvinyl n-pentyl ether and polyvinyl n-hexyl ether, and the molecular weight of the acetal-terminated polyvinyl ether is 800-3000.
3. The polyvinyl ether compound according to claim 1, wherein: the cationic initiator is protonic acid or Lewis acid.
4. The polyvinyl ether compound according to claim 3, wherein: the protonic acid is one of concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, trichloroacetic acid, trifluoroacetic acid and trifluoromethanesulfonic acid.
5. The polyvinyl ether compound according to claim 3, wherein: the Lewis acid is one of boron trifluoride, aluminum trichloride, titanium tetrachloride, stannic chloride, zinc chloride and antimony pentachloride.
6. The polyvinyl ether compound according to claim 1, wherein: the organic solvent is one of n-hexane, cyclohexane, dichloromethane, trichloromethane, dichloroethane and carbon tetrachloride.
7. The polyvinyl ether compound according to claim 1, wherein: the olefin is one of ethylene, propylene, 1-butene, 2-butene, isobutene, styrene, alpha-methyl styrene, butadiene, isoprene, hexene, 1-octene, 1-decene, dodecene and tetradecene.
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