CN116589619A - Polyvinyl alcohol/ethylene/1-octene terpolymer and preparation method thereof - Google Patents
Polyvinyl alcohol/ethylene/1-octene terpolymer and preparation method thereof Download PDFInfo
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- CN116589619A CN116589619A CN202310439520.1A CN202310439520A CN116589619A CN 116589619 A CN116589619 A CN 116589619A CN 202310439520 A CN202310439520 A CN 202310439520A CN 116589619 A CN116589619 A CN 116589619A
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- Prior art keywords
- ethylene
- polyvinyl alcohol
- octene
- octene terpolymer
- borate
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 26
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 239000012442 inert solvent Substances 0.000 claims abstract description 6
- 239000012005 post-metallocene catalyst Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- -1 isoparaffin Chemical class 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- UEEXYHHZSOEEDG-UHFFFAOYSA-N methylaluminum(2+);oxygen(2-) Chemical compound [O-2].[Al+2]C UEEXYHHZSOEEDG-UHFFFAOYSA-N 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 229920006124 polyolefin elastomer Polymers 0.000 abstract description 16
- 238000005191 phase separation Methods 0.000 abstract description 4
- 238000002464 physical blending Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- LMEUPNMVGMAVEF-UHFFFAOYSA-L CC(C=CC=C1C=[Ti+2]=NC(C(F)=C(C(F)=C2F)F)=C2F)=C1O.[Cl-].[Cl-] Chemical compound CC(C=CC=C1C=[Ti+2]=NC(C(F)=C(C(F)=C2F)F)=C2F)=C1O.[Cl-].[Cl-] LMEUPNMVGMAVEF-UHFFFAOYSA-L 0.000 description 2
- BHTKQUGPJWEUOJ-UHFFFAOYSA-N C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 Chemical compound C[SiH](C)C[Ti](C)(NC(C(C)(C)C)(CC)C)C1C=CC=C1 BHTKQUGPJWEUOJ-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- YQRRFEPNTPQQHU-UHFFFAOYSA-L [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 Chemical compound [Cl-].[Cl-].C(C=1C(O)=CC=CC1)=C1C(C=CC=C1)N=[Ti+2]=NC1C(C=CC=C1)=CC=1C(O)=CC=CC1 YQRRFEPNTPQQHU-UHFFFAOYSA-L 0.000 description 2
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 2
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- JDEDKRLRGDEWKM-UHFFFAOYSA-N n,n-dioctadecylaniline Chemical compound CCCCCCCCCCCCCCCCCCN(CCCCCCCCCCCCCCCCCC)C1=CC=CC=C1 JDEDKRLRGDEWKM-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water 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
- C08F8/12—Hydrolysis
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
The invention discloses a polyvinyl alcohol/ethylene/1-octene terpolymer and a preparation method thereof, which is prepared by using a catalyst composition consisting of a metallocene catalyst or a post-metallocene catalyst and borate or aluminum alkyl, taking vinyl acetate and 1-octene as reactants and catalyzing the polymerization of the reactants in an inert solvent. The polyvinyl alcohol/ethylene/1-octene terpolymer is obtained by a chemical synthesis method for the first time, has stable performance, does not generate phase separation, and effectively solves the problems of the prior polyolefin elastomer prepared by physical blending.
Description
Technical Field
The invention relates to a copolymer and a preparation method thereof, in particular to a polyvinyl alcohol/ethylene/1-octene terpolymer and a preparation method thereof.
Background
Olefin copolymers (olefin copolymers) are formed by copolymerizing more than one olefin monomer, and such polymers have been well-established in technology and widespread use. Polyolefin elastomer (POE) is a copolymer of ethylene and alpha-olefin, is rubber elastic at normal temperature, and has the characteristics of small density, large bending, high low-temperature impact resistance, easy processing, repeated use and the like.
In terms of the polymerization of POE, there are a number of patents which mainly use metallocene catalysis technology (CN 1328580A, CN 102190687A, CN 1049849A, CN 1166695C, WO 1992000333A2, etc.) and solution polymerization technology (CN 1328580A, CN 1049849A, US 5132381A, CN 1324370a, etc.) for production. Wherein, the microstructure of the polymer can be regulated and controlled by controlling the structure of the metallocene catalyst, thereby obtaining products with different chain structures and applications.
In order to enhance the usability of POE, a series of POE modification researches are developed at home and abroad, but the POE has some defects, such as large demand of POE in the current market, but the production marks of domestic enterprises are mainly concentrated on C4/C6/C8 alpha-olefin copolymerization, so that the competition among products is large, and the surplus productivity is easy to occur; metallocene polyolefin has lower melting point and obvious melting area, and has obvious advantages in toughness, low temperature resistance and the like, but the barrier property to nonpolar solvents and grease is required to be improved; the adoption of the polyvinyl alcohol fiber modified metallocene POE can improve the barrier property of the POE to nonpolar solvents and grease, but the physical blending method is unstable, phase separation is easy to occur, and the material performance is influenced.
Disclosure of Invention
Aiming at the problems that the prior modification mode of polyolefin elastomer (POE) is mainly physical blending, the material performance can be improved and the method is easy to implement in industry, but the material performance is unstable and phase separation is easy to occur, and the like, the invention provides a preparation method of a polyvinyl alcohol/ethylene/1-octene ternary polymerization polymer material.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polyvinyl alcohol/ethylene/1-octene terpolymer comprising units represented by the following formulas 1, 2, 3;
，
wherein the molar ratio of m, n and o is 0.1-500:1:0.1-500.
The preparation method of the polyvinyl alcohol/ethylene/1-octene terpolymer is characterized in that vinyl acetate, ethylene and 1-octene are used as reactants, polymerization of the reactants is catalyzed by a catalyst composition in an inert solvent, and alcoholysis is carried out to prepare the polyvinyl alcohol/ethylene/1-octene terpolymer.
Further, the inert solvent is a linear alkane, isoparaffin, cycloalkane or aralkane having 4 to 10 carbon atoms, which is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isopar E, toluene, xylene.
Further, the catalyst composition consists of a single-site metallocene catalyst or a post-metallocene catalyst serving as a main catalyst and borate or aluminum alkyl serving as a cocatalyst according to a molar ratio of 1:50-10000, and has the advantages of high catalyst activity, high comonomer content, stable structure, better solvent resistance and the like.
Further, the single site metallocene catalyst may be selected from any of biscyclopentadienyl hafnium dichloride, bisindenyl zirconium dichloride, ethylenebridge bis indenyl zirconium dichloride, diphenylcarbobridge-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilicoyl bridge-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, bisindenyl zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxyzirconium, rac-dimethylsilylbis (1-indenyl) zirconium dichloride, diphenylcarbobridge-cyclopentadienyl zirconium dichloride, diphenylcarbobridge-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilicbridge-tetramethylcyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilicyclobridge-3-pyrrolylindanyl-tert-butylamino-monomethyl titanium, pentamethylcyclopentadienyl- (2-phenyl) -mono-phenoxy) -titanium pentacyclopentadienyl-bis- (2, 6-dichlorophenyl-titanium dichloride; the single-site post-metallocene catalyst can be selected from any one of bis (3-methylsalicylidene-pentafluorophenylimino) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride and [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenimine ] titanium trichloride.
Further, the borate is any one of tri (pentafluorophenyl) boron, N-dioctadecyl methylammonium tetrakis (pentafluorophenyl) borate and N, N-dioctadecyl anilinium tetrakis (pentafluorophenyl) borate; the alkyl aluminum is any one of methyl aluminum oxide, modified methyl aluminum oxide, triisobutyl aluminum, triethyl aluminum and trimethyl aluminum.
Further, the catalyst composition is used in an amount of 0.1 to 100. Mu. Mol per liter of the system solution.
Further, the temperature of the polymerization reaction is 60-300 ℃, the pressure is 0.1-10MPa, and the time is 5-60 min.
Further, the alcoholysis is carried out in a sodium hydroxide/methanol solution at a temperature of 45-48 ℃ for a time of 0.5-3 h. Wherein, the dosage of sodium hydroxide is 12 percent of the molar weight of vinyl acetate, and the mass concentration of sodium hydroxide in the sodium hydroxide/methanol solution is 3 percent.
The invention has the remarkable advantages that:
at present, polyvinyl alcohol is rarely applied to ternary polymerization, and the modification mode of POE is mainly modified by physical blending. Compared with the prior art, the invention introduces the polyvinyl alcohol component into POE for the first time through a chemical synthesis method, and obtains a novel polyvinyl alcohol/ethylene/1-octene terpolymer polymer. The product has the elasticity and the thermoplasticity of rubber due to the physical crosslinking generated by polyolefin branched chains; meanwhile, due to the existence of hydroxyl groups in the chain structure, the free volume among molecular chains is reduced through the strong hydrogen bond action of polyhydroxy groups, the barrier property and solvent resistance of the material are improved, and the components are synthesized in a copolymerization mode, so that the composition is stable, the performance is excellent, and the problem of phase separation does not occur.
Detailed Description
A process for preparing the ternary copolymer of polyvinyl alcohol/ethylene/1-octene includes such steps as polymerizing the reactants including vinyl acetate, ethylene and 1-octene in inertial solvent under catalysis of catalyst composition, and alcoholysis.
Wherein the inert solvent is a linear alkane, isoparaffin, cycloalkane or aralkane having 4-10 carbon atoms.
The catalyst composition consists of a single-site metallocene catalyst or a post-metallocene catalyst serving as a main catalyst and borate or aluminum alkyl serving as a cocatalyst according to a molar ratio of 1:50-10000, and the dosage of the catalyst composition is converted by adding 0.1-100 mu mol per liter of system solution. The single site metallocene catalyst may be selected from any of biscyclopentadienyl hafnium dichloride, bisindenyl zirconium dichloride, ethylenebridge bis indenyl zirconium dichloride, diphenylcarbobridge-cyclopentadienyl-fluorenyl zirconium dichloride, dimethylsilyl-tetramethylcyclopentadienyl-mono-tert-butylamino-dimethyl titanium, bisindenyl zirconium dichloride, bis [2- (3 ',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, biscyclopentadienyl-bisphenoxyzirconium, rac-dimethylsilyl bis (1-indenyl) zirconium dichloride, diphenylcarbobridge-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbobridge-cyclopentadienyl- (2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilyl-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, dimethylsilyl-3-pyrrolyl-tert-butylamino-monomethyl titanium, pentamethyl cyclopentadienyl- (2-phenylphenoxy) -mono-cyclopentadienyl-penta-6-isopropyl titanium dichloride. The single-site post-metallocene catalyst may be selected from any one of bis (3-methylsalicylidene-pentafluorophenylimino) titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride, and [ N- (3, 5-di-tert-butylsalicylidene) -2-diphenylphosphinophenimine ] titanium trichloride. The borate is any one of tri (pentafluorophenyl) boron, N-dioctadecyl methylammonium tetra (pentafluorophenyl) borate and N, N-dioctadecyl anilinium tetra (pentafluorophenyl) borate; the alkyl aluminum is any one of methyl aluminum oxide, modified methyl aluminum oxide, triisobutyl aluminum, triethyl aluminum and trimethyl aluminum.
The polymerization reaction temperature is 60-300 ℃, the pressure is 0.1-10MPa, and the time is 5-60 min.
The alcoholysis is carried out in a sodium hydroxide/methanol solution at a temperature of 45-48 ℃ for a time of 0.5-3 h. Wherein, the dosage of sodium hydroxide is 12 percent of the molar weight of vinyl acetate, and the mass concentration of sodium hydroxide in the sodium hydroxide/methanol solution is 3 percent.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1:
1.88 mg of rac-dimethylsilylbis (1-indenyl) zirconium dichloride was weighed and dissolved in water-removed 10 mL toluene to prepare a main catalyst solution; a toluene solution of methylaluminoxane having a concentration of 0.73, 0.73 g in 10 wt% was prepared as a cocatalyst solution.
The polymerization of vinyl acetate/ethylene/1-octene was carried out in a high pressure stainless steel reactor. Before the reaction, the reaction kettle is connected to an evaluation system, the reaction kettle is heated to 120 ℃ in a sealing way, the nitrogen is pumped for three times, and the vacuum pumping and the pressure maintaining are carried out for overnight. The next day is vacuumized and heated to 120 ℃, filled with nitrogen, and then vacuumized and repeated three times to remove residual water, oxygen and oxygen-containing impurities, thereby ensuring that the air is replaced completely. Then pumping nitrogen by a vacuum pump, filling with ethylene, repeating for three times, and ensuring that the kettle body is full of ethylene. Then the temperature is set to be the reaction temperature of 60 ℃ to naturally reduce the temperature.
Under stirring, 420 ml toluene, 86.09 g vinyl acetate and 112.21 g 1-octene (the mol ratio of the vinyl acetate to the 1-octene is 1:1) are sequentially injected into a charging tank by using an injector, a reaction system is added in a nitrogen pressurization mode, after the temperature is stabilized to be 60 ℃, the prepared main catalyst solution and cocatalyst solution are sequentially injected by using the injector, a charging valve is closed, a pressure reducing valve and a rotating speed are regulated, timing is started after the pressure is increased to be 3MPa, flowmeter data are recorded, after the reaction is carried out for 10 minutes, an air inlet valve is closed, the ethylene pressure is removed, the rotating speed is reduced, a certain amount of 5 ml of 10% HCl/ethanol solution is injected for quenching, and the reaction kettle is cooled to 10 ℃ by a circulating condensation system.
The reactor contents were transferred to a glass vessel containing a sodium hydroxide/methanol solution (wherein the amount of sodium hydroxide was 12% of the molar amount of vinyl acetate, and the mass concentration of sodium hydroxide in the sodium hydroxide/methanol solution was 3%) and subjected to stirring alcoholysis at 45℃for 2 h to obtain a polyvinyl alcohol/ethylene/1-octene terpolymer. And (3) carrying out suction filtration and press drying on the formed polymer precipitate, vacuum drying overnight at 100 ℃ in a vacuum oven, collecting the obtained polymer, and pressing for 5 min at 160 ℃ and 5MPa in a hot press to obtain a test piece of 2 mm, and preparing a tensile and osmotic sample after cooling the test piece, and carrying out performance test, wherein the tensile performance is tested according to GB/T1040-2006, the tensile rate is 50 mm/min for a 5A type sample. Penetration test with reference to GB/T21529-2008 test, sample size 76 mm ×76 mm ×2 mm, medium xylene, test conditions 40 ℃, 50% relative humidity. The data results are shown in Table 1.
Example 2:
the procedure is as in example 1, except that the reaction temperature is 100 ℃. The data results are shown in Table 1.
Example 3:
the difference from example 1 is that the reaction pressure is 5MPa. The data results are shown in Table 1.
Example 4:
the procedure is as in example 1, except that no vinyl acetate is added during the reaction. The data results are shown in Table 1.
Comparative example 1:
POE resin was mixed with polyvinyl alcohol (PVA) and kneaded at 100℃for 15 minutes by a torque rheometer. And cooling and granulating after discharging to obtain blend particles. The polymer sample was pressed in a hot press at 160℃and 5MPa for 5 min to obtain a test piece of 2 mm, and after cooling, a tensile and permeation test piece was prepared for performance testing. The data results are shown in Table 1.
TABLE 1
As is clear from Table 1, the polyvinyl alcohol/ethylene/1-octene terpolymer obtained by the chemical synthesis method has excellent barrier property against nonpolar solvents (xylene) and has good elongation at break, and can be industrially used as a polyolefin elastomer having barrier property.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. A polyvinyl alcohol/ethylene/1-octene terpolymer characterized in that said copolymer comprises units represented by the following formulas 1, 2, 3:
，
wherein the molar ratio of m, n and o is 0.1-500:1:0.1-500.
2. The method for preparing the polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 1, wherein the polyvinyl alcohol/ethylene/1-octene terpolymer is prepared by taking vinyl acetate, ethylene and 1-octene as reactants, polymerizing the reactants in an inert solvent under the catalysis of a catalyst composition, and then conducting alcoholysis.
3. The method for producing a polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 2, wherein the inert solvent is a linear alkane, isoparaffin, cycloalkane or aralkane having 4 to 10 carbon atoms.
4. The method for preparing a polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 2, wherein the catalyst composition consists of a single-site metallocene catalyst or post-metallocene catalyst as a main catalyst and borate or alkylaluminum as a cocatalyst in a molar ratio of 1:50-10000; the dosage is converted by adding 0.1-100 mu mol per liter of system solution.
5. The method for producing a polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 4, wherein said borate is any one of tris (pentafluorophenyl) boron, N-dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, N-dioctadecylammonium tetrakis (pentafluorophenyl) borate; the alkyl aluminum is any one of methyl aluminum oxide, modified methyl aluminum oxide, triisobutyl aluminum, triethyl aluminum and trimethyl aluminum.
6. The method for preparing a polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 2, wherein the polymerization reaction is carried out at a temperature of 60-300 ℃, a pressure of 0.1-10MPa and a time of 5-60 min.
7. The method for producing a polyvinyl alcohol/ethylene/1-octene terpolymer according to claim 2, wherein the alcoholysis is carried out in a sodium hydroxide/methanol solution at a temperature of 45-48 ℃ for a time of 0.5-3 h.
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