CN114133489B - Blow molding material for hollow container, preparation method and application thereof - Google Patents
Blow molding material for hollow container, preparation method and application thereof Download PDFInfo
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- CN114133489B CN114133489B CN202111633754.7A CN202111633754A CN114133489B CN 114133489 B CN114133489 B CN 114133489B CN 202111633754 A CN202111633754 A CN 202111633754A CN 114133489 B CN114133489 B CN 114133489B
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- 238000000071 blow moulding Methods 0.000 title claims abstract description 91
- 239000012778 molding material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000005977 Ethylene Substances 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000000155 melt Substances 0.000 claims abstract description 75
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- -1 polyethylene Polymers 0.000 claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004698 Polyethylene Substances 0.000 claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 claims abstract description 56
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 15
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 17
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 150000002681 magnesium compounds Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- RVHQZJJAIFXDBE-UHFFFAOYSA-N tert-butyl diethyl propan-2-yl silicate Chemical compound C(C)O[Si](OC(C)(C)C)(OC(C)C)OCC RVHQZJJAIFXDBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000012611 container material Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000006353 environmental stress Effects 0.000 abstract description 14
- 238000005336 cracking Methods 0.000 abstract description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000001276 controlling effect Effects 0.000 description 15
- 239000011651 chromium Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 238000011086 high cleaning Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BVNZLSHMOBSFKP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxysilane Chemical compound CC(C)(C)O[SiH3] BVNZLSHMOBSFKP-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000007670 carcinogenicity Effects 0.000 description 2
- 231100000260 carcinogenicity Toxicity 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- JTYIRGULYHOBKS-UHFFFAOYSA-N ditert-butyl dipropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)(C)C)OC(C)(C)C JTYIRGULYHOBKS-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WUMPEOHBANXWLM-UHFFFAOYSA-N tert-butyl cyclohexyl diethyl silicate Chemical compound C(C)O[Si](OC(C)(C)C)(OC1CCCCC1)OCC WUMPEOHBANXWLM-UHFFFAOYSA-N 0.000 description 2
- ZVIVFKZOXGIKPJ-UHFFFAOYSA-N tert-butyl ethyl dipropan-2-yl silicate Chemical compound C(C)O[Si](OC(C)(C)C)(OC(C)C)OC(C)C ZVIVFKZOXGIKPJ-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XNPPQWFAKVLIOW-UHFFFAOYSA-N triethyl propan-2-yl silicate Chemical compound CCO[Si](OCC)(OCC)OC(C)C XNPPQWFAKVLIOW-UHFFFAOYSA-N 0.000 description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- WPJDQSHKILZBTH-UHFFFAOYSA-N CCO[SiH](OCC)OC(C)C Chemical compound CCO[SiH](OCC)OC(C)C WPJDQSHKILZBTH-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ALSOCDGAZNNNME-UHFFFAOYSA-N ethene;hex-1-ene Chemical compound C=C.CCCCC=C ALSOCDGAZNNNME-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- SUNJMSSZSJWXNY-UHFFFAOYSA-N tert-butyl cyclohexyl ethyl propan-2-yl silicate Chemical compound C(C)O[Si](OC1CCCCC1)(OC(C)(C)C)OC(C)C SUNJMSSZSJWXNY-UHFFFAOYSA-N 0.000 description 1
- UPKPRIMTYGRLGL-UHFFFAOYSA-N tert-butyl diethyl phenyl silicate Chemical compound C(C)O[Si](OC(C)(C)C)(OC1=CC=CC=C1)OCC UPKPRIMTYGRLGL-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a blow molding material of a hollow container, a preparation method and application thereof, wherein the preparation method comprises the steps of enabling a first part of ethylene to enter a first reactor, and carrying out a first polymerization reaction in the presence of a titanium catalyst and hydrogen to generate polyethylene with a melt index of 100g/10 min-200 g/10 min; transferring the material in the first reactor to a second reactor, adding monomer raw material containing second part of ethylene into the second reactor, and carrying out second polymerization on the material in the second reactor in the presence of hydrogen to prepare the hollow container blow molding material with the melt index of 1.0g/10 min-2.0 g/10 min. The invention can improve the performances of the blow molding material of the hollow container, such as environmental stress cracking resistance and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a blow molding material for a hollow container, a preparation method and application thereof.
Background
The high-density polyethylene (HDPE) has high density, good balance between rigidity and toughness, excellent chemical corrosion resistance, no moisture absorption, good water resistance and the like, and can be used for producing large container containers, and hollow container products with various volumes such as 200L barrels, automobile oil tanks, fruit milk bottles and the like.
In the conventional polyethylene material production process, chromium (Cr) catalyst is used to catalyze and synthesize small hollow container special material, and because the resin produced by catalytic synthesis contains a certain amount of components with relatively high molecular weight, the processing requirement and mechanical property requirement of the small hollow container can be met to a certain extent, for example, patent document CN103554631a discloses a small hollow container blow molding material and a preparation method thereof, in which raw materials ethylene and 1-hexene are placed in a reaction container in a circulating state all the time as a diluent, and an activated catalyst is added, the reaction temperature in the reaction container is regulated to 99-101 ℃, and the melt flow rate of the reaction product is regulated to 0.45-0.55 g/10min and the density is regulated to 0.953-0.955 kg/m 3 When the method is used, the ethylene-hexene copolymerized polyethylene base resin is prepared, the base resin, an antioxidant and an auxiliary antioxidant are uniformly mixed, and then the mixture is added into a mixer to extrude particles into cooling water, so that the corrosion-resistant small hollow blow molding material of a granular polyethylene product is obtained, and the catalyst is 969MPI-788-RCP3, which belongs to Cr catalysts. However, the Cr-based catalyst has low activity, which results in low synthesis efficiency and high ash content in the final product, and the Cr-based catalyst has strong toxicity and carcinogenicity, so that the prepared small hollow container is difficult to meet the requirements of food, medicine and high-cleanliness chemical products.
In addition, a process for synthesizing polyolefin materials by using titanium (Ti) series catalysts is adopted, the activity of the Ti series catalysts is higher than that of Cr series catalysts, so that catalyst components in the polymeric materials are reduced, the polymeric materials are cleaner, the Ti series catalysts have no harmful properties such as carcinogenicity and the like of the Cr series catalysts, and the prepared polymeric materials can be applied to aspects such as food packaging, and the like, therefore, the Ti series catalytic synthesis process adopting the Ti series catalysts gradually becomes a development trend of synthesizing polyolefin materials, for example, patent document CN103113499A discloses a wide-distribution polyolefin catalyst and a preparation method and application thereof, the catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst consists of a carrier, a transition metal halide, an organic alcohol compound and a siloxane electron donor, the transition metal halide is generated by reacting with silicon halide in the preparation process of the catalyst, and the catalyst belongs to the Ti series catalysts for ethylene polymerization or copolymerization of ethylene and a comonomer to prepare the wide-distribution polyolefin materials.
Although researches and reports on polyethylene materials and preparation methods thereof are presented at present, the polyethylene materials have higher requirements on performances such as environmental stress cracking resistance of the polyethylene materials as hollow container blow molding materials, the preparation process of the hollow container blow molding materials is optimized, and performances such as environmental stress cracking resistance of the hollow container blow molding materials are improved, so that the polyethylene materials are still an important subject faced by the technicians in the field.
Disclosure of Invention
The invention provides a hollow container blow molding material, a preparation method and application thereof, which can improve the performances of the hollow container blow molding material such as environmental stress cracking resistance and the like.
In one aspect of the present invention, there is provided a method of preparing a blow molding material for a hollow container, comprising: feeding a first part of ethylene into a first reactor, and carrying out a first polymerization reaction in the presence of a titanium catalyst and hydrogen to generate polyethylene with a melt index of 100g/10 min-200 g/10 min; wherein the melt index of the polyethylene is the melt mass flow rate of the polyethylene measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 2.16kg load; then transferring the materials in the first reactor to a second reactor, adding monomer raw materials containing a second part of ethylene into the second reactor, and carrying out second polymerization on the materials in the second reactor in the presence of hydrogen to prepare a hollow container blow molding material with a melt index of 1.0g/10 min-2.0 g/10 min; wherein the melt index of the hollow container blow molding material refers to the melt mass flow rate of the hollow container blow molding material measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 5kg load.
According to an embodiment of the present invention, the ratio of the weight average molecular weight to the number average molecular weight of the hollow container blow molding material is 8 to 15; and/or the hollow container blow molding material has a density of 0.950g/cm 3 ～0.955g/cm 3 。
According to an embodiment of the present invention, the mass of the first portion of ethylene is 45% to 55% of the sum of the mass of the first portion of ethylene and the mass of the second portion of ethylene.
According to an embodiment of the invention, the monomer feed further comprises butene.
According to an embodiment of the present invention, the conditions of the first polymerization reaction are: the temperature is 75-87 ℃ and the pressure is 0.2-0.5 MPa; and/or, the conditions of the second polymerization reaction are: the temperature is 75-87 ℃ and the pressure is 0.05-0.3 MPa.
According to one embodiment of the invention, the titanium-based catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is compounded by a magnesium compound, fatty alcohol, an organosilicon compound and titanium halide, and the organosilicon compound comprises tetraalkoxysilane with the following structure of formula 1:
wherein R is 2 、R 3 、R 4 、R 5 Each independently selected from C 1 -C 15 Alkyl, C of (2) 3 -C 20 Cycloalkyl or C of (C) 6 -C 30 Aryl of (a);
the cocatalyst comprises a catalyst of the formula AlR' n X 3-n An organoaluminum compound of the formula (I), wherein R' is hydrogen or C 1 ～C 20 X is halogen, 1<n≤3。
According to an embodiment of the present invention, the mass of the organosilicon compound is 1% to 20% of the mass of the main catalyst; and/or the cocatalyst comprises triethylaluminum (AlEt) 3 ) Triisobutylaluminum (Al (iso-Bu) 3 ) Tri-n-hexylaluminum (Al (n)-C 6 H 13 ) 3 ) Tri-n-octyl aluminum (Al (n-C) 8 H 17 ) 3 ) Diethylaluminum chloride (AlEt) 2 Cl).
According to an embodiment of the invention, the molar ratio of the cocatalyst to the titanium in the procatalyst is (1-500): 1.
in another aspect of the present invention, there is provided a blow molding material for hollow containers, prepared according to the above-described preparation method.
In still another aspect of the present invention, there is provided a method for preparing a hollow container, comprising: blow molding the hollow container into a hollow container by adopting the blow molding material of the hollow container; alternatively, a hollow container blow molding material is produced according to the above production method, and the produced hollow container blow molding material is blow molded to form a hollow container.
In the invention, the titanium catalyst is adopted, and a double-reactor (namely a first reactor and a second reactor) serial process is adopted, so that not only can the blow molding material suitable for blow molding to form a hollow container be prepared, but also the quality of the blow molding material such as environmental stress cracking resistance, mechanical property and the like can be obviously improved, and researches show that the tensile yield strength of the blow molding material is more than 25MPa, the flexural modulus is more than 1000MPa, and the impact strength of a simply supported beam is more than 10kJ/m 2 The melt strength is not less than 22cN, and the environmental stress cracking resistance test result is not less than 168 hours; meanwhile, the titanium catalyst is adopted, so that the method has the advantages of good reaction efficiency, low catalyst toxicity, low consumption, capability of meeting the high cleaning requirement of hollow container products, application to aspects of electronic-grade hollow containers with high cleaning requirement, high-cleaning chemical products, foods, medicines and the like, and the hollow container blow molding material prepared by the method also has the advantages of high cleaning degree, wide application range and the like, and in addition, the method also has the advantages of simple preparation process, mild reaction conditions, low energy consumption and the like, and has important significance for practical industrialized application.
Detailed Description
The present invention will be described in further detail below for the purpose of better understanding of the aspects of the present invention by those skilled in the art. The following detailed description is merely illustrative of the principles and features of the present invention, and examples are set forth for the purpose of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the examples of the invention without making any inventive effort, are intended to be within the scope of the invention. In the description of the present invention, the terms "first", "second", etc. are used for descriptive purposes only, for example to distinguish between components, in order to more clearly illustrate/explain the technical solution, and are not to be understood as indicating or implying a quantity of technical features indicated or an order of substantial significance, etc.
The preparation method of the blow molding material for the hollow container provided by the invention comprises the following steps: feeding a first part of ethylene into a first reactor, and carrying out a first polymerization reaction in the presence of a titanium catalyst and hydrogen to generate polyethylene with a melt index of 100g/10 min-200 g/10 min; wherein, the melt index of the polyethylene refers to the melt mass flow rate of the polyethylene measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 2.16kg load; transferring the material in the first reactor to a second reactor, and adding monomer feed comprising a second portion of ethylene to the second reactor; carrying out a second polymerization reaction on the materials in the second reactor in the presence of hydrogen to prepare a hollow container blow molding material with a melt index of 1.0g/10 min-2.0 g/10 min; wherein, the melt index of the hollow container blow molding material refers to the melt mass flow rate of the hollow container blow molding material measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 5kg load.
Illustratively, the polyethylene produced in the first reactor has a melt index in the range of 100g/10min, 110g/10min, 120g/10min, 130g/10min, 140g/10min, 150g/10min, 160g/10min, 170g/10min, 180g/10min, 190g/10min, 200g/10min, or any two thereof; the blow molded material of the hollow container has a melt index in the range of 1.0g/10min, 1.1g/10min, 1.2g/10min, 1.3g/10min, 1.4g/10min, 1.5g/10min, 1.6g/10min, 1.7g/10min, 1.8g/10min, 1.9g/10min, 2.0g/10min, or any two thereof.
Specifically, in the first reactor, after the first polymerization reaction, a first portion of ethylene generates polyethylene (referred to as a first polymer) having a melt index of 100g/10min to 200g/10min, and at the same time, the titanium-based catalyst may be partially deactivated, whereby the materials in the first reactor are all transferred to the second reactor in the presence of polyethylene generated by the reaction, ethylene which may be unreacted, and the non-deactivated titanium-based catalyst and the partially deactivated titanium-based catalyst which may be present, and the monomers in the second reactor are subjected to a second polymerization reaction in the presence of the titanium-based catalyst from the first reactor, and the generated second polymer is compounded with the first polymer from the first reactor, thereby producing the hollow container blow-molded material.
In general, the first polymer produced in the first reactor is in the form of particles (denoted as first polymer particles) which, following the entry of the material in the first reactor into the second reactor, adhere to the surface of the first polymer particles, forming a hollow container blow-molded material in the form of particles. Through the preparation process, the first polymer and the second polymer with different melt indexes are compounded from the molecular level, so that each particle basically contains the first polymer and the second polymer existing on the surface of the first polymer, the first polymer and the second polymer are dispersed more uniformly, and the second polymer coats the first polymer, thereby improving the quality of the blow molding material, such as environmental stress cracking resistance, mechanical property and the like, and being used as a special material for blow molding polyethylene of hollow containers, in particular a special material for blow molding polyethylene of small hollow containers.
In general, the first polymer produced in the first reactor may be controlled to be 48% to 52% of the mass of the hollow container blow molded material produced, and the second polymer produced in the second reactor may be controlled to be 48% to 52% of the mass of the hollow container blow molded material produced, wherein the sum of the mass percent of the first polymer and the mass percent of the second polymer is substantially 100% of the hollow container blow molded material. In the concrete implementation, the mass percentage of the first polymer and the second polymer in the prepared hollow blow molding material can be controlled by regulating and controlling the conditions of the dosage of the first part of ethylene, the dosage of the second part of ethylene and the like.
In some preferred embodiments, the mass of the first portion of ethylene is in the range of 45% to 55%, e.g., 45%, 48%, 50%, 52%, 55% or any two thereof, of the sum of the masses of the first portion of ethylene and the second portion of ethylene, and correspondingly, the mass of the second portion of ethylene is in the range of 45% to 55%, e.g., 45%, 48%, 50%, 52%, 55% or any two thereof, of the sum of the masses of the first portion of ethylene and the second portion of ethylene.
In the specific implementation, the first part of ethylene in the first reactor can be reacted as completely as possible and then enter the second reactor, and the monomer in the second reactor is discharged after being reacted as completely as possible, so that the hollow container blow molding material is obtained through further purification. The invention can detect the polymerization reaction degree of ethylene and other monomers by a conventional method in the field, and is not particularly limited and will not be repeated.
In addition, the material in the first reactor is in the form of a mixture of solids, liquids (such as polymerization medium) and gases, wherein the solids are mainly solid particles such as the first polymer and titanium catalyst formed, and in some embodiments, the solid content (by mass) in the material in the first reactor can be detected, and the material can be generally introduced into the second reactor when the solid content reaches 20% -50%.
In the invention, other small molecular olefins can be introduced into the preparation system as comonomers, and the comonomers comprise butylene, so that the properties of the prepared hollow container blow molding material, such as density, and the like, can be regulated and controlled, and the service performance of the hollow container blow molding material can be further optimized. Furthermore, the comonomer may in particular be added in the second reactor, for example as monomer feed together with a second portion of ethylene. In some preferred embodiments, the above monomer feed further comprises butene, which may specifically consist of a second portion of ethylene and butene; wherein the butene may comprise 1-butene, and the mass of butene may be in the range of 0.01% to 0.30%, such as 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, or any two of these, of the sum of the masses of the first portion of ethylene and the second portion of ethylene.
In some embodiments, the hollow container blow molding material produced may have a density of 0.950g/cm 3 ～0.955g/cm 3 For example 0.950g/cm 3 、0.951g/cm 3 、0.952g/cm 3 、0.953g/cm 3 、0.954g/cm 3 、0.955g/cm 3 Or a range of any two of these.
In the invention, the first polymerization reaction and the second polymerization reaction are respectively carried out in the presence of hydrogen, and in general, the larger the addition amount of hydrogen in a reactor (namely the larger the partial pressure of hydrogen), the larger the melt index of the polymer such as the synthesized polyethylene and the like, and the partial pressure of hydrogen in the first reactor is larger than that in the second reactor, so that the first polymer is polymerized under the condition of larger partial pressure of hydrogen through the first reactor, and then the second polymer is polymerized under the condition of smaller partial pressure of hydrogen through the second reactor, thereby preparing the hollow container blow molding material containing the first polymer and the second polymer.
In the present invention, the amount of hydrogen to be added (hydrogen partial pressure) in the first reactor and the second reactor is not particularly limited, as long as the above-mentioned polymers having the respective melt indexes can be synthesized. In specific implementation, the polymer with the corresponding melt index can be synthesized by controlling the conditions such as the addition amount of hydrogen (hydrogen partial pressure) in each reactor, for example, the melt index of the polymer generated by each reactor can be detected, and the conditions such as the hydrogen partial pressure in the reactor can be adjusted according to the detection result so as to meet the polymer with the required melt index.
Further, by the above-described preparation process, the hollow container blow molding material is produced with a wide molecular weight distribution, and in some embodiments, the hollow container blow molding material has a molecular weight distribution width (i.e., a ratio of weight average molecular weight to number average molecular weight) in the range of 8 to 15, such as 8, 9, 10, 11, 12, 13, 14, 15, or any two of them. In the concrete implementation, the blow molding material of the hollow container with wide molecular weight distribution can be obtained by regulating and controlling the conditions such as the hydrogen content in each reactor.
In some embodiments, the conditions of the first polymerization reaction are: the temperature is 75-87 ℃ (i.e. the temperature of the first reactor is 75-87 ℃), such as 75 ℃, 77 ℃, 80 ℃, 82 ℃, 85 ℃, 87 ℃ or any two of them, the pressure is 0.2-0.5 MPa (i.e. the pressure of the first reactor is 0.2-0.5 MPa), such as 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.42MPa, 0.45MPa, 0.48MPa, 0.5MPa or any two of them, the reaction conditions are mild, the energy consumption is low, and the performances such as the environmental stress cracking resistance of the produced hollow container blow molding material can be further optimized.
In some embodiments, the conditions of the second polymerization reaction are: the temperature is 75-87 ℃ (i.e. the temperature of the second reactor is 75-87 ℃), such as 75 ℃, 77 ℃, 80 ℃, 82 ℃, 85 ℃, 87 ℃ or any two of them, the pressure is 0.05-0.5 MPa (i.e. the pressure of the second reactor is 0.15-0.5 MPa), such as 0.05MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa, 0.5MPa or any two of them, the reaction conditions are mild, the energy consumption is low, and the performances such as the environmental stress cracking resistance of the produced hollow container blow molding material can be further optimized.
The titanium-based catalyst used in the present invention may be a widely distributed polyolefin catalyst disclosed in chinese patent document CN103113499a or a catalyst prepared according to the preparation method of the catalyst disclosed therein. According to the research of the invention, by adopting the titanium catalyst and combining the slurry method double-reactor serial polymerization process of the invention, the blow molding material suitable for the hollow container can be prepared, and the performances of the prepared blow molding material such as environmental stress cracking resistance and the like can be improved.
In some preferred embodiments, the titanium-based catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is compounded from a magnesium compound, a fatty alcohol, an organosilicon compound, and a titanium halide, and the organosilicon compound comprises a tetraalkoxysilane having a structure of the following formula 1:
wherein R is 2 、R 3 、R 4 、R 5 Each independently selected from C 1 -C 15 Alkyl, C of (2) 3 -C 20 Cycloalkyl or C of (C) 6 -C 30 Aryl radicals R of (2) 2 、R 3 、R 4 、R 5 May be the same or different, for example, three of which are the same, or two of which are the same, or four of which are all different from each other.
Illustratively C 1 -C 15 The number of carbons (C) of the alkyl group of (a) may be 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or any two thereof; c (C) 3 -C 20 The number of carbons of the cycloalkyl group of (C) may be 3, 6, 8, 10, 12, 15, 18, 20 or any two thereof, C 6 -C 30 The number of carbons of the aryl group of (a) may be 6, 12, 15, 18, 20, 24, 30 or any two thereof. In some embodiments, the organosilicon compound comprises one or more of triethoxy isopropoxysilane, diethoxy isopropoxysilane, triisopropoxy tert-butoxy silane, diisopropoxy di-tert-butoxy silane, diethoxy cyclohexyloxy tert-butoxy silane, diethoxy phenoxy tert-butoxy silane, monoethoxy diisopropyl oxy tert-butoxy silane, or ethoxy isopropoxy tert-butoxy cyclohexyloxy silane. At least one of triethoxy isopropoxy silane, diethoxy isopropoxy tert-butoxy silane, triisopropoxy tert-butoxy silane, diisopropoxy di-tert-butoxy silane, diethoxy cyclohexyloxy tert-butoxy silane or monoethoxy diisopropyloxy tert-butoxy silane is preferred.
The addition of the above-described organosilicon compounds facilitates the catalytic synthesis of blow molding materials having a broad molecular weight distribution, and in some embodiments the organosilicon compounds are present in an amount ranging from 1% to 20% by mass, such as 1%, 3%, 5%, 7%, 10%, 12%, 15%, 18%, 20% by mass, or any two of these compositions of the procatalyst.
The fatty alcohol may include a fatty alcohol having R at the same time 1 Alcohols of OH, R 1 Is C 1 -C 20 Examples of the alkyl group include methyl, ethyl, propyl, butyl and octyl. In some embodiments, the fatty alcohol comprises at least one of methanol, ethanol, n-propanol, glycerol, n-butanol, isooctanol. In addition, the magnesium compound may include magnesium chloride and/or magnesium ethoxide, and the titanium halide includes titanium tetrachloride.
Specifically, the procatalyst may be prepared according to a process comprising the steps of: mixing a magnesium compound, fatty alcohol and a solvent, adding an organic silicon compound into the mixture, stirring the mixture for 1 to 5 hours at a temperature of between 50 and 150 ℃, adding titanium halide into the mixture, maintaining the stirring at the temperature of between 10 and 150 ℃ for 1 to 4 hours, filtering the mixture, and drying the obtained solid product to obtain the main catalyst.
In the specific implementation, the magnesium compound is firstly dispersed in a solvent, the fatty alcohol is added, the solution is maintained at 50-150 ℃ until the magnesium compound is completely dissolved (the maintaining time can be generally 1-6 h), then the organosilicon compound is added into the solution under the condition of maintaining the system temperature at 50-150 ℃, the solution is stirred for 1-4 h, then the titanium halide is slowly added into the solution under the condition of maintaining the system temperature at 10-150 ℃ and stirring (for example, the solution containing the titanium halide is dropwise added into the system), the adding time of the titanium halide can be generally controlled to be 1-5 h, the reaction is continuously maintained at 10-150 ℃ under the stirring condition for 1-4 h after the adding is finished, the reaction is stopped, the solution is kept for precipitation after the filtering, and the obtained solid product is dried to obtain the main catalyst. Among them, the solvent used includes an organic solvent including, for example, at least one of toluene, cyclohexane, chlorocyclohexane, chlorobenzene and n-hexane, preferably toluene.
In addition, the above-mentioned cocatalysts include those of the formula AlR' n X 3-n In the general formula, R' is hydrogen or C 1 ～C 20 X is halogen, 1<n is less than or equal to 3. Wherein X is, for example, chlorine (Cl), R' is, for example, C 2 ～C 10 Alkyl or C of (2) 2 ～C 8 Is a hydrocarbon group. In some embodiments, the cocatalyst comprises triethylaluminum (AlEt) 3 ) Triisobutylaluminum (Al (iso-Bu) 3 ) Tri-n-hexylaluminum (Al (n-C) 6 H 13 ) 3 ) Tri-n-octyl aluminum (Al (n-C) 8 H 17 ) 3 ) Diethylaluminum chloride (AlEt) 2 Cl).
In some embodiments, the molar ratio of promoter to titanium in the procatalyst is (1-500): 1, for example 1: 1.5: 1. 10: 1. 30: 1. 50: 1. 100: 1. 150: 1. 200: 1. 250: 1. 300: 1. 350: 1. 400: 1. 450: 1. 500:1 or any two ratios thereof.
In addition, in the above-mentioned first reactor and second reactor, a polymerization medium including hexane, for example, may be added.
In the present invention, a continuous reaction apparatus comprising a first reactor and a second reactor connected in series may be generally used to continuously produce a blow molded material in a hollow container by converting the first polymerization reaction and the second polymerization reaction into continuous reactions. In the specific implementation, the main catalyst and the cocatalyst can be added into a first reactor, then a first part of ethylene and hydrogen are added into the first reactor to perform a first polymerization reaction, the materials in the first reactor flow into a second reactor, meanwhile, the monomer raw materials and the hydrogen are added into the second reactor to perform a second polymerization reaction, the output product of the second reactor is dried, mediums such as hexane are removed, and the residual catalyst is removed in the modes such as steam decomposition, so that the hollow container blow molding material is obtained.
The hollow container blow molding material provided by the invention is prepared according to the preparation method, specifically, the hollow container blow molding material is in a particle (or granule) shape, and comprises a first polymer and a second polymer existing on the surface of the first polymer, wherein the mass content of the first polymer can be 48% -52%, and the balance is the second polymer.
According to a study of the present invention, the hollow container blow molding material has the following characteristics: the melt index is 1.0g/10 min-2.0 g/10min, the ratio of weight average molecular weight to number average molecular weight is 8-15, and the density is 0.950g/cm 3 ～0.955g/cm 3 Tensile yield strength of more than 25MPa and bending dieThe weight of the impact strength is more than 1000MPa, further more than 1100MPa, and the impact strength of the simply supported beam is more than 10kJ/m 2 The melt strength is not less than 22cN, and the environmental stress cracking resistance test result is not less than 168h. The blow molding material for hollow containers has wide molecular weight distribution, good environmental stress cracking resistance, high strength, high modulus and other mechanical properties, and can be used as blow molding material for hollow containers, in particular as blow molding material for small hollow containers with the volume of 1-20 liters.
The preparation method of the hollow container provided by the invention comprises the following steps: blow molding the hollow container into a hollow container by adopting the blow molding material of the hollow container; or preparing the hollow container blow molding material according to the preparation method of the hollow container blow molding material; blow molding the hollow container blow molding material to form a hollow container. The hollow container may include a small hollow container having a volume of 1 to 20 liters, and the volume thereof is, for example, 1 liter, 3 liters, 5 liters, 7 liters, 10 liters, 12 liters, 15 liters, 18 liters, 20 liters, or a range of any two of them.
In the invention, the material performance test process is as follows, unless otherwise specified:
(1) Determining the melt index of the material by referring to the standard GB/T3682-2000;
(2) Determining the density of the material by referring to standard GB/T1033-1986;
(3) Determining environmental stress cracking resistance according to the standard GB/T1842-2008;
(4) Material molecular weight distribution test: using a full-automatic high-temperature gel chromatograph of Spain Polymer char company, wherein the chromatograph is provided with 3 mix-edB chromatographic columns, 5 mg-10 mg of samples are placed in a glass bottle during testing, the testing temperature is set to 160 ℃, the used solvent is 1,2, 4-trichlorobenzene, 0.05% of antioxidant 1010 is added into the 1,2, 4-trichlorobenzene solvent for preventing degradation, and the flow rate is set to 1mL/min during testing;
(5) Tensile property test: measuring tensile property by adopting an electronic universal testing machine of Zwick/Roell instrument technology limited company according to reference standard GB/T1040.2-2006, wherein the tensile speed when measuring tensile yield stress (namely tensile yield strength) of a sample is set to be 50mm/min, the speed when measuring tensile elastic modulus (namely bending modulus) is set to be 1mm/min, the tested sample is ensured to be horizontal with the axis of the machine, and an adjusted digital extensometer is arranged in the middle of the sample and adjusted after pretensioning, so that the deformation and damage generated by the sample are minimized;
(6) Impact performance test: according to the standard GB/T1043.1-2008, a pendulum impact tester produced by ZWICK corporation in Germany is used for testing the impact strength of a material simply supported beam in a constant temperature and humidity environment with the temperature of 26 ℃ and the humidity of 50%, in the testing process, the pendulum is lifted to a specified height, and a sample to be tested is aligned, so that a punching cutter faces to the center of a notch of the sample;
(7) Melt strength test: the device for testing the melt strength comprises a single screw extruder and a melt strength testing unit, wherein a material melt is extruded from the extruder at 200 ℃ to obtain a melt bundle (spline), the melt bundle is pulled by two rollers which are arranged on a balance beam and have opposite movement directions, the rollers uniformly accelerate to move until the melt bundle breaks, and the force applied when the melt bundle breaks is defined as the melt strength and is expressed as centinewton (cN).
For the purpose of promoting an understanding of the principles of the invention, reference will now be made in detail to specific examples, some but not all of which are illustrated in the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, the main catalyst used was prepared according to the method of preparing the main catalyst in example 1 of chinese patent document CN103113499a, and the cocatalyst was triethylaluminum. In the following examples and comparative examples 3 to 6, hexane was used as a polymerization medium.
In the following examples and comparative examples, the melt index of the polyethylene produced in the first reactor refers to the melt mass flow rate of the polyethylene measured at 190℃under a load of 2.16kg according to the GB/T3682-2000 standard, and the melt index of the hollow container blow molded material produced in the second reactor refers to the melt mass flow rate of the hollow container blow molded material measured at 190℃under a load of 5kg according to the GB/T3682-2000 standard, unless otherwise specified.
Example 1
In this example, a twin reactor series continuous reactor unit was used, with 50wt% of each of the first and second portions of ethylene based on the total mass of the first and second portions of ethylene, and the hollow container blow molding material was prepared as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 84 ℃ and 0.48MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 100g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 84 ℃ and 0.48MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.0g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.0g/10 min.
Example 2
In this example, a continuous reaction apparatus with two reactors in series was used, the first portion of ethylene accounting for 45wt% and the second portion of ethylene accounting for 55wt% based on the total mass of the first portion of ethylene and the second portion of ethylene, and the process for preparing the blow molding material for the hollow container was as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 84 ℃ and 0.47MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 130g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 84 ℃ and 0.22MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.2g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.2g/10 min.
Example 3
In this example, a twin reactor series continuous reactor unit was used, based on the total mass of the first portion of ethylene and the second portion of ethylene, the first portion of ethylene was 48wt%, the second portion of ethylene was 52wt%, and the hollow container blow molding material was prepared as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 84 ℃ and 0.45MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 170g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 84 ℃ and 0.22MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.9g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.9g/10 min.
Example 4
In this example, a twin reactor series continuous reactor unit was used, with 50wt% of each of the first and second portions of ethylene based on the total mass of the first and second portions of ethylene, and the hollow container blow molding material was prepared as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 84 ℃ and 0.48MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 190g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 84 ℃ and 0.22MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.5g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.5g/10 min.
Example 5
In this example, a twin reactor series continuous reactor unit was used, with 50wt% of each of the first and second portions of ethylene based on the total mass of the first and second portions of ethylene, and the hollow container blow molding material was prepared as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 80 ℃ and 0.46MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 160g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 85 ℃ and 0.18MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.1g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.1g/10 min.
Example 6
In this example, a twin reactor series continuous reactor unit was used, based on the total mass of the first portion of ethylene and the second portion of ethylene, the first portion of ethylene was 55wt%, the second portion of ethylene was 45wt%, and the hollow container blow molding material was prepared as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 82 ℃ and 0.45MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 160g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 80 ℃ and 0.25MPa, and the addition amount of the hydrogen is controlled, so that a hollow container blow molding material with the melt index of 1.5g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the blow molding material of the hollow container with the melt index of 1.5g/10 min.
Comparative example 1
A Cr-based catalyst and a promoter are used, wherein the carrier of the Cr-based catalyst is porous silica gel, the average particle diameter of the porous silica gel is 40Um, and the bulk density is 0.26g/cm 3 The catalyst activation temperature is 600 ℃; the catalyst promoter is triethylaluminum, and the dosages of the Cr catalyst and the catalyst promoter are as follows: in the catalyst composed of the two, the molar ratio of aluminum to chromium is 1.5:1;
a gas-phase fluidized bed device of a single reactor is adopted, the reaction pressure in the gas-phase fluidized bed is 2.0MPa, the ethylene partial pressure is 1.0MPa, the reaction temperature is 95 ℃, hydrogen is added at the same time, and the molecular weight of the synthesized polyethylene is regulated by controlling the addition amount of the hydrogen; in the polymerization process, hexene and ethylene are used as synthetic monomers, and the molar ratio of hexene to ethylene is controlled to be 0.003:1 for regulating and controlling the density of polyethylene; after the polymerization reaction was completed, the catalyst remained in the polyethylene product outputted from the reactor was removed by steam decomposition to obtain a polyethylene material having a melt index of 1.5g/10min, which is a melt mass flow rate of the polyethylene material measured at 190℃under a load of 5kg according to GB/T3682-2000 standard.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that: (1) The catalyst used was one in which the amounts of Cr-based catalyst and cocatalyst were as follows: the molar ratio of aluminum to chromium is 1.5:1;
(2) Butene is adopted to replace hexene (namely, butene and ethylene are adopted as synthetic monomers), and the molar ratio of butene to ethylene is 0.005:1;
(3) Removing the catalyst remained in the polyethylene product output by the reactor through steam decomposition after the polymerization reaction is completed to prepare a polyethylene material with a melt index of 1.1g/10min, wherein the melt index refers to the mass flow rate of the polyethylene material measured according to GB/T3682-2000 standard under the conditions of 190 ℃ and 5kg load;
the remaining conditions were the same as in comparative example 1.
Comparative example 3
An RZ titanium-based catalyst available from Mitsui chemical Co., ltd. In Japan was used as a main catalyst, and a cocatalyst was the same as in example 1;
the continuous reaction device with double reactors connected in series is adopted, the weight of the first part of ethylene and the weight of the second part of ethylene are respectively 50 percent based on the total weight of the first part of ethylene and the second part of ethylene, and the preparation process of the polyethylene material is as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 85 ℃ and 0.46MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 110g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 85 ℃ and 0.18MPa, and the addition amount of the hydrogen is controlled, so that a polyethylene material with a melt index of 1.5g/10min is prepared; and drying the material output from the second reactor, removing impurities such as hexane and the like, and decomposing with steam to remove residual catalyst, thereby obtaining the polyethylene material with the melt index of 1.5g/10 min.
Comparative example 4
The same catalyst promoter as in example 1 was used as the main catalyst using a PZ titanium-based catalyst available from Mitsui chemical Co., ltd;
the continuous reaction device with double reactors connected in series is adopted, the weight of the first part of ethylene and the weight of the second part of ethylene are respectively 50 percent based on the total weight of the first part of ethylene and the second part of ethylene, and the preparation process of the polyethylene material is as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 85 ℃ and 0.46MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 115g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 85 ℃ and 0.18MPa, and the addition amount of the hydrogen is controlled, so that a polyethylene material with the melt index of 1.7g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the polyethylene material with the melt index of 1.7g/10 min.
Comparative example 5
The catalyst was prepared by using a BCH titanium catalyst obtained from medium petrifaction as a main catalyst, and a cocatalyst was the same as in example 1;
the continuous reaction device with double reactors connected in series is adopted, the weight of the first part of ethylene and the weight of the second part of ethylene are respectively 50 percent based on the total weight of the first part of ethylene and the second part of ethylene, and the preparation process of the polyethylene material is as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 85 ℃ and 0.46MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 165g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 85 ℃ and 0.18MPa, and the addition amount of the hydrogen is controlled, so that a polyethylene material with a melt index of 1.7g/10min is prepared; wherein, the material output from the second reactor is dried to remove impurities such as hexane and the like, and the residual catalyst is removed by vapor decomposition, thus obtaining the polyethylene material with the melt index of 1.7g/10 min.
Comparative example 6
The catalyst was prepared in the same manner as in example 1 using a BCE titanium catalyst from medium petrifaction as the main catalyst;
the continuous reaction device with double reactors connected in series is adopted, the weight of the first part of ethylene and the weight of the second part of ethylene are respectively 50 percent based on the total weight of the first part of ethylene and the second part of ethylene, and the preparation process of the polyethylene material is as follows: adding a main catalyst and a cocatalyst into a first reactor, adding a first part of ethylene and hydrogen into the first reactor, performing a first polymerization reaction at 85 ℃ and 0.46MPa, and controlling the addition amount of the hydrogen to generate polyethylene with a melt index of 118g/10 min; the materials in the first reactor flow into a second reactor, and simultaneously, monomer raw materials consisting of a second part of ethylene and a small amount of 1-butene and hydrogen are added into the second reactor, and a second polymerization reaction is carried out under the conditions of 85 ℃ and 0.18MPa, and the addition amount of the hydrogen is controlled, so that a polyethylene material with a melt index of 1.2g/10min is prepared; and drying the material output from the second reactor, removing impurities such as hexane and the like, and decomposing with steam to remove residual catalyst, thereby obtaining the polyethylene material with the melt index of 1.2g/10 min.
The blow molding materials for hollow containers, the polyethylene materials for comparative examples were measured for density, molecular weight distribution width tensile yield strength DP, flexural modulus, impact strength of the simply supported beams, and environmental stress crack resistance, as shown in table 1.
Table 1 results of the Material Performance test made in each example and comparative example
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method of making a blow molded material for a hollow container comprising:
feeding a first part of ethylene into a first reactor, and carrying out a first polymerization reaction in the presence of a titanium catalyst and hydrogen to generate polyethylene with a melt index of 100g/10 min-200 g/10 min; wherein the melt index of the polyethylene is the melt mass flow rate of the polyethylene measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 2.16kg load;
then transferring the materials in the first reactor to a second reactor, adding monomer raw materials containing a second part of ethylene into the second reactor, and carrying out second polymerization on the materials in the second reactor in the presence of hydrogen to prepare a hollow container blow molding material with a melt index of 1.0g/10 min-2.0 g/10 min; wherein the melt index of the hollow container blow molding material refers to the melt mass flow rate of the hollow container blow molding material measured according to GB/T3682-2000 standard under the conditions of 190 ℃ +/-1 ℃ and 5kg load;
the ratio of the weight average molecular weight to the number average molecular weight of the blow molding material of the hollow container is 8-15;
the density of the blow molding material of the hollow container is 0.950g/cm 3 ～0.955g/cm 3 ；
The pressure of the first polymerization reaction is 0.2MPa to 0.5MPa;
the titanium-based catalyst comprises a main catalyst and a cocatalyst, wherein,
the main catalyst is formed by compounding a magnesium compound, fatty alcohol, an organosilicon compound and titanium halide, wherein the organosilicon compound comprises diethoxy isopropoxy tert-butoxy silane;
the cocatalyst comprises a catalyst of the formula AlR' n X 3-n An organoaluminum compound of the formula (I), wherein R' is hydrogen or C 1 ～C 20 X is halogen, 1<n≤3；
The mass of the organosilicon compound is 1-20% of the mass of the main catalyst;
the molar ratio of the cocatalyst to the titanium in the main catalyst is (1-500): 1.
2. the method of claim 1, wherein the cocatalyst comprises at least one of triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethylaluminum chloride.
3. The process according to claim 1 or 2, wherein the mass of the first portion of ethylene is 45% to 55% of the sum of the mass of the first portion of ethylene and the mass of the second portion of ethylene.
4. A process according to any one of claims 1 to 3, wherein the monomer feed further comprises butene.
5. The method according to claim 1, wherein,
the conditions of the first polymerization reaction are as follows: the temperature is 75-87 ℃; and/or the number of the groups of groups,
the conditions of the second polymerization reaction are as follows: the temperature is 75-87 ℃ and the pressure is 0.05-0.3 MPa.
6. A blow molded hollow container material produced according to the production method of any one of claims 1 to 5.
7. A method of making a hollow container comprising:
blow molding a hollow container using the hollow container blow molding material of claim 6; or,
a hollow container blow molded material produced according to the production method of any one of claims 1 to 5; blow molding the hollow container blow molding material to form a hollow container.
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| CN202111633754.7A CN114133489B (en) | 2021-12-28 | 2021-12-28 | Blow molding material for hollow container, preparation method and application thereof |
| PCT/CN2022/136460 WO2023124790A1 (en) | 2021-12-28 | 2022-12-05 | Hollow container blow molding material, and preparation method therefor and use thereof |
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