CN115304699A - Special resin for PPR (polypropylene random copolymer) pipe and preparation method thereof - Google Patents
Special resin for PPR (polypropylene random copolymer) pipe and preparation method thereof Download PDFInfo
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- CN115304699A CN115304699A CN202110492773.6A CN202110492773A CN115304699A CN 115304699 A CN115304699 A CN 115304699A CN 202110492773 A CN202110492773 A CN 202110492773A CN 115304699 A CN115304699 A CN 115304699A
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- Prior art keywords
- resin
- compound
- special
- ppr pipe
- antioxidant
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- 239000011347 resin Substances 0.000 title claims abstract description 108
- 229920005989 resin Polymers 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920005630 polypropylene random copolymer Polymers 0.000 title description 6
- -1 polypropylene Polymers 0.000 claims abstract description 166
- 239000004743 Polypropylene Substances 0.000 claims abstract description 114
- 229920001155 polypropylene Polymers 0.000 claims abstract description 114
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 56
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 56
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005977 Ethylene Substances 0.000 claims abstract description 28
- 239000000155 melt Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 79
- 238000010438 heat treatment Methods 0.000 claims description 60
- 239000011777 magnesium Substances 0.000 claims description 54
- 229910052749 magnesium Inorganic materials 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 30
- 150000003609 titanium compounds Chemical class 0.000 claims description 30
- 150000003682 vanadium compounds Chemical class 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 7
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000351 vanadium(III) sulfate Inorganic materials 0.000 claims description 3
- OYCGXLKTCYDJNJ-UHFFFAOYSA-H vanadium;trisulfate Chemical compound [V].[V].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OYCGXLKTCYDJNJ-UHFFFAOYSA-H 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims 2
- DRUIQJLDWXQJOA-UHFFFAOYSA-J O.[V+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound O.[V+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DRUIQJLDWXQJOA-UHFFFAOYSA-J 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 description 37
- 239000008187 granular material Substances 0.000 description 36
- 238000002844 melting Methods 0.000 description 36
- 230000008018 melting Effects 0.000 description 36
- 238000005303 weighing Methods 0.000 description 36
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 19
- 239000002667 nucleating agent Substances 0.000 description 16
- 239000012745 toughening agent Substances 0.000 description 16
- 229920001083 polybutene Polymers 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 13
- 229910052720 vanadium Inorganic materials 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 12
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 11
- 229920005604 random copolymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 230000007774 longterm Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000002706 hydrostatic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 4
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 4
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 4
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 101150019148 Slc7a3 gene Proteins 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- 230000006353 environmental stress Effects 0.000 description 3
- 235000011147 magnesium chloride Nutrition 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- HLDPWJREWQOPAV-UHFFFAOYSA-K [O--].[Cl-].[Cl-].[Cl-].[V+5] Chemical compound [O--].[Cl-].[Cl-].[Cl-].[V+5] HLDPWJREWQOPAV-UHFFFAOYSA-K 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BQTGDGVUGBFFNW-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate;hydrate Chemical compound O.[O-2].[V+4].[O-]S([O-])(=O)=O BQTGDGVUGBFFNW-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- IPEHNWZTLUQKMA-UHFFFAOYSA-N 2-(methoxymethyl)dibenzofuran Chemical compound COCC1=CC2=C(OC3=C2C=CC=C3)C=C1 IPEHNWZTLUQKMA-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical class CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- LNKJESSHRFPVPE-UHFFFAOYSA-N 5-(diethylamino)pentyl 3,4,5-trimethoxybenzoate;hydrochloride Chemical compound Cl.CCN(CC)CCCCCOC(=O)C1=CC(OC)=C(OC)C(OC)=C1 LNKJESSHRFPVPE-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- NOWFQOWNIXZVPF-UHFFFAOYSA-N C(CCCCCCC(C)C)OP(OCCCCCCCC(C)C)OP(O)O.C(O)C(CO)(CO)CO Chemical compound C(CCCCCCC(C)C)OP(OCCCCCCCC(C)C)OP(O)O.C(O)C(CO)(CO)CO NOWFQOWNIXZVPF-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- KTFSKSJNPRMGEW-UHFFFAOYSA-N [Mg]OCCl Chemical compound [Mg]OCCl KTFSKSJNPRMGEW-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N alpha-aminonaphthalene Natural products C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- USYJXNNLQOTDLW-UHFFFAOYSA-L calcium;heptanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCC([O-])=O USYJXNNLQOTDLW-UHFFFAOYSA-L 0.000 description 1
- JILYTPDQRCHWPA-UHFFFAOYSA-L calcium;octanedioate Chemical compound [Ca+2].[O-]C(=O)CCCCCCC([O-])=O JILYTPDQRCHWPA-UHFFFAOYSA-L 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- NQSVPQIOJRYMGQ-UHFFFAOYSA-N diethyl 2-methyl-2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C)(C(C)C)C(=O)OCC NQSVPQIOJRYMGQ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- OANIYCQMEVXZCJ-UHFFFAOYSA-N ditert-butyl(dimethoxy)silane Chemical compound CO[Si](OC)(C(C)(C)C)C(C)(C)C OANIYCQMEVXZCJ-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- KRTCPMDBLDWJQY-UHFFFAOYSA-M magnesium;ethanolate;chloride Chemical compound [Mg+2].[Cl-].CC[O-] KRTCPMDBLDWJQY-UHFFFAOYSA-M 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JHZHWVQTOXIXIV-UHFFFAOYSA-N oxo-[[1-[3-[4-(oxoazaniumylmethylidene)pyridin-1-yl]propyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCCN1C=CC(=C[NH+]=O)C=C1 JHZHWVQTOXIXIV-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-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
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- 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
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a special resin for PPR (polypropylene random) pipes and a preparation method thereof, wherein the special resin for PPR pipes comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin and 0.1-3 parts of antioxidant; wherein the random copolymerization polypropylene resin has a load at 230 ℃ of2.16Kg, the melt flow rate is 0.2-0.5g/10min, the comonomer ethylene content is 2-10 wt%, and the impact strength of the simply supported beam is more than 30KJ/m 2 . The PPR pipe produced by the special resin for the PPR pipe has high strength and good creep resistance, and the hydraulic resistance of the PPR pipe product is greatly improved.
Description
Technical Field
The invention belongs to the field of resin, and particularly relates to special resin for a PPR (polypropylene random copolymer) pipe and a preparation method of the special resin for the PPR pipe.
Background
Plastic pipes are increasingly favored in today's life and industrial fields due to their corrosion resistance, aging resistance, environmental protection and safety, and play an important and irreplaceable role. The random copolymerization polypropylene hot water pipe has the characteristics of energy conservation, sanitation, corrosion resistance, heat resistance, pressure resistance, long service life, convenient installation, reliable connection, material recycling and the like, and can be widely used for hot water pipes, pipes for hot water heating systems, industrial hot water pipes, hot spring water pipes, solar house hot water pipes and the like.
Random copolymer polypropylene tubing originated from europe, 90 s in the 20 th century, and the first propylene copolymer tubing line in the world that was developed by KRAVSSMAFFEI (KRAVSSMAFFEI) in germany. The pipe has the advantages that the pipe is superior in performance and attracts people's attention, the German plastic pipe is repositioned in the format in short years, the random copolymerization polypropylene pipe jumps to the second place in competition with other pipes, and the random copolymerization polypropylene pipe is adopted in 80 percent of Germany indoor tap water and heating pipes. Then, polypropylene copolymer pipes are developed and produced in all countries in the world, and random copolymer polypropylene pipes are developed at a higher speed. In 1998, the government of China also sends out the stipulations about rapid popularization and application of chemical building materials, restriction and elimination of laggard products, the newly built buildings are forbidden to be galvanized and cast iron pipes from 6 months to 1 day in 2000, the environment-friendly random copolymerization polypropylene pipes are popularized and used, under the guidance of national policies, the random copolymerization polypropylene pipes show strong vitality in the market, the development prospect is very good, and merchants also invest in PPR pipe production lines at times, and until now, china has 130 introduced and domestic random copolymerization polypropylene production lines to form the production capacity of 6-7 ten thousand tons of random copolymerization polypropylene pipes. However, the domestic polypropylene random copolymer pipe generally has the problems of poor processability, poor long-term aging resistance and the like.
The uneven pipe wall thickness or the sharkskin phenomenon on the outer wall of the pipe and unsmooth pipe inner wall can be caused by low melt strength and narrow molecular weight distribution in the forming and processing process of the random copolymerization polypropylene resin, in addition, because the random copolymerization polypropylene hot water pipe needs to bear certain water pressure and environmental aging in the using process, the random copolymerization polypropylene hot water pipe is required to have excellent long-term aging resistance and certain annular stress, when the random copolymerization polypropylene pipe is produced, a certain amount of special auxiliary agent is required to be added to improve the processing performance of the random copolymerization polypropylene, the pipe is endowed with excellent aging resistance and mechanical property, and the using requirement of the building industry on the random copolymerization polypropylene hot water pipe is met.
Disclosure of Invention
The invention mainly aims to provide a special resin for PPR pipes and a preparation method thereof, which overcome the defects of lower melt strength and rigidity, and weaker impact resistance and processability of the special resin for PPR pipes in the prior art.
To achieve the above objectThe invention provides a special resin for PPR pipes, which comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin and 0.1-3 parts of antioxidant; wherein, the random copolymerization polypropylene resin has a melt flow rate of 0.2-0.5g/10min at 230 ℃ and a load of 2.16Kg, the comonomer ethylene content is between 2wt% and 10wt%, and the impact strength of the simply supported beam is more than 30KJ/m 2 。
The special resin for the PPR pipe is characterized in that in the random copolymerization polypropylene resin, part of ethylene molecules are randomly distributed in a polypropylene chain segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70-100:100.
the resin special for the PPR pipe is characterized in that the antioxidant is one or more of a phenol antioxidant, an amine antioxidant, a phosphite antioxidant and a sulfur-containing ester antioxidant.
The resin special for the PPR pipe further comprises a processing aid, an acid absorbent and a coupling agent, wherein the processing aid is at least one of organic silicon, organic fluorine polymers, low molecular polypropylene and low molecular polyethylene wax, the acid absorbent is at least one of calcium stearate, zinc stearate, magnesium stearate and hydrotalcite, and the coupling agent is at least one of silane, phthalate esters, aluminate esters and rare earth coupling agents.
In order to achieve the above object, the present invention also provides a method for preparing a resin dedicated for PPR pipes, the resin dedicated for PPR pipes comprising a random copolymerized polypropylene resin, the random copolymerized polypropylene resin being synthesized by a one-step process using a Ziegler-Natta catalyst system, the Ziegler-Natta catalyst system comprising a procatalyst, the method for preparing the procatalyst comprising the steps of:
step 1, adding a spherical magnesium alkoxide compound into a mixture containing a titanium compound and a vanadium compound at the temperature of-20-10 ℃ for reaction, wherein the molar ratio of titanium to magnesium is 1;
step 2, raising the temperature to 30-80 ℃, and adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l;
and 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding a titanium-vanadium-containing compound which is equal to the titanium-vanadium-containing compound in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
The invention relates to a preparation method of special resin for PPR pipes, wherein the titanium compound is at least one of chloro trialkoxy titanium, dichloro dialkoxy titanium, trichloro alkoxy titanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxide trichloride, sodium orthovanadate and sodium metavanadate.
The preparation method of the special resin for the PPR pipe comprises the step of preparing a special resin for the PPR pipe, wherein the internal electron donor is selected from one or more of aliphatic carboxylic ester, aromatic carboxylic ester, phosphate ester, dihydric alcohol ester, aliphatic diether and aromatic ether.
The invention relates to a preparation method of special resin for PPR pipes, wherein the preparation method of the spherical magnesium alkoxide compound comprises the following steps: under the protection of inert gas, anhydrous MgCl 2 Adding ethanol into a three-neck flask, heating to 110-140 ℃ to obtain a homogeneous solution, stirring at a high speed for 0.5-2 hours, transferring into n-hexane at the temperature of-20 to-10 ℃, slowly heating, decompressing and distilling out excessive n-hexane and ethanol, cooling magnesium chloride, crystallizing, separating out balls, drying in vacuum, and storing under inert gas.
The invention relates to a preparation method of special resin for PPR pipes, wherein the preparation method of random copolymerization polypropylene resin comprises the following steps: and polymerizing propylene and ethylene in the presence of a main catalyst, a cocatalyst and an external electron donor to obtain the random copolymerization polypropylene resin.
The invention relates to a preparation method of special resin for PPR (polypropylene random) pipes, wherein a cocatalyst is an organic aluminum compound, and an external electron donor is a silane compound.
The preparation method of the resin special for the PPR pipe comprises the steps of uniformly stirring and mixing the random copolymer polypropylene resin and the auxiliary agent at the stirring speed of 300-500r/min, and performing extrusion granulation to obtain the resin special for the PPR pipe; the auxiliary agent comprises at least one of an antioxidant, an acid absorbent and a coupling agent.
The invention has the beneficial effects that:
the special resin for the PPR pipe provided by the invention obviously overcomes the defects of poor processability caused by uneven dispersion of monomers when ethylene monomers are randomly added into polypropylene and unsmooth inner wall of the pipe due to narrow molecular weight distribution by adjusting the preparation method of the random copolymer polypropylene, obviously improves the processability, mechanical property, environmental stress cracking resistance and long-term aging resistance of the random copolymer polypropylene resin, and has good cost performance and popularization prospect. Furthermore, the special resin for the PPR pipe has higher melt strength and rigidity, and simultaneously has good impact resistance and processability, thereby solving the contradiction that the rigidity and the toughness of the polypropylene resin need to be improved. The technical index of the special material for the PPR pipe reaches the level of foreign similar products,
drawings
FIG. 1 is a schematic view showing the structure of a random copolymerized polypropylene resin of the present invention.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
In the present invention, when a quality, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary range l-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
The invention provides a special resin for PPR pipes, which comprises the following components in parts by weight: 100 parts of random copolymerization polypropylene resin and 0.1-3 parts of antioxidant.
In one embodiment, in the random copolymerized polypropylene resin, a part of ethylene molecules are randomly distributed in the polypropylene segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70 to 100:100. it is considered that a structure in which a single ethylene molecule is inserted into a polypropylene segment is distributed randomly, and a structure in which two or more ethylene molecules are inserted into a polypropylene segment in succession is distributed regularly (i.e., non-randomly). In the invention, part of ethylene molecules form a regular distribution structure, part of ethylene molecules form a random distribution structure, and the molar ratio of the randomly distributed ethylene molecules to all ethylene molecules (randomly distributed ethylene and regularly distributed ethylene) is 70-100:100. in another embodiment, the random copolymerized polypropylene resin has a melt flow rate of 0.2-0.5g/10min at 230 ℃ and a load of 2.16Kg, a comonomer ethylene content of 2-10 wt%, and a simple beam impact strength of greater than 30KJ/m 2 。
In one embodiment, the present invention further provides a preparation method of the above random copolymerized polypropylene resin, which is synthesized by a one-step method using propylene as a raw material, ethylene as a comonomer, and a Ziegler-Natta catalyst system, wherein the Ziegler-Natta catalyst system includes a main catalyst, a cocatalyst, and an external electron donor, and the preparation method of the main catalyst includes the following steps:
step 1, adding a spherical magnesium alkoxide compound into a mixture containing a titanium compound and a vanadium compound at the temperature of-20-10 ℃ for reaction, wherein the molar ratio of titanium to magnesium is 1;
step 2, raising the temperature to 30-80 ℃, adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l, namely the molar ratio of the spherical magnesium alkoxide compound to the internal electron donor compound is 2-15 l based on magnesium;
and 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding the titanium compound and the vanadium compound which are equal to those in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
In one embodiment, the titanium compound is at least one of chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) oxide sulfate hydrate, vanadium (III) sulfate, vanadium oxide trichloride, sodium orthovanadate and sodium metavanadate.
In one embodiment, the spherical magnesium alkoxide compound is prepared by: adding a magnesium compound and alcohol into a three-neck flask under the protection of inert gas, heating to 110-140 ℃ to form a homogeneous solution, stirring at a high speed for 0.5-2 hours, transferring into n-hexane at the temperature of-20 to-10 ℃, slowly heating and distilling under reduced pressure to remove excessive n-hexane and alcohol, cooling and crystallizing the magnesium compound to separate out balls, drying in vacuum, and storing under inert gas. The magnesium compound is one of anhydrous magnesium dichloride, magnesium dibromide, chloromethoxymagnesium and chloroethoxymagnesium; the alcohol is selected from one of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.
In one embodiment, the internal electron donor is selected from one or more of aliphatic carboxylic acid esters, aromatic carboxylic acid esters, phosphoric acid esters, glycol esters, aliphatic diethers and aromatic ethers, such as diisobutyl phthalate, di-n-butyl phthalate, diethyl 2-methyl-2-isopropylmalonate, 9-bis (methoxymethyl) fluorene, phenetole, o-diethylether and 2-methoxymethyl dibenzofuran.
Therefore, the main catalyst obtained by the invention is a solid catalyst component taking magnesium, titanium, vanadium, halogen and an internal electron donor as main components, and the main catalyst simultaneously contains a Ti active site and a V active site on the same spherical magnesium alkoxide compound.
In one embodiment, a method for preparing a random copolymerized polypropylene resin includes: and polymerizing propylene and ethylene in the presence of a main catalyst, a cocatalyst and an external electron donor, such as liquid-phase bulk polymerization or gas-phase polymerization, to obtain the random copolymer polypropylene resin.
In another embodiment, the cocatalyst is an organoaluminum compound and the external electron donor is a silane-based compound. In a further embodiment, the cocatalyst is an alkylaluminum compound, more preferably a trialkylaluminum compound; the external electron donor is at least one of tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane and di-tert-butyldimethoxysilane.
In the random copolymerization polypropylene resin obtained by the method, a large number of long-chain tie molecules exist, so that the random copolymerization polypropylene resin forms an aggregation state structure similar to a reinforcing steel bar-concrete type structure, the random copolymerization polypropylene resin has high strength and good creep resistance, the hydraulic resistance of a PPR pipe product is greatly improved, and the random copolymerization polypropylene resin has a structure shown in figure 1.
In one embodiment, the special resin for the PPR pipe further comprises 2-15 parts by weight of polybutene so as to improve the creep resistance of the product. In another embodiment, the polybutene of the present invention is an extrusion grade poly l-butene having a melt flow rate of 0.2 to 0.8g/10min at 230 ℃ under a load of 2.16Kg and a tensile strength greater than 20MPa.
In one embodiment, the resin special for the PPR pipe further comprises 0.05-1 part by weight of a nucleating agent and 2-15 parts by weight of a toughening agent, so as to solve the problem of low-temperature toughness of the product.
In another embodiment, the nucleating agent of the invention is one or more of calcium suberate, calcium pimelate, calcium terephthalate, TMB-4, TMB-5, NA-85, NB-328, WBG-II, STARNU-100; the toughening agent is one or more of ethylene-octene copolymer, ethylene-propylene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer and hydrogenated styrene-isoprene-styrene triblock copolymer.
In one embodiment, the antioxidant of the present invention may be one or more of a phenol type antioxidant, an amine type antioxidant, a phosphite type antioxidant, and a sulfur-containing ester type antioxidant, such as 2, 6-di-t-butyl-4-methylphenol, 2, 6-di-t-butyl-4-N-butylphenol, 4-hydroxymethyl-2, 6-di-t-butylphenol, N-phenyl- α -naphthylamine, butylated hydroxyaldehyde- α -naphthylamine, N '-diphenyl-p-phenylenediamine, pentaerythritol diisodecyl diphosphite, triisodecyl phosphite, diisodecyl phosphite, distearyl thiodipropionate, and dioctadecyl β, β' -thiodibutyrate.
The special resin for the PPR pipe can also comprise other auxiliary agents, such as processing aids, acid-absorbing agents and coupling agents, wherein the processing aids are organic silicon and organic fluorine polymer processing aids, such as PDMS (polydimethylsiloxane) of Doe Coning, fluoroelastomer FX-5920, FX-5911, FX-5924, FX-5916 and FPA-102 of 3M company, one or a mixture of a plurality of low molecular polypropylene and low molecular polyethylene wax in any proportion, the acid-absorbing agents are one or a plurality of calcium stearate, zinc stearate, magnesium stearate, hydrotalcite and the like, and the coupling agents are one or a plurality of silanes, phthalate esters, aluminate esters and rare earth coupling agents.
The special resin for the PPR pipe is prepared by uniformly mixing the polypropylene resin and various additives according to the proportion by a general method, and granulating by an extruder.
In order to improve the long-term hydrostatic pressure resistance of the PPR pipe, improve the creep property of the PPR pipe and well keep the strength of the PPR pipe, the poly-1-butylene is added into the atactic polypropylene and is mixed to extrude the pipe, so that the creep property of the pipe is improved.
The invention aims to improve the defect of insufficient low-temperature impact performance of the PPR pipe, and the phenomenon of brittle fracture easily occurs when external force is applied in the construction or transportation process in winter, particularly in the north, so that the normal use is influenced. The nucleating agent and the toughening agent are added into the atactic polypropylene, and the mixture is mixed and extruded out of the pipe, so that the low-temperature resistance of the pipe is improved.
According to the invention, the poly-1-butene, the nucleating agent and the toughening agent can also be added into the atactic polypropylene at the same time, and the pipes are extruded after being mixed, so that the creep property and the low temperature resistance of the pipes are improved at the same time.
In conclusion, the special resin for the PPR pipe has higher melt strength and rigidity, and simultaneously has good impact resistance and processability, and solves the problem that the polypropylene needs to improve the rigidity and the toughness. The technical indexes of the special resin for the PPR pipe reach the level of foreign like products, the defects of poor processability caused by uneven dispersion of monomers when ethylene monomers are randomly added into polypropylene and low molecular weight distribution, so that the outer wall of the pipe is shark-skin-shaped and the inner wall of the pipe is not smooth, the processability, the mechanical property, the environmental stress cracking resistance and the long-term aging resistance of the random copolymerization polypropylene resin are obviously improved, and the special resin has good cost performance and popularization prospect.
The technical solution of the present invention is further described in detail by the following specific examples.
(1) Preparing a main catalyst:
cat1# (1) adding spherical magnesium alkoxide compound into TiCl at-20-10 deg.C 4 And VCl 3 In a molar ratio of titanium to magnesium of 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound of diisobutyl phthalate, magnesium and an internal donorThe molar ratio of the electron compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat1#.
The preparation method of the spherical magnesium alkoxide compound comprises the following steps: under the protection of nitrogen, anhydrous MgCl with certain mass is added 2 Adding ethanol into a three-neck flask, heating to 130 ℃ to obtain a homogeneous solution, stirring at a high speed for 1 hour, transferring into n-hexane at-15 ℃, slowly heating and distilling under reduced pressure to remove excessive n-hexane and ethanol, cooling magnesium chloride, crystallizing, separating out balls, drying in vacuum, and storing under nitrogen.
The following preparation method of the magnesium alkoxide compound in Cat2# to Cat12# is the same as that in Cat1#, and the mixture of titanium and vanadium is TiCl 4 And VCl 3 A mixture of (a).
Cat2# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat2#.
Cat3# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding titanium compound and vanadium compound in the same amount as that in the step (1), reacting at 120 ℃ for 3 hours, filtering, washing and drying to obtain a catalyst Cat3#.
Cat4# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat4#.
Cat5# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat5#.
Cat6# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat6#.
Cat7# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat7#.
Cat8# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat8#.
Cat9# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound, namely diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat9#.
Cat10# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain the catalyst Cat10#.
Cat11# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding titanium compound and vanadium compound in the same amount as that in the step (1), reacting at 120 ℃ for 3 hours, filtering, washing and drying to obtain a catalyst Cat11#.
Cat12# (1) adding a spherical magnesium alkoxide compound into a mixture containing titanium and vanadium at the temperature of-20-10 ℃ for reaction for 3 hours, wherein the molar ratio of titanium to magnesium is 1; (2) Raising the temperature to 60 ℃, adding an internal electron donor compound diisobutyl phthalate, wherein the molar ratio of magnesium to the internal electron donor compound is 10 l; (3) heating to 120 ℃ again, and reacting for 3 hours; (4) And (2) filtering, adding the titanium compound and the vanadium compound which are equal to the titanium compound and the vanadium compound in the step (1), reacting for 3 hours at 120 ℃, and filtering, washing and drying to obtain a catalyst Cat12#.
(2) Preparation of random copolymerized polypropylene
Resin # 1: the main catalyst is Cat1#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the molar ratio of ethylene to propylene is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 1#.
Resin # 2: the main catalyst is Cat2#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin No. 2 is obtained.
Resin # 3: the main catalyst is Cat3#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 3#.
Resin 4#: the main catalyst is Cat4#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin No. 4 is obtained.
Resin # 5: the main catalyst is Cat5#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin No. 5 is obtained.
Resin 6#: the main catalyst is Cat6#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 6#.
Resin 7#: the main catalyst is Cat7#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin 7#.
Resin # 8: the main catalyst is Cat8#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin 8#.
Resin 9#: the main catalyst is Cat9#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 9#.
Resin 10#: the main catalyst is Cat10#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 10#.
Resin 11#: the main catalyst is Cat10#, the cocatalyst is triethylaluminum, the external electron donor is cyclohexyl methyldimethoxysilane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymer polypropylene resin 11#.
Resin 12#: the main catalyst is Cat12#, the cocatalyst is triethyl aluminum, the external electron donor is cyclohexyl methyl dimethoxy silane, propylene is subjected to liquid phase polymerization under the reaction conditions of 70 ℃ and 3.4MPa, and the ethylene/propylene molar ratio is controlled to be 3.5% in the reaction process, so that the spherical porous random copolymerization polypropylene resin 12#.
(3) Preparation of special material for PPR pipe (the following materials are calculated by weight portion)
Example 1:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 2:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 3:
1 part of rare earth coupling agent
Weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 4:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 5:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 6:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 7:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 8:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 9:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 10:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 11:
weighing the polypropylene, the antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 12:
weighing polypropylene, antioxidant and other additives according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 3-5 minutes at a stirring speed of 500r/min to obtain uniform mixture;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
(4) Preparation of creep-resistant PPR pipe special resin (the following substances are calculated by weight portion)
Example 13:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 14:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 15:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 16:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 17:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 18:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 19:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 20:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 21:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 22:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 23:
weighing polypropylene, polybutene, antioxidant and other assistants according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at a stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 24:
weighing polypropylene, polybutene, antioxidant and other assistants in the proportion, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes at the stirring speed of 500r/min to obtain uniform components;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
(5) Preparation of special resin for toughened PPR (polypropylene random copolymer) pipe
Example 25:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 26:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 27:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 28:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 29:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 30:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 31:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 32:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 33:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 34:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 35:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Example 36:
weighing polypropylene, a nucleating agent, a toughening agent, an antioxidant and other auxiliaries according to the parts of the components in the formula, and stirring and mixing the components in a high-speed stirrer at normal temperature for 5 minutes to ensure that the components are uniform, wherein the stirring speed is 500r/min;
and transferring the uniformly mixed raw materials into a double-screw granulator for heating and melting, and extruding and granulating at 230 ℃ to obtain granules.
Comparative example:
the special material for foreign imported pipes is selected as the comparative example of the invention.
Table 1 shows the results of the performance analyses of examples and comparative examples
TABLE 1
As can be seen from Table 1, the special material for the PPR pipe provided by the invention has higher rigidity and toughness.
Testing the performance of the pipe:
the special pipe materials prepared in the examples 1 to 36 are extruded to prepare pipes 1 to 36, the hydrostatic performance of the pipes is tested, the imported material is also selected as a comparative example, and the test results are shown in the following table 2:
TABLE 2 hydrostatic test of pipes
Note: the time in the table is the explosion time of the hydrostatic test pipe, and when the ring stress is 16MPa and 17MPa, the standard is met after more than 1 hour; when tested at a high temperature of 95 ℃, the hydrostatic pressure of the pipe exceeds the standard time, but the pipe does not burst, so no specific time is listed.
As shown in Table 2, the PPR pipe obtained by the invention has high rigidity and toughness to meet various performance requirements of indexes, and completely meets the requirements of users.
As shown in tables 1 and 2, the special material for the PPR pipe, which is developed by the invention, has higher melt strength and rigidity, and simultaneously has good impact resistance and processability, solves the problem that the polypropylene needs to improve the rigidity and the toughness, obviously improves the processability, the mechanical property, the environmental stress cracking resistance and the long-term aging resistance of the random copolymer polypropylene resin, and has good cost performance and popularization prospect.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. The special resin for the PPR pipe is characterized by comprising the following components in parts by weight: 100 parts of random copolymerization polypropylene resin and 0.1-3 parts of antioxidant; wherein, when the random copolymerization polypropylene resin is at 230 ℃ and the load is 2.16Kg, the melt flow rate is 0.2-0.5g/10min, the comonomer ethylene content is 2-10 wt%, and the impact strength of the simply supported beam is more than 30KJ/m 2 。
2. The resin special for the PPR pipe as claimed in claim 1, wherein in the random copolymerization polypropylene resin, part of ethylene molecules are randomly distributed in the polypropylene chain segment, and the molar ratio of the randomly distributed ethylene molecules to the ethylene molecules is 70-100:100.
3. the resin special for the PPR pipe as claimed in claim 1, wherein the antioxidant is one or more of phenolic antioxidant, amine antioxidant, phosphite antioxidant and sulfur-containing ester antioxidant.
4. The resin special for the PPR pipe as claimed in claim 1, further comprising a processing aid, an acid scavenger and a coupling agent, wherein the processing aid is at least one of silicone, organic fluorine polymer, low molecular polypropylene and low molecular polyethylene wax, the acid scavenger is at least one of calcium stearate, zinc stearate, magnesium stearate and hydrotalcite, and the coupling agent is at least one of silane, phthalate, aluminate and rare earth coupling agent.
5. The preparation method of the special resin for the PPR pipe is characterized in that the special resin for the PPR pipe comprises a random copolymerization polypropylene resin, the random copolymerization polypropylene resin is synthesized by a one-step method by adopting a Ziegler-Natta catalyst system, the Ziegler-Natta catalyst system comprises a main catalyst, and the preparation method of the main catalyst comprises the following steps:
step 1, adding a spherical magnesium alkoxide compound into a mixture containing a titanium compound and a vanadium compound at the temperature of-20-10 ℃ for reaction, wherein the molar ratio of titanium to magnesium is 1-1;
step 2, raising the temperature to 30-80 ℃, and adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2-15 l;
and 3, heating to 100-150 ℃ for reaction, filtering the reaction mixture, adding the titanium compound and the vanadium compound which are equal to those in the step 1, reacting at 100-150 ℃, filtering, washing and drying to obtain the catalyst.
6. The method for producing a resin specialized for PPR pipe according to claim 5, wherein said titanium compound is at least one of chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride and titanium tetrabromide; the vanadium compound is at least one of ammonium hexafluorovanadate, vanadium nitrate, vanadyl oxalate, ammonium metavanadate, vanadyl sulfate, vanadium (IV) sulfate hydrate, vanadium (III) sulfate, vanadium oxychloride, sodium orthovanadate and sodium metavanadate.
7. The method for preparing resin special for the PPR pipe as claimed in claim 5, wherein the internal electron donor is selected from one or more of aliphatic carboxylic acid ester, aromatic carboxylic acid ester, phosphoric acid ester, glycol ester, aliphatic diether and aromatic ether.
8. The method for preparing the resin special for the PPR pipe as claimed in claim 5, wherein the method for preparing the spherical magnesium alkoxide compound comprises the following steps: under the protection of inert gas, anhydrous MgCl 2 And ethanol are added into a three-mouth bottle, then the temperature is raised to 110 to 140 ℃ to form a homogeneous solution, the homogeneous solution is stirred at a high speed for 0.5 to 2 hours and then transferred into n-hexane at the temperature of between 20 ℃ below zero and 10 ℃ below zero, the excessive n-hexane and ethanol are distilled out by slow heating and pressure reduction, magnesium chloride is cooled, crystallized and separated out to form spheres, and the spheres are dried in vacuum and stored under inert gas.
9. The method for preparing the special resin for the PPR pipe as claimed in claim 5, wherein the method for preparing the random copolymerization polypropylene resin comprises the following steps: and polymerizing propylene and ethylene in the presence of a main catalyst, a cocatalyst and an external electron donor to obtain the random copolymerization polypropylene resin.
10. The method for preparing resin special for the PPR pipe as claimed in claim 9, wherein the cocatalyst is an organic aluminum compound, and the external electron donor is a silane compound.
11. The preparation method of the resin special for the PPR pipe as claimed in claim 5, which comprises the following steps: uniformly stirring and mixing the random copolymerization polypropylene resin and the auxiliary agent at the stirring speed of 300-500r/min, and performing extrusion granulation to obtain special resin for the PPR pipe; the auxiliary agent comprises at least one of an antioxidant, an acid acceptor and a coupling agent.
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| CN102850663A (en) * | 2011-06-29 | 2013-01-02 | 合肥杰事杰新材料股份有限公司 | Low temperature-resistant polypropylene random copolymer material, and its preparation method and application |
| CN106995563A (en) * | 2017-04-14 | 2017-08-01 | 中国石油化工股份有限公司 | A kind of high strength heat resistant atactic copolymerized polypropene resin |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
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2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850663A (en) * | 2011-06-29 | 2013-01-02 | 合肥杰事杰新材料股份有限公司 | Low temperature-resistant polypropylene random copolymer material, and its preparation method and application |
| CN106995563A (en) * | 2017-04-14 | 2017-08-01 | 中国石油化工股份有限公司 | A kind of high strength heat resistant atactic copolymerized polypropene resin |
| CN108864347A (en) * | 2018-06-22 | 2018-11-23 | 云南云天化石化有限公司 | The production method of PPR pipe PP Pipe Compound |
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