CN113980394A - MPP (modified Polypropylene) pipe for electric power engineering and production process thereof - Google Patents
MPP (modified Polypropylene) pipe for electric power engineering and production process thereof Download PDFInfo
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- CN113980394A CN113980394A CN202111359793.2A CN202111359793A CN113980394A CN 113980394 A CN113980394 A CN 113980394A CN 202111359793 A CN202111359793 A CN 202111359793A CN 113980394 A CN113980394 A CN 113980394A
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- Prior art keywords
- stirring
- modified
- hyperbranched polysiloxane
- electric power
- heating
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- -1 Polypropylene Polymers 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 title abstract description 30
- 229920001155 polypropylene Polymers 0.000 title abstract description 13
- 238000005516 engineering process Methods 0.000 title description 2
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 48
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000002667 nucleating agent Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 70
- 238000010438 heat treatment Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000001816 cooling Methods 0.000 claims description 39
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000004595 color masterbatch Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- BEYOBVMPDRKTNR-BUHFOSPRSA-N 4-Hydroxyazobenzene Chemical compound C1=CC(O)=CC=C1\N=N\C1=CC=CC=C1 BEYOBVMPDRKTNR-BUHFOSPRSA-N 0.000 claims description 7
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 claims description 6
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 10
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000006757 chemical reactions by type Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- 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 group 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 5
- 238000007792 addition Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 241000220317 Rosa Species 0.000 description 3
- MMCPOSDMTGQNKG-UJZMCJRSSA-N aniline;hydrochloride Chemical compound Cl.N[14C]1=[14CH][14CH]=[14CH][14CH]=[14CH]1 MMCPOSDMTGQNKG-UJZMCJRSSA-N 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- GHMWZRWCBLXYBX-UHFFFAOYSA-M sodium;4-chlorobenzoate Chemical compound [Na+].[O-]C(=O)C1=CC=C(Cl)C=C1 GHMWZRWCBLXYBX-UHFFFAOYSA-M 0.000 description 2
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-M 3-chlorobenzoate Chemical compound [O-]C(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to an MPP (modified Polypropylene) pipe for electric power engineering and a production process thereof, belonging to the technical field of pipes. And the MPP pipe comprises the following raw materials: modified PP resin, modified hyperbranched polysiloxane, antioxidant, solubilizer, nucleating agent, filler, coupling agent and master batch. The modified hyperbranched polysiloxane has the characteristics of high branching structure, low melting point, low viscosity and easiness in processing, the molecule of the modified hyperbranched polysiloxane is composed of a hard chain and a soft chain, and a long chain section composed of an azobenzene chain and a benzamide chain is a crystalline phase at low temperature, so that the expansion and extension of cracks in a modified PP resin substrate can be prevented, and the low-temperature impact resistance of the MPP pipe is further improved; the modified hyperbranched polysiloxane molecular chain contains a benzotriazole structure, and the benzotriazole structure is connected into hyperbranched polysiloxane molecules in a chemical bond mode, so that the weather resistance and the stability of the weather resistance of the MPP pipe are improved.
Description
Technical Field
The invention belongs to the technical field of pipes, and particularly relates to an MPP pipe for electric power engineering and a production process thereof.
Background
The MPP pipe takes modified polypropylene as a main raw material, and has the advantages of high strength, good insulating property, easy construction and the like. The method is widely applied to trenchless pipeline construction in the urban construction process, overcomes the defects of repeated excavation of urban roads, environmental pollution, influence on urban traffic and the like, and protects the urban appearance environment. However, the impact resistance of the conventional modified polypropylene is low at low temperature, which means that microcracks or cracks are generated after physical impact is applied at low temperature, loss is caused, and the practical application value of the modified polypropylene is reduced. Therefore, the toughening modification of the MPP pipe is continuously researched. Common toughening modification methods include beta crystal form nucleating agent toughening modification, inorganic rigid particle toughening modification, rubber elastomer toughening modification and the like. However, the methods can increase the difficulty of the pipe production process, so that the toughening effect is not obvious, the mechanical strength of the toughened polypropylene is reduced, and the pressure resistance of the MPP pipe is reduced.
For example, the rose crystal form nano calcium carbonate multidimensional reinforced MPP cable protection tube material and the preparation method thereof disclosed in Chinese patent CN107446244B, the protection tube material comprises the following components by weight: PP resin: 30-100 parts; rose crystal form nano calcium carbonate: 10-70 parts; coupling agent: 1-5 parts; a toughening agent: 5-15 parts; a compatilizer: 3-10 parts; lubricant: 1-5 parts; dispersing agent: 2-5 parts; 0.5-2 parts of antioxidant; in the patent, the rose crystal form nano calcium carbonate is used for toughening and modifying polypropylene, so that the reduction of mechanical property caused by the introduction of the traditional crystal form structure nano calcium carbonate is avoided. However, the MPP cable protection pipe material provided by the patent is easy to age under the conditions of long-term high temperature and pressure bearing, and the weather resistance is poor, so that the weather resistance needs to be further improved.
Therefore, the invention provides the compression-resistant and weather-resistant MPP pipe to meet the requirements of electric power engineering.
Disclosure of Invention
The invention aims to provide an MPP pipe for electric power engineering and a production process thereof, so as to solve the problems mentioned in the background.
The purpose of the invention can be realized by the following technical scheme:
an MPP pipe for electric power engineering comprises the following raw materials in parts by weight: 95-135 parts of modified PP resin, 6-30 parts of modified hyperbranched polysiloxane, 1.5-5.5 parts of antioxidant, 1-6.5 parts of solubilizer, 1-4.5 parts of nucleating agent, 1-14 parts of filler, 0.3-3.5 parts of coupling agent and 0.1-5.5 parts of color masterbatch.
Further, the modified PP resin is block copolymer polypropylene and homopolymerized polypropylene according to the mass ratio of 1-3: 1-3, mixing.
Further, the antioxidant is an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is 2-4: 1-3, mixing.
Further, the solubilizer is one or a mixture of more of maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene and maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer in any ratio.
Further, the nucleating agent is one of sodium p-phenolsulfonate, sodium phenolate, calcium stearate, sodium m-chlorobenzoate and sodium p-chlorobenzoate.
Further, the filler is one of nano calcium carbonate, nano silicon dioxide and glass fiber.
Further, the coupling agent is one of a titanate coupling agent and a silane coupling agent, and is preferably a titanate coupling agent.
Further, the color master batch is one or a mixture of several of white master batch, red master batch, black master batch, yellow master batch, blue master batch, green master batch, purple master batch, orange master batch, gray master batch and cyan master batch in any ratio.
Further, the modified hyperbranched polysiloxane is prepared by the following steps:
a1, under the protection of nitrogen and at a temperature of 0-5 ℃, uniformly mixing carboxyl-terminated siloxane, azobenzene derivatives and dimethylformamide, adding a condensation agent dicyclohexylcarbodiimide, stirring and activating at room temperature for 1.5h, dropwise adding a dimethylformamide solution in which a hydroxyl-terminated diamine compound is dissolved after activation is finished, heating to 45 ℃ after dropwise adding is finished, and stirring and reacting for 8h to obtain a siloxane monomer, wherein the molar ratio of the carboxyl-terminated siloxane to the azobenzene derivatives to the dicyclohexylcarbodiimide to the hydroxyl-terminated diamine compound is 1.3-1.6: 1.3-1.6: 3-3.5: 1;
in the reaction of the step A1, firstly, dicyclohexylcarbodiimide is utilized to activate carboxyl in terminal carboxyl siloxane and azobenzene derivatives, and then the carboxyl reacts with amino in a terminal hydroxyl diamine compound to obtain a siloxane monomer, wherein the molecular structural formula of the siloxane monomer is shown as follows;
as can be seen from the molecular structural formula of the siloxane monomer, the siloxane monomer molecule consists of a hard chain (azobenzene chain and benzamide chain) and a soft chain (ether chain and siloxane chain), and contains a terminal hydroxyl group;
a2, adding siloxane monomers into an ethanol solution containing deionized water in a nitrogen atmosphere, keeping the mixture at room temperature for 30min, carrying out hydrolysis reaction at 50 ℃ for 3h, cooling to room temperature, adding an end-capping agent hexamethyldisilane, stirring for 30min, heating to 60 ℃, stirring for 2h, stopping the reaction, cooling to room temperature, washing with water, and drying to obtain the hyperbranched polysiloxane, wherein the use ratio of the siloxane monomers, the deionized water, the ethanol and the hexamethyldisilane is 7-10 g: 0.83-1.64 g: 45-60 mL: 0.63-1 g;
in the reaction of the step A2, hydrolysis of a siloxane chain in a siloxane monomer is utilized, and then hexamethyldisilane is used as an end-capping agent to obtain hyperbranched polysiloxane, wherein the hyperbranched polysiloxane molecules contain end hydroxyl groups;
a3, stirring hyperbranched polysiloxane and tetrahydrofuran at 30 ℃ for 1h for full swelling, then cooling to 15 ℃, adding a reactive weather-resistant agent and p-toluenesulfonic acid, stirring for 30min, heating for reflux reaction for 6h, stopping the reaction, performing rotary evaporation, washing with water, and performing vacuum drying to obtain the modified hyperbranched polysiloxane, wherein the mass ratio of the hyperbranched polysiloxane to the reactive weather-resistant agent is 100: 20-30 percent of p-toluenesulfonic acid, wherein the addition mass of the p-toluenesulfonic acid is 4-7 percent of that of the reactive weather-resistant agent.
In the step A3, the reaction of the terminal hydroxyl group in the hyperbranched polysiloxane and the carboxyl group in the reactive weather resistant agent is utilized, so that the benzotriazole structure is connected into the hyperbranched polysiloxane, and the modified hyperbranched polysiloxane is obtained.
Further, the carboxyl-terminated siloxane is prepared by the following steps:
x1, adding succinic anhydride and tris (hydroxymethyl) aminomethane into a four-neck flask, adding ethanol to completely dissolve the succinic anhydride and tris (hydroxymethyl) aminomethane, heating and refluxing for 10 hours under the protection of nitrogen, then cooling to room temperature, stopping reaction, cooling to room temperature, spin-drying, dissolving with dichloromethane, washing with water for several times, merging organic phases, spin-steaming, and drying to obtain the polyol, wherein the dosage ratio of the succinic anhydride, the tris (hydroxymethyl) aminomethane and the ethanol is 0.1 mol: 0.11-0.13 mol: 60-100 mL;
in the step X1 reaction, succinic anhydride is utilized to react with amino in tris (hydroxymethyl) aminomethane to generate polyol, and the molecular structural formula of the polyol is shown as follows;
x2, adding potassium hydroxide after uniformly stirring polyhydric alcohol, 3-glycidyl ether oxypropyltrimethoxysilane and glacial acetic acid, heating to 83 ℃, reacting for 6 hours, stopping the reaction, reducing the temperature and the pressure, performing rotary evaporation, and performing vacuum drying to obtain carboxyl-terminated siloxane, wherein the dosage ratio of the polyhydric alcohol, the 3-glycidyl ether oxypropyltrimethoxysilane, the glacial acetic acid and the potassium hydroxide is 0.1 mol: 0.35-0.4 mol: 80-150 mL: 6-10 g.
In the step X2 reaction, the ring-opening reaction of hydroxyl in the polyhydric alcohol and epoxy in 3-glycidoxypropyltrimethoxysilane is utilized under alkaline conditions to generate carboxyl-terminated siloxane, and the molecular structural formula of the carboxyl-terminated siloxane is shown as follows.
Further, the hydroxyl-terminated diamine compound is prepared by the steps of:
uniformly mixing 2-hydroxybenzaldehyde, aniline and aniline hydrochloride, heating to 110 ℃ under the protection of nitrogen, stirring for reaction for 2 hours, heating to 150 ℃, stirring for reaction for 1.5 hours, reducing pressure for distillation when the reaction is finished and the temperature of a system is reduced to 55 ℃, dissolving the rest substances with hydrochloric acid, filtering, neutralizing the filtrate with a sodium hydroxide solution until the pH value is 7-8, generating a precipitate, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3-5 times, recrystallizing the obtained crude product with ethanol/water for two times, and finally drying in vacuum to constant weight to obtain a hydroxyl-terminated diamine compound, wherein the dosage ratio of 2-hydroxybenzaldehyde, aniline and aniline hydrochloride is 0.1 mol: 0.11-0.13 mol: 3-5 g.
In the reaction, under the action of aniline hydrochloride, aldehyde group of 2-hydroxybenzaldehyde and aniline produce condensation reaction with hydrogen on benzene ring to obtain hydroxyl-terminated diamine compound, and the molecular mechanism formula is shown as follows;
further, the azobenzene derivative is prepared by the following steps:
uniformly mixing 4-hydroxyazobenzene, malonic acid and tetrahydrofuran, adding p-toluenesulfonic acid, heating and refluxing for 5 hours under stirring, stopping reaction, filtering, drying, recrystallizing a crude product with acetic anhydride twice to obtain an azobenzene derivative, wherein the dosage ratio of 4-hydroxyazobenzene, malonic acid and tetrahydrofuran is 0.1 mol: 0.11-0.13 mol: 70-120mL, wherein the adding mass of the p-toluenesulfonic acid is 2-4% of the total mass of the 4-hydroxyazobenzene and the malonic acid.
In the reaction, hydroxyl in 4-hydroxyazobenzene is utilized to react with carboxyl of malonic acid to obtain azobenzene derivative, so that carboxyl is introduced into the azobenzene derivative.
Further, the reactive weather-resistant agent is prepared by the following steps:
mixing 2- (2' -hydroxy-5-methylphenyl) benzotriazole, methyl hydroquinone, triethylamine and tetrahydrofuran uniformly, stirring at 55 ℃ to completely dissolve 2- (2 '-hydroxy-5-methylphenyl) benzotriazole, then dropwise adding tetrahydrofuran solution of malonic acid methyl ester acyl chloride at the speed of 3 drops/second, continuously stirring for 12 hours after dropwise adding, cooling to room temperature, adding sodium hydroxide solution, adjusting the pH value of the solution to 10-11, heating, refluxing for 6 hours, stopping reaction, cooling to room temperature, adjusting the pH value of the solution to 6.5-7 with hydrochloric acid, performing rotary evaporation, water washing, and recrystallizing with ethanol to obtain a reaction type weather resisting agent, wherein the molar ratio of 2- (2' -hydroxy-5-methylphenyl) benzotriazole to malonic acid methyl ester acyl chloride is 1: 1.
in the reaction, tetrahydrofuran is used as a solvent, triethylamine is used as an acid-binding agent, methyl hydroquinone is used as a polymerization inhibitor, hydroxyl in 2- (2' -hydroxyl-5-methylphenyl) benzotriazole and acyl chloride in methyl malonate acyl chloride are used for reacting to obtain a compound containing methyl ester, then the methyl ester is hydrolyzed under an alkaline condition, the pH value of the solution is adjusted by hydrochloric acid to obtain carboxyl by carboxyl salt, and the reaction type weather resisting agent is obtained, and the molecular structural formula of the reaction type weather resisting agent is shown as follows:
a production process of an MPP pipe for electric power engineering comprises the following steps:
step one, premixing: mixing modified PP resin, modified hyperbranched polysiloxane and nucleating agent according to the weight part ratio, heating and stirring for 10-15min, cooling to 40-50 ℃, adding coupling agent, stirring for 3-5min, adding filler, keeping the temperature and stirring for 8-13min to obtain a first mixed material; then heating and stirring the antioxidant, the solubilizer and the color master batch for 10-12min, adding the first mixed material, continuing to heat and stir for 3-5min, stopping stirring, cooling to 40-50 ℃ to obtain a premix for later use, wherein the heating rate is 8 ℃/min;
extruding and granulating the premix through a single-screw or double-screw extruder, and then performing extrusion molding, traction and cooling to obtain the MPP pipe for the electric power engineering, wherein the granulating process comprises the following steps: the temperature of the first zone of the extruder barrel is 155-175 ℃, the temperature of the second zone is 170-200 ℃, the temperature of the third zone is 180-215 ℃, the temperature of the fourth zone is 185-235 ℃, and the extrusion molding process comprises the following steps: the temperature of the die is 200 ℃ and 250 ℃, and the rotating speed of the screw of the extruder is 15-30 r/min.
The invention has the beneficial effects that:
in order to improve the low-temperature impact resistance of the existing MPP pipe, the modified hyperbranched polysiloxane is introduced into the modified PP resin base material, so that the impact resistance, the high-temperature resistance and the weather resistance of the obtained MPP pipe are improved, and the principle of the MPP pipe is explained as follows:
firstly, the modified hyperbranched polysiloxane has a highly branched structure, has the characteristics of low melting point, low viscosity and easiness in processing, reduces the processing difficulty of the MPP pipe, has excellent elastic performance, and has a molecular chain consisting of a hard chain (azobenzene chain and a benzamide chain) and a soft chain (polysiloxane chain), wherein a long chain section consisting of the azobenzene chain and the benzamide chain is a crystalline phase at low temperature, so that the expansion and extension of cracks in a modified PP resin base material can be prevented, and the low-temperature impact resistance of the MPP pipe is further improved;
secondly, the molecular chain of the modified hyperbranched polysiloxane contains a large number of silicon-oxygen bonds, and the silicon-oxygen bonds have high energy, are not easy to break and have certain flame retardant property, so that the high temperature resistance and the flame retardance of the MPP pipe are improved;
and the modified hyperbranched polysiloxane molecular chain contains a benzotriazole structure, and the benzotriazole structure has excellent weather resistance, so that the MPP pipe has excellent weather resistance, and the benzotriazole structure is connected into the hyperbranched polysiloxane molecule in a chemical bond mode, so that the structure is prevented from migrating in the MPP pipe, and the weather resistance stability of the MPP pipe is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of a reactive weather resistant agent:
mixing 0.1mol of 2- (2 '-hydroxy-5-methylphenyl) benzotriazole, 20mL of methyl hydroquinone, 0.1mol of triethylamine and 80mL of tetrahydrofuran, stirring at 55 ℃ to completely dissolve the 2- (2' -hydroxy-5-methylphenyl) benzotriazole, then dropwise adding 50mL of tetrahydrofuran solution dissolved with 0.1mol of malonic acid methyl ester acyl chloride at the dropping speed of 3 drops/second, continuously stirring for 12 hours after dropwise adding, cooling to room temperature, adding 1M of sodium hydroxide solution, adjusting the pH value of the solution to 10, heating and refluxing for 6 hours, stopping the reaction, cooling to room temperature, adjusting the pH value of the solution to 6.5 with 1M of hydrochloric acid, carrying out rotary evaporation at 50 ℃, washing for 2 times with water, and recrystallizing with ethanol to obtain the reaction type weather-resistant agent.
Example 2
Preparation of a reactive weather resistant agent:
mixing 0.15mol of 2- (2 '-hydroxy-5-methylphenyl) benzotriazole, 25mL of methyl hydroquinone, 0.15mol of triethylamine and 80mL of tetrahydrofuran, stirring at 55 ℃ to completely dissolve the 2- (2' -hydroxy-5-methylphenyl) benzotriazole, then dropwise adding 50mL of tetrahydrofuran solution dissolved with 0.15mol of malonic acid methyl ester acyl chloride at the dropping speed of 3 drops/second, continuously stirring for 12 hours after dropwise adding, cooling to room temperature, adding 1M of sodium hydroxide solution, adjusting the pH value of the solution to be 11, heating and refluxing for 6 hours, stopping the reaction, cooling to room temperature, adjusting the pH value of the solution to be 7 by using 1M of hydrochloric acid, carrying out rotary evaporation at 50 ℃, washing for 2 times, and recrystallizing by using ethanol to obtain the reaction type weather-resistant agent.
Example 3
Preparation of azobenzene derivative:
uniformly mixing 0.1mol of 4-hydroxyazobenzene, 0.11mol of malonic acid and 70mL of tetrahydrofuran, adding 0.61g of p-toluenesulfonic acid, heating and refluxing for 5 hours under stirring, stopping reaction, filtering, drying, and recrystallizing a crude product twice by using 70mL of acetic anhydride to obtain the azobenzene derivative.
Example 4
Preparation of azobenzene derivative:
uniformly mixing 0.1mol of 4-hydroxyazobenzene, 0.13mol of malonic acid and 120mL of tetrahydrofuran, adding 2.52g of p-toluenesulfonic acid, heating and refluxing for 5 hours under stirring, stopping reaction, filtering, drying, and recrystallizing the crude product twice by using 70mL of acetic anhydride to obtain the azobenzene derivative.
Example 5
Preparation of hydroxyl-terminated diamine compound:
uniformly mixing 0.1mol of 2-hydroxybenzaldehyde, 0.11mol of aniline and 3g of aniline hydrochloride, heating to 110 ℃ under the protection of nitrogen, stirring for reacting for 2 hours, heating to 150 ℃, stirring for reacting for 1.5 hours, reducing pressure for distilling when the temperature of a system is reduced to 55 ℃, dissolving the rest substances by using 1M hydrochloric acid, filtering, neutralizing the filtrate by using 1M sodium hydroxide solution until the pH value is 7, generating precipitate at the moment, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 3 times by using deionized water, recrystallizing the obtained crude product twice by using 50mL of ethanol/water solution, and finally drying in vacuum to constant weight to obtain a hydroxyl-terminated diamine compound.
Example 6
Preparation of hydroxyl-terminated diamine compound:
uniformly mixing 0.1mol of 2-hydroxybenzaldehyde, 0.13mol of aniline and 5g of aniline hydrochloride, heating to 110 ℃ under the protection of nitrogen, stirring for reaction for 2 hours, heating to 150 ℃, stirring for reaction for 1.5 hours, reducing pressure for distillation when the temperature of a system is reduced to 55 ℃, dissolving the rest substances by using 1M hydrochloric acid, filtering, neutralizing the filtrate by using 1M sodium hydroxide solution until the pH value is 7.5, generating precipitate at the moment, filtering after the precipitate is completely precipitated, repeatedly washing a filter cake for 5 times by using deionized water, recrystallizing the obtained crude product twice by using 50mL of ethanol/water solution, and finally drying in vacuum to constant weight to obtain a hydroxyl-terminated diamine compound.
Example 7
Preparation of carboxyl-terminated siloxane:
x1, adding 0.1mol of succinic anhydride and 0.11mol of tris (hydroxymethyl) aminomethane into a four-neck flask, adding 60mL of ethanol to completely dissolve the succinic anhydride and the tris (hydroxymethyl) aminomethane, heating and refluxing for 10 hours under the protection of nitrogen, cooling to room temperature, stopping reaction, cooling to room temperature, spin-drying, dissolving with 60mL of dichloromethane, washing with 30mL of water for 2 times, combining organic phases, spin-steaming, and drying to obtain polyhydric alcohol;
and X2, uniformly stirring 0.1mol of polyhydric alcohol, 0.35mol of 3-glycidyl ether oxy propyl trimethoxy silane and 80mL of glacial acetic acid, adding 6g of potassium hydroxide, heating to 83 ℃, reacting for 6h, stopping the reaction, reducing the temperature and the pressure, performing rotary evaporation, and performing vacuum drying to obtain the carboxyl-terminated siloxane.
Example 8
Preparation of carboxyl-terminated siloxane:
x1, adding 0.1mol of succinic anhydride and 0.13mol of tris (hydroxymethyl) aminomethane into a four-neck flask, adding 100mL of ethanol to completely dissolve the succinic anhydride and the tris (hydroxymethyl) aminomethane, heating and refluxing for 10 hours under the protection of nitrogen, then cooling to room temperature, stopping reaction, cooling to room temperature, spin-drying, dissolving with 70mL of dichloromethane, washing with 30mL of water for 3 times, combining organic phases, spin-evaporating, and drying to obtain polyhydric alcohol;
and X2, uniformly stirring 0.1mol of polyhydric alcohol, 0.4mol of 3-glycidyl ether oxy propyl trimethoxy silane and 150mL of glacial acetic acid, adding 10g of potassium hydroxide, heating to 83 ℃, reacting for 6h, stopping the reaction, reducing the temperature and the pressure, performing rotary evaporation, and performing vacuum drying to obtain the carboxyl-terminated siloxane.
Example 9
Preparation of modified hyperbranched polysiloxane:
a1, under the protection of nitrogen and at 0 ℃, 0.13mol of carboxyl-terminated siloxane, 0.13mol of azobenzene derivative prepared in example 3 and 50mL of dimethylformamide are uniformly mixed, 0.3mol of condensation agent dicyclohexylcarbodiimide is added, stirring and activation are carried out at room temperature for 1.5h, after the activation is finished, 40mL of dimethylformamide solution in which 0.1mol of hydroxyl-terminated diamine compound prepared in example 5 is dissolved is dropwise added, after the dropwise addition is finished, the temperature is raised to 45 ℃, and stirring and reaction are carried out for 8h, so that siloxane monomers are obtained;
a2, under the nitrogen atmosphere, adding 7g of siloxane monomer into 45mL of ethanol solution containing 0.83g of deionized water, keeping the mixture at room temperature for 30min, carrying out hydrolysis reaction at 50 ℃ for 3h, cooling to room temperature, adding 0.63g of end-capping agent hexamethyldisilane, stirring for 30min, heating to 60 ℃, stirring for 2h, stopping the reaction, cooling to room temperature, washing with water for 2 times, and drying at 50 ℃ to obtain hyperbranched polysiloxane;
a3, stirring 100g of hyperbranched polysiloxane and tetrahydrofuran at 30 ℃ for 1h for full swelling, then cooling to 15 ℃, adding 20g of the reaction type weather resisting agent prepared in the example 1 and 0.8g of p-toluenesulfonic acid, stirring for 30min, heating for reflux reaction for 6h, stopping the reaction, carrying out rotary evaporation, washing with water, and carrying out vacuum drying at 50 ℃ to obtain the modified hyperbranched polysiloxane.
The viscosity of the hyperbranched polysiloxane is 300-330 mPas through the detection of a viscosity detector.
Example 10
Preparation of modified hyperbranched polysiloxane:
a1, under the protection of nitrogen and at the temperature of 5 ℃, 0.16mol of carboxyl-terminated siloxane, 0.16mol of azobenzene derivative prepared in example 4 and 50mL of dimethylformamide are uniformly mixed, 0.35mol of condensation agent dicyclohexylcarbodiimide is added, stirring and activation are carried out at room temperature for 1.5h, after the activation is finished, 40mL of dimethylformamide solution in which 0.1mol of hydroxyl-terminated diamine compound prepared in example 6 is dissolved is dropwise added, after the dropwise addition is finished, the temperature is raised to 45 ℃, and stirring and reaction are carried out for 8h, so that siloxane monomers are obtained;
a2, under the nitrogen atmosphere, adding 10g of siloxane monomer into 60mL of ethanol solution containing 1.64g of deionized water, keeping the mixture at room temperature for 30min, carrying out hydrolysis reaction at 50 ℃ for 3h, cooling to room temperature, adding 1g of end-capping agent hexamethyldisilane, stirring for 30min, heating to 60 ℃, stirring for 2h, stopping the reaction, cooling to room temperature, washing with water, and drying at 50 ℃ to obtain hyperbranched polysiloxane;
a3, stirring 100g of hyperbranched polysiloxane and tetrahydrofuran at 30 ℃ for 1h for full swelling, then cooling to 15 ℃, adding 30g of the reaction type weather resisting agent prepared in the embodiment 2 and 2.1g of p-toluenesulfonic acid, stirring for 30min, heating for reflux reaction for 6h, stopping the reaction, carrying out rotary evaporation, washing with water, and carrying out vacuum drying at 50 ℃ to obtain the modified hyperbranched polysiloxane.
The viscosity of the hyperbranched polysiloxane is 340-plus 360 mPa.s detected by a viscosity detector
Example 11
Preparation of an MPP pipe for electric power engineering:
step one, preparing raw materials: comprises the following raw materials by weight: 95g of modified PP resin, 6g of modified hyperbranched polysiloxane prepared in example 9, 1.5g of antioxidant, 1g of solubilizer, 1g of nucleating agent, 1g of filler, 0.3g of coupling agent and 0.1g of color masterbatch;
the modified PP resin is block copolymerization polypropylene and homo-polypropylene according to the mass ratio of 1: 3, mixing; the antioxidant is an antioxidant 1010 and an antioxidant 168 according to the mass ratio of 2: 1, mixing; the solubilizer is maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene according to the mass ratio of 1: 1, mixing; the nucleating agent is sodium p-phenolsulfonate; the filler is nano calcium carbonate; the coupling agent is titanate coupling agent 109; the color master batch is white master batch;
step two, premixing: mixing modified PP resin, modified hyperbranched polysiloxane and nucleating agent according to the weight part ratio, heating and stirring for 10min, cooling to 40 ℃, adding coupling agent, stirring for 3min, adding filler, keeping the temperature and stirring for 8min to obtain a first mixed material; then heating and stirring the antioxidant, the solubilizer and the color master batch for 10min, adding the first mixed material, continuing to heat and stir for 5min, stopping stirring, and cooling to 40 ℃ to obtain a premix for later use, wherein the heating rate is 8 ℃/min;
and step three, extruding and granulating the premix through a single-screw or double-screw extruder, and then performing extrusion molding, traction and cooling to obtain the MPP pipe for the electric power engineering, wherein the granulating process comprises the following steps: the first zone temperature of the extruder cylinder is 155 ℃, the second zone temperature is 170 ℃, the third zone temperature is 180 ℃, the fourth zone temperature is 185 ℃, and the extrusion molding process comprises the following steps: the temperature of the die is 200 ℃, and the rotating speed of the screw of the extruder is 15 r/min.
Example 12
Preparation of an MPP pipe for electric power engineering:
step one, preparing raw materials: comprises the following raw materials by weight: 115g of modified PP resin, 20g of modified hyperbranched polysiloxane prepared in example 10, 3g of antioxidant, 4g of solubilizer, 3g of nucleating agent, 11 g of filler, 2g of coupling agent and 3g of color masterbatch;
the modified PP resin is block copolymerization polypropylene and homo-polypropylene according to the mass ratio of 2: 3, mixing; the antioxidant is an antioxidant 1010 and an antioxidant 168 according to the mass ratio of 3: 1, mixing; the solubilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer; the nucleating agent is sodium p-phenolate; the filler is nano silicon dioxide; the coupling agent is KH560 silane coupling agent; the color master batch is a red master batch, a yellow master batch and a blue master batch according to the mass ratio of 1: 1: 1, mixing;
step two, premixing: mixing modified PP resin, modified hyperbranched polysiloxane and nucleating agent according to the weight part ratio, heating and stirring for 15min, cooling to 50 ℃, adding coupling agent, stirring for 3min, adding filler, keeping the temperature and stirring for 13min to obtain a first mixed material; then heating and stirring the antioxidant, the solubilizer and the color master batch for 12min, adding the first mixed material, continuing to heat and stir for 3-5min, stopping stirring, and cooling to 50 ℃ to obtain a premix for later use, wherein the heating rate is 8 ℃/min;
and step three, extruding and granulating the premix through a single-screw or double-screw extruder, and then performing extrusion molding, traction and cooling to obtain the MPP pipe for the electric power engineering, wherein the granulating process comprises the following steps: the temperature of a first zone of a machine barrel of the extruder is 165 ℃, the temperature of a second zone is 175 ℃, the temperature of a third zone is 190 ℃, the temperature of a fourth zone is 195 ℃, and the extrusion molding process comprises the following steps: the temperature of the die is 210 ℃, and the rotating speed of the screw of the extruder is 120 r/min.
Example 13
Preparation of an MPP pipe for electric power engineering:
step one, preparing raw materials: comprises the following raw materials by weight: 135g of modified PP resin, 30g of modified hyperbranched polysiloxane prepared in example 9, 5.5g of antioxidant, 6.5g of solubilizer, 4.5g of nucleating agent, 14g of filler, 3.5g of coupling agent and 5.5g of color masterbatch;
the modified PP resin is block copolymerization polypropylene and homo-polypropylene according to the mass ratio of 2: 2.6 mixing; the antioxidant is an antioxidant 1010 and an antioxidant 168 according to the mass ratio of 3: 1.7 mixing; the solubilizer is maleic anhydride grafted polypropylene; the nucleating agent is sodium p-chlorobenzoate; the filler is glass fiber; the coupling agent is titanate coupling agent 109; the color master batch is an orange master batch.
Step two, premixing: the same procedure as in example 11, step two;
step three, the same as example 11.
Comparative example 1
Hyperbranched polysiloxane was prepared for example 9, step a 2.
Comparative example 2
Preparation of modified hyperbranched polysiloxane:
a1, under the protection of nitrogen and at 0 ℃, uniformly mixing 0.13mol of carboxyl-terminated siloxane with 50mL of dimethylformamide, adding 0.15mol of condensation agent dicyclohexylcarbodiimide, stirring and activating at room temperature for 1.5h, after the activation is finished, dropwise adding 40mL of dimethylformamide solution in which 0.1mol of hydroxyl-terminated diamine compound prepared in example 5 is dissolved, after the dropwise addition is finished, heating to 45 ℃, and stirring and reacting for 8h to obtain a siloxane monomer;
a2, same as step A2 in example 9;
a3 same as in step A3 of example 9.
Comparative example 3
Preparation of an MPP pipe for electric power engineering: in comparison with example 11, the modified hyperbranched siloxane in the starting material replaces the hyperbranched siloxane in comparative example 1.
Comparative example 4
Preparation of an MPP pipe for electric power engineering: in comparison with example 12, the modified hyperbranched siloxane in the starting material was replaced by the modified hyperbranched siloxane prepared in comparative example 2.
Example 14
The MPP pipes obtained in examples 11 to 13 and comparative examples 3 to 4 were subjected to the following property preparation:
impact strength: testing the impact strength without a groove at room temperature by adopting an XCJ-L type pendulum impact tester, wherein the reference standard is GB/T2571, and the test data is shown in Table 1;
low-temperature drop hammer impact bending strength: the bending strength is tested by a RIGER-20 type microcomputer control electronic universal testing machine (China) at room temperature, the reference standard is GB/T2570, and the test data is shown in table 1;
the Vicat soft temperature was tested according to GB/T8802-2001, the test data are shown in Table 1;
xenon lamp artificial accelerated aging test: the test was carried out according to GB/T16442.2-1999 at a temperature of 65 ℃ C. + -. 3 ℃ and a relative humidity (65 ℃ C. + -. 3)%, the test data being shown in Table 2.
TABLE 1
As can be seen from the data in table 1, the impact strength and flexural strength of the MPP pipes obtained in examples 11-13 are superior to the corresponding properties of the MPP pipe obtained in comparative example 4, and the vicat soft temperature of the MPP pipes obtained in examples 11-13 and comparative examples 3-4 are significantly improved compared to the vicat soft temperature (150 ℃) of the pure PP material, probably because the overall framework of the material incorporated in examples 11-13 and comparative examples 3-4 contains a large amount of silicon-oxygen bonds.
As can be seen from the data in table 2, the weathering performance of the MPP pipes obtained in examples 11-13 is superior to the corresponding performance of the MPP pipes obtained in comparative example 3.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The utility model provides a MPP tubular product for electric power engineering which characterized in that: the method comprises the following raw materials: modified PP resin, modified hyperbranched polysiloxane, antioxidant, solubilizer, nucleating agent, filler, coupling agent and master batch;
the modified hyperbranched polysiloxane is prepared by the following steps:
stirring hyperbranched polysiloxane and tetrahydrofuran at 30 ℃ for 1h for full swelling, then cooling to 15 ℃, adding a reactive weather-resistant agent and p-toluenesulfonic acid, stirring for 30min, heating for reflux reaction for 6h, stopping the reaction, performing rotary evaporation, washing with water, and performing vacuum drying to obtain the modified hyperbranched polysiloxane.
2. The MPP pipe for electric power engineering of claim 1, wherein: the mass ratio of the hyperbranched polysiloxane to the reactive weather resistant agent is 100: 20-30.
3. The MPP pipe for electric power engineering of claim 1, wherein: the hyperbranched polysiloxane is prepared by the following steps:
adding siloxane monomers into an ethanol solution containing deionized water in a nitrogen atmosphere, keeping the temperature at room temperature for 30min, carrying out hydrolysis reaction at 50 ℃ for 3h, cooling to room temperature, adding an end-capping agent hexamethyldisilane, stirring for 30min, heating to 60 ℃, stirring for 2h, stopping the reaction, cooling to room temperature, washing with water, and drying to obtain the hyperbranched polysiloxane.
4. The MPP pipe for electric power engineering of claim 3, wherein: the siloxane monomer is prepared by the following steps:
under the protection of nitrogen and at the temperature of 0-5 ℃, uniformly mixing carboxyl-terminated siloxane, azobenzene derivatives and dimethylformamide, adding a condensing agent dicyclohexylcarbodiimide, stirring and activating at room temperature for 1.5h, dropwise adding a dimethylformamide solution in which a hydroxyl-terminated diamine compound is dissolved after activation is finished, heating to 45 ℃ after dropwise adding, and stirring and reacting for 8h to obtain a siloxane monomer.
5. The MPP pipe for electric power engineering of claim 4, wherein: the azobenzene derivative is prepared by the following steps:
uniformly mixing 4-hydroxyazobenzene, malonic acid and tetrahydrofuran, adding p-toluenesulfonic acid, heating and refluxing for 5 hours under stirring, stopping reaction, filtering, drying, and recrystallizing a crude product twice with acetic anhydride to obtain the azobenzene derivative.
6. The MPP pipe for electric power engineering of claim 4, wherein: the carboxyl-terminated siloxane comprises the following steps:
stirring polyalcohol, 3-glycidyl ether oxypropyltrimethoxysilane and glacial acetic acid uniformly, adding potassium hydroxide, heating to 83 ℃, reacting for 6h, stopping reaction, cooling, depressurizing, rotary steaming, and vacuum drying to obtain carboxyl-terminated siloxane.
7. The MPP pipe for electric power engineering of claim 6, wherein: the polyol is prepared by the following steps:
adding succinic anhydride and tris (hydroxymethyl) aminomethane into a four-neck flask, adding ethanol to completely dissolve, heating and refluxing for 10h under the protection of nitrogen, then cooling to room temperature, stopping reaction, cooling to room temperature, spin-drying, dissolving with dichloromethane, washing with water for several times, combining organic phases, spin-steaming, and drying to obtain the polyhydric alcohol.
8. The production process of the MPP pipe for the electric power engineering as set forth in claim 1, characterized in that: the method comprises the following steps:
step one, premixing: mixing modified PP resin, modified hyperbranched polysiloxane and nucleating agent, heating and stirring for 10-15min, cooling to 40-50 ℃, adding coupling agent, stirring for 3-5min, adding filler, keeping the temperature and stirring for 8-13min to obtain a first mixed material; then heating and stirring the antioxidant, the solubilizer and the color master batch for 10-12min, adding the first mixed material, continuing heating and stirring for 3-5min, stopping stirring, and cooling to 40-50 ℃ to obtain a premix;
and secondly, extruding and granulating the premix through a single-screw or double-screw extruder, and then performing extrusion molding, traction and cooling to obtain the MPP pipe for the electric power engineering.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591589A (en) * | 2022-03-22 | 2022-06-07 | 广东安拓普聚合物科技有限公司 | Styrene elastomer for new energy charging pile cable and preparation method thereof |
| CN115466459A (en) * | 2022-09-06 | 2022-12-13 | 成都航空职业技术学院 | Modified polypropylene fused deposition molding granule and preparation method thereof |
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2021
- 2021-11-17 CN CN202111359793.2A patent/CN113980394A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591589A (en) * | 2022-03-22 | 2022-06-07 | 广东安拓普聚合物科技有限公司 | Styrene elastomer for new energy charging pile cable and preparation method thereof |
| CN114591589B (en) * | 2022-03-22 | 2022-10-21 | 广东安拓普聚合物科技有限公司 | Styrene elastomer for new energy charging pile cable and preparation method thereof |
| CN115466459A (en) * | 2022-09-06 | 2022-12-13 | 成都航空职业技术学院 | Modified polypropylene fused deposition molding granule and preparation method thereof |
| CN115466459B (en) * | 2022-09-06 | 2024-02-27 | 成都航空职业技术学院 | Modified polypropylene fused deposition molding granule and preparation method thereof |
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