CN117186320A - Oxygen-blocking antibacterial heat-resistant polyethylene pipe and preparation method thereof - Google Patents
Oxygen-blocking antibacterial heat-resistant polyethylene pipe and preparation method thereof Download PDFInfo
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- -1 polyethylene Polymers 0.000 title claims abstract description 72
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 34
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 32
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003607 modifier Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 12
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 62
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 229920001661 Chitosan Polymers 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 44
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 40
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 40
- 229920001296 polysiloxane Polymers 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 21
- 244000028419 Styrax benzoin Species 0.000 claims description 20
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 20
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 20
- 229960002130 benzoin Drugs 0.000 claims description 20
- 235000019382 gum benzoic Nutrition 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 18
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 17
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 claims description 17
- FLNRHACWTVIBQS-UHFFFAOYSA-N triphenyl(prop-2-enyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FLNRHACWTVIBQS-UHFFFAOYSA-N 0.000 claims description 17
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 11
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 10
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 8
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 230000001580 bacterial effect Effects 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 abstract description 2
- 230000030833 cell death Effects 0.000 abstract description 2
- 210000000170 cell membrane Anatomy 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 150000004714 phosphonium salts Chemical group 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application discloses an oxygen-blocking antibacterial heat-resistant polyethylene pipe and a preparation method thereof, wherein ethylene is introduced into a reaction kettle, toluene is added, a modifier and a Ziegler-Natta catalyst are stirred and added for reaction, then ethanol is added for terminating reaction, a reaction product is added into acidified ethanol, filtrate is filtered and removed, filter cakes and reinforcing fillers are added into an extruder, the polyethylene pipe is prepared by extrusion cooling, the molecular side chains of the modifier contain double bonds and can form polyethylene with the ethylene, the polyethylene is blended with the reinforcing fillers for extrusion, a benzoxazine structure can be subjected to ring opening polymerization in a high-temperature environment, the crosslinking property of the molecule is increased, so that the prepared pipe has a good barrier effect, the molecules of the modifier contain quaternary ammonium salt and quaternary phosphonium salt structures, bacteria can be adsorbed to destroy bacterial cell membranes, bacterial cell liquid flows out, cell death is caused, and the molecules contain organic silicon chain segments and benzene ring structures, so that the high-temperature resistance of the pipe can be improved.
Description
Technical Field
The application relates to the field of oxygen-blocking antibacterial heat-resistant polyethylene pipes and a preparation method thereof.
Background
The polyethylene resin has the advantages of light weight, good toughness, easy manufacture of various shapes and specifications, and the like, and is widely applied to food containers, gas pipes, water supply pipes and floor heating pipes. The barrier property of the floor heating pipe plays an important role in protecting metal parts of heating and air conditioning systems and avoiding oxygen corrosion and acid corrosion formed by bacterial reproduction. Simple PP, PE, PET and other floor heating pipes are high in oxygen or water vapor permeability and poor in barrier property, and a common method for improving the barrier property is to adopt a high-barrier material or blend the high-barrier material with a multilayer coextrusion method, coat a compact barrier layer and the like.
Disclosure of Invention
The application aims to provide an oxygen-blocking antibacterial heat-resistant polyethylene pipe and a preparation method thereof, which solve the problems that the polyethylene pipe has common oxygen-blocking and antibacterial effects at present and is easy to reduce the performance of the polyethylene pipe when being used in a high-temperature environment.
The aim of the application can be achieved by the following technical scheme:
the preparation method of the oxygen-blocking antibacterial heat-resistant polyethylene pipe comprises the following steps:
step A1: uniformly mixing KH572, dimethylaminoethyl methacrylate, benzoin dimethyl ether and DMF, reacting for 1-1.5h under the condition of ultraviolet irradiation at the temperature of 25-30 ℃ and the rotation speed of 25-300 r/min, preparing an intermediate 1, mixing diphenyl dichlorosilane, the intermediate 1 and deionized water, stirring for 10-15min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4-6h, and regulating the pH value to be neutral to prepare dihydro-terminal polysiloxane;
step A2: uniformly mixing dihydro-terminated polysiloxane, 4-vinylaniline and DMF (dimethyl formamide), stirring at the rotation speed of 200-300r/min and the temperature of 60-65 ℃, adding chloroplatinic acid, reacting for 3-5h to obtain modified polysiloxane, uniformly mixing the modified polysiloxane, 2' -diallyl bisphenol A, paraformaldehyde and DMF, reacting for 6-8h at the rotation speed of 150-200r/min and the temperature of 130-135 ℃ to obtain a modified monomer, uniformly mixing mercaptoacetic acid, allyl triphenylphosphine bromide, benzoin dimethyl ether and DMF, introducing nitrogen for protection, and reacting for 4-6h under the irradiation of ultraviolet light of 360nm to obtain an intermediate 2;
step A3: uniformly mixing a modified monomer, an intermediate 2, DCC and DMF (dimethyl formamide), reacting for 3-5 hours at the rotation speed of 200-300r/min and the temperature of 25-30 ℃, preparing a modifier, introducing ethylene into a reaction kettle, adding toluene, stirring and adding the modifier and a Ziegler-Natta catalyst at the rotation speed of 60-80r/min and the temperature of 40-50 ℃ and the pressure of 0.1-0.15MPa, reacting for 30-40 minutes, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding filter cakes and reinforcing fillers into an extruder, extruding and cooling to prepare the polyethylene pipe.
Further, the molar ratio of KH572 to dimethylaminoethyl methacrylate in the step A1 is 1:1, the amount of benzoin dimethyl ether is 3 per mill of the sum of KH572 and dimethylaminoethyl methacrylate, the amount of diphenyldichlorosilane, intermediate 1, deionized water and 1, 3-tetramethyldisiloxane is 1mmol:2mmol:20mL:2mmol, and the amount of concentrated sulfuric acid is 1% of the sum of diphenyldichlorosilane, intermediate 1 and 1, 3-tetramethyldisiloxane.
Further, the molar ratio of the dihydro-terminated polysiloxane to the 4-vinylaniline in the step A2 is 1:2, the concentration of chloroplatinic acid in the mixture of the dihydro-terminated polysiloxane and the 4-vinylaniline is 10-15ppm, the molar ratio of the modified polysiloxane, the 2,2' -diallyl bisphenol A and the paraformaldehyde is 2:1:2, the molar ratio of the thioglycollic acid to the allyl triphenylphosphine bromide is 1:1, and the dosage of benzoin dimethyl ether is 3% of the sum of the masses of the thioglycollic acid and the allyl triphenylphosphine bromide.
Further, the molar ratio of the modified monomer to the intermediate 2 to the DCC in the step A3 is 1:2:2.1, the dosage ratio of the ethylene to the modifier is 1L:160mmol, and the dosage of the Ziegler-Natta catalyst is 5 per mill of the mass of the modifier.
Further, the modified filler is prepared by the following steps:
step B1: mixing chitosan, sodium dodecyl sulfate, glacial acetic acid solution and deionized water, stirring for 4-6 hours at the rotating speed of 200-300r/min, regulating the pH value to be neutral to obtain pretreated chitosan, uniformly mixing 4, 5-dicarboxyimidazole, monopotassium phosphate and deionized water, stirring and adding pretreated chitosan at the rotating speed of 150-200r/min and the temperature of 90-95 ℃, heating to 120-130 ℃, reacting for 3-5 hours, filtering to remove filtrate, adding a substrate into Tris/methanol solution, and soaking for 1-1.5 hours to obtain modified chitosan;
step B2: dispersing graphene oxide in methanol, stirring and adding KH560 and deionized water at the rotation speed of 150-200r/min and the temperature of 60-70 ℃, reacting for 3-5h, filtering to remove filtrate, dispersing a substrate in DMF, adding modified chitosan, reacting for 6-8h at the rotation speed of 200-300r/min and the temperature of 20-25 ℃ and the pH value of 10-11 to obtain a modified matrix, mixing the modified matrix, zinc nitrate hexahydrate and methanol, stirring for 10-15h at the rotation speed of 200-300r/min and the temperature of 20-25 ℃, and filtering to remove filtrate to obtain the modified filler.
Further, the dosage ratio of the chitosan, the sodium dodecyl sulfate, the glacial acetic acid solution and the deionized water in the step B1 is 1:1:2:10, the mass fraction of the glacial acetic acid solution is 1%, the dosage ratio of the 4, 5-dicarboxyimidazole, the potassium dihydrogen phosphate, the deionized water and the pretreated chitosan is 1g:0.5g:45mL:1g, and the mass fraction of the Tris/methanol solution is 15%.
Further, the dosage of KH560 in the step B2 is 3% of the mass of graphene oxide, the dosage ratio of the substrate to the modified chitosan is 1:3, and the mass ratio of the modified substrate to the zinc nitrate hexahydrate is 3:1.
The application has the beneficial effects that: the application provides an oxygen-blocking antibacterial heat-resistant polyethylene pipe, which is prepared by introducing ethylene into a reaction kettle, adding toluene, stirring, adding a modifier and a Ziegler-Natta catalyst, reacting, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding filter cakes and reinforcing filler into an extruder, extruding and cooling to obtain the polyethylene pipe, wherein the modifier takes KH572 and dimethylaminoethyl methacrylate as raw materials, the mercapto on KH572 and the double bond on dimethylaminoethyl methacrylate react under the condition of illumination to obtain an intermediate 1, diphenyl dichlorosilane and the intermediate 1 are firstly hydrolyzed to generate silanol groups, then the silanol groups are polymerized with 1, 3-tetramethyl disiloxane under the action of concentrated sulfuric acid to form dihydro-end polysiloxane, and the dihydro-end polysiloxane and 4-vinylaniline react under the action of chloroplatinic acid, the Si-H on the dihydro terminal polysiloxane reacts with the double bond on the 4-vinylaniline to prepare modified polysiloxane, the 2,2' -diallyl bisphenol A reacts with paraformaldehyde to form a benzoxazine structure to prepare modified monomers, thioglycollic acid and allyl triphenylphosphine bromide are subjected to ultraviolet light treatment to react the mercapto group on the thioglycollic acid with the double bond on the allyl triphenylphosphine bromide to prepare an intermediate 2, the modified monomers and the intermediate 2 react with the amino group on the modified monomers and the carboxyl group on the intermediate 2 under the action of DCC to prepare a modifier, the molecular side chain of the modifier contains the double bond, polyethylene can be formed by blending extrusion with reinforcing filler, the benzoxazine structure can be subjected to ring-opening polymerization under high temperature environment to increase the crosslinking property of the molecules, so that the prepared pipe has good barrier effect, the modified agent molecule contains quaternary ammonium salt and quaternary phosphonium salt structure, can absorb bacteria to destroy bacterial cell membrane, and enable bacterial cell fluid to flow out, so that cell death is caused, and the molecule contains organic silicon chain segments and benzene ring structure, so that high temperature resistance of the pipe is improved, modified filler is treated by sodium dodecyl sulfate with chitosan as raw material to form amino protection, 4, 5-dicarboxyimidazole and pretreated chitosan are esterified, and then Tris/methanol solution is used for deprotection to prepare modified chitosan, graphene oxide is treated by KH560, so that epoxy groups are grafted on the surface of graphene oxide, and then under alkaline condition, epoxy groups react with amino groups on the modified chitosan to form a structure of chitosan coated graphene, so that a modified matrix is prepared, the modified matrix reacts with zinc nitrate hexahydrate, imidazole structure on the modified matrix can be matched with zinc ions, the modified filler contains chitosan and metallic zinc, and can further destroy bacterial cell membrane structure, and antibacterial efficiency is improved through organic antibacterial and inorganic antibacterial compounding, and meanwhile, the effect of coating the pipe with chitosan coated structure is better.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the oxygen-blocking antibacterial heat-resistant polyethylene pipe comprises the following steps:
step A1: uniformly mixing KH572, dimethylaminoethyl methacrylate, benzoin dimethyl ether and DMF, reacting for 1h under the condition of the rotation speed of 200r/min, the temperature of 25 ℃ and the ultraviolet irradiation of 360nm to obtain an intermediate 1, mixing diphenyldichlorosilane, the intermediate 1 and deionized water, stirring for 10min under the condition of the rotation speed of 200r/min and the temperature of 60 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 4h, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A2: uniformly mixing dihydro-terminated polysiloxane, 4-vinylaniline and DMF (dimethyl formamide), stirring and adding chloroplatinic acid at the rotating speed of 200r/min and the temperature of 60 ℃ for reaction for 3 hours to obtain modified polysiloxane, uniformly mixing the modified polysiloxane, 2' -diallyl bisphenol A, paraformaldehyde and DMF, reacting for 6 hours at the rotating speed of 150r/min and the temperature of 130 ℃ to obtain a modified monomer, uniformly mixing thioglycollic acid, allyl triphenylphosphine bromide, benzoin dimethyl ether and DMF, introducing nitrogen for protection, and reacting for 4 hours under the irradiation of 360nm ultraviolet light to obtain an intermediate 2;
step A3: uniformly mixing a modified monomer, an intermediate 2, DCC and DMF (dimethyl formamide), reacting for 3 hours at the temperature of 25 ℃ at the rotating speed of 200r/min to obtain a modifier, introducing ethylene into a reaction kettle, adding toluene, stirring and adding the modifier and a Ziegler-Natta catalyst at the rotating speed of 60r/min, the temperature of 40 ℃ and the pressure of 0.1MPa, reacting for 30 minutes, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding a filter cake and reinforcing filler into an extruder, and extruding and cooling to obtain the polyethylene pipe.
The molar ratio of KH572 to dimethylaminoethyl methacrylate in the step A1 is 1:1, the amount of benzoin dimethyl ether is 3 per mill of the sum of KH572 and dimethylaminoethyl methacrylate, the amount of diphenyldichlorosilane, intermediate 1, deionized water and 1, 3-tetramethyldisiloxane is 1mmol:2mmol:20mL:2mmol, and the amount of concentrated sulfuric acid is 1% of the sum of diphenyldichlorosilane, intermediate 1 and 1, 3-tetramethyldisiloxane.
The molar ratio of the dihydro-terminated polysiloxane to the 4-vinylaniline in the step A2 is 1:2, the concentration of chloroplatinic acid in the mixture of the dihydro-terminated polysiloxane and the 4-vinylaniline is 10ppm, the molar ratio of the modified polysiloxane, the 2,2' -diallyl bisphenol A and the paraformaldehyde is 2:1:2, the molar ratio of the thioglycollic acid to the allyl triphenylphosphine bromide is 1:1, and the dosage of benzoin dimethyl ether is 3% of the sum of the masses of the thioglycollic acid and the allyl triphenylphosphine bromide.
The mole ratio of the modified monomer to the intermediate 2 to the DCC in the step A3 is 1:2:2.1, the dosage ratio of the ethylene to the modifier is 1L:160mmol, and the dosage of the Ziegler-Natta catalyst is 5 per mill of the mass of the modifier.
The modified filler is prepared by the following steps:
step B1: mixing chitosan, sodium dodecyl sulfate, glacial acetic acid solution and deionized water, stirring for 4 hours at the rotating speed of 200r/min, regulating the pH value to be neutral to obtain pretreated chitosan, uniformly mixing 4, 5-dicarboxyimidazole, potassium dihydrogen phosphate and deionized water, stirring and adding pretreated chitosan at the rotating speed of 150r/min and the temperature of 90 ℃, heating to 120 ℃, reacting for 3 hours, filtering to remove filtrate, adding a substrate into Tris/methanol solution, and soaking for 1 hour to obtain modified chitosan;
step B2: dispersing graphene oxide in methanol, stirring and adding KH560 and deionized water at the rotation speed of 150r/min and the temperature of 60 ℃ for reaction for 3 hours, filtering to remove filtrate, dispersing a substrate in DMF, adding modified chitosan, reacting for 6 hours at the rotation speed of 200r/min and the temperature of 20 ℃ and the pH value of 10 to obtain a modified matrix, mixing the modified matrix, zinc nitrate hexahydrate and methanol at the rotation speed of 200r/min and the temperature of 20 ℃ for stirring for 10 hours, and filtering to remove filtrate to obtain the modified filler.
The dosage ratio of the chitosan, the sodium dodecyl sulfate, the glacial acetic acid solution and the deionized water in the step B1 is 1:1:2:10, the mass fraction of the glacial acetic acid solution is 1%, the dosage ratio of the 4, 5-dicarboxyimidazole, the potassium dihydrogen phosphate, the deionized water and the pretreated chitosan is 1g:0.5g:45mL:1g, and the mass fraction of the Tris/methanol solution is 15%.
The dosage of KH560 in the step B2 is 3% of the mass of graphene oxide, the dosage ratio of substrate to modified chitosan is 1:3, and the mass ratio of modified substrate to zinc nitrate hexahydrate is 3:1.
Example 2
The preparation method of the oxygen-blocking antibacterial heat-resistant polyethylene pipe comprises the following steps:
step A1: uniformly mixing KH572, dimethylaminoethyl methacrylate, benzoin dimethyl ether and DMF, reacting for 1.3 hours under the conditions of the rotating speed of 200r/min, the temperature of 28 ℃ and the ultraviolet irradiation of 360nm to obtain an intermediate 1, mixing diphenyldichlorosilane, the intermediate 1 and deionized water, stirring for 13 minutes under the conditions of the rotating speed of 200r/min and the temperature of 65 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 5 hours, and regulating the pH value to be neutral to obtain dihydro-terminal polysiloxane;
step A2: uniformly mixing dihydro-terminated polysiloxane, 4-vinylaniline and DMF (dimethyl formamide), stirring and adding chloroplatinic acid under the condition of the rotating speed of 200r/min and the temperature of 63 ℃ for reaction for 4 hours to obtain modified polysiloxane, uniformly mixing the modified polysiloxane, 2' -diallyl bisphenol A, paraformaldehyde and DMF, reacting for 7 hours under the condition of the rotating speed of 150r/min and the temperature of 133 ℃ to obtain modified monomer, uniformly mixing thioglycollic acid, allyl triphenylphosphine bromide, benzoin dimethyl ether and DMF, introducing nitrogen for protection, and reacting for 5 hours under the irradiation of 360nm ultraviolet light to obtain an intermediate 2;
step A3: uniformly mixing a modified monomer, an intermediate 2, DCC and DMF (dimethyl formamide), reacting for 4 hours at the temperature of 28 ℃ at the rotating speed of 200r/min to obtain a modifier, introducing ethylene into a reaction kettle, adding toluene, stirring and adding the modifier and a Ziegler-Natta catalyst at the rotating speed of 60r/min, the temperature of 45 ℃ and the pressure of 0.1MPa, reacting for 35 minutes, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding a filter cake and reinforcing filler into an extruder, and extruding and cooling to obtain the polyethylene pipe.
The molar ratio of KH572 to dimethylaminoethyl methacrylate in the step A1 is 1:1, the amount of benzoin dimethyl ether is 3 per mill of the sum of KH572 and dimethylaminoethyl methacrylate, the amount of diphenyldichlorosilane, intermediate 1, deionized water and 1, 3-tetramethyldisiloxane is 1mmol:2mmol:20mL:2mmol, and the amount of concentrated sulfuric acid is 1% of the sum of diphenyldichlorosilane, intermediate 1 and 1, 3-tetramethyldisiloxane.
The molar ratio of the dihydro-terminated polysiloxane to the 4-vinylaniline in the step A2 is 1:2, the concentration of chloroplatinic acid in the mixture of the dihydro-terminated polysiloxane and the 4-vinylaniline is 13ppm, the molar ratio of the modified polysiloxane, the 2,2' -diallyl bisphenol A and the paraformaldehyde is 2:1:2, the molar ratio of the thioglycollic acid to the allyl triphenylphosphine bromide is 1:1, and the dosage of benzoin dimethyl ether is 3% of the sum of the masses of the thioglycollic acid and the allyl triphenylphosphine bromide.
The mole ratio of the modified monomer to the intermediate 2 to the DCC in the step A3 is 1:2:2.1, the dosage ratio of the ethylene to the modifier is 1L:160mmol, and the dosage of the Ziegler-Natta catalyst is 5 per mill of the mass of the modifier.
The modified filler is prepared by the following steps:
step B1: mixing chitosan, sodium dodecyl sulfate, glacial acetic acid solution and deionized water, stirring for 5 hours at the rotating speed of 200r/min, regulating the pH value to be neutral to prepare pretreated chitosan, uniformly mixing 4, 5-dicarboxyimidazole, potassium dihydrogen phosphate and deionized water, stirring and adding pretreated chitosan at the rotating speed of 200r/min and the temperature of 93 ℃, heating to 125 ℃, reacting for 4 hours, filtering to remove filtrate, adding a substrate into Tris/methanol solution, and soaking for 1.3 hours to prepare modified chitosan;
step B2: dispersing graphene oxide in methanol, stirring and adding KH560 and deionized water at the rotation speed of 150r/min and the temperature of 65 ℃ for reaction for 4 hours, filtering to remove filtrate, dispersing a substrate in DMF, adding modified chitosan, reacting for 7 hours at the rotation speed of 200r/min and the temperature of 23 ℃ and the pH value of 10 to obtain a modified matrix, mixing the modified matrix, zinc nitrate hexahydrate and methanol at the rotation speed of 200r/min and the temperature of 23 ℃ for stirring for 13 hours, and filtering to remove filtrate to obtain the modified filler.
The dosage ratio of the chitosan, the sodium dodecyl sulfate, the glacial acetic acid solution and the deionized water in the step B1 is 1:1:2:10, the mass fraction of the glacial acetic acid solution is 1%, the dosage ratio of the 4, 5-dicarboxyimidazole, the potassium dihydrogen phosphate, the deionized water and the pretreated chitosan is 1g:0.5g:45mL:1g, and the mass fraction of the Tris/methanol solution is 15%.
The dosage of KH560 in the step B2 is 3% of the mass of graphene oxide, the dosage ratio of substrate to modified chitosan is 1:3, and the mass ratio of modified substrate to zinc nitrate hexahydrate is 3:1.
Example 3
The preparation method of the oxygen-blocking antibacterial heat-resistant polyethylene pipe comprises the following steps:
step A1: uniformly mixing KH572, dimethylaminoethyl methacrylate, benzoin dimethyl ether and DMF, reacting for 1-1.5h under the condition of the rotation speed of 300r/min, the temperature of 30 ℃ and the ultraviolet irradiation of 360nm to obtain an intermediate 1, mixing diphenyldichlorosilane, the intermediate 1 and deionized water, stirring for 15min under the condition of the rotation speed of 300r/min and the temperature of 70 ℃, adding concentrated sulfuric acid and 1, 3-tetramethyl disiloxane, reacting for 6h, and regulating the pH value to be neutral to obtain the dihydro-terminal polysiloxane;
step A2: uniformly mixing dihydro-terminated polysiloxane, 4-vinylaniline and DMF (dimethyl formamide), stirring and adding chloroplatinic acid under the conditions of the rotating speed of 300r/min and the temperature of 65 ℃ for reaction for 5 hours to obtain modified polysiloxane, uniformly mixing the modified polysiloxane, 2' -diallyl bisphenol A, paraformaldehyde and DMF, reacting for 8 hours under the conditions of the rotating speed of 200r/min and the temperature of 135 ℃ to obtain modified monomer, uniformly mixing thioglycollic acid, allyl triphenylphosphine bromide, benzoin dimethyl ether and DMF, introducing nitrogen for protection, and reacting for 6 hours under the irradiation of 360nm ultraviolet light to obtain an intermediate 2;
step A3: uniformly mixing a modified monomer, an intermediate 2, DCC and DMF (dimethyl formamide), reacting for 5 hours at the temperature of 30 ℃ at the rotating speed of 300r/min to obtain a modifier, introducing ethylene into a reaction kettle, adding toluene, stirring and adding the modifier and a Ziegler-Natta catalyst at the rotating speed of 80r/min, the temperature of 50 ℃ and the pressure of 0.15MPa, reacting for 40 minutes, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding a filter cake and reinforcing filler into an extruder, and extruding and cooling to obtain the polyethylene pipe.
The molar ratio of KH572 to dimethylaminoethyl methacrylate in the step A1 is 1:1, the amount of benzoin dimethyl ether is 3 per mill of the sum of KH572 and dimethylaminoethyl methacrylate, the amount of diphenyldichlorosilane, intermediate 1, deionized water and 1, 3-tetramethyldisiloxane is 1mmol:2mmol:20mL:2mmol, and the amount of concentrated sulfuric acid is 1% of the sum of diphenyldichlorosilane, intermediate 1 and 1, 3-tetramethyldisiloxane.
The molar ratio of the dihydro-terminated polysiloxane to the 4-vinylaniline in the step A2 is 1:2, the concentration of chloroplatinic acid in the mixture of the dihydro-terminated polysiloxane and the 4-vinylaniline is 15ppm, the molar ratio of the modified polysiloxane, the 2,2' -diallyl bisphenol A and the paraformaldehyde is 2:1:2, the molar ratio of the thioglycollic acid to the allyl triphenylphosphine bromide is 1:1, and the dosage of benzoin dimethyl ether is 3% of the sum of the masses of the thioglycollic acid and the allyl triphenylphosphine bromide.
The mole ratio of the modified monomer to the intermediate 2 to the DCC in the step A3 is 1:2:2.1, the dosage ratio of the ethylene to the modifier is 1L:160mmol, and the dosage of the Ziegler-Natta catalyst is 5 per mill of the mass of the modifier.
The modified filler is prepared by the following steps:
step B1: mixing chitosan, sodium dodecyl sulfate, glacial acetic acid solution and deionized water, stirring for 6 hours at the rotating speed of 300r/min, regulating the pH value to be neutral to prepare pretreated chitosan, uniformly mixing 4, 5-dicarboxyimidazole, potassium dihydrogen phosphate and deionized water, stirring and adding pretreated chitosan at the rotating speed of 200r/min and the temperature of 95 ℃, heating to 130 ℃, reacting for 5 hours, filtering to remove filtrate, adding a substrate into Tris/methanol solution, and soaking for 1.5 hours to prepare modified chitosan;
step B2: dispersing graphene oxide in methanol, stirring and adding KH560 and deionized water at the rotation speed of 200r/min and the temperature of 70 ℃ for reaction for 5 hours, filtering to remove filtrate, dispersing a substrate in DMF, adding modified chitosan, reacting for 8 hours at the rotation speed of 300r/min and the temperature of 25 ℃ and the pH value of 11 to obtain a modified matrix, mixing the modified matrix, zinc nitrate hexahydrate and methanol at the rotation speed of 300r/min and the temperature of 25 ℃, stirring for 15 hours, and filtering to remove filtrate to obtain the modified filler.
The dosage ratio of the chitosan, the sodium dodecyl sulfate, the glacial acetic acid solution and the deionized water in the step B1 is 1:1:2:10, the mass fraction of the glacial acetic acid solution is 1%, the dosage ratio of the 4, 5-dicarboxyimidazole, the potassium dihydrogen phosphate, the deionized water and the pretreated chitosan is 1g:0.5g:45mL:1g, and the mass fraction of the Tris/methanol solution is 15%.
The dosage of KH560 in the step B2 is 3% of the mass of graphene oxide, the dosage ratio of substrate to modified chitosan is 1:3, and the mass ratio of modified substrate to zinc nitrate hexahydrate is 3:1.
Comparative example 1
This comparative example uses graphene oxide instead of modified filler as compared to example 1, the rest of the procedure being the same.
Comparative example 2
This comparative example uses chitosan instead of modified chitosan as compared to example 1, with the remainder of the procedure being the same.
Comparative example 3
This comparative example uses modified polysiloxane instead of modified monomer as compared with example 1, and the rest of the procedure is the same.
The polyethylene pipes prepared in examples 1-3 and comparative examples 1-3 were tested for oxygen permeability coefficient of the composite film according to the principle of differential pressure method, and oxygen blocking effect was measured, and the concentrations were 10, respectively 7 The CFU/mLDE staphylococcus aureus bacterial liquid and the escherichia coli bacterial liquid are smeared on the surfaces of the pipes of the examples 1-3 and the comparative examples 1-3, a layer of sterile PE film is covered, after the pipes are placed for 1h, the pipes are washed by a phosphate buffer solution, the washing solution is smeared in a culture medium, the culture is carried out for 24h, the colony count is counted, the antibacterial rate is calculated, the tensile strength of the polyethylene pipes of the examples 1-3 and the comparative examples 1-3 at the temperature of 20 ℃ and 50 ℃ and 120 ℃ is detected by using the standard of GB/T8804.3-2003, and the detection results are shown in the following table.
The table shows that the application has good effects of oxygen resistance, bacteria resistance and high temperature resistance.
The foregoing is merely illustrative and explanatory of the principles of the application, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the application or beyond the scope of the appended claims.
Claims (8)
1. A preparation method of an oxygen-blocking antibacterial heat-resistant polyethylene pipe is characterized by comprising the following steps of: the method specifically comprises the following steps:
step A1: KH572, dimethylaminoethyl methacrylate, benzoin dimethyl ether and DMF are mixed for reaction to prepare an intermediate 1, diphenyl dichlorosilane, the intermediate 1 and deionized water are mixed and stirred, concentrated sulfuric acid and 1, 3-tetramethyl disiloxane are added for reaction, and pH is adjusted to be neutral to prepare dihydro-terminal polysiloxane;
step A2: mixing and stirring dihydro-terminated polysiloxane, 4-vinylaniline and DMF, adding chloroplatinic acid, reacting to obtain modified polysiloxane, mixing and reacting modified polysiloxane, 2' -diallyl bisphenol A, paraformaldehyde and DMF to obtain modified monomer, mixing and reacting thioglycollic acid, allyl triphenylphosphine bromide, benzoin dimethyl ether and DMF to obtain intermediate 2;
step A3: mixing modified monomer, intermediate 2, DCC and DMF to react to obtain modifier, introducing ethylene into a reaction kettle, adding toluene, stirring, adding modifier and Ziegler-Natta catalyst, reacting, adding ethanol to terminate the reaction, adding the reaction product into acidified ethanol, filtering to remove filtrate, adding filter cake and reinforcing filler into an extruder, extruding and cooling to obtain polyethylene pipe.
2. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 1, which is characterized in that: the molar ratio of KH572 to dimethylaminoethyl methacrylate in the step A1 is 1:1, the amount of benzoin dimethyl ether is 3 per mill of the sum of KH572 and dimethylaminoethyl methacrylate, the amount of diphenyldichlorosilane, intermediate 1, deionized water and 1, 3-tetramethyldisiloxane is 1mmol:2mmol:20mL:2mmol, and the amount of concentrated sulfuric acid is 1% of the sum of diphenyldichlorosilane, intermediate 1 and 1, 3-tetramethyldisiloxane.
3. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 1, which is characterized in that: the mol ratio of the dihydro-end polysiloxane to the 4-vinylaniline in the step A2 is 1:2, the concentration of chloroplatinic acid in the mixture of the dihydro-end polysiloxane and the 4-vinylaniline is 10-15ppm, the mol ratio of the modified polysiloxane, the 2,2' -diallyl bisphenol A and the paraformaldehyde is 2:1:2, the mol ratio of the thioglycollic acid to the allyl triphenylphosphine bromide is 1:1, and the dosage of benzoin dimethyl ether is 3 percent of the sum of the masses of the thioglycollic acid and the allyl triphenylphosphine bromide.
4. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 1, which is characterized in that: the mole ratio of the modified monomer to the intermediate 2 to the DCC in the step A3 is 1:2:2.1, the dosage ratio of the ethylene to the modifier is 1L:160mmol, and the dosage of the Ziegler-Natta catalyst is 5 per mill of the mass of the modifier.
5. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 1, which is characterized in that: the modified filler is prepared by the following steps:
step B1: mixing and stirring chitosan, sodium dodecyl sulfate, glacial acetic acid solution and deionized water, regulating the pH value to be neutral to prepare pretreated chitosan, mixing and stirring 4, 5-dicarboxylimidazole, potassium dihydrogen phosphate and deionized water, adding pretreated chitosan, heating for reaction, filtering to remove filtrate, adding a substrate into Tris/methanol solution, and soaking to prepare modified chitosan;
step B2: dispersing graphene oxide in methanol, stirring, adding KH560 and deionized water, reacting, filtering to remove filtrate, dispersing a substrate in DMF, adding modified chitosan, reacting to obtain a modified matrix, mixing and stirring the modified matrix, zinc nitrate hexahydrate and methanol, and filtering to remove filtrate to obtain the modified filler.
6. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 5, which is characterized in that: the dosage ratio of the chitosan, the sodium dodecyl sulfate, the glacial acetic acid solution and the deionized water in the step B1 is 1:1:2:10, the dosage ratio of the 4, 5-dicarboxyimidazole, the monopotassium phosphate, the deionized water and the pretreated chitosan is 1g:0.5g:45mL:1g.
7. The method for preparing the oxygen-blocking antibacterial heat-resistant polyethylene pipe according to claim 5, which is characterized in that: the dosage of KH560 in the step B2 is 3% of the mass of graphene oxide, the dosage ratio of substrate to modified chitosan is 1:3, and the mass ratio of modified substrate to zinc nitrate hexahydrate is 3:1.
8. An oxygen-blocking antibacterial heat-resistant polyethylene pipe is characterized in that: the preparation method according to any one of claims 1 to 7.
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| CN117801782B (en) * | 2024-03-01 | 2024-05-07 | 上海连宝建材有限公司 | Organosilicon sealant and preparation method thereof |
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