CN116656034A - Toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products - Google Patents
Toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products Download PDFInfo
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- CN116656034A CN116656034A CN202310666631.6A CN202310666631A CN116656034A CN 116656034 A CN116656034 A CN 116656034A CN 202310666631 A CN202310666631 A CN 202310666631A CN 116656034 A CN116656034 A CN 116656034A
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- neck flask
- toughening
- master batch
- antibacterial
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- -1 polypropylene Polymers 0.000 title claims abstract description 67
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 58
- 239000004033 plastic Substances 0.000 title claims abstract description 56
- 229920003023 plastic Polymers 0.000 title claims abstract description 56
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 52
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 44
- 230000032683 aging Effects 0.000 title claims abstract description 31
- 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 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008213 purified water Substances 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 8
- 238000004321 preservation Methods 0.000 claims abstract description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000012745 toughening agent Substances 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 21
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 16
- 230000003712 anti-aging effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 12
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 9
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 9
- AZQGFVRDZTUHBU-UHFFFAOYSA-N isocyanic acid;triethoxy(propyl)silane Chemical compound N=C=O.CCC[Si](OCC)(OCC)OCC AZQGFVRDZTUHBU-UHFFFAOYSA-N 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 235000011087 fumaric acid Nutrition 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 3
- MTUBBMSQXXJFQP-UHFFFAOYSA-N OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O Chemical compound OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O MTUBBMSQXXJFQP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 20
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
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- 150000001412 amines Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 238000010438 heat treatment Methods 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
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- 239000000779 smoke Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
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- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2423/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a toughening modified master batch for an antibacterial and ageing-resistant polypropylene plastic product, and belongs to the technical field of preparation of toughening master batches. The invention is used for solving the technical problems of the prior art that the toughness, the antibacterial performance, the ageing resistance and the flame retardant performance of polypropylene plastic are to be further improved, and discloses a preparation method of toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products, which comprises the following steps: adding ethanol, purified water and a flame retardant into a three-neck flask, performing ultrasonic dispersion for 30-50min, transferring the three-neck flask to an iron stand with mechanical stirring for stirring, adding ammonia water and fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 45-55 ℃, slowly dropwise adding tetraethoxysilane into the three-neck flask, and performing heat preservation reaction for 3-4h after dropwise addition is completed. The invention not only effectively improves the toughness and antibacterial property of the polypropylene plastic, but also effectively improves the ageing resistance and flame retardance of the polypropylene plastic.
Description
Technical Field
The invention relates to the technical field of preparation of toughening master batches, in particular to a toughening modified master batch for an antibacterial and ageing-resistant polypropylene plastic product.
Background
Polypropylene (PP) is thermoplastic synthetic resin with excellent performance, and is colorless and semitransparent thermoplastic light general plastic. The thermoplastic plastic has chemical resistance, heat resistance, electrical insulation, high strength mechanical property, good high wear resistance processing property and the like, and is widely developed and applied in a plurality of fields of machinery, automobiles, electronic appliances, buildings, textiles, packaging, agriculture, forestry, fishery, food industry and the like.
The polypropylene plastic is easy to burn, a large amount of heat and smoke are released in the burning process, and tertiary carbon atoms connected with side methyl groups in a polypropylene molecular chain are easy to age in the environment to change the structure, so that the main chain is broken, the ageing resistance of the polypropylene plastic is poor, and in order to improve the flame retardant property and ageing resistance of the polypropylene plastic, a flame retardant and an ageing resistance agent are usually added into raw materials of the polypropylene plastic in the preparation process of the polypropylene plastic.
The polypropylene in the prior art has no antibacterial property, and is often matched with an antibacterial auxiliary agent, so that the antibacterial property of the polypropylene plastic is improved, the antibacterial auxiliary agent, the flame retardant and the anti-aging agent are added into the polypropylene plastic in a mixing manner, the compatibility between a large amount of doped additive auxiliary agents and the polypropylene is poor, weak interfacial property exists, the toughness of the polypropylene is reduced, in the use process, the antibacterial auxiliary agent, the flame retardant and the anti-aging agent are easy to migrate out of the polypropylene plastic, the existing acidic flame retardant can react with the anti-aging agent containing a hindered amine structure, active groups on the anti-aging agent are deactivated, and the ageing resistance and the flame retardant performance of the polypropylene plastic are required to be further improved.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a toughening modified master batch for an antibacterial and anti-aging polypropylene plastic product, which is used for solving the technical problems that in the prior art, a large amount of additives are doped into polypropylene plastic, so that the toughness of the polypropylene plastic is reduced, the additives are easy to migrate out of the polypropylene plastic in the using process, an acidic flame retardant can react with imino groups on an anti-aging agent containing a hindered amine structure, so that active groups on the anti-aging agent are deactivated, and the antibacterial performance, the anti-aging performance and the flame retardant performance of the polypropylene plastic are required to be further improved.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product comprises the following steps:
s1, adding ethanol, purified water and a flame retardant into a three-neck flask, performing ultrasonic dispersion for 30-50min, transferring the three-neck flask to an iron stand with mechanical stirring for stirring, adding ammonia water and fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 45-55 ℃, slowly dropwise adding tetraethoxysilane into the three-neck flask, and performing heat preservation reaction for 3-4h after the dropwise addition is completed, so as to obtain an intermediate I;
s2, adding the intermediate I, acetone and triethylamine into a three-neck flask protected by nitrogen, uniformly stirring, raising the temperature of the three-neck flask to 45-55 ℃, dropwise adding isocyanate propyl triethoxysilane into the three-neck flask, and carrying out heat preservation reaction for 3-5h after the dropwise adding is finished, and carrying out aftertreatment to obtain a modified flame retardant;
s3, adding 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, propenol, propenamine, modified acrylic acid, 1-tetradecene and toluene into a three-neck flask protected by nitrogen, uniformly stirring, adding an initiator into the three-neck flask, raising the temperature of the three-neck flask to 80-90 ℃, reacting for 8-10 hours, and post-treating to obtain a modified copolymer;
the synthetic reaction principle of the modified copolymer is as follows:
R:
s4, coating the modified copolymer outside the modified flame retardant to prepare the composite toughening agent;
s5, uniformly mixing the composite toughening agent, POE and the auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the toughening master batch.
Further, in the step S1, the weight ratio of ethanol to purified water to the flame retardant to ammonia water to fatty alcohol-polyoxyethylene ether to ethyl orthosilicate is 9:3:2:0.7:0.15:0.9, the flame retardant is ammonium polyphosphate, and the post-treatment operation includes: after the reaction is completed, the temperature of the three-neck flask is reduced to room temperature, suction filtration is carried out, a filter cake is washed by purified water and then is transferred to a drying oven with the temperature of 75-85 ℃ for vacuum drying to constant weight, and thus the intermediate I is obtained.
Further, in the step S2, the weight ratio of the intermediate I, acetone, triethylamine and isocyanate propyltriethoxysilane is 2:5:0.5:1, and the post-treatment operation includes: and after the reaction is finished, the temperature of the three-neck flask is reduced to room temperature, suction filtration is carried out, a filter cake is rinsed by acetone and is dried by suction, and then the filter cake is transferred into a drying oven with the temperature of 50-60 ℃ for vacuum drying to constant weight, so that the modified flame retardant is obtained.
Further, in the step S3, the molar ratio of 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, propenol, propenamine, modified acrylic acid, and 1-tetradecene is 1:1:5:2:2, the toluene is used in an amount 5 times the weight of 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, the initiator is one or more of AIBN and BPO, the weight of the initiator is 0.03 times the weight of propylene, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is kept at 80-90 ℃, and reduced pressure distillation is performed until no liquid flows out, so that the modified copolymer is obtained.
Further, the preparation method of the modified acrylic acid comprises the following steps: adding guanidine hydrochloride, acrylic acid, polymerization inhibitor and ethanol into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 65-75 ℃, reacting for 6-8h, and performing post treatment to obtain modified acrylic acid.
The synthetic reaction principle of the modified acrylic acid is as follows:
further, the weight ratio of guanidine hydrochloride, acrylic acid, polymerization inhibitor and ethanol is 4:3:0.1:15, the polymerization inhibitor is hydroquinone, and the post-treatment operation comprises: after the reaction is completed, the three-neck flask is kept at 65-75 ℃, the solvent is distilled off, toluene is added into the three-neck flask and stirred until the system is dissolved, then 10wt% of sodium hydroxide aqueous solution is added into the three-neck flask and stirred for 20-30min, the mixture is kept stand and separated, the organic phase is transferred into a rotary evaporator, the water bath temperature is set at 80-90 ℃, and the mixture is distilled under reduced pressure until no liquid flows out, so that the modified acrylic acid is obtained.
Further, the preparation method of the composite toughening agent comprises the following steps: adding the modified copolymer and acetone into a three-neck flask protected by nitrogen, stirring until the system is dissolved, adding the modified flame retardant into the three-neck flask, reacting for 2-3h at room temperature, and performing post-treatment to obtain the composite toughening agent.
Further, the weight ratio of the modified copolymer, the acetone and the modified flame retardant is 3:10:1, and the post-treatment operation comprises: after the reaction is finished, slowly adding purified water into the three-neck flask, stirring for 30-50min, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 65-75 ℃ and carrying out vacuum drying to constant weight, thus obtaining the composite toughening agent.
Further, the weight ratio of the composite toughening agent to POE to the auxiliary agent is 3:5:0.2, the auxiliary agent is composed of a dispersing agent, a lubricating agent and a crosslinking agent according to the weight ratio of 1:1:2, the dispersing agent is one or more of glyceryl monostearate, zinc stearate, calcium stearate and polyethylene wax, the lubricating agent is one or more of ethylene bis-stearamide, butyl stearate and glycerol trihydroxystearate, the crosslinking agent is a crosslinking agent TAIC, the temperature of a plurality of temperature sections from a feeding end to a discharging end of a charging barrel of a double-screw extruder is 160 ℃, 180 ℃ and 180 ℃ in sequence, the screw rotating speed is 20r/min, after the samples are extruded by the double-screw extruder, the samples are cut into toughened master batch wet products at the rotating speed of 200r/min by a granulator after being subjected to water cooling molding, and the toughened master batch wet products are transferred into a drying box with the temperature of 80-90 ℃ to be dried to constant weight in vacuum, and the toughened master batch wet products are obtained.
The toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product, which is prepared by the preparation method of the toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product according to any one of claims 1 to 9.
The invention has the following beneficial effects:
1. the invention relates to a toughening modified master batch for an antibacterial and anti-aging polypropylene plastic product, which is prepared by grafting guanidine hydrochloride onto acrylic acid through the reaction of guanidine hydrochloride and acrylic acid to obtain modified acrylic acid, and under the action of a free radical initiator, the free radical reaction of 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidyl) ester, propenol, propylene, modified acrylic acid and 1-tetradecene in toluene environment is carried out to generate a modified copolymer; the guanidine groups on the modified copolymer have higher activity, so that the modified copolymer is positive, and various bacteria and viruses are generally negative, so that guanidine salts are easily adsorbed, so that the bacteria and viruses cannot be split and propagated, the activity is lost, the antibacterial effect is achieved, two hindered amines carried on 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester are used as commonly used light stabilizers, the ageing resistance of the modified copolymer can be effectively improved, the structural similarity of propylene monomers in the modified copolymer and polypropylene can be improved, the compatibility of the propylene monomers and the polypropylene is improved, the weak interface property is reduced, and the modified copolymer is coated outside the modified flame retardant to be prepared into a toughening agent and then is blended with POE to prepare a toughening master batch; the toughness of POE is large and the compatibility with polyolefin is good, and the toughening effect of the toughening master batch on polypropylene can be effectively improved by mixing and granulating the toughening agent through POE.
2. According to the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product, in the preparation process, through the reaction of ammonium polyphosphate and tetraethoxysilane, under alkaline conditions, after hydrolysis of the tetraethoxysilane, condensation polymerization is carried out to generate polysiloxane which is coated on the outside of the ammonium polyphosphate, and then under the condition that triethylamine is used as a catalyst, a silicon-oxygen bond on isocyanate propyl triethoxysilane is broken and reacts with a polysiloxane active group on the outside of the ammonium polyphosphate, and isocyanate propyl triethoxysilane is grafted on the outside of the polysiloxane to obtain modified ammonium polyphosphate; isocyanate on modified ammonium polyphosphate can react with active groups such as hydroxyl or amino on modified copolymer, so that the bonding strength between the high-efficiency ammonium polyphosphate and the modified copolymer is improved, the ammonium polyphosphate is coated by polysiloxane, a separation layer is formed between the ammonium polyphosphate and the modified copolymer, the acid structure on the ammonium polyphosphate is prevented from reacting with N-H bond on the hindered amine structure on the modified copolymer, the deactivation of the hindered amine group is avoided, and the ageing resistance of polypropylene plastic is improved; in the flame retardant process of polypropylene plastic, the nitrogen-containing compound on the modified copolymer reacts with ammonium polyphosphate to generate an intermediate containing nitrogen-phosphorus bond, and the nitrogen compound can delay the volatilization loss of the phosphorus compound, thereby playing a role in promoting char formation and inhibiting the flame retardant effect of smoke generation.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products, which comprises the following steps:
s1, preparing a modified flame retardant
Weighing the following components in parts by weight: adding 900g of ethanol, 300g of purified water and 200g of flame retardant APP into a three-neck flask, performing ultrasonic dispersion for 30min, transferring the three-neck flask onto an iron stand with mechanical stirring, adding 70g of ammonia water and 15g of fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 45 ℃, slowly dropwise adding 90g of tetraethoxysilane into the three-neck flask, performing heat preservation reaction for 3h after the dropwise addition is completed, reducing the temperature of the three-neck flask to room temperature, performing suction filtration, washing a filter cake with purified water, and transferring to a drying box with the temperature of 75 ℃ for vacuum drying to constant weight to obtain an intermediate I;
weighing the following components in parts by weight: 200g of intermediate I, 500g of acetone and 50g of triethylamine are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 45 ℃, 100g of isocyanate propyl triethoxysilane is dropwise added into the three-neck flask, the reaction is carried out for 3 hours after the dropwise addition is finished, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is subjected to suction filtration, and a filter cake is rinsed by acetone and is dried in a drying oven at 50 ℃ in vacuum until the weight is constant, so that the modified flame retardant is obtained.
S2, preparing modified acrylic acid
Weighing the following components in parts by weight: adding 400g of guanidine hydrochloride, 300g of acrylic acid, 10g of hydroquinone and 1500g of ethanol into a three-neck flask, stirring, heating the three-neck flask to 65 ℃, reacting for 6 hours, after the reaction is completed, preserving the temperature of the three-neck flask to 65 ℃, steaming to remove the solvent, adding 1000g of toluene into the three-neck flask, stirring until the system is dissolved, adding 800g of 10wt% of sodium hydroxide aqueous solution into the three-neck flask, stirring for 20min, standing, separating the liquid, transferring the organic phase into a rotary evaporator, setting the water bath temperature to 80 ℃, and distilling under reduced pressure until no liquid flows out, thereby obtaining the modified acrylic acid.
S3, preparing modified copolymer
Weighing the following components in parts by weight: 197g of 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidyl) ester, 28g of propenol, 110g of propenamine, 113g of modified acrylic acid, 197g of 1-tetradecene and 985g of toluene are added into a three-neck flask protected by nitrogen and uniformly stirred, 29.5g of AIBN is added into the three-neck flask, the temperature of the three-neck flask is increased to 80 ℃ for 8 hours of reaction, the temperature of the three-neck flask is kept at 80 ℃ after the reaction is finished, and reduced pressure distillation is carried out until no liquid flows out, so that a modified copolymer is obtained.
S4, preparing a composite toughening agent
Weighing the following components in parts by weight: adding 300g of modified copolymer and 1000g of acetone into a three-neck flask protected by nitrogen, stirring until the system is dissolved, adding 100g of modified flame retardant into the three-neck flask, reacting for 2 hours at room temperature, slowly adding 2000g of purified water into the three-neck flask after the reaction is completed, stirring for 30 minutes, carrying out suction filtration, transferring a filter cake into a drying box with the temperature of 65 ℃ and carrying out vacuum drying until the weight is constant, thus obtaining the composite toughening agent.
S5, preparing toughening master batch
Weighing the following components in parts by weight: 150g of composite toughening agent, 250g of POE, 2.5g of stearic acid monoglyceride, 2.5g of ethylene bisstearamide and 5g of cross-linking agent TAIC are uniformly mixed, the mixture is added into a double-screw extruder, the mixture is subjected to melt extrusion, the temperatures of a plurality of temperature sections from a feeding end to a discharging end of a charging barrel of the double-screw extruder are 160 ℃, 180 ℃ and 180 ℃ in sequence, the screw rotating speed is 20r/min, a sample is subjected to water cooling molding after the extrusion of the double-screw extruder, the sample is cut into a toughening master batch wet product by a granulator at the rotating speed of 200r/min, the toughening master batch wet product is transferred into a drying box at the temperature of 80 ℃ and is dried to constant weight in vacuum, and the toughening master batch is granulated, so that the toughening master batch is obtained.
Example 2
The embodiment provides a preparation method of toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products, which comprises the following steps:
s1, preparing a modified flame retardant
Weighing the following components in parts by weight: adding 900g of ethanol, 300g of purified water and 200g of flame retardant APP into a three-neck flask, performing ultrasonic dispersion for 40min, transferring the three-neck flask onto an iron stand with mechanical stirring, adding 70g of ammonia water and 15g of fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 50 ℃, slowly dropwise adding 90g of tetraethoxysilane into the three-neck flask, performing heat preservation reaction for 3.5h after the dropwise addition is completed, reducing the temperature of the three-neck flask to room temperature, performing suction filtration, washing a filter cake with purified water, and transferring to a drying box with the temperature of 80 ℃ for vacuum drying to constant weight to obtain an intermediate I;
weighing the following components in parts by weight: 200g of intermediate I, 500g of acetone and 50g of triethylamine are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 50 ℃, 100g of isocyanate propyl triethoxysilane is dropwise added into the three-neck flask, the reaction is carried out for 4 hours after the dropwise addition is completed, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is subjected to suction filtration, and a filter cake is rinsed by acetone and is dried in a vacuum manner in a drying oven with the temperature of 55 ℃ until the weight is constant, so that the modified flame retardant is obtained.
S2, preparing modified acrylic acid
Weighing the following components in parts by weight: adding 400g of guanidine hydrochloride, 300g of acrylic acid, 10g of hydroquinone and 1500g of ethanol into a three-neck flask, stirring, heating the three-neck flask to 70 ℃, reacting for 7h, after the reaction is completed, preserving the temperature of the three-neck flask to 70 ℃, steaming to remove the solvent, adding 1000g of toluene into the three-neck flask, stirring until the system is dissolved, adding 800g of 10wt% sodium hydroxide aqueous solution into the three-neck flask, stirring for 25min, standing, separating the liquid, transferring the organic phase into a rotary evaporator, setting the water bath temperature to 85 ℃, and distilling under reduced pressure until no liquid flows out, thereby obtaining the modified acrylic acid.
S3, preparing modified copolymer
Weighing the following components in parts by weight: 197g of 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidyl) ester, 28g of propenol, 110g of propenamine, 113g of modified acrylic acid, 197g of 1-tetradecene and 985g of toluene are added into a three-neck flask protected by nitrogen and uniformly stirred, 29.5g of BPO is added into the three-neck flask, the temperature of the three-neck flask is increased to 85 ℃ for 9 hours, the temperature of the three-neck flask is kept at 85 ℃ after the reaction is completed, and reduced pressure distillation is carried out until no liquid flows out, so that a modified copolymer is obtained.
S4, preparing a composite toughening agent
Weighing the following components in parts by weight: adding 300g of modified copolymer and 1000g of acetone into a three-neck flask protected by nitrogen, stirring until the system is dissolved, adding 100g of modified flame retardant into the three-neck flask, reacting for 2.5 hours at room temperature, slowly adding 2000g of purified water into the three-neck flask after the reaction is completed, stirring for 40 minutes, carrying out suction filtration, transferring a filter cake into a drying box with the temperature of 70 ℃ and carrying out vacuum drying until the weight is constant, thus obtaining the composite toughening agent.
S5, preparing toughening master batch
Weighing the following components in parts by weight: 150g of composite toughening agent, 250g of POE, 2.5g of zinc stearate, 2.5g of butyl stearate and 5g of cross-linking agent TAIC are uniformly mixed, the mixture is added into a double-screw extruder, the mixture is subjected to melt extrusion, the temperatures of a plurality of temperature sections from a feeding end to a discharging end of a charging barrel of the double-screw extruder are 160 ℃, 180 ℃ and 180 ℃ in sequence, the screw rotating speed is 20r/min, a sample is subjected to water cooling molding after the extrusion of the double-screw extruder, the sample is cut into a toughening master batch wet product at the rotating speed of 200r/min by a granulator, the toughening master batch wet product is transferred into a drying box at the temperature of 85 ℃ and is dried to constant weight in vacuum, and the toughening master batch is granulated, so that the toughening master batch is obtained.
Example 3
The embodiment provides a preparation method of toughening modified master batch for antibacterial and ageing-resistant polypropylene plastic products, which comprises the following steps:
s1, preparing a modified flame retardant
Weighing the following components in parts by weight: adding 900g of ethanol, 300g of purified water and 200g of flame retardant APP into a three-neck flask, carrying out ultrasonic dispersion for 50min, transferring the three-neck flask onto an iron stand with mechanical stirring, adding 70g of ammonia water and 15g of fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 55 ℃, slowly dropwise adding 90g of tetraethoxysilane into the three-neck flask, carrying out heat preservation reaction for 3-4h after the dropwise addition is completed, reducing the temperature of the three-neck flask to room temperature, carrying out suction filtration, washing a filter cake with purified water, and then transferring the filter cake into a drying box with the temperature of 85 ℃ to be dried to constant weight in vacuum, thus obtaining an intermediate I;
weighing the following components in parts by weight: 200g of intermediate I, 500g of acetone and 50g of triethylamine are added into a three-neck flask protected by nitrogen, the temperature of the three-neck flask is increased to 55 ℃, 100g of isocyanate propyl triethoxysilane is dropwise added into the three-neck flask, the reaction is carried out for 5 hours after the dropwise addition is completed, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is subjected to suction filtration, and a filter cake is rinsed by acetone and is dried in a vacuum manner in a drying oven with the temperature of 60 ℃ until the weight is constant, so that the modified flame retardant is obtained.
S2, preparing modified acrylic acid
Weighing the following components in parts by weight: adding 400g of guanidine hydrochloride, 300g of acrylic acid, 10g of hydroquinone and 1500g of ethanol into a three-neck flask, stirring, heating the three-neck flask to 75 ℃, reacting for 8 hours, after the reaction is completed, preserving the temperature of the three-neck flask by 75 ℃, steaming to remove the solvent, adding 1000g of toluene into the three-neck flask, stirring until the system is dissolved, adding 800g of 10wt% of sodium hydroxide aqueous solution into the three-neck flask, stirring for 30min, standing, separating the liquid, transferring the organic phase into a rotary evaporator, setting the water bath temperature to 90 ℃, and distilling under reduced pressure until no liquid flows out, thereby obtaining the modified acrylic acid.
S3, preparing modified copolymer
Weighing the following components in parts by weight: 197g of 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidyl) ester, 28g of propenol, 110g of propenamine, 113g of modified acrylic acid, 197g of 1-tetradecene and 985g of toluene are added into a three-neck flask protected by nitrogen and uniformly stirred, 29.5g of AIBN is added into the three-neck flask, the temperature of the three-neck flask is increased to 90 ℃ for 10 hours, the temperature of the three-neck flask is kept at 90 ℃ after the reaction is completed, and reduced pressure distillation is carried out until no liquid flows out, so that a modified copolymer is obtained.
S4, preparing a composite toughening agent
Weighing the following components in parts by weight: adding 300g of modified copolymer and 1000g of acetone into a three-neck flask protected by nitrogen, stirring until the system is dissolved, adding 100g of modified flame retardant into the three-neck flask, reacting for 3 hours at room temperature, slowly adding 2000g of purified water into the three-neck flask after the reaction is completed, stirring for 50 minutes, carrying out suction filtration, transferring a filter cake into a drying box with the temperature of 75 ℃ and carrying out vacuum drying until the weight is constant, thus obtaining the composite toughening agent.
S5, preparing toughening master batch
Weighing the following components in parts by weight: 150g of composite toughening agent, 250g of POE, 2.5g of polyethylene wax, 2.5g of glycerol trihydroxystearate and 5g of cross-linking agent TAIC are uniformly mixed, the mixture is added into a double-screw extruder, the temperature of a plurality of temperature sections from a feeding end to a discharging end of a charging barrel of the double-screw extruder is 160 ℃, 180 ℃ and 180 ℃ in sequence, the screw rotating speed is 20r/min, after the double-screw extruder extrudes a sample, the sample is subjected to water cooling molding, the sample is cut into a toughened master batch wet product by a granulator at the rotating speed of 200r/min, the toughened master batch wet product is transferred into a drying box with the temperature of 90 ℃ to be dried to constant weight in vacuum, and the toughened master batch is obtained for granulation, thus obtaining the toughened master batch.
Comparative example 1
This comparative example differs from example 3 in that intermediate I prepared in step S1 was omitted and the flame retardant APP was equally substituted for intermediate I to participate in the next reaction.
Comparative example 2
This comparative example differs from example 3 in that modified acrylic acid and 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester are not added in step S3.
Comparative example 3
The comparative example differs from example 3 in that step S5 was omitted and the composite plasticizer prepared in step S4 was used as the toughening master batch.
Performance test:
the toughening master batches prepared in the examples 1-3 and the comparative examples 1-3 are respectively mixed with polypropylene according to the weight ratio of 1:5 to prepare polyolefin plastic samples, and antibacterial performance, flame retardant performance, ageing resistance and toughness of the samples are tested, wherein the toughness test refers to the standard GB/T1843-2008 "determination of impact strength of plastic cantilever beam", GB/T1040.1-2018 "determination of tensile Property of plastics 1 st: general rule, GB/T9341-2008 "determination of Plastic flexural Property" respectively test impact Strength, tensile Strength and flexural modulus of test pieces, and antibacterial property test is to test antibacterial properties of antibacterial plastics by flask concussion method with Staphylococcus aureus and Escherichia coli as representatives of gram-negative and gram-positive bacteria, respectively. The test piece is irradiated for 2 hours under ultraviolet light to fully sterilize, 5mL of bacterial liquid is diluted to 1 multiplied by 104cfu/mL to 5 multiplied by 104cfu/mL by 70mLPBS buffer solution to be used as bacterial suspension for antibacterial test, and 100 mu L is counted by a plate counting method before the sample is added. Placing an antibacterial plastic sample test group (75 mg) in a shaking table at 25 ℃ and 300r/min for full shaking, taking 100 mu L of each bacterial liquid at different shaking time, respectively sucking 0.5mL after gradient dilution, placing in two plates, pouring 15mL of nutrient agar culture medium, rotating the plates to fully mix, turning the plates after agar solidification, culturing in a 35 ℃ incubator for 48h, counting viable bacteria colonies, calculating the antibacterial rate of staphylococcus aureus and escherichia coli, and the aging resistance performance is that a test piece is placed in an oven at 90 ℃ for UV irradiation for 12h, the toughness and the flame resistance performance of the test piece are measured according to the standard GB/T2408-2021 (measuring level method and vertical method of plastic combustion performance) and the vertical combustion level of the test piece, wherein the specific test results are shown in the following table:
data analysis:
through the data analysis in the examples 1-3 in the table, the toughening master batch prepared by the invention is matched with polypropylene, so that the toughness, the ageing resistance, the antibacterial property and the vertical burning grade of polypropylene plastics can be effectively improved;
the data analysis of the comparative example 1 and the examples 1-3 shows that the ageing resistance of the comparative example 1 is lower than that of the examples 1-3, and the fact that the polysiloxane is used for coating the flame retardant APP can effectively avoid the reaction of an acid structure on ammonium polyphosphate and N-H bonds on a hindered amine structure on a modified copolymer, so that the hindered amine group is deactivated, and the flame retardant APP is coated, so that the activity of the hindered amine can be effectively improved, and the ageing resistance of the polypropylene plastic is further improved;
the data analysis of comparative example 2 and examples 1-3 shows that the ageing resistance, antibacterial performance and vertical burning grade of comparative example 2 are lower than those of examples 1-3, and the hindered amine structure and the guanidine group on the modified copolymer can improve the ageing resistance and antibacterial performance of the plastic, and can be matched with the flame retardant APP to improve the vertical burning grade of the polypropylene plastic;
analysis of the data of comparative example 3 and examples 1-3, the toughness of comparative example 3 was lower than examples 1-3, indicating that POE doping was effective in improving the toughness of polypropylene plastics.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The preparation method of the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product is characterized by comprising the following steps of:
s1, adding ethanol, purified water and a flame retardant into a three-neck flask, performing ultrasonic dispersion for 30-50min, transferring the three-neck flask to an iron stand with mechanical stirring for stirring, adding ammonia water and fatty alcohol polyoxyethylene ether into the three-neck flask, raising the temperature of the three-neck flask to 45-55 ℃, slowly dropwise adding tetraethoxysilane into the three-neck flask, and performing heat preservation reaction for 3-4h after the dropwise addition is completed, so as to obtain an intermediate I;
s2, adding the intermediate I, acetone and triethylamine into a three-neck flask protected by nitrogen, uniformly stirring, raising the temperature of the three-neck flask to 45-55 ℃, dropwise adding isocyanate propyl triethoxysilane into the three-neck flask, and carrying out heat preservation reaction for 3-5h after the dropwise adding is finished, and carrying out aftertreatment to obtain a modified flame retardant;
s3, adding 2-butene diacid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, propenol, propenamine, modified acrylic acid, 1-tetradecene and toluene into a three-neck flask protected by nitrogen, uniformly stirring, adding an initiator into the three-neck flask, raising the temperature of the three-neck flask to 80-90 ℃, reacting for 8-10 hours, and post-treating to obtain a modified copolymer;
s4, coating the modified copolymer outside the modified flame retardant to prepare the composite toughening agent;
s5, uniformly mixing the composite toughening agent, POE and the auxiliary agent, adding the mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the toughening master batch.
2. The method for preparing the toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product according to claim 1, wherein in the step S1, the weight ratio of ethanol, purified water, a flame retardant, ammonia water, fatty alcohol polyoxyethylene ether and tetraethoxysilane is 9:3:2:0.7:0.15:0.9, and the flame retardant is ammonium polyphosphate.
3. The method for preparing the toughening modified master batch for the antibacterial and aging-resistant polypropylene plastic product according to claim 1, wherein the weight ratio of the intermediate I to the acetone to the triethylamine to the isocyanate propyltriethoxysilane in the step S2 is 2:5:0.5:1.
4. The method for preparing the toughening modified master batch for the antibacterial and aging-resistant polypropylene plastic product according to claim 1, wherein in the step S3, the molar ratio of 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, propenol, acrylamide, modified acrylic acid and 1-tetradecene is 1:1:5:2:2, the toluene amount is 5 times of the weight of the 2-butenedioic acid (2E) -1, 4-bis (2, 6-tetramethyl-4-piperidinyl) ester, the initiator is one or more of AIBN and BPO, and the weight of the initiator is 0.03 times of the weight of propylene.
5. The method for preparing the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product, which is characterized by comprising the following steps of: adding guanidine hydrochloride, acrylic acid, polymerization inhibitor and ethanol into a three-neck flask, stirring, increasing the temperature of the three-neck flask to 65-75 ℃, reacting for 6-8h, and performing post treatment to obtain modified acrylic acid.
6. The method for preparing the toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product, which is disclosed in claim 5, is characterized in that the weight ratio of guanidine hydrochloride to acrylic acid to polymerization inhibitor to ethanol is 4:3:0.1:15, and the polymerization inhibitor is hydroquinone.
7. The method for preparing the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product, which is disclosed in claim 1, is characterized in that the preparation method of the composite toughening agent is as follows: adding the modified copolymer and acetone into a three-neck flask protected by nitrogen, stirring until the system is dissolved, adding the modified flame retardant into the three-neck flask, reacting for 2-3h at room temperature, and performing post-treatment to obtain the composite toughening agent.
8. The method for preparing the toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product, which is disclosed in claim 7, wherein the weight ratio of the modified copolymer to the acetone to the modified flame retardant is 3:10:1.
9. The method for preparing the toughening modified master batch for the antibacterial and ageing-resistant polypropylene plastic product according to claim 1, wherein the weight ratio of the composite toughening agent to the POE to the auxiliary agent is 3:5:0.2, the auxiliary agent consists of a dispersing agent, a lubricating agent and a cross-linking agent according to the weight ratio of 1:1:2, the dispersing agent is one or more of monoglyceride stearate, zinc stearate, calcium stearate and polyethylene wax, the lubricating agent is one or more of ethylene bis-stearamide, butyl stearate and glycerol trihydroxystearate, the cross-linking agent is a cross-linking agent TAIC, the temperature of a plurality of temperature sections from a feeding end to a discharging end of a barrel of the double-screw extruder is 160 ℃, 180 ℃ and 180 ℃ in turn, the screw speed is 20r/min, after the sample is extruded by the double-screw extruder, the sample is subjected to water cooling molding, the sample is cut into a toughening master batch by a cutter at the speed of 200r/min, the toughening master batch wet batch is transferred into a toughening constant weight in a drying box with the temperature of 80-90 ℃ and the toughening master batch is dried in vacuum.
10. The toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product, which is characterized by being prepared by the preparation method of the toughening modified master batch for the antibacterial and anti-aging polypropylene plastic product according to any one of claims 1 to 9.
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