CN116285111B - Biodegradable modified polypropylene material and preparation method thereof - Google Patents
Biodegradable modified polypropylene material and preparation method thereof Download PDFInfo
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- CN116285111B CN116285111B CN202310366377.8A CN202310366377A CN116285111B CN 116285111 B CN116285111 B CN 116285111B CN 202310366377 A CN202310366377 A CN 202310366377A CN 116285111 B CN116285111 B CN 116285111B
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- -1 polypropylene Polymers 0.000 title claims abstract description 139
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 120
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 119
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920005610 lignin Polymers 0.000 claims description 60
- 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 description 46
- 239000003063 flame retardant Substances 0.000 claims description 46
- 239000002131 composite material Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 16
- 229920000573 polyethylene Polymers 0.000 claims description 16
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011343 solid material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 102100027198 Sodium channel protein type 5 subunit alpha Human genes 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- WVXMNBDPVYOPLX-UHFFFAOYSA-N 2-isocyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCC[N+]#[C-] WVXMNBDPVYOPLX-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 101001093143 Homo sapiens Protein transport protein Sec61 subunit gamma Proteins 0.000 claims description 3
- 101000694017 Homo sapiens Sodium channel protein type 5 subunit alpha Proteins 0.000 claims description 3
- 101100120905 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TDH1 gene Proteins 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006366 phosphorylation reaction Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- 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)
Abstract
The invention relates to the technical field of high polymer materials and discloses a biodegradable modified polypropylene material and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a biodegradable modified polypropylene material and a preparation method thereof.
Background
The polypropylene is a colorless and odorless organic polymer material with strong corrosion resistance and higher specific strength, is one of the plastic varieties with the largest using amount in the market, and is widely applied to actual life, but polyethylene is difficult to degrade in normal state, and a large amount of polyethylene is used to cause 'white pollution', so that harm to the environment, which is not ground, is generated, and the polypropylene is required to gradually develop towards the degradable direction under the development concept of energy conservation and environmental protection, which is promoted greatly at present.
Most of the polypropylene produced industrially at present is isotactic polypropylene, presents a linear structure, has narrower molecular weight distribution, so that the melt strength is lower, the toughness is poorer, the polypropylene is difficult to foam, in addition, in the thermal forming treatment processes such as extrusion, calendaring and the like, the phenomenon of edge curling or shrinkage of the product can be caused, the produced dimensional stability is influenced, therefore, the application of the polypropylene in the thermal forming field is greatly limited, the polypropylene with the linear structure basically has no flame retardant property, the requirement of part of industrial application is difficult to meet, the development of the polypropylene is hindered, and in order to solve the problems, the chemical grafting or physical filling mode is mainly adopted at present.
The invention of China patent No. CN201810453130.9 discloses a biodegradable PP woven bag material and a preparation method thereof, corn starch and polypropylene are polymerized, and sodium bacillus powder is used as a degradation agent, and is used for inducing starch degradation to break the whole polymerized molecular chain, so that macromolecular polypropylene is decomposed into micromolecular polypropylene, and the degradation of polypropylene is facilitated, so that biomass material and polypropylene can be compounded, and the degradability of polypropylene is improved.
The Chinese patent application No. CN202110454734.7 discloses a halogen-free flame-retardant polypropylene foaming composite material and a preparation method thereof, melamine resin is used as a cross-linking agent, and is grafted with maleic anhydride serving as a compatilizer to react with ethylene-octene copolymer, so that the melt strength of polypropylene is enhanced, and after the compatilizer is added, the interface performance of a polypropylene matrix and pentaerythritol polyphosphate melamine salt serving as a flame retardant can be effectively improved, the flame-retardant effect of the polypropylene is enhanced, and therefore, the melt strength and the flame retardant performance of the polypropylene can be improved by utilizing a chemical cross-linking modification mode.
Disclosure of Invention
The invention aims to provide a biodegradable modified polypropylene material and a preparation method thereof, wherein the polypropylene is made into a three-dimensional crosslinked network structure by preparing a composite compatilizer, so that the problem of lower melt strength of the polypropylene is solved, meanwhile, the toughness and heat-resistant stability of the polypropylene material are enhanced, and the lignin-based intumescent flame retardant is prepared and mixed with the polypropylene in the form of an additive, so that the problem of poor flame retardant property of the polypropylene material is solved.
The aim of the invention can be achieved by the following technical scheme:
a biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 70-80 parts of polypropylene matrix, 20-30 parts of composite compatilizer, 2-6 parts of lignin-based intumescent flame retardant, 0.2-0.5 part of antioxidant 1010 and 0.3-0.6 part of polyethylene wax;
the composite compatilizer is prepared by introducing isocyanate groups into a polypropylene molecular chain through a melt grafting method and then connecting POSS;
the lignin-based intumescent flame retardant is prepared by modifying a phosphate group in a lignin structure, and introducing amine substances through a salifying reaction.
Further, the preparation method of the composite compatilizer specifically comprises the following steps:
SS1: uniformly mixing polypropylene, 2-isocyanoethyl acrylate and an initiator, pouring the mixture into a polymerization kettle, raising the temperature in the polymerization kettle to 160-170 ℃, performing melt grafting for 4-8min at the rotating speed of 50-60r/min, pouring the product into dimethylbenzene for dissolution and filtration, settling by using acetone, repeating the dissolution-settling process for 2-3 times, and performing vacuum drying to obtain an intermediate;
SS2: mixing the intermediate, p-aminophenyl POSS and toluene, dripping catalyst, stirring at 60-70 deg.c for 4-12 hr, vacuum distilling to eliminate solvent, filtering to obtain solid material, washing and vacuum drying to obtain the composite compatilizer.
According to the technical scheme, under the action of the initiator and high temperature, the polypropylene generates free radicals, the polymerization reaction of the 2-isocyanoethyl acrylate and the polypropylene is initiated, the isocyanate groups are introduced into the polypropylene structure to obtain the intermediate, the isocyanate groups in the intermediate structure can react with the p-aminophenyl POSS under the action of the catalyst, and the three-dimensional crosslinked network which takes the POSS as a crosslinking point and contains the isocyanate groups in the structure is formed by controlling the dosage of the intermediate and the p-aminophenyl POSS.
Further, in step SS1, the initiator is any one of benzoyl peroxide and dicumyl peroxide.
Further, in step SS2, the catalyst is any one of dibutyltin dilaurate or stannous octoate.
Further, in step SS2, the mass ratio of the intermediate to the p-aminophenyl POSS is 10:0.5-1.5.
Further, the preparation method of the lignin-based intumescent flame retardant specifically comprises the following steps:
SSS1: mixing lignin and tetrahydrofuran, adding phosphorus pentoxide, stirring at room temperature for 2-6h, distilling under reduced pressure to remove solvent, pouring purified water to precipitate solid materials, centrifuging to separate solid sample, and vacuum drying to obtain phosphorus-containing lignin;
SSS2: dissolving phosphorus-containing lignin in 1, 4-dioxane, raising the system temperature to 70 ℃, adding piperazine, stirring for 4-8h, distilling under reduced pressure to remove solvent, washing the solid material for 2-3 times by using ethanol, vacuum drying, grinding and sieving to obtain the lignin-based intumescent flame retardant.
Through the technical scheme, hydroxyl in the lignin structure can be subjected to phosphorylation reaction with phosphorus pentoxide, and a phosphate group is introduced into the lignin structure to prepare the phosphorus-containing lignin, wherein the phosphate group in the lignin structure can be subjected to salt reaction with secondary amino in the piperazine structure to form the three-source integrated intumescent flame retardant taking lignin as a carbon source, phosphoric acid as an acid source and piperazine as an air source, namely the lignin-based intumescent flame retardant.
Further, in the step SSS1, the mass ratio of the lignin to the phosphorus pentoxide is 1:2-5.
Further, in step SSS2, the mesh number of the screen is 10 to 20 mesh.
The preparation method of the biodegradable modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 500-600r/min, and stirring until a uniform premix is formed;
s2: adding premix into a double-screw extruder through a main feeding hopper, adding lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting parameters, performing extrusion granulation, and naturally cooling the materials to obtain the biodegradable modified polypropylene material.
Further, in step S2, the parameter setting: the temperature of the main feeding hopper is 200-240 ℃, the temperature of the side feeding hopper is 180-200 ℃, and the rotating speed of the screw is 300-400r/min.
The invention has the beneficial effects that:
1) According to the invention, the special isocyanate group short branched chain is introduced into the polypropylene structure, and the high activity of the isocyanate group is utilized to react with the p-aminophenyl POSS to prepare the polypropylene with the POSS as a crosslinking point and a three-dimensional network structure as a composite compatilizer, so that the polypropylene is endowed with a rich branched structure, the crosslinking density of the polypropylene matrix is improved, the melt strength of the polypropylene matrix is enhanced, the polypropylene matrix is further easier to apply in a foaming material, meanwhile, the POSS structure is stable, a large number of organic silicon-oxygen bonds are contained, and the polypropylene material has stronger toughness and more excellent heat resistance due to higher bond energy, thereby being beneficial to further expanding the application range of the polypropylene material.
2) According to the invention, the three-source integrated lignin-based intumescent flame retardant is prepared and is mixed with polypropylene as a composite flame retardant, after lignin is modified, the lipophilicity is improved, the compatibility with a polypropylene matrix is enhanced, and as the composite compatilizer contains isocyanate groups with higher activity, the interface performance of the lignin-based intumescent flame retardant and the polypropylene matrix can be further improved, so that the lignin-based intumescent flame retardant can be relatively uniformly dispersed in the polypropylene matrix, when the polypropylene material is in a combustion state, the lignin-based intumescent carbon source can rapidly form an intumescent carbon layer on the surface of the polypropylene matrix to isolate oxygen and heat, the polypropylene material is prevented from further combustion, and POSS in the composite compatilizer can generate silicon oxide after being burnt and deposited in the intumescent carbon layer, so that the structural stability of the intumescent carbon layer is improved, and the synergistic flame retardant effect is formed, and the flame retardant performance of the polypropylene material is effectively enhanced.
3) According to the invention, the lignin-based intumescent flame retardant is mixed with the polypropylene, and the lignin is a natural organic polymer material, so that the lignin can be biodegraded, and a large number of hole structures can be left in the polypropylene material after degradation, so that more polypropylene end groups are exposed in the environment, the degradable area of the polypropylene material is increased, and the degradation of the macromolecular polypropylene material into the micromolecular polypropylene material is promoted, thereby being beneficial to the degradation of the whole polypropylene material.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of a biodegradable modified polypropylene material according to the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but 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.
As shown in fig. 1, the preparation flow of the biodegradable modified polypropylene material of the present invention in examples 1 to 3 is shown in fig. 1.
Example 1
A biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 70 parts of polypropylene matrix, 20 parts of composite compatilizer, 2 parts of lignin-based intumescent flame retardant, 0.2 part of antioxidant 1010 and 0.3 part of polyethylene wax;
the preparation method of the modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 500r/min, and stirring until a uniform premix is formed;
s2: adding the premix into a double-screw extruder through a main feeding hopper, adding the lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting the temperature at the main feeding hopper to be 200 ℃, setting the temperature at the side feeding hopper to be 180 ℃, and performing extrusion granulation at the screw speed of 300r/min until the materials are naturally cooled to obtain the biodegradable modified polypropylene material.
The preparation method of the composite compatilizer specifically comprises the following steps:
SS1: uniformly mixing 15g of polypropylene, 5g of 2-isocyanoethyl acrylate and 0.1g of dicumyl peroxide, pouring into a polymerization kettle, raising the temperature in the polymerization kettle to 170 ℃, performing melt grafting for 8min at the rotating speed of 60r/min, pouring the product into xylene for dissolution and filtration, settling by using acetone, repeating the dissolution-settling process for 3 times, and vacuum drying to obtain an intermediate; weighing 1.000g of modified intermediate, pouring into 25mL of toluene solution, shaking uniformly, dripping 40mL of di-n-butylamine-toluene solution with the concentration of 0.1mol/L, shaking for 10min, adding 50mL of isopropanol and 5 drops of bromophenol blue indicator, titrating by using 0.1mol/L of HCl standard solution until the blue color of the solution disappears, gradually changing the solution from green to yellow, keeping 1min without color change as a titration end point, recording the consumption volume of the HCl standard solution, performing test for 5 times in parallel to obtain an average value, and performing a blank control experiment, wherein the method comprises the following steps of
Calculating the content of isocyanate groups in the intermediate structure, wherein V1 is the volume (mL) of an HCl standard solution consumed in a blank test, V2 is the volume (mL) of the HCl standard solution consumed by a titration sample, C is the concentration (mol/L) of the HCl standard solution, M is the mass of the sample, and obtaining W after test calculation NCO The value was 10.35%.
SS2: uniformly mixing 10g of intermediate, 1.2g of p-aminophenyl POSS and toluene, dropwise adding dibutyltin dilaurate, uniformly stirring, stirring for 8 hours at the temperature of 70 ℃, distilling under reduced pressure to remove the solvent, filtering out solid materials, washing, and drying in vacuum to obtain the composite compatilizer; as in step SS1, titration was usedTesting the content of isocyanate groups in the composite compatilizer by a method, and obtaining W through test calculation NCO The value was 2.27%, and it was presumed that the isocyanate groups in the intermediate structure reacted with p-aminophenyl POSS to form a three-dimensional crosslinked network polypropylene having POSS as a crosslinking point and isocyanate groups in the molecular chain, and that a part of the isocyanate groups was consumed, resulting in a decrease in the isocyanate group content.
The preparation method of the lignin-based intumescent flame retardant specifically comprises the following steps:
SSS1: mixing 2g of lignin with tetrahydrofuran, adding 5g of phosphorus pentoxide, stirring uniformly, stirring at room temperature for 3 hours, distilling under reduced pressure to remove solvent, pouring purified water to separate out solid materials, centrifuging to separate out a solid sample, and drying in vacuum to obtain phosphorus-containing lignin;
SSS2: dissolving 1g of phosphorus-containing lignin in 1, 4-dioxane, raising the temperature of the system to 70 ℃, adding 1.5g of piperazine, stirring for 6 hours, carrying out reduced pressure distillation to remove the solvent, washing the solid material for 3 times by using ethanol, carrying out vacuum drying, grinding and sieving by a 20-mesh sieve to obtain the lignin-based intumescent flame retardant; the nitrogen content in the lignin-based intumescent flame retardant is tested by using an NQR-4A type full-automatic element detection analyzer, and the nitrogen content in the lignin-based intumescent flame retardant is 15.84% through the test, which is supposed to be caused by the salification reaction of piperazine and phosphorus-containing lignin, and the introduction of piperazine into a lignin matrix.
Example 2
A biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 75 parts of polypropylene matrix, 25 parts of composite compatilizer, 4 parts of lignin-based intumescent flame retardant, 0.4 part of antioxidant 1010 and 0.5 part of polyethylene wax;
the preparation method of the modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 550r/min, and stirring until a uniform premix is formed;
s2: adding the premix into a double-screw extruder through a main feeding hopper, adding the lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting the temperature at the main feeding hopper to be 220 ℃, setting the temperature at the side feeding hopper to be 190 ℃, and performing extrusion granulation at the screw speed of 350r/min until the materials are naturally cooled to obtain the biodegradable modified polypropylene material.
Wherein the preparation method of the composite compatilizer and the lignin-based intumescent flame retardant is the same as that of example 1.
Example 3
A biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 80 parts of polypropylene matrix, 30 parts of composite compatilizer, 6 parts of lignin-based intumescent flame retardant, 0.5 part of antioxidant 1010 and 0.6 part of polyethylene wax;
the preparation method of the modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 600r/min, and stirring until a uniform premix is formed;
s2: adding the premix into a double-screw extruder through a main feeding hopper, adding the lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting the temperature at the position of the main feeding hopper to be 240 ℃, setting the temperature at the position of the side feeding hopper to be 200 ℃, and extruding and granulating at the screw speed of 400r/min, wherein the biodegradable modified polypropylene material is obtained after the material is naturally cooled.
Wherein the preparation method of the composite compatilizer and the lignin-based intumescent flame retardant is the same as that of example 1.
Comparative example 1
A biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 75 parts of polypropylene matrix, 4 parts of lignin-based intumescent flame retardant, 0.4 part of antioxidant 1010 and 0.5 part of polyethylene wax;
the preparation method of the modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 550r/min, and stirring until a uniform premix is formed;
s2: adding the premix into a double-screw extruder through a main feeding hopper, adding the lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting the temperature at the main feeding hopper to be 220 ℃, setting the temperature at the side feeding hopper to be 190 ℃, and performing extrusion granulation at the screw speed of 350r/min until the materials are naturally cooled to obtain the biodegradable modified polypropylene material.
Wherein the lignin-based intumescent flame retardant was prepared in the same manner as in example 1.
Comparative example 2
A biodegradable modified polypropylene material comprises the following raw materials in parts by weight: 75 parts of polypropylene matrix, 25 parts of composite compatilizer, 4 parts of lignin, 0.4 part of antioxidant 1010 and 0.5 part of polyethylene wax;
the preparation method of the modified polypropylene material comprises the following steps:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 550r/min, and stirring until a uniform premix is formed;
s2: adding premix into a double-screw extruder through a main feeding hopper, adding lignin into the double-screw extruder from a side feeding hopper, setting the temperature at the main feeding hopper to be 220 ℃, setting the temperature at the side feeding hopper to be 190 ℃, and extruding and granulating at the screw speed of 350r/min, wherein the material is naturally cooled to obtain the biodegradable modified polypropylene material.
Wherein the preparation method of the composite compatilizer is the same as that of the example 1.
Performance detection
A. Referring to national standard GB/T3682.1-2018, using an MFI-3322 type melt flow rate instrument, adding the modified polypropylene materials prepared in the examples 1-3 of the invention into a charging barrel at 230 ℃, carrying out constant temperature treatment for 5min, extruding a spline through a 2.095mm die under a load of 2.16kg, testing the melt mass flow rate of the modified polypropylene materials, and using the formula
Calculation of melt Strength of Polypropylene MaterialWherein M is S For melt strength, pa.S, MFR is the melt mass flow rate, g/10min, ΔL is the length of the extruded spline at 50% reduction in diameter, mm, r is the radius of the extruded spline at the beginning of the exit die, and the test results are given in the following Table:
as can be seen from the above table, the modified polypropylene materials prepared in examples 1-3 and comparative example 2 of the present invention have higher melt strength, which is advantageous for further application of the modified polypropylene material in the field of foaming and thermoforming materials, while the modified polypropylene material prepared in comparative example 1 is free from adding a composite compatibilizer, does not form a branched polypropylene structure, and results in lower melt strength.
B. The modified polypropylene materials prepared in examples 1 to 3 and comparative examples 1 to 2 of the present invention were tested for tensile strength with reference to national standard GB/T1040.2-2006, and the tensile strength after 24 hours of treatment in an oven at 80℃was calculated, the retention of tensile strength was evaluated, and the heat resistance of the modified polypropylene materials was evaluated, in general, the higher the retention of tensile strength, the better the heat resistance, and vice versa, and the test results were shown in the following table:
from the above table, the tensile strength and retention of the modified polypropylene materials prepared in examples 1 to 3 and comparative example 2 according to the present invention are much higher than those of the modified polypropylene material prepared in comparative example 1, presumably because the toughness and heat resistance cannot be improved by using a large number of organosiloxane bonds in the POSS structure without adding the composite compatibilizer in comparative example 1.
C. Referring to national standard GB/T2408-2021, the modified polypropylene materials prepared in examples 1-3 and comparative examples 1-2 were compression molded into 13mm by 125mm by 1.5mm samples, which were subjected to UL-94 test using a ZRS-TC type horizontal vertical burning tester at a temperature of 25℃and a relative humidity of 50.+ -. 5%, the test results of which are shown in the following Table:
as is clear from the above table, the modified polypropylene materials prepared in examples 1 to 3 of the present invention are excellent in flame retardant property, the UL-94 rating is V-0, whereas the modified polypropylene material prepared in comparative example 1 is V-1, presumably without adding a composite compatibilizer, and cannot produce a synergistic effect of silicon oxide and lignin-based intumescent flame retardant upon combustion, and thus the flame retardant property is relatively poor, whereas the modified polypropylene material prepared in comparative example 2 is V-2, because lignin and intumescent flame retardant are not added, and thus the flame retardant property is poor.
D. The modified polypropylene materials prepared in example 1-example 3 and comparative example 1-comparative example 2 were injection molded into samples of 20cm×20cm×1mm, the samples of the same mass were weighed, the samples were put into the same piece of soil for degradation for 60 days using a soil burying method, the samples were taken out, washed with water and dried, then weighed, the weight loss was calculated, the degradation rate of the samples was evaluated, and in general, a higher weight loss represents a higher degradation rate, and conversely, a lower weight loss, and the test results were shown in the following table:
from the above table, the modified polypropylene materials prepared in examples 1 to 3 and comparative example 1 of the present invention have a degradation rate higher than that of the modified polypropylene material prepared in comparative example 2, and it is presumed that the presence of lignin can promote degradation of the polypropylene material, and thus exhibit biodegradability.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means 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 are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, 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 invention or beyond the scope of the appended claims.
Claims (8)
1. The biodegradable modified polypropylene material is characterized by comprising the following raw materials in parts by weight: 70-80 parts of polypropylene matrix, 20-30 parts of composite compatilizer, 2-6 parts of lignin-based intumescent flame retardant, 0.2-0.5 part of antioxidant 1010 and 0.3-0.6 part of polyethylene wax;
the composite compatilizer is prepared by introducing isocyanate groups into a polypropylene molecular chain through a melt grafting method and then connecting POSS;
the preparation method of the composite compatilizer specifically comprises the following steps:
SS1: uniformly mixing polypropylene, 2-isocyanoethyl acrylate and an initiator, pouring the mixture into a polymerization kettle, raising the temperature in the polymerization kettle to 160-170 ℃, performing melt grafting for 4-8min at the rotating speed of 50-60r/min, pouring the product into dimethylbenzene for dissolution and filtration, settling by using acetone, repeating the dissolution-settling process for 2-3 times, and performing vacuum drying to obtain an intermediate;
SS2: uniformly mixing the intermediate, p-aminophenyl POSS and toluene, dropwise adding a catalyst, uniformly stirring, stirring for 4-12 hours at the temperature of 60-70 ℃, distilling under reduced pressure to remove the solvent, filtering out solid materials, washing, and drying in vacuum to obtain the composite compatilizer;
the lignin-based intumescent flame retardant is prepared by modifying a phosphate group in a lignin structure, and introducing amine substances through a salifying reaction;
the preparation method of the lignin-based intumescent flame retardant specifically comprises the following steps:
SSS1: mixing lignin and tetrahydrofuran, adding phosphorus pentoxide, stirring at room temperature for 2-6h, distilling under reduced pressure to remove solvent, pouring purified water to precipitate solid materials, centrifuging to separate solid sample, and vacuum drying to obtain phosphorus-containing lignin;
SSS2: dissolving phosphorus-containing lignin in 1, 4-dioxane, raising the system temperature to 70 ℃, adding piperazine, stirring for 4-8h, distilling under reduced pressure to remove solvent, washing the solid material for 2-3 times by using ethanol, vacuum drying, grinding and sieving to obtain the lignin-based intumescent flame retardant.
2. The biodegradable modified polypropylene material according to claim 1, wherein in step SS1, said initiator is any one of benzoyl peroxide or dicumyl peroxide.
3. The biodegradable modified polypropylene material according to claim 1, wherein in step SS2, said catalyst is any one of dibutyltin dilaurate or stannous octoate.
4. The biodegradable modified polypropylene material according to claim 1, characterized in that in step SS2, the mass ratio of said intermediate to p-aminophenyl POSS is 10:0.5-1.5.
5. The biodegradable modified polypropylene material according to claim 1, characterized in that in step SSS1, the mass ratio of lignin to phosphorus pentoxide is 1:2-5.
6. The biodegradable modified polypropylene material according to claim 1, characterized in that in step SSS2, said sieving has a mesh number of 10-20.
7. A process for the preparation of a biodegradable modified polypropylene material according to claim 1, comprising the steps of:
s1: adding a polypropylene matrix, a composite compatilizer, an antioxidant 1010 and polyethylene wax into a mixer, setting the stirring speed to be 500-600r/min, and stirring until a uniform premix is formed;
s2: adding premix into a double-screw extruder through a main feeding hopper, adding lignin-based intumescent flame retardant into double-screw extrusion from a side feeding hopper, setting parameters, performing extrusion granulation, and naturally cooling the materials to obtain the biodegradable modified polypropylene material.
8. The method for preparing a biodegradable modified polypropylene material according to claim 7, wherein in step S2, said parameter setting is as follows: the temperature of the main feeding hopper is 200-240 ℃, the temperature of the side feeding hopper is 180-200 ℃, and the rotating speed of the screw is 300-400r/min.
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| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| CN106543634A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of flame-retardant ABS compound material and preparation method thereof |
| CN108484930A (en) * | 2018-04-25 | 2018-09-04 | 中南林业科技大学 | A kind of lignin-base phosphate flame retardant and preparation method thereof and its application in fire-retarding epoxy resin composite material preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104371116A (en) * | 2014-11-04 | 2015-02-25 | 南京林业大学 | Preparation method and application of lignin-based intumescent flame retardant |
| CN106543634A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of flame-retardant ABS compound material and preparation method thereof |
| CN108484930A (en) * | 2018-04-25 | 2018-09-04 | 中南林业科技大学 | A kind of lignin-base phosphate flame retardant and preparation method thereof and its application in fire-retarding epoxy resin composite material preparation |
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