CN117384443A - Flame-retardant regenerated plastic and preparation method thereof - Google Patents
Flame-retardant regenerated plastic and preparation method thereof Download PDFInfo
- Publication number
- CN117384443A CN117384443A CN202311696446.8A CN202311696446A CN117384443A CN 117384443 A CN117384443 A CN 117384443A CN 202311696446 A CN202311696446 A CN 202311696446A CN 117384443 A CN117384443 A CN 117384443A
- Authority
- CN
- China
- Prior art keywords
- parts
- flame
- hydroxyl
- retardant
- terminated polybutadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- 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 title claims abstract description 78
- 229920003023 plastic Polymers 0.000 title claims abstract description 59
- 239000004033 plastic Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 67
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 36
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 34
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 34
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 32
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 32
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 21
- -1 polyethylene Polymers 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 18
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 18
- 239000008116 calcium stearate Substances 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- 239000003431 cross linking reagent Substances 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000004970 Chain extender Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 16
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 12
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 11
- 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 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 12
- 229920000573 polyethylene Polymers 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010025 steaming Methods 0.000 description 10
- 230000032683 aging Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical group O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012745 toughening agent 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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 reclaimed plastics, in particular to a flame-retardant reclaimed plastic and a preparation method thereof. The specific components of the regenerated plastic comprise 90-100 parts of regenerated high-density polyethylene, 5-10 parts of high-density polyethylene, 1-2 parts of calcium stearate, 1-2 parts of carbon black, 8-12 parts of maleic anhydride grafted polyethylene, 2-3 parts of antioxidant and 6-8 parts of polyurethane elastomer, wherein the regenerated high-density polyethylene is adopted as a main material, the high-density polyethylene is added, the maleic anhydride grafted polyethylene is adopted as a compatilizer, and then polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene and polyoxypropylene glycol are compounded and react with diphenylmethane diisocyanate to generate the polyurethane elastomer, so that the regenerated polyethylene is toughened, the flame retardant effect is realized through phosphorus-nitrogen cooperation, and the regenerated polyethylene plastic with high tensile strength and excellent flame retardant property is prepared.
Description
Technical Field
The invention relates to the technical field of reclaimed plastics, in particular to a flame-retardant reclaimed plastic and a preparation method thereof.
Background
The recycled plastic is recycled by carrying out mechanical blade crushing operation, so that the recycling of the plastic is completed, polyethylene is one of the most widely applied plastic products in the prior art, the proportion of the polyethylene in the waste plastic is relatively large, and how to recycle the polyethylene in the waste plastic is a research and development project which is important for the prior enterprises.
In addition, during plastic processing, the flame retardance is a common modification mode and is one of properties important during plastic application, so that the application discloses the flame retardance type reclaimed plastic and a preparation method thereof for solving the technical problem in order to solve the recycling of the reclaimed plastic and improve the flame retardance of a prepared product.
Disclosure of Invention
The invention aims to provide a flame-retardant regenerated plastic and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): mixing dimethyl methylphosphonate and trihydroxyethyl isocyanurate, uniformly stirring, adding tetrabutyl titanate, heating to 140-150 ℃, reacting for 2-3 hours at a temperature of 190-200 ℃ continuously, reacting for 3-4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame retardant cross-linking agent;
step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in a nitrogen environment, stirring for 1-1.5 hours at 70-80 ℃, adding a chain extender, continuing to react for 1-2 hours, removing a solvent by rotary evaporation after the reaction is finished, pouring into a mold, and carrying out vacuum curing at 45-50 ℃ to obtain a polyurethane elastomer;
the chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3, a step of;
step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
In the embodiment of the application, in the step (3), the amounts of the components are as follows: the polyurethane elastomer comprises, by mass, 90-100 parts of regenerated high-density polyethylene, 5-10 parts of high-density polyethylene, 1-2 parts of calcium stearate, 1-2 parts of carbon black, 8-12 parts of maleic anhydride grafted polyethylene, 2-3 parts of an antioxidant and 6-8 parts of a polyurethane elastomer.
In the embodiment of the application, in the step (2), the amounts of the components are as follows: the modified polyurethane comprises, by mass, 10-12 parts of polyhydroxy polybutadiene, 15-20 parts of epoxidized hydroxyl-terminated polybutadiene, 30-40 parts of polyoxypropylene glycol, 40-45 parts of diphenylmethane diisocyanate, 1-3 parts of dibutyltin dilaurate and 3-8 parts of a chain extender.
In the embodiment of the present application, in the step (1), the molar ratio of the dimethyl methylphosphonate to the tris (hydroxyethyl) isocyanurate is 1: (1-1.1); the dosage of the tetrabutyl titanate is 0.5-0.6 wt% of the total weight of the dimethyl methylphosphonate and the trihydroxyethyl isocyanuric acid ester.
In the embodiment of the application, the preparation steps of the polyhydroxy polybutadiene are as follows: and (3) taking hydroxyl-terminated polybutadiene, carrying out vacuum dehydration at 115-120 ℃, cooling to 40-45 ℃, adding isopentenol, dibenzoyl peroxide and petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 3-4 hours to obtain the polyhydroxy polybutadiene.
In the embodiment of the application, the mass ratio of the hydroxyl-terminated polybutadiene to the isopentenol is 100: (1-2); the dosage of the dibenzoyl peroxide is 0.05-0.06 wt% of the hydroxyl-terminated polybutadiene; the mass ratio of the hydroxyl-terminated polybutadiene to the petroleum ether is 1:1.
in the embodiment of the application, the preparation steps of the epoxidized hydroxyl terminated polybutadiene are as follows: and (3) taking hydroxyl-terminated polybutadiene, glacial acetic acid, toluene and a sulfonic acid catalyst, uniformly stirring, heating to 50-55 ℃, adding hydrogen peroxide, continuously reacting for 6-7 hours, standing for layering after the reaction is finished, washing an organic layer to be neutral, and steaming for 2-3 hours in a rotary way to obtain the epoxidized hydroxyl-terminated polybutadiene. The hydrogen peroxide is hydrogen peroxide water solution, and the mass fraction is 30%.
In the embodiment of the application, the mass ratio of the hydrogen peroxide to the glacial acetic acid to the hydroxyl-terminated polybutadiene is (2-2.1): (0.9-1): 1, wherein the dosage of toluene is 140-150 wt% of hydroxyl-terminated polybutadiene.
In the embodiment of the application, the sulfonic acid catalyst is 732 type cation exchange resin, and the dosage of the sulfonic acid catalyst is 15-20wt% of hydroxyl-terminated polybutadiene.
In an embodiment of the present application, a recycled plastic prepared according to the method for preparing a flame retardant recycled plastic described in any one of the above.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a flame-retardant regenerated plastic and a preparation method thereof, wherein the regenerated plastic comprises 90-100 parts of regenerated high-density polyethylene, 5-10 parts of high-density polyethylene, 1-2 parts of calcium stearate, 1-2 parts of carbon black, 8-12 parts of maleic anhydride grafted polyethylene, 2-3 parts of antioxidant and 6-8 parts of polyurethane elastomer, the regenerated high-density polyethylene is adopted as a main material, the high-density polyethylene is added, the maleic anhydride grafted polyethylene is adopted as a compatilizer, the polyurethane elastomer is adopted as a toughening agent, and flame-retardant components are introduced into the polyurethane elastomer to prepare the regenerated polyethylene plastic with high tensile strength and excellent flame retardance.
In the scheme, hydroxyl-terminated polybutadiene and isopentenol are taken as raw materials, and the isopentenol is grafted onto a hydroxyl-terminated polybutadiene chain segment under the initiation action of dibenzoyl peroxide, so that polyhydroxy polybutadiene containing a plurality of hydroxyl groups is realized, and the polyhydroxy polybutadiene is utilized to provide hydroxyl groups for a polyurethane elastomer, so that the crosslinking density of the polyurethane elastomer is improved; meanwhile, the scheme also utilizes hydroxyl-terminated polybutadiene, glacial acetic acid, toluene and sulfonic acid catalyst to prepare the epoxidized hydroxyl-terminated polybutadiene, and the mass ratio of hydrogen peroxide, glacial acetic acid and hydroxyl-terminated polybutadiene is defined as (2-2.1): (0.9-1): 1'; the introduction of the epoxidized hydroxyl-terminated polybutadiene can improve the thermal stability of the polyurethane elastomer and improve the heat aging resistance. The scheme is that polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene and polyoxypropylene glycol are compounded and react with diphenylmethane diisocyanate to generate polyurethane elastomer, so that excellent toughening of the regenerated polyethylene is realized.
The invention uses 1, 4-butanediol and flame retardant cross-linking agent as chain extender, the flame retardant cross-linking agent uses methyl dimethyl phosphonate and tri-hydroxyethyl isocyanuric acid ester with mole ratio of 1: (1-1.1), and the flame retardant effect is achieved through the cooperation of phosphorus and nitrogen, the flame retardance and the polyurethane elastomer are mutually related, other flame retardants are not needed to be added in the preparation of the polyethylene, the flame retardant performance of the product is improved, the process is greatly simplified, and the cost is reduced.
The invention discloses a flame-retardant type regenerated plastic and a preparation method thereof, wherein the scheme is used for preparing the regenerated polyethylene plastic with high mechanical property and excellent flame retardant property, and after heat aging, the regenerated polyethylene plastic still can keep excellent mechanical property, so that the practicability is high.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments 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.
It should be noted that the manufacturers of all the raw materials according to the present invention are not particularly limited, and include, for example: hydroxyl-terminated polybutadiene: the number average molecular weight is 1500g/mol, the hydroxyl value is 1.5mmol/g, and the molecular weight is provided by the Luoyang dawn chemical industry institute; the sulfonic acid catalyst is 732 type strong acid cation exchange resin, which is provided by Shanghai chemical reagent company of China medicine group; polyoxypropylene diol (N210): mn=1000, supplied by tabacco trilobate polyurethane stock limited; the regenerated high-density polyethylene is obtained after the recovery of plastic bottle caps and milk bottle caps, cutting, cleaning and drying, and has a melt index (MFI, 190 ℃/5 Kg) of 5.8g/10min, which is provided by the plastic product factory in the Shang-sea of the county; high density polyethylene 2200J, supplied by chinese petroleum and gas stock; maleic anhydride grafted polyethylene: MV206, MAH grafting ratio was 1%, which was supplied by Shanghai, inc. of New technology development. The hydrogen peroxide is hydrogen peroxide water solution, and the mass fraction is 30%. The antioxidant is antioxidant 1010.
Example 1: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 140 ℃, keeping the temperature for reaction for 3 hours, continuously heating to 190 ℃, reacting for 3 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame-retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 70 ℃ for 1.5h, adding a chain extender, continuing to react for 1h, steaming to remove a solvent after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: 12 parts of polyhydroxy polybutadiene, 20 parts of epoxidized hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene glycol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of a chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3.
wherein: the preparation steps of the polyhydroxy polybutadiene are as follows: taking 100g of hydroxyl-terminated polybutadiene, vacuum dehydrating at 120 ℃, cooling to 40 ℃, adding 2g of isopentenol, 0.05g of dibenzoyl peroxide and 100g of petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 4 hours to obtain the polyhydroxy polybutadiene.
The preparation method of the epoxidized hydroxyl terminated polybutadiene comprises the following steps: taking 30g of hydroxyl-terminated polybutadiene, 28.5g of glacial acetic acid, 45g of toluene and 4.5g of sulfonic acid catalyst, uniformly stirring, heating to 50 ℃, adding 60g of hydrogen peroxide, continuously reacting for 7h, standing for layering after the reaction is finished, washing an organic layer to be neutral, and steaming for 2h in a rotary way to obtain the epoxidized hydroxyl-terminated polybutadiene.
Step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 7 parts of polyurethane elastomer.
Example 2: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 145 ℃, reacting for 2.5 hours while maintaining the temperature, continuously heating to 190 ℃, reacting for 3.5 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 75 ℃ for 1.5 hours, adding a chain extender, continuing to react for 1.5 hours, steaming to remove a solvent after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: 12 parts of polyhydroxy polybutadiene, 20 parts of epoxidized hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene glycol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of a chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3.
wherein: the preparation steps of the polyhydroxy polybutadiene are as follows: taking 100g of hydroxyl-terminated polybutadiene, vacuum dehydrating at 120 ℃, cooling to 45 ℃, adding 2g of isopentenol, 0.05g of dibenzoyl peroxide and 100g of petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 3.5h to obtain the polyhydroxy polybutadiene.
The preparation method of the epoxidized hydroxyl terminated polybutadiene comprises the following steps: taking 30g of hydroxyl-terminated polybutadiene, 28.5g of glacial acetic acid, 45g of toluene and 4.5g of sulfonic acid catalyst, uniformly stirring, heating to 55 ℃, adding 60g of hydrogen peroxide, continuously reacting for 6.5h, standing for layering after the reaction is finished, washing an organic layer to be neutral, and steaming for 2h in a rotary way to obtain the epoxidized hydroxyl-terminated polybutadiene.
Step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 7.5 parts of polyurethane elastomer.
Example 3: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 150 ℃, keeping the temperature for 2 hours, continuing to heat to 190 ℃, reacting for 4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame-retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 80 ℃ for 1h, adding a chain extender, continuing to react for 2h, steaming to remove a solvent after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: 12 parts of polyhydroxy polybutadiene, 20 parts of epoxidized hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene glycol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of a chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3.
wherein: the preparation steps of the polyhydroxy polybutadiene are as follows: taking 100g of hydroxyl-terminated polybutadiene, vacuum dehydrating at 120 ℃, cooling to 45 ℃, adding 2g of isopentenol, 0.05g of dibenzoyl peroxide and 100g of petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 4 hours to obtain the polyhydroxy polybutadiene.
The preparation method of the epoxidized hydroxyl terminated polybutadiene comprises the following steps: taking 30g of hydroxyl-terminated polybutadiene, 28.5g of glacial acetic acid, 45g of toluene and 4.5g of sulfonic acid catalyst, uniformly stirring, heating to 55 ℃, adding 60g of hydrogen peroxide, continuously reacting for 6 hours, standing for layering after the reaction is finished, washing an organic layer to be neutral, and steaming for 2 hours in a rotary way to obtain the epoxidized hydroxyl-terminated polybutadiene.
Step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 8 parts of polyurethane elastomer.
Comparative example 1: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 150 ℃, keeping the temperature for 2 hours, continuing to heat to 190 ℃, reacting for 4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame-retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing polyhydroxy polybutadiene, hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 80 ℃ for 1h, adding a chain extender, continuing to react for 2h, removing a solvent by rotary evaporation after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: 12 parts of polyhydroxy polybutadiene, 20 parts of hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene diol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3.
wherein: the preparation steps of the polyhydroxy polybutadiene are as follows: taking 100g of hydroxyl-terminated polybutadiene, vacuum dehydrating at 120 ℃, cooling to 45 ℃, adding 2g of isopentenol, 0.05g of dibenzoyl peroxide and 100g of petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 4 hours to obtain the polyhydroxy polybutadiene.
Step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 8 parts of polyurethane elastomer.
With example 3 as a control, the epoxidized hydroxyl terminated polybutadiene was not introduced in comparative example 1, replaced with hydroxyl terminated polybutadiene, and the rest of the process was unchanged.
Comparative example 2: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 150 ℃, keeping the temperature for 2 hours, continuing to heat to 190 ℃, reacting for 4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame-retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 80 ℃ for 1h, adding a chain extender, continuing to react for 2h, steaming to remove a solvent after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: 12 parts of polyhydroxy polybutadiene, 20 parts of epoxidized hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene glycol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of a chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 3:1.
wherein: the preparation steps of the polyhydroxy polybutadiene are as follows: taking 100g of hydroxyl-terminated polybutadiene, vacuum dehydrating at 120 ℃, cooling to 45 ℃, adding 2g of isopentenol, 0.05g of dibenzoyl peroxide and 100g of petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 4 hours to obtain the polyhydroxy polybutadiene.
The preparation method of the epoxidized hydroxyl terminated polybutadiene comprises the following steps: taking 30g of hydroxyl-terminated polybutadiene, 28.5g of glacial acetic acid, 45g of toluene and 4.5g of sulfonic acid catalyst, uniformly stirring, heating to 55 ℃, adding 60g of hydrogen peroxide, continuously reacting for 6 hours, standing for layering after the reaction is finished, washing an organic layer to be neutral, and steaming for 2 hours in a rotary way to obtain the epoxidized hydroxyl-terminated polybutadiene.
Step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 8 parts of polyurethane elastomer.
Using example 3 as a control, the amounts of flame retardant cross-linking agent and 1, 4-butanediol were adjusted in comparative example 2, with the remainder of the process unchanged.
Comparative example 3: the preparation method of the flame-retardant regenerated plastic comprises the following steps:
step (1): the preparation method of the flame retardant cross-linking agent comprises the following steps: mixing 0.2mol of dimethyl methylphosphonate and 0.2mol of tris (hydroxyethyl) isocyanurate, stirring uniformly, adding tetrabutyl titanate, heating to 150 ℃, keeping the temperature for 2 hours, continuing to heat to 190 ℃, reacting for 4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame-retardant cross-linking agent. The amount of tetrabutyl titanate is 0.5wt% of the total amount of dimethyl methylphosphonate and tris (hydroxyethyl) isocyanurate.
Step (2): mixing hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in nitrogen environment, stirring at 80 ℃ for 1h, adding a chain extender, continuing to react for 2h, steaming to remove a solvent after the reaction is finished, pouring into a mould, and carrying out vacuum curing at 50 ℃ to obtain the polyurethane elastomer.
The dosages of the components are as follows: the chain extender comprises, by mass, 32 parts of hydroxyl-terminated polybutadiene, 40 parts of polyoxypropylene glycol, 45 parts of diphenylmethane diisocyanate, 2 parts of dibutyltin dilaurate and 8 parts of chain extender. The chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3.
step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
The dosages of the components are as follows: 95 parts of regenerated high-density polyethylene, 10 parts of high-density polyethylene, 2 parts of calcium stearate, 2 parts of carbon black, 10 parts of maleic anhydride grafted polyethylene, 3 parts of antioxidant and 8 parts of polyurethane elastomer.
With example 3 as a control, only hydroxyl-terminated polybutadiene was used in comparative example 3, and the rest of the process was unchanged.
Detection experiment:
1. taking the regenerated plastics prepared in examples 1-3 and comparative examples 1-3, and performing injection molding to obtain dumbbell-shaped samples, wherein the injection molding temperature is 180 ℃; the tensile strength was measured by the method disclosed in GB/T1040-2006, the tensile rate being 50mm/min and the gauge length being 25mm.
2. The recycled plastics prepared in examples 1-3 and comparative examples 1-3 were injection molded into sheets at 180℃and a spline thickness of 1mm, 5-type, heat aged at 120℃for 240 hours, and the tensile strength was retested and the rate of change in tensile strength was recorded.
3. With reference to the method disclosed in GB/T2406.2-2009, the limiting oxygen index of the sample was tested, the sample size being 50mm by 150mm by 1mm.
Conclusion: comparative example 1, in which the epoxidized hydroxyl-terminated polybutadiene was not introduced on the basis of example 3, was replaced with the hydroxyl-terminated polybutadiene, and thus the tensile strength of the product was lowered, the rate of change of tensile strength after heat aging was larger, but the flame retardant property was not substantially lowered, as compared with example 3; comparative example 2 the amount of flame retardant cross-linking agent and 1, 4-butanediol was adjusted on the basis of example 3, the tensile strength was reduced but the reduction was significantly lower than in comparative example 1; and the heat aging performance is also superior to that of the comparative example 1, and meanwhile, the flame retardant performance of the product of the comparative example 2 is reduced; in comparative example 3, the hydroxyl-terminated polybutadiene is adopted on the basis of example 3, so that the tensile strength of the product is the worst, and the tensile strength change rate after heat aging is the largest, but the flame retardant property of the product is excellent.
The invention discloses a flame-retardant type regenerated plastic and a preparation method thereof, wherein the scheme is used for preparing the regenerated polyethylene plastic with high mechanical property and excellent flame retardant property, and after heat aging, the regenerated polyethylene plastic still can keep excellent mechanical property, so that the practicability is high.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the flame-retardant regenerated plastic is characterized by comprising the following steps of:
step (1): mixing dimethyl methylphosphonate and trihydroxyethyl isocyanurate, uniformly stirring, adding tetrabutyl titanate, heating to 140-150 ℃, reacting for 2-3 hours at a temperature of 190-200 ℃ continuously, reacting for 3-4 hours, washing with absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain the flame retardant cross-linking agent;
step (2): mixing polyhydroxy polybutadiene, epoxidized hydroxyl-terminated polybutadiene, polyoxypropylene glycol and tetrahydrofuran, adding diphenylmethane diisocyanate and dibutyltin dilaurate in a nitrogen environment, stirring for 1-1.5 hours at 70-80 ℃, adding a chain extender, continuing to react for 1-2 hours, removing a solvent by rotary evaporation after the reaction is finished, pouring into a mold, and carrying out vacuum curing at 45-50 ℃ to obtain a polyurethane elastomer;
the chain extender is prepared by compounding 1, 4-butanediol and a flame-retardant cross-linking agent, and the mass ratio of the 1, 4-butanediol to the flame-retardant cross-linking agent is 1:3, a step of;
step (3): mixing the regenerated high-density polyethylene, the calcium stearate, the carbon black, the maleic anhydride grafted polyethylene and the antioxidant, adding the polyurethane elastomer, stirring uniformly, and carrying out melt extrusion to obtain the flame-retardant regenerated plastic.
2. The method for preparing the flame-retardant recycled plastic according to claim 1, wherein the method comprises the following steps: in the step (3), the dosages of each component are as follows: the polyurethane elastomer comprises, by mass, 90-100 parts of regenerated high-density polyethylene, 5-10 parts of high-density polyethylene, 1-2 parts of calcium stearate, 1-2 parts of carbon black, 8-12 parts of maleic anhydride grafted polyethylene, 2-3 parts of an antioxidant and 6-8 parts of a polyurethane elastomer.
3. The method for preparing the flame-retardant recycled plastic according to claim 1, wherein the method comprises the following steps: in the step (2), the dosages of each component are as follows: the modified polyurethane comprises, by mass, 10-12 parts of polyhydroxy polybutadiene, 15-20 parts of epoxidized hydroxyl-terminated polybutadiene, 30-40 parts of polyoxypropylene glycol, 40-45 parts of diphenylmethane diisocyanate, 1-3 parts of dibutyltin dilaurate and 3-8 parts of a chain extender.
4. The method for preparing the flame-retardant recycled plastic according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the dimethyl methylphosphonate to the tris (hydroxyethyl) isocyanurate is 1: (1-1.1); the dosage of the tetrabutyl titanate is 0.5-0.6 wt% of the total weight of the dimethyl methylphosphonate and the trihydroxyethyl isocyanuric acid ester.
5. The method for preparing the flame-retardant recycled plastic according to claim 1, wherein the method comprises the following steps: the preparation steps of the polyhydroxy polybutadiene are as follows: and (3) taking hydroxyl-terminated polybutadiene, carrying out vacuum dehydration at 115-120 ℃, cooling to 40-45 ℃, adding isopentenol, dibenzoyl peroxide and petroleum ether, uniformly stirring, heating to reaction reflux in a nitrogen environment, and continuing to react for 3-4 hours to obtain the polyhydroxy polybutadiene.
6. The method for preparing the flame-retardant recycled plastic according to claim 5, wherein the method comprises the following steps: the mass ratio of the hydroxyl-terminated polybutadiene to the isopentenol is 100: (1-2); the dosage of the dibenzoyl peroxide is 0.05-0.06 wt% of the hydroxyl-terminated polybutadiene.
7. The method for preparing the flame-retardant recycled plastic according to claim 1, wherein the method comprises the following steps: the preparation method of the epoxidized hydroxyl terminated polybutadiene comprises the following steps: and (3) taking hydroxyl-terminated polybutadiene, glacial acetic acid, toluene and a sulfonic acid catalyst, uniformly stirring, heating to 50-55 ℃, adding hydrogen peroxide, continuously reacting for 6-7 hours, standing for layering after the reaction is finished, washing an organic layer to be neutral, and performing rotary evaporation to obtain the epoxidized hydroxyl-terminated polybutadiene.
8. The method for preparing the flame-retardant recycled plastic according to claim 7, wherein: the mass ratio of the hydrogen peroxide to the glacial acetic acid to the hydroxyl-terminated polybutadiene is (2-2.1): (0.9-1): 1, wherein the dosage of toluene is 140-150 wt% of hydroxyl-terminated polybutadiene.
9. The method for preparing the flame-retardant recycled plastic according to claim 7, wherein: the sulfonic acid catalyst is 732 type cation exchange resin, and the dosage of the sulfonic acid catalyst is 15-20wt% of hydroxyl-terminated polybutadiene.
10. The recycled plastic prepared by the method for preparing a flame retardant recycled plastic according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311696446.8A CN117384443B (en) | 2023-12-12 | 2023-12-12 | Flame-retardant regenerated plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311696446.8A CN117384443B (en) | 2023-12-12 | 2023-12-12 | Flame-retardant regenerated plastic and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117384443A true CN117384443A (en) | 2024-01-12 |
| CN117384443B CN117384443B (en) | 2024-03-01 |
Family
ID=89435958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311696446.8A Active CN117384443B (en) | 2023-12-12 | 2023-12-12 | Flame-retardant regenerated plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117384443B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795281A (en) * | 2014-10-15 | 2017-05-31 | 阿科玛法国公司 | Simple function or polyfunctional urethane acrylate oligomer without isocyanates |
| CN109762020A (en) * | 2019-01-24 | 2019-05-17 | 重庆大学 | A kind of transparency liquid fire retardant, preparation method and applications |
| CN111647102A (en) * | 2020-05-29 | 2020-09-11 | 西安航天三沃化学有限公司 | Epoxidized hydroxyl-terminated polybutadiene and preparation method thereof |
| CN114085606A (en) * | 2020-08-24 | 2022-02-25 | 味之素株式会社 | Resin composition |
| CN116103930A (en) * | 2023-01-05 | 2023-05-12 | 北京化工大学 | Flame-retardant polyester and preparation method thereof |
| CN116903951A (en) * | 2023-09-12 | 2023-10-20 | 上海睿聚环保科技有限公司 | Regenerated high-density polyethylene for marine fishing net and preparation method thereof |
-
2023
- 2023-12-12 CN CN202311696446.8A patent/CN117384443B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106795281A (en) * | 2014-10-15 | 2017-05-31 | 阿科玛法国公司 | Simple function or polyfunctional urethane acrylate oligomer without isocyanates |
| CN109762020A (en) * | 2019-01-24 | 2019-05-17 | 重庆大学 | A kind of transparency liquid fire retardant, preparation method and applications |
| CN111647102A (en) * | 2020-05-29 | 2020-09-11 | 西安航天三沃化学有限公司 | Epoxidized hydroxyl-terminated polybutadiene and preparation method thereof |
| CN114085606A (en) * | 2020-08-24 | 2022-02-25 | 味之素株式会社 | Resin composition |
| CN116103930A (en) * | 2023-01-05 | 2023-05-12 | 北京化工大学 | Flame-retardant polyester and preparation method thereof |
| CN116903951A (en) * | 2023-09-12 | 2023-10-20 | 上海睿聚环保科技有限公司 | Regenerated high-density polyethylene for marine fishing net and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117384443B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111621239B (en) | Full-biodegradable adhesive tape and preparation method thereof | |
| CN111073325A (en) | Lignin/fiber thermoplastic composite material and preparation method thereof | |
| CN111393593B (en) | Demethylated lignin liquid modified phenolic resin, preparation method thereof and application thereof in phenolic foam | |
| CN115850910A (en) | Bio-based hyperbranched polymer epoxy resin and preparation method and application thereof | |
| CN117384443B (en) | Flame-retardant regenerated plastic and preparation method thereof | |
| CN114456344A (en) | Low-carbon environment-friendly full-bio-based semi-rigid polyurethane foam formula | |
| CN116903951B (en) | Regenerated high-density polyethylene for marine fishing net and preparation method thereof | |
| CN102382222A (en) | Low-density polyethylene (LDPE) resin for cable insulant having voltage level of above 110kV, and preparation method thereof | |
| CN113683638A (en) | Phosphorus-containing organic acid alkenyl amine salt and preparation method and application thereof | |
| CN115368668B (en) | Modified EVOH resin and preparation method thereof | |
| CN117229233A (en) | Cardanol-based plasticizer, application thereof and PLA film | |
| CN1302072C (en) | Modified polyurethane composition and preparation thereof | |
| CN110845954A (en) | Water-based surface treating agent with flame-retardant effect for synthetic leather and preparation method thereof | |
| CN114773797B (en) | Heat-shrinkable film and preparation method thereof | |
| CN109777083A (en) | It is a kind of efficiently to utilize regenerated sound-absorbing and flame-retardant material of polyurethane foam leftover pieces and preparation method thereof | |
| CN112898547A (en) | Preparation method of low-chroma regenerated polyester | |
| CN113956438B (en) | Preparation method of bio-based self-repairing flame-retardant material with high dielectric property | |
| CN114957627B (en) | Preparation method of polyester with low byproduct tetrahydrofuran | |
| CN112062924B (en) | Polyurethane resin for winding process, resin/fiber composite material, and preparation method and application thereof | |
| CN116199966B (en) | Flame-retardant cable material and preparation method thereof | |
| CN118126432B (en) | Composite material for plastic bucket based on recycled plastic and preparation method thereof | |
| CN118530575A (en) | Composite modified biodegradable film and preparation method and application thereof | |
| CN115785405B (en) | Melt polymerization tackifying method for recycling polylactic acid | |
| CN117659643B (en) | Polyester material resistant to wet heat aging and preparation method thereof | |
| CN116082604B (en) | Multiple dynamic covalent bond hyperbranched polymer epoxy resin and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A flame retardant recycled plastic and its preparation method Granted publication date: 20240301 Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch Pledgor: SHANGHAI RUIJU ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Registration number: Y2024310000871 |