CN112812489A - Modified plastic based on interpenetrating network structure and preparation method thereof - Google Patents
Modified plastic based on interpenetrating network structure and preparation method thereof Download PDFInfo
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- 239000004033 plastic Substances 0.000 title claims abstract description 58
- 229920003023 plastic Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 aliphatic isocyanate Chemical class 0.000 claims abstract description 34
- 239000004793 Polystyrene Substances 0.000 claims abstract description 28
- 229920002223 polystyrene Polymers 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 21
- SZTUJDINRYGMRV-UHFFFAOYSA-N [4-[1,1,1,3,3,3-hexafluoro-2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OC(=O)C=C)C=C1 SZTUJDINRYGMRV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 238000005303 weighing Methods 0.000 claims description 21
- 239000002608 ionic liquid Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 238000005349 anion exchange Methods 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002715 modification method Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 5
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- AYESKMWPTSCYSJ-UHFFFAOYSA-N bis(hydroxymethyl)phosphanylmethanol;hydrochloride Chemical compound [Cl-].OC[PH+](CO)CO AYESKMWPTSCYSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- XAAGVNUUSJZVIC-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;bromide Chemical compound [Br-].OC[P+](CO)(CO)CO XAAGVNUUSJZVIC-UHFFFAOYSA-M 0.000 claims description 4
- TZBQFYQKIFMZOW-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;iodide Chemical compound [I-].OC[P+](CO)(CO)CO TZBQFYQKIFMZOW-UHFFFAOYSA-M 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000032683 aging Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 206010042674 Swelling Diseases 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YDVJBLJCSLVMSY-UHFFFAOYSA-N carbamoyl cyanide Chemical compound NC(=O)C#N YDVJBLJCSLVMSY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08L2201/04—Antistatic
-
- 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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified plastic based on an interpenetrating network structure, which is prepared from the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber. The modified plastic based on the interpenetrating network structure has excellent mechanical properties, improves the low temperature resistance, antistatic property, flame retardance, aging resistance, hydrophobicity and other properties of polystyrene plastic, and can meet the material use requirements under different severe conditions. The invention also discloses a preparation method of the modified plastic based on the interpenetrating network structure.
Description
Technical Field
The invention relates to the technical field of modified plastics, in particular to a modified plastic based on an interpenetrating network structure and a preparation method thereof.
Background
The plastic is a high molecular compound polymerized by addition polymerization or polycondensation reaction using monomer as raw material, and is composed of synthetic resin, filler, plasticizer, stabilizer, lubricant, pigment and other additives. With the continuous development of industry, plastics are widely applied to various industries such as electronics, electrics, automobiles, buildings, household appliances, office equipment, electric power, transportation and the like.
Different plastics such as polyethylene, polypropylene, polyamide, polyformaldehyde, polycarbonate, ABS and the like exist, each plastic has the advantages and disadvantages in performance, the different performances of the plastic determine the application of the plastic in life and industry, and with the progress of technology, researches on the modification of the plastic, including antistatic performance, heat conduction performance, low temperature resistance, hydrophobicity and the like, have not been stopped. The existing heat-conducting and antistatic materials are mostly made of metal or metal-containing materials, and have the defects of poor compatibility with plastic materials, uneven dispersion, easy oxidation corrosion, short service life, high manufacturing cost, complex preparation process and the like; the plastic added with non-metallic materials such as graphite has the problems of low-temperature brittle deformation, reduced impact toughness and thermal stability and the like at low temperature, and the produced product is easy to break in winter storage and transportation, and particularly has a series of problems of glue shortage, gas decomposition mark, workpiece embrittlement and the like when a large workpiece or a thin-wall workpiece is molded.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the modified plastic based on the interpenetrating network structure so as to solve the comprehensive problem of poor performances of low temperature resistance, impact resistance, static resistance, heat conduction, hydrophobicity and the like of the conventional plastic.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
the modified plastic based on the interpenetrating network structure is prepared from the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber.
Preferably, the aliphatic isocyanate is hexamethylene diisocyanate and/or isophorone diisocyanate.
Preferably, the azo initiator is at least one of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride and azobisisobutyronitrile formamide.
Preferably, the polyol is a combination of ethylene glycol and a polyhydroxy cage silsesquioxane.
Preferably, the hydroxy acrylate is at least one of 6-hydroxyhexyl acrylate, 2, 3-dihydroxypropyl acrylate and 2-hydroxybutyl acrylate.
Preferably, the catalyst is at least one of zinc isooctanoate, dibutyltin dilaurate and tetrabutylammonium bromide.
Preferably, the inorganic filler is at least one of nano calcium carbonate, nano zinc oxide, nano cerium dioxide and nano titanium dioxide.
Preferably, the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 20-30 parts by weight of quaternary phosphonium salt compound, adding the quaternary phosphonium salt compound into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1-3, weighing 20-50 mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30-50 ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 3-8 h, and removing impurities to obtain the modified graphene. The graphene modified by the ionic liquid has excellent performances of the ionic liquid and the graphene. The ionic liquid has good compatibility with organic and inorganic components in the plastic, improves the dispersion performance of the graphene, prevents the graphene from agglomerating, and further enhances the antistatic, heat-resistant and flame-retardant performances of the modified plastic.
Preferably, the quaternary phosphonium salt compound is at least one of tetrakis (hydroxymethyl) phosphonium bromide, tetrakis (hydroxymethyl) phosphonium iodide, and tris (hydroxymethyl) phosphonium chloride.
Another aspect of the present invention is to provide a method for preparing the modified plastic based on the interpenetrating network structure, the method comprising the following steps:
s1: weighing 50-80 parts by weight of polystyrene, 20-30 parts by weight of hexafluorobisphenol A diacrylate and 1-10 parts by weight of azo initiator, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50-100 ℃, reacting for 0.5-3.5 h, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: weighing 70-110 parts of the polystyrene polymer modified in the step S1, adding 20-40 parts of hydroxyl acrylate, swelling for 0.5-2.5 h, adding 5-10 parts of aliphatic isocyanate, and continuing to swell for 0.5-2.5 h to obtain a uniformly dissolved mixed solution;
s3: and (3) adding 40-60 parts of polyol, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly mixing by magnetic stirring, maintaining the temperature at 30-70 ℃, and reacting for 3-8 hours to obtain the modified plastic based on the interpenetrating network structure.
The invention has the beneficial effects that:
the invention relates to a modified plastic based on interpenetrating network structure and a preparation method thereof, wherein polystyrene is used as a main plastic component, hexafluorobisphenol A diacrylate is modified firstly, then aliphatic isocyanate and hydroxy acrylate are swelled in sequence to enable the aliphatic isocyanate and the hydroxy acrylate to permeate into the network structure of a modified polystyrene polymer, polyol and catalyst are added, the aliphatic isocyanate, the hydroxy acrylate and the polyol are subjected to cross-linking reaction to form the modified plastic with the interpenetrating network structure, and meanwhile, inorganic filler, additive and ultraviolet absorbent are added as auxiliary additives, so that the modified plastic not only has the advantages of modified polystyrene and rubber, but also improves the mechanical property and the processing property of the polystyrene plastic, and further improves the antistatic property, the flame retardance, the UV absorption property and the processing property of the modified plastic, Aging resistance, hydrophobicity and the like.
The modified plastic based on the interpenetrating network structure can meet the use requirements of long-term severe conditions in important fields of automobile industry, consumer goods, electronic and electric appliances, building industry and the like.
The preparation method of the modified plastic based on the interpenetrating network structure has the advantages of low production cost, flexibility and controllability, and can realize large-scale production.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 50 parts of polystyrene, 20 parts of hexafluorobisphenol A diacrylate, 1 part of azobisisobutyramidine hydrochloride, 40 parts of polyol, 5 parts of hexamethylene diisocyanate, 20 parts of 6-hydroxyhexyl acrylate, 0.5 part of dibutyltin dilaurate, 1.2 parts of nano calcium carbonate, 1.5 parts of an additive and 0.1 part of an ultraviolet absorber.
The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 3: 1.
the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 20 parts by weight of tetrakis (hydroxymethyl) phosphonium bromide, adding the weighed tetrakis (hydroxymethyl) phosphonium bromide into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1, weighing 20mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 5 hours, and removing impurities to obtain the modified graphene.
The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:
s1: weighing 50 parts of polystyrene, 20 parts of hexafluorobisphenol A diacrylate and 1 part of azodiisobutyl amidine hydrochloride by weight parts, uniformly mixing by magnetic stirring, maintaining the temperature at 60 ℃, reacting for 1 hour, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: weighing 70 parts of the polystyrene polymer modified in the step S1, adding 20 parts of 6-hydroxyhexyl acrylate, swelling for 1 hour, adding 5 parts of hexamethylene diisocyanate, and continuing to swell for 2 hours to obtain a uniformly dissolved mixed solution;
s3: and (4) adding 40 parts of polyol, 0.5 part of dibutyltin dilaurate, 1.2 parts of nano calcium carbonate, 1.5 parts of additive and 0.1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly stirring and mixing by magnetic force, maintaining the temperature at 30 ℃, and reacting for 8 hours to obtain the modified plastic based on the interpenetrating network structure.
Example 2
The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 65 parts of polystyrene, 25 parts of hexafluorobisphenol A diacrylate, 5 parts of azobisisobutyrimidazoline hydrochloride, 50 parts of polyol, 7 parts of hexamethylene diisocyanate, 30 parts of 2, 3-dihydroxypropyl acrylate, 3.5 parts of tetrabutylammonium bromide, 2.5 parts of nano cerium dioxide, 3 parts of an additive and 0.4 part of an ultraviolet absorber.
The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 5: 1.
the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 25 parts by weight of tetrakis (hydroxymethyl) phosphonium iodide into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate to carry out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 2, weighing 30mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 40ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 6 hours, and removing impurities to obtain the modified graphene.
The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:
s1: weighing 65 parts of polystyrene, 25 parts of hexafluorobisphenol A diacrylate and 5 parts of azobisisobutyrimidazoline hydrochloride according to parts by weight, uniformly mixing by magnetic stirring, maintaining the temperature at 70 ℃, reacting for 2 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: weighing 90 parts of the polystyrene polymer modified in the step S1, adding 30 parts of 2, 3-dihydroxypropyl acrylate, swelling for 1.5h, adding 7 parts of hexamethylene diisocyanate, and continuing to swell for 1.5h to obtain a uniformly dissolved mixed solution;
s3: and (3) adding 50 parts of polyol, 3.5 parts of tetrabutylammonium bromide, 2.5 parts of nano cerium dioxide, 3 parts of additive and 0.4 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50 ℃, and reacting for 6 hours to obtain the modified plastic based on the interpenetrating network structure.
Example 3
The modified plastic based on the interpenetrating network structure of the embodiment is composed of the following raw materials in parts by weight: 80 parts of polystyrene, 30 parts of hexafluorobisphenol A diacrylate, 10 parts of azoisobutyryl cyanoformamide, 60 parts of polyol, 10 parts of isophorone diisocyanate, 40 parts of 2-hydroxybutyl acrylate, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of an additive and 1 part of an ultraviolet absorber.
The polyhydric alcohol is a composition of ethylene glycol and polyhydroxy cage type silsesquioxane, and the mass ratio of the ethylene glycol to the polyhydroxy cage type silsesquioxane is 7: 1.
the additive is modified graphene, and the modification method of the modified graphene comprises the following steps: weighing 30 parts by weight of tris (hydroxymethyl) phosphonium chloride, adding the tris (hydroxymethyl) phosphonium chloride into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: and 3, weighing 50mg of ionic liquid and carboxyl graphene, dissolving the ionic liquid and the carboxyl graphene in 50ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 8 hours, and removing impurities to obtain the modified graphene.
The preparation method of the modified plastic based on the interpenetrating network structure comprises the following steps:
s1: weighing 80 parts by weight of polystyrene, 30 parts by weight of hexafluorobisphenol A diacrylate and 10 parts by weight of azo initiator, uniformly mixing by magnetic stirring, maintaining the temperature at 100 ℃, reacting for 3.5 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: weighing 110 parts of the polystyrene polymer modified in the step S1, adding 40 parts of 2-hydroxybutyl acrylate, swelling for 2.5h, adding 10 parts of isophorone diisocyanate, and continuing to swell for 2.5h to obtain a uniformly dissolved mixed solution;
s3: and (4) adding 60 parts of polyol, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of additive and 1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, magnetically stirring and uniformly mixing, maintaining the temperature at 70 ℃, and reacting for 4 hours to obtain the modified plastic based on the interpenetrating network structure.
Comparative example 1
The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example are substantially the same as those of example 3, except that the modified graphene additive is not added to the composite material of the comparative example.
Comparative example 2
The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example are substantially the same as those of example 3, except that the polyhydroxy cage-type silsesquioxane is not added to the composite material of the comparative example.
Comparative example 3
The raw material composition and the preparation method of the modified plastic based on the interpenetrating network structure of the comparative example were substantially the same as those of example 3, except that hexafluorobisphenol a diacrylate was not added to the composite material of the comparative example.
Comparative example 4
The preparation method of the modified plastic based on the interpenetrating network structure of the present comparative example does not undergo the swelling treatment of step S2, and specifically, the preparation method comprises the following steps:
s1: weighing 80 parts by weight of polystyrene, 30 parts by weight of hexafluorobisphenol A diacrylate and 10 parts by weight of azo initiator, uniformly mixing by magnetic stirring, maintaining the temperature at 100 ℃, reacting for 3.5 hours, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: adding 40 parts of 2-hydroxybutyl acrylate, 10 parts of isophorone diisocyanate, 60 parts of polyol, 5.5 parts of dibutyltin dilaurate, 3.6 parts of nano titanium dioxide, 5.5 parts of additive and 1 part of ultraviolet absorbent, magnetically stirring and uniformly mixing, maintaining the temperature at 70 ℃, and reacting for 4 hours to obtain the modified plastic based on the interpenetrating network structure.
The modified plastics based on the interpenetrating network structure prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to performance tests, and the performance results are shown in table 1:
wherein: and (3) tensile test: the mechanical properties (tensile strength, elongation at break) of the material were tested using a tensile machine.
Notched impact strength: testing was performed as specified in ASTM.
And (3) testing heat resistance, namely performing continuous 168h testing in an accelerated aging box at 150 ℃, and judging the heat resistance of the composite material through the change rate of tensile strength.
And (4) testing the antistatic performance by testing the volume resistivity of the composite material.
Limiting oxygen index test: the volume fraction of oxygen in the oxygen and nitrogen mixture that the test polymer had just supported the polymerization combustion was called the limiting oxygen index (%).
Combustion experiments: the material was burned in air and the burning of the material was recorded and observed (whether there was a drop, whether there was smoke, whether it could be self-extinguished).
TABLE 1
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (10)
1. The modified plastic based on the interpenetrating network structure is characterized by comprising the following raw materials in parts by weight: 50-80 parts of polystyrene, 20-30 parts of hexafluorobisphenol A diacrylate, 1-10 parts of azo initiator, 40-60 parts of polyol, 5-10 parts of aliphatic isocyanate, 20-40 parts of hydroxyl acrylate, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorber.
2. The modified plastic based on interpenetrating network structure of claim 1, wherein the aliphatic isocyanate is hexamethylene diisocyanate and/or isophorone diisocyanate.
3. The modified plastic based on interpenetrating network structure of claim 1, wherein the azo initiator is at least one of azobisisobutyramidine hydrochloride, azobisisobutyrimidazoline hydrochloride, and azobisisobutyronitrile formamide.
4. The modified plastic based on interpenetrating network structure of claim 1, wherein the polyol is a combination of ethylene glycol and polyhydroxy cage silsesquioxane.
5. The modified plastic based on interpenetrating network structure of claim 1, wherein the hydroxy acrylate is at least one of 6-hydroxyhexyl acrylate, 2, 3-dihydroxypropyl acrylate, and 2-hydroxybutyl acrylate.
6. The modified plastic based on interpenetrating network structure of claim 1, wherein the catalyst is at least one of zinc iso-octoate, dibutyltin dilaurate, tetrabutylammonium bromide.
7. The modified plastic based on interpenetrating network structure of claim 1, wherein the inorganic filler is at least one of nano calcium carbonate, nano zinc oxide, nano cerium dioxide and nano titanium dioxide.
8. The modified plastic based on the interpenetrating network structure of claim 1, wherein the additive is modified graphene, and the modification method of the modified graphene is as follows: weighing 20-30 parts by weight of quaternary phosphonium salt compound, adding the quaternary phosphonium salt compound into 50 parts by weight of toluene, adding excessive sodium tetrafluoroborate for carrying out anion exchange reaction, and removing other reactant impurities after the reaction is finished to prepare ionic liquid; according to the weight ratio of 1: 1-3, weighing 20-50 mg of ionic liquid and carboxyl graphene in total, dissolving the ionic liquid and the carboxyl graphene in 30-50 ml of toluene, carrying out ultrasonic oscillation reaction at 50 ℃ for 3-8 h, and removing impurities to obtain the modified graphene.
9. The modified plastic based on interpenetrating network structure of claim 8, wherein the quaternary phosphonium salt compound is at least one of tetrakis (hydroxymethyl) phosphonium bromide, tetrakis (hydroxymethyl) phosphonium iodide, tris (hydroxymethyl) phosphonium chloride.
10. The preparation method of the modified plastic based on the interpenetrating network structure according to any one of claims 1 to 9, wherein the preparation method comprises the following steps:
s1: weighing 50-80 parts by weight of polystyrene, 20-30 parts by weight of hexafluorobisphenol A diacrylate and 1-10 parts by weight of azo initiator, uniformly stirring and mixing by magnetic force, maintaining the temperature at 50-100 ℃, reacting for 0.5-3.5 h, and separating and removing impurities to obtain a hexafluorobisphenol A diacrylate modified polystyrene polymer;
s2: weighing 70-110 parts of the polystyrene polymer modified in the step S1, adding 20-40 parts of hydroxyl acrylate, swelling for 0.5-2.5 h, adding 5-10 parts of aliphatic isocyanate, and continuing to swell for 0.5-2.5 h to obtain a uniformly dissolved mixed solution;
s3: and (3) adding 40-60 parts of polyol, 0.5-5.5 parts of catalyst, 1.2-3.6 parts of inorganic filler, 1.5-5.5 parts of additive and 0.1-1 part of ultraviolet absorbent into the mixed solution swelled in the step S2, uniformly mixing by magnetic stirring, maintaining the temperature at 30-70 ℃, and reacting for 3-8 hours to obtain the modified plastic based on the interpenetrating network structure.
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