CN116376261A - Preparation method of ultra-high toughness polyphenyl ether/polystyrene alloy - Google Patents
Preparation method of ultra-high toughness polyphenyl ether/polystyrene alloy Download PDFInfo
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- CN116376261A CN116376261A CN202310080461.3A CN202310080461A CN116376261A CN 116376261 A CN116376261 A CN 116376261A CN 202310080461 A CN202310080461 A CN 202310080461A CN 116376261 A CN116376261 A CN 116376261A
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- polystyrene
- ultra
- polyphenyl ether
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- high toughness
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 130
- 239000000956 alloy Substances 0.000 title claims abstract description 49
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 49
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 34
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 41
- 229920005669 high impact polystyrene Polymers 0.000 claims abstract description 24
- 239000004797 high-impact polystyrene Substances 0.000 claims abstract description 24
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 24
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims description 46
- 229920005989 resin Polymers 0.000 claims description 46
- 229920000578 graft copolymer Polymers 0.000 claims description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 23
- 239000000839 emulsion Substances 0.000 claims description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 13
- 239000011790 ferrous sulphate Substances 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 13
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 13
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 13
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 13
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 13
- 238000010559 graft polymerization reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 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
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010128 melt processing Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 42
- 229920006380 polyphenylene oxide Polymers 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 12
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 12
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000004816 latex Substances 0.000 description 11
- 229920000126 latex Polymers 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000008149 soap solution Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000015271 coagulation Effects 0.000 description 10
- 238000005345 coagulation Methods 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000010556 emulsion polymerization method Methods 0.000 description 10
- 238000009863 impact test Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical class N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000126 substance 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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- 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
- C08L51/04—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 rubbers
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 discloses a preparation method of an ultra-high toughness polyphenyl ether/polystyrene alloy, and relates to a preparation method of a plastic modified alloy. The ultra-high toughness polyphenyl ether/polystyrene alloy comprises, by weight, 0-40 parts of high impact polystyrene, 0-20 parts of grafts, 10-50 parts of polystyrene and 10-50 parts of polyphenyl ether; the graft is polybutadiene grafted polystyrene copolymer. The invention also provides a preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy. Compared with the toughening of polyphenyl ether/polystyrene by adopting a synergistic toughening system, the impact toughness of the alloy can be obviously improved by using single toughness particles. The experimental results show that: the adopted synergistic toughening is effective, and the ultra-high toughness polyphenyl ether/polystyrene alloy can be successfully produced and prepared, and the notch impact strength of the alloy can reach 672.80J/m.
Description
Technical Field
The invention relates to an alloy preparation method, in particular to a preparation method of an ultra-high toughness polyphenyl ether/polystyrene alloy.
Background
Polyphenylene Oxide (PPO) resins are very widely used, being one of five general engineering plastics in the world. It has excellent physical and mechanical properties, heat resistance and electrical insulation, low hygroscopicity, high strength and good dimensional stability, but has poor toughness, high glass transition temperature and poor melt flowability due to its existence. To overcome these disadvantages or impart new properties thereto, researchers have variously modified PPO resins, mainly divided into chemical grafting modification and physical modification (blending, filling, reinforcing, etc.).
PPO resins are developed to date in a large variety, and PPO/PS alloy is taken as the first commercialized engineering plastic alloy, and has a relatively important role in the development history of polymer blends, and is still a hot spot for research and development. The PPO is subjected to blending modification by adopting the PS with lower melt viscosity, so that the melt fluidity of the PPO resin can be greatly improved, and the PPO and the PS are completely compatible systems and can be mixed in any proportion. The pure PPO/PS alloy has poor impact toughness and unsatisfactory practical value, and people have conducted toughening modification research on the alloy for further improving the performance of the alloy. Chinese patent CN112341786 proposes the use of lubricants for toughening PPO/PS alloys, including polyethylene wax, polypropylene wax, or ester lubricants, etc. The lubricant can toughen PPO/PS alloy, but has poor compatibility with a matrix and higher cost, and the glass fiber is used for toughening the matrix, so that the melt fluidity is reduced, and the phenomenon that a die cannot be filled in the processing process occurs. In chinese patent CN109777079, it is proposed to improve the melt flowability of the PPO/PS alloy by using cucurbituril compounds, and to reinforce the mechanical properties of the PPO/PS alloy by using inorganic fillers such as nano montmorillonite and nano calcium carbonate, where the introduction of the inorganic fillers greatly reduces the toughness of the PPO/PS alloy, so that it is necessary to prepare a more effective toughening agent to modify the PPO/PS alloy on the premise of ensuring the melt flowability of the PPO/PS alloy, thereby significantly improving the impact toughness of the alloy. The inventors adopt a core-shell structure modifier to modify PPO/PS alloy, the core-shell structure modifier has been successfully used for toughening various polymer materials, the core of the rubber phase of the core-shell structure modifier can endow the matrix with toughness, and the good compatibility between the polymer of the grafting layer and the matrix can keep the shape of core-shell particles and the uniform dispersion of the core-shell particles in the matrix.
Disclosure of Invention
The invention aims to provide a preparation method of an ultra-high toughness polyphenyl ether/polystyrene alloy, HIPS with polybutadiene rubber particles with the particle size of 1-5 mu m is introduced, and particles with two different sizes are used for synergistically toughening a matrix, so that the toughening efficiency of the rubber particles is greatly improved, fewer rubber toughening PPO/PS systems can be used, higher toughness can be achieved, the production cost is reduced, and the preparation method has the characteristics of good compatibility with the toughened matrix and uniform dispersion.
The invention is realized by the following technical measures.
An ultra-high toughness polyphenyl ether/polystyrene alloy and a preparation method thereof, wherein the specific implementation process of the preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the following preparation processes:
(1) preparation of polybutadiene graft styrene copolymer (PB-g-PS graft copolymer), PB-g-PS graft copolymer was synthesized by emulsion graft polymerization technique.
(2) The preparation of the blend requires drying of the sample in a vacuum oven under the desired conditions prior to melt processing. PPO resin, PS resin, third component resin and PB-g-PS graft copolymer are uniformly mixed according to the required proportion and are melted and blended in a double screw extruder, so that the polyphenyl ether polystyrene alloy resin with ultrahigh impact strength is prepared.
The emulsion graft polymerization reaction in the step (1) is carried out, wherein the polybutadiene is added in 30-70 parts, and the styrene is added in 70-30 parts.
The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the emulsion graft polymerization reaction in the step (1), wherein the temperature of a water bath or an oil bath heating device used in the reaction process is 50-80 ℃.
The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the emulsion graft polymerization reaction in the step (1), wherein various auxiliary agents are as follows: one or more of azobisisobutyronitrile, dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide, glucose, sodium thiosulfate, ferrous sulfate, potassium hydrogen sulfite, sodium pyrophosphate, disodium ethylenediamine tetraacetate, sodium tripolyphosphate, potassium hydroxide, 2' -methylenebis- (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-p-cresol, and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the emulsion graft polymerization reaction in the step (1), wherein the particle size of polybutadiene rubber particles is 100-300 nanometers.
The third component resin in the step (2) is one or a mixture of a plurality of High Impact Polystyrene (HIPS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS) and Styrene Butadiene Rubber (SBR).
The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the step (2) of melt blending in a double-screw extruder, wherein the extrusion blending temperature is 180-220 ℃.
The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy comprises the following steps of (2) carrying out melt blending in a double-screw extruder, wherein extrusion blending modification is adopted, and the feeding components are specifically as follows: the high impact polystyrene content is 0-40 parts, PB-g-PS graft content is 0-20 parts, polystyrene content is 10-50 parts, and polyphenyl ether content is 10-50 parts.
The invention has the advantages that:
1. compared with the traditional method for toughening the PPO/PS alloy, the ultra-high toughness polyphenyl ether/polystyrene alloy provided and implemented by the invention can obviously improve the impact toughness of the PPO/PS alloy. Because the PB-g-PS graft copolymer is a polymer with a core-shell structure, PS which is completely compatible with PPO is grafted on the surface of PB rubber particles in the polymerization process, HIPS which is completely compatible with PPO/PS alloy is introduced on the basis, so that the PPO/PS system can be further toughened, and the PPO/PS system is synergistically toughened.
2. The invention uses HIPS, PB-g-PS grafted copolymer and two toughening agents containing polybutadiene particles to toughen and modify PPO/PS matrix, and the two polybutadiene rubber particles are different in that: the particle size of polybutadiene rubber particles contained in HIPS is 1-5 μm; the polybutadiene rubber particles used in the PB-g-PS graft copolymer prepared in the laboratory had a particle size of 300nm. The two particles with different sizes are used for cooperatively toughening the matrix, so that the toughening efficiency of the rubber particles is greatly improved.
3. The dispersion medium of the reactive core-shell structure toughening agent prepared in the step (1) is water, and has the advantages of energy conservation and no pollution of organic solvents.
4. The processing equipment required by the invention is simple, and the ultra-high toughness polyphenyl ether/polystyrene alloy can be produced only by simple mechanical blending. Compared with the situation of toughening by using single rubber, the invention achieves better effect compared with the prior art by using less rubber through synergistic toughening, which clearly brings great market competitiveness for the material and creates great profits for enterprises.
Detailed Description
The present invention is described in detail below by way of specific examples, which are given herein for further illustration only and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations of the invention will be apparent to those skilled in the art in light of the foregoing disclosure.
Required raw materials
Polybutadiene latex with a particle size of 300nm; styrene; glucose; sodium pyrophosphate; potassium hydroxide; cumene hydroperoxide; tertiary dodecyl mercaptan; rosin soap solution, rosin soap content 25wt%; antioxidant solution, mixed solution of OBP and MBP; potassium persulfate; ferrous sulfate; a polystyrene; polyphenylene ether.
Comparative example 1
PS resin 75 parts
PB-g-PS graft copolymer 25 parts
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing PS resin and PB-g-PS graft copolymer, then melt-blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, setting the screw rotating speed to 60r/min, cooling extruded sample bars by water, and granulating for later use. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Comparative example 2
10 parts of PPO resin
65 parts of PS resin
PB-g-PS graft copolymer 25 parts
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing PPO, PS resin and PB-g-PS graft copolymer, then melt blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, the screw rotating speed to 60r/min, and granulating the extruded sample bars after water cooling for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Comparative example 3
PPO resin 20 parts
PS resin 55 parts
PB-g-PS graft copolymer 25 parts
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing PPO, PS resin and PB-g-PS graft copolymer, then melt blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, the screw rotating speed to 60r/min, and granulating the extruded sample bars after water cooling for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Comparative example 4
PPO resin 30 parts
45 parts of PS resin
PB-g-PS graft copolymer 25 parts
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing PPO, PS resin and PB-g-PS graft copolymer, then melt blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, the screw rotating speed to 60r/min, and granulating the extruded sample bars after water cooling for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Comparative example 5
40 parts of PPO resin
PS resin 35 parts
PB-g-PS graft copolymer 25 parts
The polybutadiene grafted styrene copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing PPO, PS resin and PB-g-PS graft copolymer, then melt blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, the screw rotating speed to 60r/min, and granulating the extruded sample bars after water cooling for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Example 1
HIPS resin 40 parts
PS resin 40 parts
20 parts of PB-g-PS graft copolymer
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
HIPS, PS resin and PB-g-PS graft copolymer are evenly mixed and then are melt blended in a double-screw extruder, the temperature of each section of the extruder is set to 255-265 ℃, the screw rotating speed is 60r/min, and extruded bars are cut into particles after being cooled by water for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Example 2
HIPS resin 40 parts
10 parts of PPO resin
PS resin 30 parts
20 parts of PB-g-PS graft copolymer
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing HIPS, PPO, PS resin and PB-g-PS graft copolymer, then melt-blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, setting the screw rotating speed to 60r/min, cooling extruded sample bars by water, and granulating for later use. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Example 3
HIPS resin 40 parts
PPO resin 20 parts
20 parts of PS resin
20 parts of PB-g-PS graft copolymer
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing HIPS, PPO, PS resin and PB-g-PS graft copolymer, then melt-blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, setting the screw rotating speed to 60r/min, cooling extruded sample bars by water, and granulating for later use. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Example 4
HIPS resin 40 parts
PPO resin 30 parts
10 parts of PS resin
20 parts of PB-g-PS graft copolymer
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
Uniformly mixing HIPS, PPO, PS resin and PB-g-PS graft copolymer, then melt-blending in a double-screw extruder, setting the temperature of each section of the extruder to 255-265 ℃, setting the screw rotating speed to 60r/min, cooling extruded sample bars by water, and granulating for later use. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Example 5
HIPS resin 40 parts
40 parts of PPO resin
20 parts of PB-g-PS graft copolymer
The PB-g-PS graft copolymer is synthesized by adopting a seed emulsion polymerization method. 1500mL of deionized water, 0.06g of ferrous sulfate, 3.6g of glucose, 2.4g of sodium pyrophosphate, 3.0g of rosin soap solution and 0.6g of potassium hydroxide are added into a three-port bottle, after uniform mixing, 988g of polybutadiene latex with the particle size of 100nm is added, then the three-port bottle is placed into a constant-temperature water bath with the temperature of 65 ℃ and stirred for 20min under the protection of nitrogen, and then a mixed solution consisting of 180g of styrene and 0.4mL of cumene hydroperoxide is continuously added dropwise. After the monomer is added dropwise, adding 0.1mL of cumene hydroperoxide, continuing to react for 1h, adding 15mL of antioxidant solution when the temperature is reduced to below 60 ℃ for continuous reaction for 30min, and finishing the polymerization reaction. The obtained emulsion was subjected to the steps of demulsification, coagulation, dehydration, drying and the like using 25g of magnesium sulfate to obtain PB-g-PS graft copolymer.
HIPS, PPO resin and PB-g-PS graft copolymer are evenly mixed and then are melt blended in a double-screw extruder, the temperature of each section of the extruder is set to 255-265 ℃, the screw rotating speed is 60r/min, and extruded sample bars are cut into particles after being cooled by water for standby. Standard impact test bars were then injection molded according to ASTM-D256, and the bars were left at 23 ℃ for 24 hours prior to testing.
Table 1 impact Strength of samples of ultra high toughness polyphenylene ether/polystyrene alloy and comparative examples
In Table 1, the total PB content (wt%) means the sum of the rubber particles of 1 to 5 μm contained in HIPS and the rubber particles of 300nm contained in PB-g-PS; the total PS content (wt%) refers to the sum of PS contained in HIPS, PS contained in the matrix, and PS contained in PB-g-PS.
As can be seen from the comparison of the table data of examples 1-5 and comparative examples 1-5, the notched impact strength of the samples using HIPS containing rubber particles having a particle size of 1-5 μm and the core-shell type toughening agent containing rubber particles having a particle size of 300nm is significantly improved, which means that the use of 1-5 μm rubber particles together with 300nm rubber particles can achieve higher toughening efficiency without changing the total rubber content.
Claims (8)
1. The preparation method of the ultra-high toughness polyphenyl ether/polystyrene alloy is characterized by comprising the following preparation processes:
(1) preparing polybutadiene grafted styrene copolymer (PB-g-PS grafted copolymer), and synthesizing the PB-g-PS grafted copolymer by using emulsion graft polymerization technology;
(2) preparing a blend, and placing a sample into a vacuum oven to be dried under the required conditions before melt processing; PPO resin, PS resin, third component resin and PB-g-PS graft copolymer are uniformly mixed according to the required proportion and are melted and blended in a double screw extruder, so that the polyphenyl ether polystyrene alloy resin with ultrahigh impact strength is prepared.
2. The method for preparing an ultra-high toughness polyphenyl ether/polystyrene alloy according to claim 1, wherein the emulsion graft polymerization reaction in the step (1) is carried out, wherein the polybutadiene is added in an amount of 30 to 70 parts, and the styrene is added in an amount of 70 to 30 parts.
3. The method for preparing ultra-high toughness polyphenyl ether/polystyrene alloy according to claim 1, wherein the emulsion graft polymerization reaction in the step (1) is carried out by using a water bath or an oil bath heating device with the temperature of 50-80 ℃.
4. The method for preparing ultra-high toughness polyphenyl ether/polystyrene alloy according to claim 1, wherein the emulsion graft polymerization reaction in the step (1) is carried out, and various auxiliary agents are: one or more of azobisisobutyronitrile, dicumyl peroxide, cumene hydroperoxide, dibenzoyl peroxide, glucose, sodium thiosulfate, ferrous sulfate, potassium hydrogen sulfite, sodium pyrophosphate, disodium ethylenediamine tetraacetate, sodium tripolyphosphate, potassium hydroxide, 2' -methylenebis- (4-methyl-6-tert-butylphenol), 2, 6-di-tert-butyl-p-cresol, and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
5. The method for preparing ultra-high toughness polyphenylene ether/polystyrene alloy according to claim 1, wherein said emulsion graft polymerization in step (1) is performed, wherein the polybutadiene rubber particles used have a particle size of 100 to 300nm.
6. The method for preparing ultra-high toughness polyphenyl ether/polystyrene alloy according to claim 1, wherein the third component resin in the step (2) is one or a mixture of several of High Impact Polystyrene (HIPS), styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-butadiene-styrene block copolymer (SBS) and styrene-butadiene rubber (SBR).
7. The method for producing an ultra-high toughness polyphenylene ether/polystyrene alloy according to claim 1, wherein said step (2) is melt-blended in a twin-screw extruder at an extrusion blending temperature of 180 to 220 ℃.
8. The method for preparing an ultra-high toughness polyphenyl ether/polystyrene alloy according to claim 1, wherein the step (2) is melt blended in a twin screw extruder, wherein the extrusion blending modification is performed, and the feeding components are specifically as follows: the high impact polystyrene content is 0-40 parts, PB-g-PS graft content is 0-20 parts, polystyrene content is 10-50 parts, and polyphenyl ether content is 10-50 parts.
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