CN108276730A - A kind of matt uvioresistant engineering plastics and preparation method thereof - Google Patents
A kind of matt uvioresistant engineering plastics and preparation method thereof Download PDFInfo
- Publication number
- CN108276730A CN108276730A CN201810029342.4A CN201810029342A CN108276730A CN 108276730 A CN108276730 A CN 108276730A CN 201810029342 A CN201810029342 A CN 201810029342A CN 108276730 A CN108276730 A CN 108276730A
- Authority
- CN
- China
- Prior art keywords
- organic
- matt
- uvioresistant
- engineering plastics
- titanium dioxide
- 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.)
- Pending
Links
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 284
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000004005 microsphere Substances 0.000 claims abstract description 93
- 239000002131 composite material Substances 0.000 claims abstract description 80
- 238000004132 cross linking Methods 0.000 claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 claims abstract description 53
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 37
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical class CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006096 absorbing agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005453 pelletization Methods 0.000 claims abstract description 17
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 121
- 239000007788 liquid Substances 0.000 claims description 116
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 55
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 48
- 239000006185 dispersion Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 claims description 30
- 239000007921 spray Substances 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 26
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 24
- 229960004889 salicylic acid Drugs 0.000 claims description 24
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical group C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 23
- 238000005452 bending Methods 0.000 claims description 22
- 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 22
- 239000000178 monomer Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 20
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 19
- 239000012964 benzotriazole Substances 0.000 claims description 19
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 239000000052 vinegar Substances 0.000 claims description 14
- 235000021419 vinegar Nutrition 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- MQFDMZNZEHTLND-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]benzoic acid Chemical compound CC(C)(C)OC1=CC=CC=C1C(O)=O MQFDMZNZEHTLND-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- 238000003287 bathing Methods 0.000 claims description 11
- 239000012965 benzophenone Substances 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 229920000459 Nitrile rubber Polymers 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 235000013339 cereals Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- -1 γ-methacryloxypropyl trimethoxy silicon Alkane Chemical class 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims 1
- RFVHVYKVRGKLNK-UHFFFAOYSA-N bis(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1 RFVHVYKVRGKLNK-UHFFFAOYSA-N 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 9
- 230000003712 anti-aging effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 46
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 12
- 241000790917 Dioxys <bee> Species 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 239000003595 mist Substances 0.000 description 9
- 238000005253 cladding Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 240000000203 Salix gracilistyla Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F212/00—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
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of matt uvioresistant engineering plastics and preparation method thereof, preparation methods：Nucleocapsid organic/inorganic composite hollow porous microsphere is added in ABS resin and toughener after mixing, is dried after melt pelletization after mixing obtains matt uvioresistant engineering plastics again.It is finally evenly dispersed by the nucleocapsid organic/inorganic composite hollow porous microsphere being mainly made of crosslinking ball, titania nanoparticles and organic uv absorbers in obtained product；It is crosslinked ball inner hollow, porous surface and with by the structure formed that is cross-linked with each other between the copolymer molecule chain containing styrene and bifunctionality dimethylacrylate class monomeric building blocks；Titania nanoparticles are coated in crosslinking ball and between crosslinking ball by being covalently keyed；Organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall.Product matt of the present invention, UVResistant effect are good, and anti-aging property is good, using wide；Method and process is easy, and flow is reasonable.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of matt uvioresistant engineering plastics and preparation method thereof.
Background technology
Engineering plastics can be used as engineering material and replace the plastics of metal manufacture element part etc., with excellent comprehensive
Performance is closed, rigidity is big, and creep is small, high mechanical strength, heat-resist, and electrical insulating property is good, can be in harsher chemistry, physical environment
Medium-term and long-term use, alternative metal are used as structural timber, but expensive, and yield is smaller.It is compared with general-purpose plastics,
Engineering plastics can reach higher requirement in mechanical performance, durability, corrosion resistance, heat resistance, weight etc., and process
More convenient and alternative metal material, suitable for being used as structural material.From later stage the 1950s polyformaldehyde and poly- carbonic acid
Since ester is succeeded in developing, what engineering plastics were rapidly developed.At present engineering plastics be widely used in electric, automobile,
The industries such as building, office equipment, machinery, aerospace, to mould Dai Gang, have become international popular trend to mould Dai Mu.Engineering plastic
Material has become the field that growth rate is most fast in world today's plastics industry, and development is not only high to national pillar industry and modern times
New technological industry plays supporting role, while also pushing the adjustment of Transform of Traditional Industrial Equipment and product structure.
For automotive interior material, under the premise of meeting the basic mechanical performance and thermal property of part requirement, generally
Require that it has the function of matt, to help to reduce the visual fatigue of driver, to improve drive safety.Low gloss ABS
Because it is with outstanding matt performance, it is widely used in the automotive interior materials such as car hands upper shield, armrest box, inner decoration strip.But
It is matt function admirable and the product of common ABS mechanical properties and processing performance can be kept less.
In addition, the ultraviolet light in sunlight is the main reason for causing high molecular material that aging occurs, high molecular material meeting
It absorbs ultraviolet light and causes self oxidation, lead to polymer degradation, this process is known as photoredox or light aging.Ultraviolet light
Although only accounting for 5% or so of sunlight, energy is but very big, and energy is enough to destroy the chemical bond of polymer, makes its strand
Fracture, crosslinking, cause its mechanical property that canceration occurs.
Therefore, the engineering plastics pole that a kind of matt effect is good, UVResistant effect is good and has excellent mechanical property is developed
Has realistic meaning.
Invention content
The purpose of the invention is to overcome above-mentioned problems of the prior art, provide a kind of matt effect it is good,
Matt uvioresistant engineering plastics that uvioresistant performance is good and mechanical property is good and preparation method thereof.
In order to achieve the above object, the technical solution adopted by the present invention is：
A kind of matt uvioresistant engineering plastics, in matt uvioresistant engineering plastics it is evenly dispersed have nucleocapsid it is organic/nothing
Machine composite hollow porous microsphere；
The nucleocapsid organic/inorganic composite hollow porous microsphere mainly by crosslinking ball, titania nanoparticles and
Organic uv absorbers form；
The crosslinking ball inner hollow, porous surface and has cross-linked structure, and the cross-linked structure is by containing styrene and double
It is cross-linked with each other to be formed between the copolymer molecule chain of degree of functionality dimethylacrylate class monomeric building blocks；
The titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball；
The organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall；
45 degree of glossiness of the matt uvioresistant engineering plastics are less than 30%, and matt uvioresistant engineering plastics plank is in wave
The reduced rate of tensile strength is less than 14.0% after radiation 240h under the ultraviolet light of a length of 290~400nm, the drop of fracture point elongation percentage
Low rate is less than 2.1%, and the reduced rate of varicose intensity is less than 4.5%, and the reduced rate of bending modulus is less than 12.5%, matt uvioresistant
Engineering plastics plank anti-aging property is good.
As preferred technical solution：
A kind of matt uvioresistant engineering plastics as described above, titanium dioxide contains in the matt uvioresistant engineering plastics
Amount is 0.34~0.74wt%, and the content of organic uv absorbers is 0.41~0.92wt%；
The thickness of the matt uvioresistant engineering plastics plank is 2.5mm, and tensile strength is 34~38MPa, and fracture point prolongs
It is 16.3~16.8% to stretch rate, and varicose intensity is 58.2~62.3MPa, and bending modulus is 2052~2248MPa.
A kind of matt uvioresistant engineering plastics as described above, the nucleocapsid organic/inorganic composite hollow are porous micro-
The melting temperature of ball>500 DEG C, heat decomposition temperature>350 DEG C, the load factor of organic uv absorbers is 3.6~11.2wt%；One
As the base material processing temperature compound with titanium dioxide be both less than 280 DEG C, thus when machining composite material, nucleocapsid of the invention
Organic/inorganic composite hollow porous microsphere can keep preferable three-dimensional structure not to be damaged, and be conducive to give full play to its effect.
The wall thickness of a diameter of 500~1500nm of the crosslinking ball, the crosslinking ball are 60~100nm；The titanium dioxide
A diameter of 300~400nm of titanium nano particle；
The quantity of the crosslinking ball inner silica titanium nano particle is 1~4；When crosslinking ball inner silica titanium nanometer
When the quantity of particle≤2, the distribution density of the surface aperture of the crosslinking ball is 1~60/1000nm2, the aperture of aperture is
10~20nm；When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution of the surface aperture of the crosslinking ball is close
Degree is 1~20/1000nm2, the aperture of aperture is 10~40nm.
A kind of matt uvioresistant engineering plastics as described above, the nucleocapsid organic/inorganic composite hollow are porous micro-
The preparation method of ball is：
Styrene, bifunctionality dimethylacrylate class organic monomer, photoinitiator and organic uv absorbers are molten
Solution obtains EFI solution in a solvent, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed,
Electrostatic spray is carried out under visible light conditions, nucleocapsid organic/inorganic composite hollow porous microsphere is made, finally washed with methanol
It washs and dries, the effect for washing and drying nucleocapsid organic/inorganic composite hollow porous microsphere is removal electrostatic spray process
The impurity of middle microsphere surface, such as extra polymerized monomer and photoinitiator etc..The double bond containing modified dioxy in surface in the present invention
Change titanium, in a solvent can be evenly dispersed since surface carries organo-functional group, is conducive to prepare uniform electrostatic spray system.
A kind of matt uvioresistant engineering plastics as described above, the bifunctionality dimethylacrylate class organic monomer
For Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA；
The photoinitiator be DMPOH (N, N- dimethylanunuphenylelhvl alcohol) and/or CQ (1,7,7- trimethyl bicyclics (2,2,
1) -2,3 heptadione)；
The organic uv absorbers are salicylic acid, benzophenone or benzotriazole；
Organic uv absorbers absorption mechanism：
Salicylic acid：There are intramolecular hydrogen bond, wavelength models very low in the energy for starting to absorb, and absorbing for this substance
When enclosing extremely narrow and be less than 340nm, but being irradiated through ultraviolet light, intramolecular rearrangement occurs, it is stronger to be converted into ultraviolet absorption ability
Benzophenone structural, to make absorption gradually increase, until absorption maximum；
Benzophenone：Carbonyl in molecule, at holy intramolecular hydrogen bond, constitutes a chelate ring, when molecule is by purple with hydroxyl
Outside line absorbs energy, molecule thermal vibration aggravation when irradiating, intramolecular hydrogen bond destroys, and ultraviolet luminous energy is converted to by chelate ring open loop
Discharged for thermal energy, in addition, in molecule carbonyl can also the energy of absorbed ultraviolet light excited, generate isomerism, generation alkene
Alcohol of formula structure, to consume part energy；
Benzotriazole：Similar with benzophenone, cis-trans isomerization makes the energy of light change into thermal energy and releases；It can
Other substances for meeting above-mentioned acceptance condition also can be used as the organic uv absorbers of the present invention；
The wavelength of the visible light is 400~500nm；The solvent is DMF, chloroform, dichloromethane and tetrahydrochysene furan
One or more of mutter；Described be uniformly dispersed refers to 30~50min of rotating speed mechanical agitation with 200~500rpm；
In the EFI solution, bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality diformazan
5~28wt% of base esters of acrylic acid organic monomer total amount；The organic list of bifunctionality dimethylacrylate class in EFI solution
Body accounts for the friendship of the ratio and microsphere surface cross-linked structure of styrene and bifunctionality dimethylacrylate class organic monomer total amount
Connection degree is directly proportional, and the degree of cross linking is higher, and crosslinking mesh is bigger, and exchange velocity is faster, but can reduce crosslinking knot to a certain extent
The intensity of structure, conversely, the degree of cross linking is lower, crosslinking mesh is smaller, and cross-link intensity is higher, but poor to the swellability of water；EFI is molten
It is low to cross low crosslinking degree for the concentration of bifunctionality dimethylacrylate class organic monomer in liquid, can not be applied to melt-processed, mistake
Height influences the viscosity of compound system, can not form microballoon；
Photoinitiator accounts for 0.6~1.8wt% of styrene and bifunctionality dimethylacrylate class organic monomer total amount；
The too low efficiency of initiation of the concentration of photoinitiator is too low in EFI solution can not cause monomer polymerization.
Organic uv absorbers account for styrene and bifunctionality dimethylacrylate class organic monomer total amount 10~
25wt%；Organic uv absorbers adding too much can influence the molding of microballoon, cause microballoon broken, reduction dissipates incident light
Ability is penetrated, additive amount is too low, cannot reach ideal ultraviolet shielded effect；
Solvent accounts for 56~83wt% of styrene and bifunctionality dimethylacrylate class organic monomer total amount；It is described to change
Property titanium dioxide addition be EFI solution quality 18~42%；
The parameter of the electrostatic spray is：10~15kV of output voltage of high voltage power supply, atomizing nozzle with solidification bathing pool away from
From 7~13cm, 20~40 DEG C of temperature promotes 1~4mL/h of fltting speed of pump, 5~15mm of diameter of propeller, propeller
3~10mL of volume.
A kind of matt uvioresistant engineering plastics as described above, the salicylic acid is for phenylo salicylic acid acid or to tertiary butyl
Bigcatkin willow vinegar, the benzophenone are ESCALOL 567 or 2,2 '-dihydroxy -4,4 '-dimethoxys two
Benzophenone, the benzotriazole are 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzotriazole or 2- (2 '-hydroxyls -2 '-tertiary fourth
Base benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole.
A kind of matt uvioresistant engineering plastics as described above, the preparation process of the modifying titanium dioxide are as follows：
(1) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid；The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h of reaction at 60~70 DEG C, room temperature ageing 10~
12h obtains ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the ethyl alcohol water mixed liquid adds
Enter 20~30% that amount is mixed dispersion liquid volume；
(3) silane coupling agent is instilled in ethanol water, 2~3h of hydrolysis is stirred at room temperature, is added to ultrasonic disperse
In the ageing liquid of 30~60min, 4~5h of back flow reaction at 60~70 DEG C；The quality of ethyl alcohol and water in the ethanol water
Than being 2~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent
It is 5~10% of titanium dioxide quality in ageing liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy
Silane；
(4) it is dried in vacuo 12~16h at 70~80 DEG C after rotating evaporation drying at 50~70 DEG C, obtains surface containing double
The modifying titanium dioxide of key.
The present invention also provides a kind of method of matt uvioresistant engineering plastics as described above is prepared, by ABS resin and increasing
Tough dose is added nucleocapsid organic/inorganic composite hollow porous microsphere after mixing, again after mixing after melt pelletization
Drying process obtains matt uvioresistant engineering plastics.
As preferred technical solution：
Method as described above, is counted in parts by weight, and when the melt pelletization, ABS resin is 100 parts, and toughener is 10~
15 parts, nucleocapsid organic/inorganic composite hollow porous microsphere is 15~35 parts.
Method as described above, the toughener are nitrile rubber or ABS high glue powders；It is described to be uniformly mixed or mix again equal
Even refers to mixing 1~2h with the rotating speed of 100~150 turns/min；The melt pelletization carries out in dual-screw pelletizer, double
The temperature of screw pelletizer is 190~240 DEG C, and screw speed is 150~300 turns/min；The temperature of the drying process is 80
~90 DEG C, the time is 3~5h.
Invention mechanism：
The present invention is more by electrostatic spray-obtained nucleocapsid organic/inorganic composite hollow of light initiation polymerization crosslinking first
Hole microballoon, then nucleocapsid organic/inorganic composite hollow porous microsphere is added in the mixture of ABS resin and toughener and is melted
It is dried after granulation and matt uvioresistant engineering plastics is made.
The prior art prepares hollow microsphere commonly used in fields such as medicament slow releases, generally by that will polymerize using electrostatic spray
Electrostatic spray obtains microballoon in a solvent for object dissolving, after this method obtains microballoon, polymer can still keep its original thermal property and
It is melted in melt-processed and its microballoon pattern cannot be kept, be not used to melt-processed.
The preparation process of the nucleocapsid organic/inorganic composite hollow porous microsphere of the present invention：First single functionality
Styrene monomer, the bifunctionality dimethylacrylate class organic monomer of bifunctionality, photoinitiator and organic ultraviolet absorb
EFI solution is made in agent dissolving in a solvent, and the double bond containing modifying titanium dioxide in surface is then added and is uniformly mixed, then in height
Lower progress electrostatic spray of having a meeting, an audience, etc. well under one's control forms drop, is caused in drop using visible light (according to initiation wavelength law of photoinitiator)
The double bond of styrene monomer, bifunctionality dimethylacrylate class monomer and modifying titanium dioxide surface carries out radical polymerization
It closes, forms the copolymer of styrene and bifunctionality dimethylacrylate class monomeric building blocks in titanium dioxide surface, together
When due to dimethylacrylate class monomer bifunctionality, contain styrene and bifunctionality dimethylacrylate class monomer knot
It can be cross-linked with each other to form three-dimensional-structure between the strand of the copolymer of structure unit, because of polymerization shrinkage and molten in forming process
The volatilization of agent and the diffusion in coagulating bath and form nucleocapsid organic/inorganic composite hollow porous microsphere, while being molded
Organic uv absorbers can be entrained in cross-linked structure in the process, or be attached on the inner and outer wall of hollow porous micro sphere,
The organic uv absorbers of attachment on the outer wall are removed in last handling process, finally obtained melting temperature and thermal degradation temperature
High nucleocapsid organic/inorganic composite hollow porous microsphere, three-dimensional structure can be kept in subsequent melt process, is filled
Its function is waved in distribution, has expanded the application range of hollow microsphere structure in actual use.
The porous structure of hollow microsphere can effectively scatter incident light, improve the utilization rate to incident light, light is micro-
Scattering (and being scattered repeatedly to be multiple), increases the distance that light is contacted in organic uv absorbers, therefore organic in spherical structure
The efficiency of ultraviolet absorber is obviously improved, and being added to ultraviolet shielded effect after matrix will also get a promotion, simultaneously as this hair
Bright middle organic uv absorbers are in crosslinked micro-sphere structure, after being added in matrix, can keep its UV absorption for a long time
Ability, and the influence to substrate performance is smaller.
In addition, titanium dioxide itself possesses the ultraviolet shielded effect of good matt effect (scattering) and good middle long wave
The strong anti-uv-ray of (scattering+absorption), nano-titanium dioxide is since it is with high refractivity and high photolytic activity, anti-purple
Outside line ability and its mechanism are related with its grain size：When grain size is larger, the barrier to ultraviolet light be based on reflecting, scatter, and
It is effective to medium wave area and long-wavelength region ultraviolet light.Porous structure can effectively scatter incident light, improve the utilization to incident light
Rate.By coated by titanium dioxide inside porous microsphere, light is incident on titanium dioxide surface across porous structure to be passed through the present invention
After the scattering of titanium dioxide, it can be repeated as many times and scatter between titanium dioxide and microballoon inner wall, finally only a small amount of light can
It is overflowed through microballoon, thus improves matt effect and ultraviolet shielded effect.
Nucleocapsid organic/inorganic composite hollow porous microsphere is made with drying process after ABS resin, toughener melt pelletization
Matt uvioresistant engineering plastics are obtained, it is more that matt uvioresistant engineering plastics inherit wherein nucleocapsid organic/inorganic composite hollow
The characteristic that the matt effect of hole microballoon is good, uvioresistant performance is good, melting temperature and thermal degradation temperature are high.
Advantageous effect：
(1) a kind of matt uvioresistant engineering plastics of the invention, with uvioresistant performance is good, usage time is long, melting temperature
Degree and thermal degradation temperature are high, matt effect is good and disperses the advantages that compatible good, have a wide range of application；
(2) preparation method of a kind of matt uvioresistant engineering plastics of the invention, simple process, preparation flow is reasonable, tool
There is fabulous promotional value.
Description of the drawings
Fig. 1 is the nucleocapsid schematic diagram of the nucleocapsid organic/inorganic composite hollow porous microsphere in the present invention.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) styrene, Bis-GMA, DMPOH and phenylo salicylic acid acid are dissolved in DMF and obtain EFI solution, wherein electricity
It sprays in solution, Bis-GMA accounts for the 5wt% of styrene and Bis-GMA total amounts, and DMPOH accounts for styrene and Bis-GMA total amounts
1.0wt%, phenylo salicylic acid acid account for the 10wt% of styrene and Bis-GMA total amounts, and DMF accounts for styrene and Bis-GMA total amounts
80wt%；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
Solve 2h, be added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4h at 60 DEG C, wherein in ethanol water ethyl alcohol with
The mass ratio of water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:12,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) it is dried in vacuo 13h at 70 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 250rpm
30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 460nm
Nucleocapsid organic/inorganic composite hollow porous microsphere is made in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter
The 35% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 9cm, temperature
20 DEG C of degree, promotes the fltting speed 1mL/h of pump, the diameter 5mm of propeller, the volume 5mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and nitrile rubber with the rotating speed mixing 1h of 100 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1h of 100 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, nitrile rubber and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:10:15, the temperature of dual-screw pelletizer is 19 DEG C, screw speed is 150 turns/
The temperature of min, drying process are 80 DEG C, time 3h.
Structural schematic diagram such as Fig. 1 institutes of the nucleocapsid organic/inorganic composite hollow porous microsphere made from step (1)
Show, be mainly made of crosslinking ball, titania nanoparticles and phenylo salicylic acid acid, be crosslinked ball inner hollow, porous surface and
With cross-linked structure, cross-linked structure is by containing the shape that is cross-linked with each other between styrene and the copolymer molecule chain of Bis-GMA structural units
At titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid is mixed
It is miscellaneous in cross-linked structure.It is crosslinked a diameter of 800nm, wall thickness 100nm of ball；A diameter of 300nm of titania nanoparticles；
Be crosslinked ball inner silica titanium nano particle quantity be 1, be crosslinked the surface aperture of ball distribution density be 1/
1000nm2, the aperture of aperture is 20nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 510 DEG C,
Heat decomposition temperature is 380 DEG C, and the load factor of phenylo salicylic acid acid is 3.6wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.41wt% in matt uvioresistant engineering plastics, and the content of phenylo salicylic acid acid is
0.51wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 29%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 34MPa, and fracture point elongation percentage is
16.3%, varicose intensity is 62.3MPa, bending modulus 2248MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.5% after radiation 240h under the ultraviolet light of 400nm, and the reduced rate of fracture point elongation percentage is
2.0%, the reduced rate of varicose intensity is 4.4%, and the reduced rate of bending modulus is 12.4%.
The step of matt uvioresistant engineering plastics plank is made by matt uvioresistant engineering plastics is as follows：
Matt uvioresistant engineering plastics obtained are sent through automatic feeding device to the loading hopper of Single screw extrusion machine production line
In, by loading hopper autofeed flexible sheet material, wherein the processing temperature of extruder are extruded into through mold to Single screw extrusion machine production line
Degree is 190 DEG C, and the temperature of mold is 220 DEG C.Flexible sheet material is cut into using being sent again to cutter after three roll pressings, cooling and shaping
Defined size, finally packaging and warehousing obtains matt uvioresistant engineering plastics plank after testing, wherein the temperature of three roll pressing upper rollers
Degree is 75 DEG C, the temperature of central roll is 85 DEG C, and the temperature of lower roll is 65 DEG C.
Embodiment 2
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) it by styrene, EBPADMA, CQ and tert-butyl salicylic acid vinegar is dissolved in chloroform obtains EFI solution,
EBPADMA accounts for the 15wt% of styrene and EBPADMA total amounts in EFI solution, and chloroform accounts for styrene and EBPADMA total amounts
56wt%, CQ accounts for the 0.6wt% of styrene EBPADMA total amounts, styrene EBPADMA total amounts accounted for tert-butyl salicylic acid vinegar
15wt%；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 wherein in mixed dispersion liquid:200:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 60 DEG C, room temperature ageing 10h is aged
Liquid, in ethyl alcohol water mixed liquid ethyl alcohol with addition is mixed dispersion liquid volume 30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
3h is solved, is added in the ageing liquid of ultrasonic disperse 40min, the back flow reaction 4.5h at 65 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 11, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 6%；
D) it is dried in vacuo 14h at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 300rpm
35min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 420nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter
The 18% of amount, the parameter of electrostatic spray are：The output voltage 11kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 12cm,
30 DEG C of temperature promotes the fltting speed 3mL/h of pump, the diameter 13mm of propeller, the volume 4mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and ABS high glue powders with the rotating speed mixing 2h of 150 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 2h of 150 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, ABS high glue powders and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:15:35, the temperature of dual-screw pelletizer is 240 DEG C, screw speed 300
Turn/min, the temperature of drying process is 90 DEG C, time 5h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and to tert-butyl salicylic acid vinegar form, be crosslinked ball inner hollow, porous surface and have cross-linked structure, cross-linked structure
By being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of EBPADMA structural units, titania nanoparticles packet
It overlays in crosslinking ball, and by being covalently keyed between crosslinking ball, receiving agent to tert-butyl salicylic acid vinegar is entrained in cross-linked structure
Neutralization is attached on crosslinking ball inner wall.It is crosslinked a diameter of 1500nm, wall thickness 80nm of ball；The diameter of titania nanoparticles
For 350nm；Be crosslinked ball inner silica titanium nano particle quantity be 2, be crosslinked the surface aperture of ball distribution density be 30/
1000nm2, the aperture of aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 520 DEG C,
Heat decomposition temperature is 400 DEG C, and the load factor to tert-butyl salicylic acid vinegar is 4.9wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.53wt% in matt uvioresistant engineering plastics, and the content to tert-butyl salicylic acid vinegar is
0.58wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 27%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 38MPa, and fracture point elongation percentage is
16.8%, varicose intensity is 62.3MPa, bending modulus 2052MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.9% after radiation 240h under the ultraviolet light of 290nm, and the reduced rate of fracture point elongation percentage is
1.8%, the reduced rate of varicose intensity is 4.0%, and the reduced rate of bending modulus is 11.3%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 3
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by styrene, the mixture (mass ratio 1 of UDMA, DMPOH and CQ:And 2- hydroxyl -4- methoxyl group hexichol 1)
Ketone dissolves obtains EFI solution in methylene chloride, and UDMA accounts for the 5wt% of styrene and UDMA total amounts, dichloro in EFI solution
The mixture that methane accounts for styrene and 70wt%, DMPOH and the CQ of UDMA total amounts accounts for the 1.8wt% of styrene and UDMA total amounts,
ESCALOL 567 accounts for the 20wt% of styrene and UDMA total amounts；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:250:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
25%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 50min, the back flow reaction 5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 10, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 7%；
D) it is dried in vacuo 12h at 75 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 400rpm
40min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 440nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 25% of liquid quality, electrostatic spray is：The output voltage 12kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
11cm, 35 DEG C of temperature promote the fltting speed 2mL/h of pump, the diameter 11mm of propeller, the volume 5mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and nitrile rubber with the rotating speed mixing 1.5h of 125 turns/min after, nucleocapsid organic/inorganic is added
Composite hollow porous microsphere, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1.5h of 125 turns/min, most
It is dried afterwards and obtains matt uvioresistant engineering plastics, wherein ABS resin, nitrile rubber and nucleocapsid organic/inorganic is compound
The mass ratio of the addition of hollow porous micro sphere is 100:12.5:25, the temperature of dual-screw pelletizer is 215 DEG C, screw speed
Temperature for 225 turns/min, drying process is 85 DEG C, time 4h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and ESCALOL 567 composition, be crosslinked ball inner hollow, porous surface and have cross-linked structure,
Cross-linked structure by being formed containing being cross-linked with each other between styrene and the copolymer molecule chain of UDMA monomeric building blocks, receive by titanium dioxide
Rice grain is coated in crosslinking ball, and by being covalently keyed between crosslinking ball, ESCALOL 567 attachment
On crosslinking ball inner wall.It is crosslinked a diameter of 900nm, wall thickness 60nm of ball；A diameter of 340nm of titania nanoparticles；
Be crosslinked ball inner silica titanium nano particle quantity be 3 when, be crosslinked the surface aperture of ball distribution density be 20/
1000nm2, the aperture of aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 580 DEG C,
Heat decomposition temperature is 370 DEG C, and the load factor of ESCALOL 567 is 10.5wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.34wt% in matt uvioresistant engineering plastics, and ESCALOL 567 contains
Amount is 0.41wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 28%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 36MPa, and fracture point elongation percentage is
16.5%, varicose intensity is 60.3MPa, bending modulus 2151MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.2% after radiation 240h under the ultraviolet light of 345nm, and the reduced rate of fracture point elongation percentage is
1.9%, the reduced rate of varicose intensity is 4.2%, and the reduced rate of bending modulus is 11.9%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 4
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) styrene, TEGDMA, CQ and 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone are dissolved in tetrahydrochysene furan
Obtain EFI solution in muttering, TEGDMA accounts for the 20wt% of styrene and TEGDMA total amounts in EFI solution, and tetrahydrofuran accounts for benzene second
The 56wt% of alkene and TEGDMA total amounts, CQ account for the 0.8wt% of styrene and TEGDMA total amounts, 2,2 '-dihydroxy -4,4 '-diformazans
Oxygroup benzophenone accounts for the 25wt% of styrene and TEGDMA total amounts；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:180:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 63 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
22%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
Solve 3h, be added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 5h at 60 DEG C, wherein in ethanol water ethyl alcohol with
The mass ratio of water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 8%；
D) it is dried in vacuo 15h at 70 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 500rpm
45min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 450nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 30% of liquid quality, electrostatic spray is：The output voltage 13kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
10cm, 40 DEG C of temperature promote the fltting speed 1mL/h of pump, the diameter 10mm of propeller, the volume 6mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and ABS high glue powders with the rotating speed mixing 1.2h of 110 turns/min after, nucleocapsid organic/inorganic is added
Composite hollow porous microsphere, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1.2h of 110 turns/min, most
It is dried afterwards and obtains matt uvioresistant engineering plastics, wherein ABS resin, ABS high glue powders and nucleocapsid organic/inorganic is compound
The mass ratio of the addition of hollow porous micro sphere is 100:15:15, the temperature of dual-screw pelletizer is 200 DEG C, and screw speed is
250 turns/min, the temperature of drying process is 86 DEG C, time 4.5h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and 2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenones composition are crosslinked ball inner hollow, porous surface and have
Cross-linked structure, cross-linked structure containing being cross-linked with each other between styrene and the copolymer molecule chain of TEGDMA structural units by forming, and two
Titanium dioxide nanoparticle is coated in crosslinking ball, and by being covalently keyed between crosslinking ball, 2,2 '-dihydroxy -4, and 4 '-two
Methoxy benzophenone is entrained in cross-linked structure.It is crosslinked a diameter of 700nm, wall thickness 100nm of ball；Nano titania
A diameter of 300nm of grain；The quantity for being crosslinked ball inner silica titanium nano particle is 4, and the distribution for being crosslinked the surface aperture of ball is close
Degree is 10/1000nm2, the aperture of aperture is 40nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere
It it is 550 DEG C, heat decomposition temperature is 390 DEG C, 2,2 '-dihydroxy -4, and the load factor of 4 '-dimethoxy-benzophenones is 8.9wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.74wt%, 2,2 '-dihydroxy -4,4 '-dimethoxys two in matt uvioresistant engineering plastics
The content of Benzophenone is 0.68wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 28.5%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 35MPa, and fracture point elongation percentage is
16.5%, varicose intensity is 59.8MPa, bending modulus 2100MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.0% after radiation 240h under the ultraviolet light of 320nm, and the reduced rate of fracture point elongation percentage is
2.0%, the reduced rate of varicose intensity is 4.1%, and the reduced rate of bending modulus is 12.3%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 5
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by styrene, D3MA, DMPOH and 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzotriazole be dissolved in DMF and
Mixture (the mass ratio 1 of chloroform:2) EFI solution is obtained in, D in EFI solution3MA accounts for styrene and D3MA total amounts
The mixture of 25wt%, DMF and chloroform accounts for styrene and D3The 75wt% of MA total amounts, DMPOH account for styrene and D3MA total amounts
1.8wt%, 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzotriazole accounts for styrene and D3The 18wt% of MA total amounts；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 5 wherein in mixed dispersion liquid:240:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 5h is reacted at 60 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
28%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 35min, the back flow reaction 4h at 65 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 2:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:8,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 9%；
D) it is dried in vacuo 12h at 80 DEG C after rotating evaporation drying at 65 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 250rpm
50min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 460nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, and the wherein addition of modifying titanium dioxide is EFI solution matter
The 35% of amount, the parameter of electrostatic spray are：The output voltage 14kV of high voltage power supply, atomizing nozzle and solidification bathing pool distance 7cm, temperature
25 DEG C of degree, promotes the fltting speed 2mL/h of pump, the diameter 8mm of propeller, the volume 3mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and nitrile rubber with the rotating speed mixing 2h of 100 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1h of 150 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, nitrile rubber and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:15:25, the temperature of dual-screw pelletizer is 210 DEG C, screw speed 250
Turn/min, the temperature of drying process is 85 DEG C, time 4h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from the above method
Titanium nano particle and 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzotriazole composition, are crosslinked ball inner hollow, porous surface and tool
Crosslinking structure, cross-linked structure is by containing styrene and D3It is cross-linked with each other to be formed between the copolymer molecule chain of MA structural units, two
Titanium dioxide nanoparticle is coated in crosslinking ball, and by being covalently keyed between crosslinking ball, 2- (2 '-hydroxyls -2 '-tertiary fourth
Base phenyl) benzotriazole be entrained in cross-linked structure neutralization be attached to crosslinking ball inner wall on.It is crosslinked a diameter of 1200nm of ball, wall thickness
For 60nm；A diameter of 400nm of titania nanoparticles；The quantity for being crosslinked ball inner silica titanium nano particle is 2, crosslinking
The distribution density of the surface aperture of ball is 40/1000nm2, the aperture of aperture is 17nm.During nucleocapsid organic/inorganic is compound
The melting temperature of empty porous microsphere is 540 DEG C, and heat decomposition temperature is 400 DEG C, 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzo three
The load factor of azoles is 11.2wt%.There is good dispersion effect to visible light, when the additive amount of titanium dioxide in fiber is
When 2.2wt%, you can reach full-dull, for the fiber number of fiber up to 117dtex, centering long wave ultraviolet has preferable shielding effect
Fruit, made fibrous fracture intensity and elongation at break are 3.02cN/dtex and 59.6%, after ultraviolet lighting 240h fracture strength and
Elongation at break is 2.96cN/dtex and 15.6%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.68wt%, 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzene in matt uvioresistant engineering plastics
And the content of triazole is 0.87wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 29.2%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 34MPa, and fracture point elongation percentage is
16.4%, varicose intensity is 59.2MPa, bending modulus 2080MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.0% after radiation 240h under the ultraviolet light of 330nm, and the reduced rate of fracture point elongation percentage is
1.8%, the reduced rate of varicose intensity is 4.0%, and the reduced rate of bending modulus is 12.0%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 6
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by the mixture (mass ratio 2 of Bis-GMA and EBPADMA:1), (mass ratio is the mixture of DMPOH and CQ
1:1), styrene and 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole are dissolved in dichloromethane
With the mixture (mass ratio 1 of tetrahydrofuran:2) EFI solution is obtained in, Bis-GMA's and EBPADMA is mixed in EFI solution
Close the 28wt% that object accounts for the amount of the mixture of styrene and Bis-GMA and EBPADMA, the mixture of dichloromethane and tetrahydrofuran
Account for 83wt%, DMPOH and the CQ of the amount of the mixture of styrene and Bis-GMA and EBPADMA mixture account for styrene and
The 1.3wt% of the amount of the mixture of Bis-GMA and EBPADMA, 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5-
Chlorine) benzotriazole account for styrene and Bis-GMA and EBPADMA amount of the mixture 13wt%；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:170:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 62 DEG C, room temperature ageing 11h is aged
Liquid, the mass ratio of ethyl alcohol and water is 4 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
24%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2h is solved, is added in the ageing liquid of ultrasonic disperse 45min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 3:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 12, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 10%；
D) it is dried in vacuo 16h at 75 DEG C after rotating evaporation drying at 55 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 350rpm
30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 480nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 42% of liquid quality, electrostatic spray is：The output voltage 15kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
8cm, 30 DEG C of temperature promote the fltting speed 3mL/h of pump, the diameter 7mm of propeller, the volume 7mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and ABS high glue powders with the rotating speed mixing 1h of 150 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1h of 125 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, ABS high glue powders and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:12:24, the temperature of dual-screw pelletizer is 220 DEG C, screw speed 190
Turn/min, the temperature of drying process is 85 DEG C, time 4.2h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole composition, are crosslinked in ball inside
Sky, porous surface and have cross-linked structure, cross-linked structure is by the mixture structure list containing styrene and Bis-GMA and EBPADMA
Member copolymer molecule chain between be cross-linked with each other to be formed, titania nanoparticles be coated on crosslinking ball in, and with crosslinking ball it
Between by being covalently keyed 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole be attached to crosslinking ball
On inner wall.It is crosslinked a diameter of 500nm, wall thickness 70nm of ball；A diameter of 370nm of titania nanoparticles；It is crosslinked in ball
When the quantity of portion's titania nanoparticles is 2, the distribution density for being crosslinked the surface aperture of ball is 60/1000nm2, aperture
Aperture is 18nm；The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 600 DEG C, heat decomposition temperature 385
DEG C, the load factor of 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole is 3.6wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.57wt%, 2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-in matt uvioresistant engineering plastics
Aminomethyl phenyl -5- chlorine) benzotriazole content be 0.86wt%；45 degree of glossiness of matt uvioresistant engineering plastics are
28.6%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 38MPa, and fracture point elongation percentage is
16.5%, varicose intensity is 58.2MPa, bending modulus 2090MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.0% after radiation 240h under the ultraviolet light of 400nm, and the reduced rate of fracture point elongation percentage is
1.8%, the reduced rate of varicose intensity is 4.3%, and the reduced rate of bending modulus is 12.2%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 7
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by UDMA and D3Mixture (the mass ratio 1 of MA:2), styrene, DMPOH and the dissolving of phenylo salicylic acid acid
In the mixture (mass ratio 1 of DMF, chloroform and dichloromethane:1:2) EFI solution is obtained in, UDMA in EFI solution
With D3The mixture of MA accounts for styrene and UDMA and D3The 5wt% of the amount of the mixture of MA, DMF, chloroform and dichloromethane
Mixture accounts for styrene and UDMA and D3The 75wt% of the amount of the mixture of MA, DMPOH account for styrene and UDMA and D3The mixing of MA
The 1.1wt% of object total amount, phenylo salicylic acid acid account for styrene and UDMA and D3The 10wt% of the amount of the mixture of MA；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:230:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4.5h is reacted at 65 DEG C, room temperature ageing 10h is aged
Liquid, the mass ratio of ethyl alcohol and water is 2 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
30%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
3h is solved, is added in the ageing liquid of ultrasonic disperse 55min, the back flow reaction 4.5h at 60 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 4:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 10, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 9%；
D) it is dried in vacuo 16h at 80 DEG C after rotating evaporation drying at 50 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 450rpm
50min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 500nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 18% of liquid quality, electrostatic spray is：The output voltage 10kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
7cm, 25 DEG C of temperature promote the fltting speed 1mL/h of pump, the diameter 6mm of propeller, the volume 8mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and ABS high glue powders with the rotating speed mixing 1h of 150 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1h of 150 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, ABS high glue powders and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:12:20, the temperature of dual-screw pelletizer is 210 DEG C, screw speed 200
Turn/min, the temperature of drying process is 88 DEG C, time 3.5h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and phenylo salicylic acid acid composition, be crosslinked ball inner hollow, porous surface and have cross-linked structure, cross-linked structure is by containing
Styrene and UDMA and D3It is cross-linked with each other to be formed between the copolymer molecule chain of the mixture structural unit of MA, nano titania
For particles coat in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid is attached to crosslinking ball inner wall
On.It is crosslinked a diameter of 1400nm, wall thickness 90nm of ball；A diameter of 300nm of titania nanoparticles；It is crosslinked two inside ball
When the quantity of Titanium dioxide nanoparticle is 1, the distribution density for being crosslinked the surface aperture of ball is 50/1000nm2, the aperture of aperture
For 20nm；The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 590 DEG C, and heat decomposition temperature is 390 DEG C,
The load factor of phenylo salicylic acid acid is 11.2wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.74wt% in matt uvioresistant engineering plastics, and the content of phenylo salicylic acid acid is
0.92wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 28.5%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 35MPa, and fracture point elongation percentage is
16.5%, varicose intensity is 61.3MPa, bending modulus 2158MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.0% after radiation 240h under the ultraviolet light of 400nm, and the reduced rate of fracture point elongation percentage is
1.8%, the reduced rate of varicose intensity is 4.2%, and the reduced rate of bending modulus is 12.0%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 8
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
1) by the mixture (mass ratio 1 of Bis-GMA, EBPADMA and UDMA:1:1), styrene, CQ and to tertiary fourth
Base bigcatkin willow vinegar, which is dissolved in DMF, obtains EFI solution, and the mixture of Bis-GMA, EBPADMA and UDMA account for benzene in EFI solution
The 10wt% of ethylene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA, DMF account for styrene and Bis-GMA, EBPADMA
With the 80wt% of the amount of the mixture of UDMA, styrene and Bis-GMA, EBPADMA and UDMA are accounted for tert-butyl salicylic acid vinegar
The 12wt% of amount of the mixture, CQ account for the 1.2wt% of styrene and the amount of the mixture of Bis-GMA, EBPADMA and UDMA；
2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 6 wherein in mixed dispersion liquid:150:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 67 DEG C, room temperature ageing 12h is aged
Liquid, the mass ratio of ethyl alcohol and water is 5 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
26%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2.5h is solved, is added in the ageing liquid of ultrasonic disperse 30min, the back flow reaction 4.5h at 65 DEG C, wherein second in ethanol water
The mass ratio of alcohol and water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:
The addition of 12, γ-methacryloxypropyl trimethoxy silanes is be aged titanium dioxide quality in liquid 7%；
D) it is dried in vacuo 14h at 70 DEG C after rotating evaporation drying at 70 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 500rpm
45min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 400nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 27% of liquid quality, electrostatic spray is：The output voltage 12kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
13cm, 35 DEG C of temperature promote the fltting speed 2mL/h of pump, the diameter 15mm of propeller, the volume 9mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and ABS high glue powders with the rotating speed mixing 2h of 100 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 2h of 100 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, ABS high glue powders and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:14:34, the temperature of dual-screw pelletizer is 238 DEG C, screw speed 238
Turn/min, the temperature of drying process is 88 DEG C, time 4h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and to tert-butyl salicylic acid vinegar form, be crosslinked ball inner hollow, porous surface and have cross-linked structure, cross-linked structure
By the shape that is cross-linked with each other between the copolymer molecule chain containing styrene and the mixture structural unit of Bis-GMA, EBPADMA and UDMA
At titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball, to tert-butyl salicylic acid
Vinegar is entrained in cross-linked structure neutralization and is attached on crosslinking ball inner wall.It is crosslinked a diameter of 500nm, wall thickness 100nm of ball；Titanium dioxide
A diameter of 400nm of titanium nano particle；The quantity for being crosslinked ball inner silica titanium nano particle is 3, is crosslinked the surface aperture of ball
Distribution density be 15/1000nm2, the aperture of aperture is 30nm.Nucleocapsid organic/inorganic composite hollow porous microsphere
Melting temperature is 620 DEG C, and heat decomposition temperature is 420 DEG C, and the load factor to tert-butyl salicylic acid vinegar is 5.8wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.52wt% in matt uvioresistant engineering plastics, and the content to tert-butyl salicylic acid vinegar is
0.71wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 28.8%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 36MPa, and fracture point elongation percentage is
16.6%, varicose intensity is 61.5MPa, bending modulus 2140MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.0% after radiation 240h under the ultraviolet light of 380nm, and the reduced rate of fracture point elongation percentage is
2.0%, the reduced rate of varicose intensity is 4.1%, and the reduced rate of bending modulus is 11.2%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Embodiment 9
A kind of matt uvioresistant engineering plastics and preparation method thereof, steps are as follows：
(1) nucleocapsid organic/inorganic composite hollow porous microsphere is prepared：
(1) by UDMA, TEGDMA and D3Mixture (the mass ratio 1 of MA:2:2), the mixture (quality of DMPOH and CQ
Than being 2:1), styrene and phenylo salicylic acid acid, which are dissolved in chloroform, obtains EFI solution, UDMA in EFI solution,
TEGDMA and D3The mixture of MA accounts for styrene and UDMA, TEGDMA and D3The 28wt% of the amount of the mixture of MA, chloroform account for
Styrene and UDMA, TEGDMA and D3The mixture of 56wt%, DMPOH and the CQ of the amount of the mixture of MA account for styrene and
UDMA, TEGDMA and D3The 0.6wt% of the amount of the mixture of MA, phenylo salicylic acid acid account for styrene and UDMA, TEGDMA and D3MA
Amount of the mixture 25wt%；
(2) modifying titanium dioxide is prepared：
A) titanium dioxide is dispersed in that tetrabutyl titanate is added dropwise and obtains mixing after being stirred by ultrasonic in absolute ethyl alcohol and disperseed
Liquid, the mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4 wherein in mixed dispersion liquid:220:1；
B) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4h is reacted at 70 DEG C, room temperature ageing 10h is aged
Liquid, the mass ratio of ethyl alcohol and water is 3 in ethyl alcohol water mixed liquid:1, the addition of ethyl alcohol water mixed liquid is mixed dispersion liquid volume
20%；
C) γ-methacryloxypropyl trimethoxy silane is instilled in ethanol water, water is stirred at room temperature
2h is solved, is added in the ageing liquid of ultrasonic disperse 60min, the back flow reaction 4.5h at 70 DEG C, wherein ethyl alcohol in ethanol water
Mass ratio with water is 5:The mass ratio of 1, γ-methacryloxypropyl trimethoxy silane and ethanol water is 1:9,
The addition of γ-methacryloxypropyl trimethoxy silane is be aged titanium dioxide quality in liquid 5%；
D) it is dried in vacuo 15h at 80 DEG C after rotating evaporation drying at 60 DEG C, obtains the double bond containing modified dioxy in surface
Change titanium；
3) the double bond containing modifying titanium dioxide in surface is added to the rotating speed mechanical agitation in EFI solution with 200rpm
30min makes modifying titanium dioxide be uniformly dispersed in EFI solution, and electrostatic is carried out in the case where wavelength is the visible light conditions of 430nm
The hollow porous micro sphere of cladding titanium dioxide nano particle is made in mist, wherein the addition of the modifying titanium dioxide is that EFI is molten
The parameter of the 39% of liquid quality, electrostatic spray is：The output voltage 14kV of high voltage power supply, atomizing nozzle is at a distance from solidification bathing pool
10cm, 40 DEG C of temperature promote the fltting speed 4mL/h of pump, the diameter 15mm of propeller, the volume 10mL of propeller；
4) nucleocapsid organic/inorganic composite hollow porous microsphere and drying are washed with methanol after electrostatic spray.
(2) matt uvioresistant engineering plastics are synthesized：
By ABS resin and nitrile rubber with the rotating speed mixing 1h of 100 turns/min after, it is multiple that nucleocapsid organic/inorganic is added
Hollow porous micro sphere is closed, then to carry out melt pelletization in dual-screw pelletizer after the rotating speed mixing 1h of 100 turns/min, is finally done
Dry processing obtains matt uvioresistant engineering plastics, wherein ABS resin, nitrile rubber and nucleocapsid organic/inorganic composite hollow
The mass ratio of the addition of porous microsphere is 100:14:24, the temperature of dual-screw pelletizer is 240 DEG C, screw speed 300
Turn/min, the temperature of drying process is 80 DEG C, time 3h.
Nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titanium dioxide made from step (1)
Nano particle and phenylo salicylic acid acid composition, be crosslinked ball inner hollow, porous surface and have cross-linked structure, cross-linked structure is by containing
Styrene and UDMA, TEGDMA and D3It is cross-linked with each other to be formed between the copolymer molecule chain of the mixture structural unit of MA, dioxy
Change titanium nano particle to be coated in crosslinking ball, and by being covalently keyed between crosslinking ball, phenylo salicylic acid acid doping is being handed over
It is coupled in structure.It is crosslinked a diameter of 1500nm, wall thickness 70nm of ball；A diameter of 310nm of titania nanoparticles；It is crosslinked ball
The quantity of inner silica titanium nano particle is 4, and the distribution density for being crosslinked the surface aperture of ball is 1/1000nm2, aperture
Aperture is 10nm.The melting temperature of nucleocapsid organic/inorganic composite hollow porous microsphere is 520 DEG C, heat decomposition temperature 440
DEG C, the load factor of phenylo salicylic acid acid is 11.4wt%.
It is evenly dispersed in final matt uvioresistant engineering plastics obtained to have nucleocapsid organic/inorganic composite hollow porous
Microballoon；The content of titanium dioxide is 0.49wt% in matt uvioresistant engineering plastics, and the content of phenylo salicylic acid acid is
0.43wt%；45 degree of glossiness of matt uvioresistant engineering plastics are 28.2%.
The tensile strength for the matt uvioresistant engineering plastics plank that thickness is 2.5mm is 37.8MPa, and fracture point elongation percentage is
16.3%, varicose intensity is 62.3MPa, bending modulus 2238MPa；Matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is 13.8% after radiation 240h under the ultraviolet light of 340nm, and the reduced rate of fracture point elongation percentage is
1.8%, the reduced rate of varicose intensity is 3.8%, and the reduced rate of bending modulus is 11.5%.Wherein matt uvioresistant engineering plastics
Plank preparation process is same as Example 1.
Claims (10)
1. a kind of matt uvioresistant engineering plastics, it is characterized in that：It is evenly dispersed in matt uvioresistant engineering plastics to have nucleocapsid
Organic/inorganic composite hollow porous microsphere；
The nucleocapsid organic/inorganic composite hollow porous microsphere is mainly by crosslinking ball, titania nanoparticles and organic
Ultraviolet absorber forms；
The crosslinking ball inner hollow, porous surface and have cross-linked structure, the cross-linked structure is by containing styrene and difunctionality
It is cross-linked with each other to be formed between the copolymer molecule chain of degree dimethylacrylate class monomeric building blocks；
The titania nanoparticles are coated in crosslinking ball, and by being covalently keyed between crosslinking ball；
The organic uv absorbers are entrained in cross-linked structure and/or are attached on crosslinking ball inner wall；
45 degree of glossiness of the matt uvioresistant engineering plastics are less than 30%, and matt uvioresistant engineering plastics plank is in wavelength
The reduced rate of tensile strength is less than 14.0% after radiation 240h under the ultraviolet light of 290~400nm, the reduced rate of fracture point elongation percentage
Less than 2.1%, the reduced rate of varicose intensity is less than 4.5%, and the reduced rate of bending modulus is less than 12.5%.
2. a kind of matt uvioresistant engineering plastics according to claim 1, which is characterized in that the matt uvioresistant engineering
The content of titanium dioxide is 0.34~0.74wt% in plastics, and the content of organic uv absorbers is 0.41~0.92wt%；
The thickness of the matt uvioresistant engineering plastics plank is 2.5mm, and tensile strength is 34~38MPa, fracture point elongation percentage
It is 16.3~16.8%, varicose intensity is 58.2~62.3MPa, and bending modulus is 2052~2248MPa.
3. a kind of matt uvioresistant engineering plastics according to claim 1, which is characterized in that the nucleocapsid is organic/
The melting temperature of inorganic compounding hollow porous micro sphere>500 DEG C, heat decomposition temperature>350 DEG C, the load factor of organic uv absorbers
For 3.6~11.2wt%；
The wall thickness of a diameter of 500~1500nm of the crosslinking ball, the crosslinking ball are 60~100nm；The titanium dioxide is received
A diameter of 300~400nm of rice grain；
The quantity of the crosslinking ball inner silica titanium nano particle is 1~4；When crosslinking ball inner silica titanium nano particle
Quantity≤2 when, it is described crosslinking ball surface aperture distribution density be 1~60/1000nm2, the aperture of aperture is 10~
20nm；When the quantity of crosslinking ball inner silica titanium nano particle>When 2, the distribution density of the surface aperture of the crosslinking ball is 1
~20/1000nm2, the aperture of aperture is 10~40nm.
4. according to a kind of matt uvioresistant engineering plastics of claims 1 to 3 any one of them, which is characterized in that the nucleocapsid
The preparation method of structure organic/inorganic composite hollow porous microsphere is：
Styrene, bifunctionality dimethylacrylate class organic monomer, photoinitiator and organic uv absorbers are dissolved in
EFI solution is obtained in solvent, then the double bond containing modifying titanium dioxide in surface is added in EFI solution and is uniformly dispersed, can
Electrostatic spray is carried out under the conditions of light-exposed, nucleocapsid organic/inorganic composite hollow porous microsphere is made, finally washed simultaneously with methanol
It is dry.
5. a kind of matt uvioresistant engineering plastics according to claim 4, which is characterized in that the bifunctionality dimethyl
Esters of acrylic acid organic monomer is Bis-GMA, EBPADMA, UDMA, TEGDMA and D3One or more of MA；It is described light-initiated
Agent is DMPOH and/or CQ；The organic uv absorbers are salicylic acid, benzophenone or benzotriazole；It is described visible
The wavelength of light is 400~500nm；The solvent is one or more of DMF, chloroform, dichloromethane and tetrahydrofuran；Institute
State that be uniformly dispersed refer to 30~50min of rotating speed mechanical agitation with 200~500rpm；
In the EFI solution, bifunctionality dimethylacrylate class organic monomer accounts for styrene and bifunctionality dimethyl propylene
5~28wt% of olefin(e) acid esters organic monomer total amount；Photoinitiator, which accounts for styrene and bifunctionality dimethylacrylate class, to be had
0.6~1.8wt% of machine monomer total amount；Organic uv absorbers account for styrene and bifunctionality dimethylacrylate class is organic
10~25wt% of monomer total amount；Solvent account for styrene and bifunctionality dimethylacrylate class organic monomer total amount 56~
83wt%；The addition of the modifying titanium dioxide is the 18~42% of EFI solution quality；
The parameter of the electrostatic spray is：10~15kV of output voltage of high voltage power supply, atomizing nozzle with solidification bathing pool at a distance from 7~
13cm, 20~40 DEG C of temperature promote 1~4mL/h of fltting speed of pump, 5~15mm of diameter of propeller, the volume 3 of propeller
~10mL.
6. a kind of matt uvioresistant engineering plastics according to claim 5, which is characterized in that the salicylic acid is phenyl
Salcylic acid or to tert-butyl salicylic acid vinegar, the benzophenone is ESCALOL 567 or 2,2 '-dihydroxies
4,4 '-dimethoxy-benzophenone of base -, the benzotriazole be 2- (2 '-hydroxyls -2 '-tert-butyl-phenyl) benzotriazole or
2- (2 '-hydroxyls -2 '-tert-butyl benzene -5 '-aminomethyl phenyl -5- chlorine) benzotriazole.
7. a kind of matt uvioresistant engineering plastics according to claim 4, which is characterized in that the modifying titanium dioxide
Preparation process is as follows：
(1) titanium dioxide is dispersed in after being stirred by ultrasonic in absolute ethyl alcohol and tetrabutyl titanate is added dropwise obtains mixed dispersion liquid；
The mass ratio of titanium dioxide, absolute ethyl alcohol and tetrabutyl titanate is 4~6 in the mixed dispersion liquid:150~250:1；
(2) ethyl alcohol water mixed liquid is added dropwise into mixed dispersion liquid, 4~5h is reacted at 60~70 DEG C, room temperature is aged 10~12h and obtains
To ageing liquid；The mass ratio of ethyl alcohol and water is 2~5 in the ethyl alcohol water mixed liquid:1, the addition of the ethyl alcohol water mixed liquid
It is the 20~30% of mixed dispersion liquid volume；
(3) by silane coupling agent instill ethanol water in, 2~3h of hydrolysis is stirred at room temperature, be added to ultrasonic disperse 30~
In the ageing liquid of 60min, 4~5h of back flow reaction at 60~70 DEG C；The mass ratio of ethyl alcohol and water is 2 in the ethanol water
~5:1, the mass ratio of the silane coupling agent and ethanol water is 1:8~12, the addition of the silane coupling agent is old
Change 5~10% of titanium dioxide quality in liquid, the silane coupling agent is γ-methacryloxypropyl trimethoxy silicon
Alkane；
(4) it is dried in vacuo 12~16h at 70~80 DEG C after rotating evaporation drying at 50~70 DEG C, it is double bond containing to obtain surface
Modifying titanium dioxide.
8. a kind of such as method of matt uvioresistant engineering plastics of claim 1~7 any one of them is prepared, it is characterized in that：It will
Nucleocapsid organic/inorganic composite hollow porous microsphere is added with toughener in ABS resin after mixing, again after mixing
It is dried after melt pelletization and obtains matt uvioresistant engineering plastics.
9. method according to claim 8, which is characterized in that count in parts by weight, when the melt pelletization, ABS resin is
100 parts, toughener is 10~15 parts, and nucleocapsid organic/inorganic composite hollow porous microsphere is 15~35 parts.
10. method according to claim 8, which is characterized in that the toughener is nitrile rubber or ABS high glue powders；It is described
It refers to mixing 1~2h with the rotating speed of 100~150 turns/min to be uniformly mixed or be uniformly mixed again；The melt pelletization is double
It is carried out in screw pelletizer, the temperature of dual-screw pelletizer is 190~240 DEG C, and screw speed is 150~300 turns/min；Institute
The temperature for stating drying process is 80~90 DEG C, and the time is 3~5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810029342.4A CN108276730A (en) | 2018-01-12 | 2018-01-12 | A kind of matt uvioresistant engineering plastics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810029342.4A CN108276730A (en) | 2018-01-12 | 2018-01-12 | A kind of matt uvioresistant engineering plastics and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108276730A true CN108276730A (en) | 2018-07-13 |
Family
ID=62803559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810029342.4A Pending CN108276730A (en) | 2018-01-12 | 2018-01-12 | A kind of matt uvioresistant engineering plastics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108276730A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115364782A (en) * | 2022-07-14 | 2022-11-22 | 重庆中烟工业有限责任公司 | Preparation method and application of slow-release essence material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210097A (en) * | 2006-12-30 | 2008-07-02 | 上海普利特复合材料有限公司 | ABS material with excellent light aging resisting property and preparing method thereof |
| CN103333453A (en) * | 2013-06-28 | 2013-10-02 | 广东银禧科技股份有限公司 | High-light-shading acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof |
| CN104250350A (en) * | 2014-09-30 | 2014-12-31 | 复旦大学 | Method for preparing porous polymer material with through-pore structure |
-
2018
- 2018-01-12 CN CN201810029342.4A patent/CN108276730A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210097A (en) * | 2006-12-30 | 2008-07-02 | 上海普利特复合材料有限公司 | ABS material with excellent light aging resisting property and preparing method thereof |
| CN103333453A (en) * | 2013-06-28 | 2013-10-02 | 广东银禧科技股份有限公司 | High-light-shading acrylonitrile butadiene styrene (ABS) composite material and preparation method thereof |
| CN104250350A (en) * | 2014-09-30 | 2014-12-31 | 复旦大学 | Method for preparing porous polymer material with through-pore structure |
Non-Patent Citations (3)
| Title |
|---|
| DAYANE CARVALHO RAMOS SALLES DE OLIVEIRA 等: ""Effect of different photoinitiators and reducing agent on cure efficiency and color stability of resin-based composites using different LED wavelengths"", 《JOURNAL OF DENTISTRY》 * |
| 张子成 等编著: "《塑料产品设计》", 31 January 2012, 第198页 * |
| 王澜 等编著: "《高分子材料》", 31 January 2009, 中国轻工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115364782A (en) * | 2022-07-14 | 2022-11-22 | 重庆中烟工业有限责任公司 | Preparation method and application of slow-release essence material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192299A (en) | A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof | |
| CN108246216B (en) | Core-shell structure organic/inorganic composite hollow porous microsphere and preparation method thereof | |
| CN108144558A (en) | A kind of hollow porous micro sphere of cladding titanium dioxide nano particle and preparation method thereof | |
| CN102161736B (en) | Method for preparing micro/nanocomposite photocurable resin | |
| CN110172258A (en) | A kind of composite polyolefine material and preparation method thereof containing coffee grounds | |
| CN108277550B (en) | A kind of delustring PET fiber and its slice electrospinning method for preparing | |
| CN101602871B (en) | Wood-plastic composite powder for selective laser sintering rapid forming and preparation method thereof | |
| CN109054323B (en) | Lignin/microcrystalline cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof | |
| CN102181140B (en) | Carbon fiber silk waste reinforced polycarbonate composite material and preparation method of the carbon fiber silk waste reinforced polycarbonate composite material | |
| CN104292400A (en) | Carbon-nanotube-reinforced photocuring three-dimensional printing material and preparation method thereof | |
| CN108060468A (en) | A kind of fused mass directly spinning preparation method of delustring PET fiber | |
| CN105440399A (en) | Polyvinyl wood-plastic composite and preparation method thereof | |
| CN108276730A (en) | A kind of matt uvioresistant engineering plastics and preparation method thereof | |
| CN110042665A (en) | A kind of surface modified ultra-high molecular weight polyethylene fiber and preparation method thereof | |
| CN108148364A (en) | A kind of delustring uvioresistant high-performance PET film and preparation method thereof | |
| CN113788914B (en) | SEBS/AT composite toughening agent, preparation method thereof and high-performance PET/PA6 foaming material | |
| CN109735070B (en) | A kind of preparation method of polylactic acid/bamboo particle/bamboo charcoal composite material | |
| CN1521209A (en) | Continuous fibre reinforced thermoplastic composite material | |
| CN108642888A (en) | A kind of preparation method of shear thickening gel and its application on anti-broken fabric | |
| CN101457024A (en) | Method for producing wood-plastic composite material and produced wood-plastic composite material | |
| CN106832893B (en) | A kind of isomerism recycling nylon of the crosslinking agent containing L-POSS and preparation method thereof | |
| CN108129596A (en) | A kind of hollow porous micro sphere of compound organic uv absorbers and preparation method thereof | |
| CN108456947B (en) | Anti-ultraviolet PET fiber and preparation method thereof | |
| CN106700393A (en) | Preparation method of basalt fiber-ABS resin composite material | |
| CN108059825A (en) | A kind of delustring PA master batches and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180713 |
|
| WD01 | Invention patent application deemed withdrawn after publication |