CN1631975A - Nano composite functional master batch for sunlight plate and preparation method thereof - Google Patents
Nano composite functional master batch for sunlight plate and preparation method thereof Download PDFInfo
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- CN1631975A CN1631975A CNA2004100812710A CN200410081271A CN1631975A CN 1631975 A CN1631975 A CN 1631975A CN A2004100812710 A CNA2004100812710 A CN A2004100812710A CN 200410081271 A CN200410081271 A CN 200410081271A CN 1631975 A CN1631975 A CN 1631975A
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- nano composite
- composite functional
- functional agglomerate
- master batch
- surface treatment
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004594 Masterbatch (MB) Substances 0.000 title abstract 9
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 32
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 29
- 239000004417 polycarbonate Substances 0.000 claims abstract description 29
- 238000004381 surface treatment Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000004611 light stabiliser Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 15
- -1 pentaerythritol ester Chemical class 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 12
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 150000004645 aluminates Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
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- 150000008301 phosphite esters Chemical class 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 239000012756 surface treatment agent Substances 0.000 claims description 5
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical class CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001398 aluminium Chemical class 0.000 claims description 2
- 229940074391 gallic acid Drugs 0.000 claims description 2
- 235000004515 gallic acid Nutrition 0.000 claims description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 claims 1
- FANGQVKSFHFPBY-UHFFFAOYSA-N 2-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FANGQVKSFHFPBY-UHFFFAOYSA-N 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 31
- 230000032683 aging Effects 0.000 abstract description 24
- 229910052724 xenon Inorganic materials 0.000 abstract description 14
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
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- 230000006866 deterioration Effects 0.000 description 14
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 206010051246 Photodermatosis Diseases 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
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- 229920005668 polycarbonate resin Polymers 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- FTFAAPWTELRKAH-UHFFFAOYSA-N (5-benzoyl-2,4-dihydroxy-3-methylphenyl)-phenylmethanone Chemical compound OC=1C(C)=C(O)C(C(=O)C=2C=CC=CC=2)=CC=1C(=O)C1=CC=CC=C1 FTFAAPWTELRKAH-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- JTHRRMFZHSDGNJ-UHFFFAOYSA-N piperazine-2,3-dione Chemical compound O=C1NCCNC1=O JTHRRMFZHSDGNJ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a nano composite functional master batch for a sunlight plate and a preparation method thereof, wherein the nano composite functional master batch is prepared by carrying out surface treatment and compounding on an inorganic nano composite material, polycarbonate copolymer, an antioxidant, a light stabilizer, a toughening agent and other raw materials through procedures of ultrahigh speed mixing, melt extrusion, cooling, granulation and the like. The nano composite functional master batch provided by the invention has excellent impact resistance and weather resistance, the notch impact strength of the nano composite functional master batch is improved by 20-100% compared with that of pure polycarbonate, after a 1500-hour artificial accelerated aging test of a xenon lamp weather tester, the color change grade of the nano composite functional master batch is 0-1 grade, the gloss retention rate of the nano composite functional master batch is more than 80%, the impact resistance retention rate of the nano composite functional master batch is more than 80%, and the nano composite functional master batch is suitable for manufacturing solid, hollow, wave and other outdoor sunlight panels with higher requirements on working conditions and weather resistance.
Description
Technical field
The present invention relates to a kind of nano composite functional agglomerate, particularly a kind of sunlight board functional agglomerate.
Technical background
Sunlight board is born in Europe the eighties in eighties of last century, it is the trade name of polycarbonate (PC) transparent panel, be called for short the PC plate, be a kind of novel high strength, heat insulation, printing opacity material of construction, be widely used in the places such as interval of commercial building, gymnasium, exhibition center, shopping street, parking lot, Waiting Lounge, terminal, swimming pool, viaduct, call box, building curtain wall, room or office as daylighting ceiling or finishing material.Have many excellent physical and mechanical performance though the matrix resin of sunlight board is a polycarbonate resin, the same with other organic polymer material, photoaging can take place and cause degraded in polycarbonate under action of ultraviolet ray.Degradation product reacts with oxygen or other activeconstituents in air, thereby etiolation appears, transmittance, glossiness and mechanical property all will reduce significantly simultaneously, cause reducing its actual service life [Zhou Dagang at last, Xie Gecheng, Deng. ageing of plastics and anti-aging technology [M]. Beijing: China Light Industry Press, 1992.].
In order to prevent that sunlight board is in use too fast aging, mainly taking both at home and abroad at present to the sunlight board matrix resin is to add organic photostabilizer in the polycarbonate material and adhere to two kinds of methods of the organic photostabilizer of one deck at the outside surface that sunlight board is accepted solar radiation and solve.The RF Sai Luofu of GE has reported the polycarbonate compositions that contains two (2,6-dihydroxyl-3,5-dibenzoyl phenyl) methane ultraviolet absorption thing in publication number is the patent of invention of CN 1177612A; The JE pik top grade of GE in publication number is the patent of invention of CN 1209446A, reported contain piperazine ketone or piperazinedione be HALS (hindered amine as light stabilizer) can weatherable polycarbonate compositions (title complex or blend); The CTE Fan Nafeier of Dow Chemical company has reported cyanoacrylate-containing type UV (ultraviolet ray) absorption agent and in conjunction with sulfite type stablizer and the optional hindered phenol stabilizer and/or the polycarbonate compositions of lactone type stablizer in publication number is the patent of invention of CN 1371404A; The TM Si clo models of AM General company etc. have been reported the method for preparing the block copolycarbonate ester and have been improved the method for weathering resistance with other polymer blendings such as poly carboxylic acid alkylidene diol esters in publication number is the patent of invention of CN 1332760A, CN 1331711A.Above patent has all only been reported and has been adopted organic photostabilizer or introduce the method that other group improves the polycarbonate weather resistance in the technological process of polycarbonate synthesis, and photostabilizer classification that is adopted or trade mark difference can cause the effect difference of modification, but all there is same problem in these class methods, be that self understands degradation with aging behind organic photostabilizer life-time service, thereby cause that its function of shielding ultraviolet radiation lost efficacy.
And second method is divided into two kinds---cladding process and coextruding method.Cladding process technology is simple, but the coating firmness is poor, and is inhomogeneous, easily comes off.And the every performance of absorption layer that adopts coextruding method to form all is better than the coating that cladding process is made, coextruding method is to form one by co-extrusion machine on the surface of sheet material to merge even and firm uvioresistant coextruded layer (being the UV layer), and its thickness can evenly be controlled at 50 μ m.The patent co-extrusion technology of Bayer A.G's utilization oneself by using the special-purpose polycarbonate resin (containing the high density UV light absorber) of coextruded layer, has effectively guaranteed the weather resistance of sunlight board.But the thickness of uvioresistant coextruded layer (UV layer) must be guaranteed when producing, because sun exposure can consume UV light absorber for a long time, thereby causes the ultraviolet radiation absorption agent concentration in the UV layer to reduce, and influences every physicochemical property of sunlight board.Coextruding method is very high to the production unit requirement simultaneously, and the double-layer coextrusion that needs to be equipped with the high special use of price goes out equipment, the specification of quality height, and production technique is very complicated, and many enterprises often can't guarantee the correct enforcement of this procedure, thereby have limited the development of sunlight board.
Summary of the invention
Aging in order to overcome the organic photostabilizer degraded of sunlight board, thus the defective that its function of shielding ultraviolet radiation lost efficacy caused, and material of the present invention provides a kind of have excellent weather resistance and toughness, is suitable for the nano composite functional agglomerate of production sunlight board.Simultaneously, the present invention also provides the production technique of this nano composite functional agglomerate, and it is inhomogeneous to have overcome cladding process, the defective of coextruding method complex process.
Nano composite functional agglomerate of the present invention is to be prepared from by following materials of weight proportions:
92.7～99.1 parts of Copolycarbonates
0.2～1.3 part of inorganic nano composite material
0.1～0.5 part in oxidation inhibitor
0.1～0.5 part of photostabilizer
0.5～5 part of toughner.
Further, it is to be prepared from by following materials of weight proportions:
96.2 parts of Copolycarbonates
0.3 part of inorganic nano composite material
0.4 part in oxidation inhibitor
0.1 part of photostabilizer
3 parts of toughner.
Wherein, described Copolycarbonate is the bisphenol A polycarbonate multipolymer of melting index between 3～15g/10min, the feature molecular weight (M of Copolycarbonate
w) be 40000～80000.
Described inorganic nano composite material is a nano-TiO
2, nano-ZnO and nanometer SiO
2In at least aly carry out surface treatment and composite, again with surface treatment and composite after material carrying out forming inorganic nano composite material after the technological processs such as spraying drying, ultra-high speed mixing, comminution by gas stream under 80～250 ℃ the condition.The characteristic diameter of nano composite material is 10～70nm.
Wherein, described surface treatment and composite being meant median size are the TiO of 10～70m
2, ZnO and SiO
2Powder under 80～120 ℃ condition dry 2～4 hours, wherein at least a nanoparticle reacts in ball mill high speed ground and mixed by 1: 1～5: 1 proportioning with surface treatment agent and finished surface treatment in 15～30 minutes, the formation complex material.
Described surface treatment agent is at least a in stearic acid and salt, titanate coupling agent, aluminate coupling agent or the silane coupling agent.
Described oxidation inhibitor is phenolic antioxidant four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester such as Irganox1010 or β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) at least a in the combination of positive octadecanol ester of propionic acid such as Irganox1076 and phosphite ester kind antioxidant three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester such as Irgafos168.
Described photostabilizer is hindered amines (HALS) photostabilizer 4-benzoyloxy-2,2,6, at least a among 6-tetramethyl piperidine such as Tinuvin744 or benzotriazole category (BZT) photostabilizer 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole such as the Tinuvin329.
Described toughner is MBS MBS, have at least a among the acrylate copolymer ACR of nucleocapsid structure or the ethylene-vinyl acetate copolymer EVA.
Further, it is to be prepared from by following materials of weight proportions:
96.2 parts of Copolycarbonates
0.3 part of inorganic nano composite material
0.1 part of phenolic antioxidant
0.3 part of phosphite ester kind antioxidant
0.04 part of hindered amine light stabilizer HALS
0.06 part of benzotriazole light stabilizer BZT
1.5 parts of acrylate copolymer ACR
1 part of MBS MBS
0.5 part of ethylene-vinyl acetate copolymer EVA
Wherein, above-mentioned inorganic nano composite material is by 0.15 part of nano-TiO
2, 0.05 part of nanometer SiO
2Carry out surface treatment and composite forming with 0.05 part of nano-ZnO and 0.02 part of silane coupling agent, 0.02 part of titanate coupling agent and 0.01 part of aluminium esters of gallic acid coupling agent.
The preparation method of nano composite functional agglomerate of the present invention comprises the steps:
(1) with median size is the TiO of 10～70nm
2, ZnO and SiO
2Powder under 80～120 ℃ condition dry 2～4 hours, become at least a proportioning in inorganic nano composite powder and stearic acid and salt, titanate coupling agent, aluminate coupling agent or the silane coupling agent to grind (about general rotating speed 1000r/min) in the ball mill high speed at least a nanoparticle proportioning wherein by 1: 1～5: 1, hybrid reaction was finished surface treatment and composite in 15～30 minutes, and the processes such as spraying drying, ultra-high speed mixing, comminution by gas stream of again it being carried out under 80～250 ℃ condition form inorganic nano composite material;
(2) with above-mentioned carried out surface treatment and composite after inorganic nano composite material under 70～110 ℃ condition dry 1～3 hour, with polycarbonate under 110～130 ℃ condition dry 4～8 hours, inorganic nano composite material and Copolycarbonate, oxidation inhibitor, photostabilizer, toughner were carried out pre-mixing 3～10 minutes at superhigh speed mixing machine, and pre-mixing speed is 1000～1500rpm;
(3) material that premix is got togather melt extrudes under 220～280 ℃ greater than 40 twin screw extrusion equipment with length-to-diameter ratio, screw speed is 50～200rpm, then extruded material is carried out granulation after with water cooling under the rotating speed of 60～150rpm and forms nano composite functional agglomerate for sunshine plate.
Wherein, step (1) is the TiO of 10～70nm with median size
2, ZnO and SiO
2In at least aly carry out surface treatment, composite, spraying drying and comminution by gas stream, can make nanoparticle and coupling agent reaction improvement inorganic particulate surface property, improve bonding force and dispersiveness between the different particles, improve the consistency of inorganic nano composite material and organic resin, be not nanoparticle and nanoparticle, the simple adduction of inorganic and organic phase, but by nanoparticle and nanoparticle, inorganicly in nanometer range, combine formation with organic phase, exist chemical bonding force between particle and between two-phase interface, thereby can bring into play the nano effect and the synergistic effect of inorganic nano composite material and give composite functional agglomerate more excellent over-all properties.
Step (2) is carried out inorganic nano composite material, polycarbonate, oxidation inhibitor, photostabilizer and toughner the pre-mixing of 1000～1500rpm in high-speed mixer, can promote inorganic nano composite material and other raw material thorough mixing, avoid before melt extruding, forming coacervate.
The material that step (3) gets togather premix melt extrudes under 220～280 ℃ greater than 40 twin screw extrusion equipment with length-to-diameter ratio, 220～280 ℃ processing temperature can guarantee that resin reaches the good fusion thickness state of processing fluidity, and it is the uniform distribution system that forms in the polycarbonate in the nanometer range at the sunlight board matrix resin that length-to-diameter ratio can make shearing force field satisfy inorganic nano material greater than 40 twin screw and rotating speed thereof.
According to GB/T 16422.2-1999 standard, adopt the xenon lamp climatic cabinet that the standard testing batten of nano composite functional agglomerate for sunshine plate was carried out the weather accelerated deterioration after 1500 hours, according to its colour-change grade of GB/T 15596-1995 standard testing is 0～1 grade, according to its glossiness conservation rate of GB/T 8807-1988 standard testing more than 80%, according to its shock resistance conservation rate of GB/T 1843-1996 standard testing more than 80%.In addition, improve 20～100% according to the purer polycarbonate of the notched Izod impact strength of its unaged batten of GB/T1843-1996 standard testing, its nano composite functional agglomerate is applicable to the manufacturing to outdoor sunlight board such as operating mode and weather-proof solid, hollow with high requirement and waves.
Copolycarbonate is as the matrix resin of sunlight board, comprise polycarbonate such as aliphatics, aliphatic-aromatic and aromatic series, because the abundant raw material of industrial synthesis of bisphenol A type polycarbonate, production technique is simple, and over-all properties is superior, therefore select bisphenol A polycarbonate for use,, select for use melting index between 3～15g/10min and feature molecular weight (M in view of the processing request and the actual applying working condition condition of sunlight board
w) be 40000～80000 Copolycarbonate, the range of molecular weight distributions broad is good.
The nano composite material that the inorganic nano semiconductor particle is re-dubbed to ultraviolet (UV) A (315～400nm), UVB (280～315nm) and UVC (190～280nm) wave bands all have excellent shielding effect, absorb do not decompose after the ultraviolet ray, nondiscoloration, have advantages of excellent stability and persistence, it can fall most of ultraviolet ray by large specific surface behind the super-refinement and interface scattering, and discharge with forms such as heat or fluorescence, thereby realize that to ultraviolet shielding process avoiding the sunlight board matrix resin is to rupture after the molecular chain of polycarbonate absorbs the UV-light of high energy.In addition, after rigid particles reaches nanoscale, specific surface area increases, Surface Physical and chemical imperfection increase, particle and resin generation physics or Chemical bond chance increase, and by after the surface treatment of coupling agent, cohesiveness and consistency between nano material and the resin are improved, and cause the intensity of sunlight board to be improved.The stress of dispersed particle and matrix Young's modulus, the generation of Poisson's ratio difference can make rigid particles produce surrender simultaneously, and impels matrix generation shear yielding, absorbs striking energy, thereby reaches toughness reinforcing purpose, and the impact resistance of sunlight board is improved.In view of above situation, selecting characteristic diameter for use is the nano-TiO of 10～70nm
2, ZnO and SiO
2In at least aly carry out surface treatment and be re-dubbed inorganic nano composite material.
Oxidation inhibitor makes nano composite functional agglomerate and sunlight board that good processing stability be arranged in the course of processing, avoid color and luster, performance to change, especially in the life-time service process and collaborative coming into force such as inorganic nano composite material, photostabilizer, improve the good thermal-oxidative aging property of sunlight board.The oxidation inhibitor kind of selecting for use comprises the combination of primary antioxidant and auxiliary anti-oxidant, primary antioxidant can be chosen with Hinered phenols antioxidant four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester such as Irganox1010, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) positive octadecanol ester of propionic acid such as Irganox1076, auxiliary anti-oxidant can be selected phosphorous acid esters three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester such as Irgafos168 for use.
Photostabilizer can be that the degradation with aging reaction chain of polycarbonate protects sunlight board not to be subjected to ultraviolet destruction by blocking the sunlight board matrix resin; in view of the thermostability of photostabilizer and to the influence of sunlight board color; therefore select Heat stability is good and the sunlight board color is influenced little hindered amines (HALS) photostabilizer 4-benzoyloxy-2; 2; 6, at least a among 6-tetramethyl piperidine such as Tinuvin744 or benzotriazole category (BZT) photostabilizer 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole such as the Tinuvin329.
Toughner can improve the shock resistance and the breach cracking behavior of improving in the sunlight board use of sunlight board, in view of sunlight board to daylighting, weather-proofly all have higher requirements, therefore select at least a greater than among the transparent MBS MBS more than 80%, acrylate copolymer ACR or the ethylene-vinyl acetate copolymer EVA of transmittance for use with nucleocapsid structure.
In sum, the present invention and traditional weather resistant sunlight board and production technique thereof or disclosed weather resistant sunlight board technology are compared and are had the following advantages:
(1) overcome the shortcoming of the easy photoaging of sunlight board, wide band, the ability of long-acting shielding ultraviolet rays and the synergy that organic photostabilizer blocks sunlight board degradation with aging reaction chain by the performance inorganic nano composite material increase substantially the weather-proof ability of sunlight board;
(2) solved the problem that organic uv absorbers easily lost efficacy,, made most of ultraviolet ray can not enter sunlight board inside, and organic photostabilizer is effectively protected by the wide band of performance inorganic nano composite material, the ability of long-acting shielding ultraviolet rays;
(3) improved the mechanical property of sunlight board,, made sunlight board obtain especially shock resistance of excellent comprehensive mechanical properties by the synergy of inorganic nano composite material and toughner;
(4) given sunlight board the good feature of environmental protection, can reduce the usage quantity of organic photostabilizer behind the use inorganic nano composite material, reduce the environmentally harmful product that the especially organic photostabilizer degraded of sunlight board matrix resin back produces, therefore aspect environment protection, also had more advantage;
(5) avoided production weather resistant sunlight board to be equipped with specific equipment; thereby reduced facility investment, simplified production technique, the production unit of sunlight board and technology are routinized and be easy to industrial scale; make production weather resistant sunlight board be easy to realize, can promote the development of sunlight board.
Therefore by after implementing the present invention, can give weather resistance and mechanical property to outdoor sunlight board excellences such as operating mode and weather-proof solid, hollow with high requirement and waves, prolong the outdoor work-ing life of sunlight board.
Obviously, according to foregoing of the present invention,,, can also make modification, replacement or the change of other various ways not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite according to the ordinary skill knowledge and the customary means of this area.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
Carrying out concrete to the present invention and be described in further detail below by embodiment, is limiting the scope of the invention but should not be construed as.
Embodiment 1:
Embodiment 1 prescription of table 1 nano composite functional agglomerate for sunshine plate
| Recipe ingredient | Polycarbonate | Nano composite material | Oxidation inhibitor (1076) | Oxidation inhibitor (168) | Photostabilizer (744) | Toughner (MBS) | |
| Nano-TiO 2 | Silane coupling agent (KH550) | ||||||
| Weight/(kilogram) | ???96.2 | ??0.1 | ???0.1 | ?????0.1 | ????0.3 | ????0.2 | ????3 |
With median size is 1 kilogram of nano-TiO of 20～30nm
2Drying is 2～4 hours under 90～110 ℃ condition, with 0.5 kilogram of nano-TiO that drying is good
220 minute finish surface treatment and composite by 1: 1 proportioning in the reaction of ball mill high speed ground and mixed with 0.5 kilogram of silane coupling agent KH550, the processes such as spraying drying, ultra-high speed mixing, comminution by gas stream of again it being carried out under 80～250 ℃ condition form inorganic nano composite material; Then with above-mentioned inorganic nano composite material under 80～100 ℃ condition dry 2～3 hours, with polycarbonate under 120～130 ℃ condition dry 6～8 hours, 0.2 kilogram of inorganic nano composite material and 96.2 kilograms of Copolycarbonates, 0.1 kilogram of Irganox1076,0.3 kilogram of Irgafos168,0.2 kilogram of Tinuvin744,3 kilograms of MBS were carried out pre-mixing 8～10 minutes, and pre-mixing speed is 1200～1300rpm; The material that premix is got togather melt extrudes under 220～280 ℃ greater than 40 twin screw extrusion equipment with length-to-diameter ratio, screw speed is 50～180rpm, then extruded material is carried out granulation after with water cooling under the rotating speed of 80～120rpm and forms nano composite functional agglomerate for sunshine plate.
According to GB/T 1843-1996 plastics socle girder impact experiment method, nano composite functional agglomerate is injection molded into the standard testing batten, according to GB/T 16422.2-1999 standard, adopt the xenon lamp climatic cabinet that the standard testing batten of nano composite functional agglomerate for sunshine plate was carried out the weather accelerated deterioration 1500 hours then.According to GB/T 15596-1995, use CR-10 type color difference meter respectively test sample aging before and aging after color value (L, a, b tristimulus colo(u)r), the colour-change grade of xenon lamp weather accelerated deterioration after 1500 hours is 0 grade.According to GB/T 8807-1988, use GG-66C type Grossmeters respectively test sample aging before and aging after gloss value, the glossiness conservation rate of xenon lamp weather accelerated deterioration after 1500 hours is 82.53%.According to GB/T 1843-1996 plastics socle girder impact experiment method, use the outstanding letter combination of XJC-25D shock-testing machine respectively test sample aging before and aging after IZOD breach and non-notch intensity, the nano composite functional agglomerate test bars before aging is carried out non-notch, and (calculated impact strength is greater than 550KJ/m for " constantly " when impacting
2), the notched Izod impact strength of self-control " V " type sharp notch batten is 42.5KJ/m
2, the notched Izod impact strength conservation rate of xenon lamp weather accelerated deterioration after 1500 hours is 85.46%, it is that " constantly " (calculated impact strength is greater than 550KJ/m that 22J socle girder pendulum carries out when non-notch impacts
2).According to GB/T 2410-1980 transparent plastics transmittance and mist degree test method, the thickness before using the test of full-automatic whiteness instrument WSD-III type aging is 65% as the transmittance of the nano composite functional agglomerate test sample plate of 2mm.
Same testing method, the pure material of common sheet material level PC (is the import material of 143R as the trade mark) is prepared into the standard testing batten, and it is that " constantly " (the 22J pendulum is adopted in experiment, and calculated impact strength is greater than 550KJ/m that unaged batten carries out when non-notch impacts
2), the notched Izod impact strength of its self-control " V " type sharp notch batten is 21.5KJ/m
2, then through the accelerated deterioration of xenon lamp weather after 1500 hours, its notched Izod impact strength conservation rate is 31.5%, (its shock strength was 221.5KJ/m in fracture when non-notch impacted
2), the colour-change grade is 2 grades, and the glossiness conservation rate is 40.83%, and the transmittance of the test sample plate of 2mm is 85%.
Embodiment 2:
Embodiment 2 prescriptions of table 2 nano composite functional agglomerate for sunshine plate
| Recipe ingredient | Polycarbonate | Nano composite material | Oxidation inhibitor (1010) | Oxidation inhibitor (168) | Photostabilizer (329) | Toughner (ACR) | ||
| Nano-TiO 2 | Nanometer SiO 2 | Titanate coupling agent | ||||||
| Weight/(kilogram) | ???96.7 | ???0.16 | ???0.04 | ?????0.1 | ?????0.1 | ?????0.3 | ?????0.1 | ?????2.5 |
Concrete preparation method is with embodiment 1.According to GB/T 16422.2-1999 standard, adopt the xenon lamp climatic cabinet that the standard testing batten of nano composite functional agglomerate for sunshine plate was carried out the weather accelerated deterioration 1500 hours.After tested, pure polycarbonate test bars before the notched Izod impact strength of the nano composite functional agglomerate test bars before the accelerated deterioration is aging improves 75%, thickness before the accelerated deterioration is that the transmittance of the test sample plate of 2mm is 45%, the accelerated deterioration of xenon lamp weather is after 1500 hours, the colour-change grade is 0 grade, the glossiness conservation rate is 86.75%, and the notched Izod impact strength conservation rate is 86.54%, and 25J socle girder pendulum carries out being when non-notch impacts " constantly ".
Embodiment 3:
Embodiment 3 prescriptions of table 3 nano composite functional agglomerate for sunshine plate
| Recipe ingredient | Polycarbonate | Nano composite material | Oxidation inhibitor (1010) | Oxidation inhibitor (168) | Photostabilizer (329) | Toughner (EVA) | |||
| Nano-TiO 2 | Nano-ZnO | Nanometer SiO 2 | Aluminate coupling agent | ||||||
| Weight/(kilogram) | ???95.7 | ??0.12 | ??0.04 | ??0.04 | ??0.1 | ????0.1 | ????0.3 | ?????0.1 | ????3.5 |
Concrete preparation method is with embodiment 1.According to GB/T 16422.2-1999 standard, adopt the xenon lamp climatic cabinet that the standard testing batten of nano composite functional agglomerate for sunshine plate was carried out the weather accelerated deterioration 1500 hours.Pure polycarbonate test bars before the notched Izod impact strength of the nano composite functional agglomerate test bars before aging after tested is aging improves 95%, thickness before aging is that the transmittance of the test sample plate of 2mm is 42%, the accelerated deterioration of xenon lamp weather is after 1500 hours, the colour-change grade is 0 grade, the glossiness conservation rate is 83.24%, the notched Izod impact strength conservation rate is 84.79%, and 25J socle girder pendulum carries out being when non-notch impacts " constantly ".
Embodiment 4:
Embodiment 4 prescriptions of table 4 nano composite functional agglomerate for sunshine plate
| Recipe ingredient | Polycarbonate | Nano composite material | Oxidation inhibitor | Photostabilizer | Toughner | |||||||||
| Nano-TiO 2 | Nano-ZnO | Nanometer SiO 2 | Silane coupling agent | Titanate coupling agent | Aluminate coupling agent | ??1076 | ??168 | ?329 | ?744 | ?ACR | ?MBS | ?EVA | ||
| Weight/(kilogram) | ?96.2 | 0.12 | 0.04 | 0.04 | 0.03 | 0.03 | 0.04 | ??0.1 | ??0.3 | ?0.06 | ?0.04 | ?1 | ?1 | ?1 |
Concrete preparation method is with embodiment 1.According to GB/T 16422.2-1999 standard, adopt the xenon lamp climatic cabinet that the standard testing batten of nano composite functional agglomerate for sunshine plate was carried out the weather accelerated deterioration 1500 hours.Pure polycarbonate test bars before the notched Izod impact strength of the nano composite functional agglomerate test bars before aging after tested is aging improves 91%, thickness before aging is that the transmittance of the test sample plate of 2mm is 44%, the accelerated deterioration of xenon lamp weather is after 1500 hours, the colour-change grade is 0 grade, the glossiness conservation rate is 85.35%, the notched Izod impact strength conservation rate is 86.42%, and 25J socle girder pendulum carries out being when non-notch impacts " constantly ".
In sum, nano composite functional agglomerate for sunshine plate preparation technology of the present invention is simple, does not need expensive special equipment; Simultaneously, solved organic light stabilizer easily degraded and the easy problem that lost efficacy of ultra-violet absorber, overcome the shortcoming of the easy light aging of sunlight board, the weather-proof ability of sunlight board is increased substantially; Compare with the common plate material, test bars by the nano composite functional agglomerate preparation of inventing, the notched Izod impact strength conservation rate of xenon lamp weather accelerated ageing after 1500 hours is that 85.46%, 22J cantilever beam pendulum carries out non-notch (calculated impact strength is greater than 550KJ/m for " constantly " when impacting2), the change color grade is 0 grade, gloss percent retension is 82.53%. This shows that the superiority of the performance of the sunlight board that the nano composite functional agglomerate of the present invention's preparation is made is apparent, is the optimal selection of preparation sunlight board.
Claims (10)
1, a kind of nano composite functional agglomerate for sunshine plate is characterized in that: it is to be prepared from by following materials of weight proportions:
92.7～99.1 parts of Copolycarbonates
0.2～1.3 part of inorganic nano composite material
0.1～0.5 part in oxidation inhibitor
0.1～0.5 part of photostabilizer
0.5～5 part of toughner.
2, nano composite functional agglomerate according to claim 1 is characterized in that: it is to be prepared from by following materials of weight proportions:
96.2 parts of Copolycarbonates
0.3 part of inorganic nano composite material
0.4 part in oxidation inhibitor
0.1 part of photostabilizer
3 parts of toughner.
3, nano composite functional agglomerate according to claim 1 and 2 is characterized in that: described Copolycarbonate is the bisphenol A polycarbonate multipolymer of melting index between 3～15g/10min, the feature molecular weight M of Copolycarbonate
wBe 40000～80000; Described inorganic nano composite material is a nano-TiO
2, ZnO and SiO
2In at least aly carry out surface treatment and composite, again with surface treatment and composite after material carrying out under 80～250 ℃ the condition that spraying drying, ultra-high speed are mixed, forming inorganic nano composite material behind the comminution by gas stream.
4, nano composite functional agglomerate according to claim 3 is characterized in that: the surface treatment of described inorganic nano composite material and composite being meant median size are the TiO of 10～70nm
2, ZnO and SiO
2Powder under 80～120 ℃ condition dry 2～4 hours, wherein in the grinding of ball mill high speed, hybrid reaction was finished surface treatment and composite in 15～30 minutes by 1: 1～5: 1 proportioning at least a nanoparticle and surface treatment agent.
5, nano composite functional agglomerate according to claim 4 is characterized in that: described surface treatment agent is at least a in stearic acid and salt, titanate coupling agent, aluminate coupling agent or the silane coupling agent.
6, nano composite functional agglomerate according to claim 1 and 2 is characterized in that: described oxidation inhibitor is the combination of phenolic antioxidant and phosphite ester kind antioxidant; Wherein, described phenolic antioxidant is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or β-positive octadecanol esters of (4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid; Described phosphite ester kind antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
7, nano composite functional agglomerate according to claim 1 and 2 is characterized in that: described photostabilizer is at least a among hindered amine as light stabilizer HALS or the benzotriazole light stabilizer BZT; Wherein, described hindered amine as light stabilizer HALS is: 4-benzoyloxy-2,2,6,6-tetramethyl piperidine; Described benzotriazole light stabilizer BZT is: 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole.
8, nano composite functional agglomerate according to claim 1 and 2 is characterized in that: described toughner is MBS MBS, have at least a among the acrylate copolymer ACR of nucleocapsid structure or the ethylene-vinyl acetate copolymer EVA.
9, according to each described nano composite functional agglomerate of claim 1-8, it is characterized in that: it is to be prepared from by following materials of weight proportions:
96.2 parts of Copolycarbonates
0.3 part of inorganic nano composite material
0.1 part of phenolic antioxidant
0.3 part of phosphite ester kind antioxidant
0.04 part of hindered amine light stabilizer HALS
0.06 part of benzotriazole light stabilizer BZT
1.5 parts of acrylate copolymer ACR
1 part of MBS MBS
0.5 part of ethylene-vinyl acetate copolymer EVA
Wherein, described inorganic nano composite material is by 0.15 part of nano-TiO
2, 0.05 part of nanometer SiO
2Carry out surface treatment and composite forming with 0.05 part of nano-ZnO and 0.02 part of silane coupling agent, 0.02 part of titanate coupling agent and 0.01 part of aluminium esters of gallic acid coupling agent.
10, a kind of preparation method of nano composite functional agglomerate for sunshine plate, it comprises the steps:
(1) with median size is the TiO of 10～70nm
2, ZnO and SiO
2Powder under 80～120 ℃ condition dry 2～4 hours, wherein at least a nanoparticle and surface treatment agent were finished surface treatment and composite in 15～30 minutes by 1: 1～5: 1 proportioning in the reaction of ball mill high speed ground and mixed, it were carried out spraying drying, ultra-high speed mixing, comminution by gas stream process formation inorganic nano composite material under 80～250 ℃ condition again;
(2) with above-mentioned inorganic nano composite material under 70～110 ℃ condition dry 1～3 hour, with polycarbonate under 110～130 ℃ condition dry 4～8 hours, inorganic nano composite material and Copolycarbonate, oxidation inhibitor, photostabilizer, toughner were carried out pre-mixing 3～10 minutes at superhigh speed mixing machine, and pre-mixing speed is 1000～1500rpm;
(3) material that premix is got togather melt extrudes under 220～280 ℃ greater than 40 twin screw extrusion equipment with length-to-diameter ratio, screw speed is 50～200rpm, then extruded material is carried out granulation after with water cooling under the rotating speed of 60～150rpm and forms nano composite functional agglomerate for sunshine plate.
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