CN1982377A - 氧化锌－二氧化铈复合粒子 - Google Patents
氧化锌－二氧化铈复合粒子 Download PDFInfo
- Publication number
- CN1982377A CN1982377A CNA2006101669437A CN200610166943A CN1982377A CN 1982377 A CN1982377 A CN 1982377A CN A2006101669437 A CNA2006101669437 A CN A2006101669437A CN 200610166943 A CN200610166943 A CN 200610166943A CN 1982377 A CN1982377 A CN 1982377A
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- CN
- China
- Prior art keywords
- composite particles
- weight
- solution
- described composite
- zinc oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011246 composite particle Substances 0.000 title claims abstract description 64
- CZEPEKPAPYAXPU-UHFFFAOYSA-N [O-2].[Ce+3].[O-2].[Zn+2] Chemical compound [O-2].[Ce+3].[O-2].[Zn+2] CZEPEKPAPYAXPU-UHFFFAOYSA-N 0.000 title description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000011787 zinc oxide Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009472 formulation Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000008199 coating composition Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
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- 239000000567 combustion gas Substances 0.000 claims description 4
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- 238000004220 aggregation Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
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- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 3
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- 238000010422 painting Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
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- 238000000576 coating method Methods 0.000 description 15
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- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 14
- -1 polysiloxane Polymers 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
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- 239000001257 hydrogen Substances 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 229910052684 Cerium Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 241000018646 Pinus brutia Species 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229940043232 butyl acetate Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 159000000000 sodium salts Chemical class 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
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- A—HUMAN NECESSITIES
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/27—Zinc; Compounds thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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Abstract
本发明提供复合粒子，其BET表面积为5－100m2/g，包括氧化锌基质和二氧化铈区域结构，其中所述区域结构位于所述基质内和所述基质上，基于所述复合粒子，氧化锌部分占80－98重量％，二氧化铈部分占2－20重量％。
Description
技术领域
本发明涉及氧化锌-二氧化铈复合粒子、其制备和用途。
背景技术
已知通过涂布光催化惰性组分来降低无机紫外线过滤剂如二氧化钛(UV-B)和氧化锌(UV-A)的光催化活性。
US 6132743公开了通过涂布聚硅氧烷化合物而降低了光催化活性的氧化锌粒子。
US 6500415公开了为使其光催化活性最小化而涂布有二氧化硅或氧化铝的二氧化钛或氧化锌粒子。
WO 03/037994公开了例如，二氧化钛粒子，其光催化活性能够通过涂覆铝、铈、锆和/或硅的氧化物、氢氧化物或氧化物氢氧化物(oxide hydroxide)而降低。在WO 03/037994公开的方法中，涂覆材料的前体通过酶促沉淀剂体系施加至二氧化钛粒子。被涂布的粒子不是聚集的，其具有小于50nm的平均粒子尺寸。作为光催化活性显著的降低的必要特征，完全的涂布是需要的。
总之，现有技术公开了其光催化活性能通过涂布光催化惰性组分而得到降低的UV-B过滤剂。通常，涂层降低了被涂布物质的紫外线吸收，最多使其保持相同。现有技术中说明的涂布物质没有改变或仅略微地改变了紫外线吸收的波长。因此，所述涂层仅具有使光催化活性最小化的作用，不会过多地对紫外线过滤剂在UV-B区域内的吸收产生不利影响。
发明内容
本发明的目的是提供一种仅具有低的或不具有光催化活性的紫外线过滤剂，该过滤剂在UV-B和UV-A区域内存在吸收。
本发明提供BET表面积为5-100m2/g的复合粒子，所述复合粒子包括氧化锌基质(matrix)和二氧化铈区域结构(domains)，其中所述区域结构位于所述基质内和所述基质上，以复合粒子为基础，氧化锌部分占80-98重量％，二氧化铈部分占2-20重量％。
根据本发明的复合粒子可以是聚集态的或者是分离的单个粒子。聚集的复合粒子在UV-A和UV-B区域内具有高吸光度并显示低光催化活性。因此，根据本发明的复合粒子优选是聚集态的。
根据本发明的粒子具有80-98重量％的氧化锌部分和2-20重量％的二氧化铈部分。在二氧化铈部分小于2重量％时，与纯氧化锌粒子相比，还不能实现光催化活性的显著降低。在二氧化铈部分大于20重量％时，仍不能实现光催化活性的进一步降低。
优选地，氧化锌部分占85至95重量％，二氧化铈部分占5至15重量％。
以复合粒子为基础，在根据本发明的复合粒子中，氧化锌部分和二氧化铈部分之和优选至少占99.9重量％。特别是，减少金属杂质部分是有利的。因此，下述复合粒子是特别有利的，该复合粒子中以复合粒子为基础计，铅小于20ppm，砷小于3ppm，镉小于15ppm，汞小于1ppm，铁小于200ppm和锑小于1ppm。
所述复合粒子的BET表面积优选是20-50m2/g。在上述范围内，复合粒子具有高UV-A和UV-B吸收，以及具有低光敏性。
所述复合粒子的基质的平均直径优选是20-100nm。在上述范围内，复合粒子具有高UV-A和UV-B吸收，以及具有低光敏性。
所述复合粒子的区域结构的平均直径优选是2-10nm。在上述范围内，复合粒子具有高UV-A和UV-B吸收，以及具有低光敏性。
本发明进一步提供一种方法，其中：
-通过喷嘴用雾化气体将包括可氧化的锌化合物的溶液1和包括可氧化的铈化合物的溶液2雾化进入反应空间中，并形成平均直径小于100μm的液滴，其中：
-所述溶剂优选是有机的，
-按ZnO计算，溶液1部分占80-98重量％，按CeO2计算，溶液2部分占2-20重量％，
-溶液1的粘度是200-5000mPas，溶液2的粘度是5-150mPas，如果适当，在各自情形中通过加热至在所述锌化合物和所述铈化合物的分解温度之内的温度而调节粘度，
-将被雾化的溶液引入反应器的高温区，在那里与氧气或含氧气体在800至1200℃的温度下进行反应，
-将高温气体和固态产品冷却，然后将固态产品从气体中分离。
优选地，高温区中所需的温度源于由含氢燃烧气体与氧气和/或空气反应得到的火焰。所述温度能够通过含氢燃烧气体和氧气的比例得到调节。合适的含氢燃烧气体可以是：氢气、甲烷、乙烷、丙烷、丁烷和/或天然气。优选使用氢气。
本发明进一步提供了一种包括根据本发明的复合粒子的分散体。以分散体的总量为基础计，复合粒子的含量可以是0.1-60重量％，优选10-40重量％。所述分散体可以是水分散体或有机分散体，或者由水和有机溶剂的混合物作为液相而组成，其中，在所有情况中，仅存在单一的液相。“水分散体”被理解为是指液相的大部分由水组成。“有机分散体”被理解为是指液相主要地或唯一地由至少一种有机溶剂组成。合适的有机溶剂可以是单-、双-、三-多元醇，醚，酯，芳香族化合物，烷烃和烯烃。尤其是，能够使用乙醇、甲醇、丙醇、丁醇、丙酮、乙酸乙酯和乙酸丁酯。所述有机溶剂也可以是活性稀释剂，例如己二醇二丙烯酸酯或三丙二醇二丙烯酸酯。
根据本发明的分散体还可以包括添加剂。所述添加剂可以是分散助剂、乳化剂、pH值调节物质和/或稳定剂。优选地，所述添加剂可以是多磷酸钠、抗坏血酸、柠檬酸、6-氨基己酸、硬脂酸和/或聚丙烯酸的盐，尤其是钠盐。此外，还可以使用Disperbyk 163、Disperbyk 180、Disperbyk 190和/或Byk 9077。以分散体的液相为基础计，所述添加剂优选地以0.1-5重量％的量存在，特别优选0.5-1.5重量％。
本发明进一步提供了一种涂布制剂，其包括根据本发明的复合粒子或根据本发明的分散体和至少一种粘合剂。
合适的粘合剂可以是聚丙烯酸酯类、聚氨酯类、聚醇酸类、聚环氧化合物、聚硅氧烷类、聚丙烯腈类和/或聚酯类。在分散体具有一种或多种活性稀释剂作为液相的情况下，脂肪族的氨基甲酸酯丙烯酸酯(aliphatic urethane acrylate)，例如购自BASF的LaromerLR8987是特别适合的。根据本发明的涂布制剂优选地包括聚丙烯酸酯类和/或聚氨酯类。
涂布制剂中粘合剂部分优选占0.1-50重量％。特别优选占1-10重量％。
涂布制剂中复合粒子部分优选占0.1-60重量％。特别优选占1-10重量％。
此外，在应用时，涂布制剂可以包括用于改变该涂布制剂的流变学的化合物。含有二氧化硅的填料是特别有利的，特别优选热解法二氧化硅。以整个涂布制剂为基础计，其含量优选地可以是0.1-20重量％。
另外，涂布制剂可以包括有机溶剂，例如乙醇、乙酸丁酯、乙酸乙酯、丙酮、丁醇、THF、烷烃或两种或多种上述列举物质的混合物，以整个涂布制剂为基础计，其量是1-98重量％。
根据本发明的涂布制剂可以用于涂布由木材、PVC、塑料、钢、铝、锌、酮、MDF、玻璃和混凝土制成的基材。
本发明进一步提供一种包括根据本发明的复合粒子的防晒配制物。
以防晒配制物为基础计，复合粒子部分优选占0.01-25重量％。此外，根据本发明的防晒组合物能够与已知的无机紫外线吸收性颜料和/或化学的紫外线过滤剂混合使用。合适的已知紫外线吸收性颜料是钛氧化物、锌氧化物、铝氧化物、铁氧化物、二氧化硅、硅酸盐、铈氧化物、锆氧化物、硫酸钡或它们的混合物。
合适的化学紫外线过滤剂是本领域技术人员已知的所有水溶性或油溶性UVA和UV-B过滤剂，其中，以示例性而非限定性的方式可以提到的是，二苯甲酮和苯并咪唑的磺酸衍生物、二苯甲酰甲烷衍生物、苯亚甲基樟脑及其衍生物、肉桂酸衍生物及其酯、或水杨酸酯。根据本发明的防晒组合物还可以包括本领域技术人员已知的溶剂，例如水、单-或多元醇，化妆品用油剂，乳化剂，稳定剂，稠度调节剂，例如卡波姆(carbomers)、纤维素衍生物、黄原酸胶、蜡、膨润土(bentones)、热解法二氧化硅和化妆品中常用的其它物质，例如维生素、抗氧化剂、防腐剂、染料和香料。
代表性地，根据本发明的防晒组合物能够呈现为乳状液(O/W、W/O或复合型)、水溶液或水-醇的凝胶或油类凝胶，并能以露、霜、乳状喷雾、泡沫、棒状或其它常用的形式提供。
本发明进一步提供了根据本发明的复合粒子、根据本发明的分散体、根据本发明的涂布组合物或根据本发明的防晒配制物作为紫外线过滤剂的用途。
实施例
使用的原料
溶液A：Octa-Soligen Zinc 10(Borchers)：
粘度(20℃)：325mPas
辛酸锌：按锌计，10重量％
试验苯：42重量％
C6-C19脂肪酸：46重量％
2-(2-丁氧基乙氧基乙醇)：2重量％
溶液B：Borchi Kat 22，Borchers，
粘度(20℃)：5017mPas
辛酸锌：按锌计，22重量％
C6-C19脂肪酸：78重量％
溶液C：Octa-Soligen Cerium 12，Borchers，
粘度(30℃)：61mPas
辛酸铈：50重量％
2-乙基己酸：50重量％。
溶液D：将硝酸铈(III)六水合物溶于丙酮中，铈含量是8重量％，粘度(20℃)：52mPas
实施例1：将在20℃的1463g/h的溶液A(在此温度下，粘度为325mPas)和在80℃的136g/h的溶液C(在此温度下，粘度为9.2mPas)通过三元-材料喷嘴(triple-material nozzle)雾化至反应空间中并形成气溶胶。所述气溶胶的平均液滴直径D30小于100μm。这时，燃烧包括氢气(3Nm3/h)和一次空气(5Nm3/h)的氢氧气火焰，使气溶胶在其中进行反应。此外，将二次空气(25Nm3/h)引入反应空间。火焰下方0.5m处温度为925℃。接着，冷却反应混合物并通过过滤器将固态产品从气态物质中分离出来。
实施例2至6以类似的方式进行。表1中列出了原料和用量。所得复合粒子的组成和BET表面积同样在表1中列出。
图1显示了来自实施例2的复合粒子的电子透射显微照片。在氧化锌基质中的较暗的二氧化铈区域结构能够被清楚的看到。氧化锌基质的直径通常是20至100nm，二氧化铈区域结构的直径通常是5至10nm。氧化锌部分为六方形，二氧化铈部分为立方体形。
图2显示ZnO(………)、CeO2(----)和来自实施例2的根据本发明复合粒子(——)的吸光度为波长(nm)的函数。在根据本发明的复合粒子的情况中，该复合粒子包括约90重量％的氧化锌和约10重量％的二氧化铈，尽管二氧化铈部分含量低，仍能清楚地看到其吸光度与纯二氧化铈情况中的吸光度相比仅有略微的减少。
表1：使用的原料和用量；产生的复合粒子的分析值
| 实施例 | 1 | 2 | 3 | 4 | 5 | 6 | |
| 溶液A | |||||||
| 浓度 | g/h | 1385 | 1463 | - | - | 1461 | 1853 |
| 温度 | ℃ | 23 | 23 | - | - | 23 | 23 |
| 粘度 | mPas | 325 | 325 | - | - | 325 | 325 |
| 溶液B | |||||||
| 浓度 | g/h | - | - | 1034 | 1057 | - | - |
| 温度 | ℃ | - | - | 23 | 23 | - | - |
| 粘度 | mPas | - | - | 5000 | 5000 | - | - |
| 溶液C | |||||||
| 浓度 | g/h | 115 | 136 | 166 | 343 | - | - |
| 温度 | ℃ | 80 | 80 | 80 | 80 | - | - |
| 粘度 | mPas | 9.2 | 9.2 | 9.2 | 9.2 | - | - |
| 溶液D | |||||||
| 浓度 | g/h | - | - | - | - | 139 | 47 |
| 温度 | ℃ | - | - | - | - | 40 | 40 |
| 粘度 | mPas | - | - | - | - | 32 | 32 |
| 氢气 | Nm3/h | 3 | 3 | 2 | 2 | 3 | 5 |
| 雾化空气 | Nm3/h | 5 | 5 | 4 | 5 | 5 | 6 |
| 一次空气 | Nm3/h | 25 | 25 | 20 | 20 | 25 | 20 |
| 二次空气 | Nm3/h | 10 | 10 | 10 | 10 | 15 | 15 |
| 温度 | ℃ | 950 | 925 | 900 | 900 | 975 | 1050 |
| ZnO | 重量％ | 91 | 90 | 92 | 85 | 93 | 98 |
| CeO2 | 重量％ | 9 | 10 | 8 | 15 | 7 | 2 |
| BET表面积 | m2/g | 28 | 36 | 30 | 45 | 26 | 25 |
另一方面，复合粒子中氧化锌部分的吸光度实际上达到了纯氧化锌的吸光度。因此，存在协同效应，在于复合粒子的整体吸光度大于由单个部分(10％二氧化铈，90％氧化锌)的算术之和。根据本发明的复合粒子的进一步的特征在于它们的组分在UV-A和UV-B区域内具有高吸收，并因此能用作宽谱带过滤剂。
实施例7：光催化活性
通过参考二氯乙酸(DCA)的降解来检测氧化锌(对比物)和来自实施例2的复合粒子的光催化活性，检测中使用恒温在20℃的辐照反应器，该反应器体积为250ml并具有一个面积为4.9cm2的石英玻璃窗。用450W的氙气灯(Osram XBO)进行辐照，辐照强度是65mW/cm2。辐照时间是至少4小时。被检测的材料是0.1％浓度的水分散体的形式。为了使离子浓度在整个实验过程中保持不变，向分散体中另加入10mM的KNO3。二氯乙酸(DCA)的初始浓度是1mM。通过滴定加入0.1M的NaOH使不断被搅拌的分散体的pH值保持不变。
通过参考为保持pH值恒定所用氢氧化钠溶液的消耗量，能直接检测到DCA的降解。下面是适用的化学计量式：
CHCl2COO-+O2→H++2Cl-+2CO2
由得到的质子形成曲线的最初增长，可以确定降解速率(nM/s)，并且由此，以辐照光强为基础确定光子效率(％)。
这样，纯氧化锌给出的DCA降解速率是21.5nM/s，光子效率是0.58％。另一方面，来自实施例2的根据本发明的复合粒子的DCA降解速率仅为4.23nM/s，光子效率是0.11％。
即使二氧化铈部分仅占10重量％，所用复合粒子表面的大部分是氧化锌，光催化活性也能够得到显著的降低。还发现在二氧化铈部分大于20重量％时，光催化活性不再有显著程度的降低。
实施例8：根据本发明的分散体的制备
向50g水中加入0.1重量％的钠盐形式的聚丙烯酸，然后将来自实施例2的复合粒子按份在搅拌下加入到所述水中，直至固体含量达到10重量％。接着，在所有情况下，将混合物用ultrasound finger(直径：7mm，仪器：超声处理器UP400s，功率：400W，Dr Hielscher)分散一分钟。
实施例9：根据本发明的丙烯酸/聚氨酯基的涂布制剂的制备
将来自实施例8的分散体，在分散条件下，加入到标准的商购丙烯酸/聚氨酯粘合剂制剂(Relius Aqua Siegel Gloss)中，以获得含有2重量％的复合粒子部分的涂布制剂。
实施例10：根椐本发明的丙烯酸基的涂布制剂的制备
按实施例9进行操作，但使用标准的商购丙烯酸粘合剂制剂。
(Macrynal SM510(Cytec)，Desmodur N75(Bayer))。
实施例11：涂布木材时的抗紫外线能力
用来自实施例9和10的涂布制剂各自涂布3个用底漆预处理的松木样品(Relius Aqua Holz Grund)(QUV-B 313；DIN EN 927-6，ISO11507，ASTM D4857)。用涂有丙烯酸/聚氨酯基的涂布制剂的松木样品(Relius Aqua Siegel Gloss)做对照，该涂布制剂不含复合粒子。
在1000小时的检测时间后，与不含复合粒子的涂层相比，来自实施例9和10的涂层显示的泛黄明显较少，光泽明显较高并且涂层中没有变脆和断裂。
实施例12：在涂布玻璃时的硬度
将来自实施例9和10的涂布制剂以150μm的层厚度施加于玻璃板，并用不含复合粒子的丙烯酸/聚氨酯基的涂布制剂(Relius AquaSiegel Gloss)作为对照。经1、6、13和34天的干燥时间后，在标准实验室条件下(20℃，65％的相对湿度)(DIN ISO 1522)确定其硬度。来源于实施例9和10的涂层的硬度达到100％，高于对比例的涂层的硬度。
实施例13：被涂布的金属板的光泽和白度
用罩面白灰(white coating)对金属板进行预处理。接着根据DIN53231将涂布组合物9和10以及标准的商购涂料组合物用有机紫外线过滤剂进行处理，并辐照55天。
在这段时间后，具有有机紫外线过滤剂的样品的伯杰白度(degreeof whiteness according to Berger)明显低于来自实施例9和10中组合物的样品的白度。
实施例14：根据本发明的防晒配制物的制备
用下述配制物制备含有4重量％的实施例2中根据本发明的粒子的防晒组合物。
| 相 | 组分 | 重量％ |
| A | Isolan GI 34蓖麻油Tegesoft OPTegesoft Liquid甘油86％ | 3.01.210.05.03.0 |
| B | Paracera W80异十六烷 | 1.85.0 |
| C | 实施例2中的复合粒子 | 4.0 |
| D | 硫酸镁软化水 | 0.566.5 |
在混合器中将相A加热到70℃。待相B在磁性加热板上于80℃熔化后，将其加入到相A中。在约300rpm和减压条件下，将相C搅拌入油相中。将相D同样加热到70℃并在减压条件下加入到A-C的混合物中。
Claims (13)
1.复合粒子，其BET表面积为5-100m2/g，包括氧化锌基质和二氧化铈区域结构，其中所述区域结构位于所述基质内和所述基质上，基于所述复合粒子，氧化锌部分占80-98重量％，二氧化铈部分占2-20重量％。
2.如权利要求1所述的复合粒子，其特征在于所述复合粒子是聚集态的。
3.如权利要求1或2所述的复合粒子，其特征在于基于所述复合粒子，氧化锌部分占85-95重量％，二氧化铈部分占5-15重量％。
4.如权利要求1至3所述的复合粒子，其特征在于基于所述复合粒子，氧化锌和二氧化铈至少占99.9重量％。
5.如权利要求1至4所述的复合粒子，其特征在于BET表面积是20-50m2/g。
6.如权利要求1至5所述的复合粒子，其特征在于所述基质的平均直径是20-100nm。
7.如权利要求1至6所述的复合粒子，其特征在于所述区域结构的平均直径是2-10nm。
8.如权利要求1至7所述的复合粒子的制备方法，其特征在于：
-通过喷嘴用雾化气体将包括可氧化的锌化合物的溶液1和包括可氧化的铈化合物的溶液2雾化进入反应空间中，并形成平均直径小于100μm的液滴，其中：
-按ZnO计算，溶液1部分占80-98重量％，按CeO2计算，溶液2部分占2-20重量％，
-溶液1的粘度是200至5000mPas，溶液2的粘度是5至150mPas，如果适当，在各自情形中通过加热至在所述锌化合物和所述铈化合物的分解温度之内的温度而调节粘度，
-将被雾化的溶液引入反应器的高温区，在那里与氧气或含氧气体在800至1200℃的温度下进行反应，
-将高温气体和固态产品冷却，然后将固态产品从气体中分离。
9.如权利要求9所述的方法，其特征在于反应温度源于由含氢燃烧气体与氧气和/或空气反应产生的火焰。
10.包括如权利要求1至7所述的复合粒子的分散体。
11.包括如权利要求1至7所述的复合粒子或如权利要求10所述的分散体、以及至少一种粘合剂的涂布组合物。
12.包括如权利要求1至7所述的复合粒子或如权利要求10所述的分散体的防晒配制物。
13.如权利要求1至7所述的聚集的复合粒子、如权利要求10所述的分散体、如权利要求11所述的涂布组合物或如权利要求12所述的防晒配制物的用途，其作为紫外线过滤剂。
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| CN111672524A (zh) * | 2019-06-13 | 2020-09-18 | 河南理工大学 | 一种二氧化铈-氧化锌-卤氧化铋-铁酸钴磁性可见光催化剂制备方法 |
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| DE10353996A1 (de) * | 2003-11-19 | 2005-06-09 | Degussa Ag | Nanoskaliges, kristallines Siliciumpulver |
| DE10353995A1 (de) * | 2003-11-19 | 2005-06-09 | Degussa Ag | Nanoskaliges, kristallines Siliciumpulver |
| DE102004012682A1 (de) * | 2004-03-16 | 2005-10-06 | Degussa Ag | Verfahren zur Herstellung von dreidimensionalen Objekten mittels Lasertechnik und Auftragen eines Absorbers per Inkjet-Verfahren |
| DE102004041747A1 (de) * | 2004-08-28 | 2006-03-02 | Degussa Ag | Indium-Zinn-Mischoxidpulver |
| DE102004041746A1 (de) * | 2004-08-28 | 2006-03-02 | Degussa Ag | Kautschukmischung, enthaltend nanoskalige, magnetische Füllstoffe |
| DE102005049136A1 (de) * | 2004-12-01 | 2006-06-08 | Degussa Ag | Zubereitung, enthaltend ein polymerisierbares Monomer und/oder ein Polymer und darin dispergiert ein superparamagnetisches Pulver |
| US7790079B2 (en) * | 2005-04-18 | 2010-09-07 | Evonik Rohm Gmbh | Thermoplastic molding material and molding elements containing nanometric Inorganic particles for making said molding material and said molding elements, and uses thereof |
| DE102005040157A1 (de) * | 2005-08-25 | 2007-03-01 | Degussa Ag | Paste aus nanoskaligem Pulver und Dispergiermittel |
| DE102005049718A1 (de) * | 2005-10-14 | 2007-04-19 | Degussa Gmbh | Durch Schweißen im elektromagnetischen Wechselfeld erhältliche Kunststoffverbundformkörper |
| DE102005056286A1 (de) * | 2005-11-24 | 2007-05-31 | Degussa Gmbh | Schweißverfahren mittels elektromagnetischer Strahlung |
| DE102005060121A1 (de) * | 2005-12-16 | 2007-06-21 | Degussa Gmbh | Verfahren zur Herstellung von Zinkoxidpulver |
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| JP6489024B2 (ja) * | 2013-12-24 | 2019-03-27 | 堺化学工業株式会社 | 酸化セリウム被覆酸化亜鉛粒子、その製造方法、紫外線遮蔽剤及び化粧料 |
| JP6493227B2 (ja) | 2014-02-07 | 2019-04-03 | 堺化学工業株式会社 | 六角板状酸化亜鉛粒子、その製造方法、化粧料、フィラー、樹脂組成物、赤外線反射材及び塗料組成物 |
| CN107683257A (zh) * | 2015-03-30 | 2018-02-09 | 谢珀德颜色公司 | 含有uv吸收纳米晶体的复合材料 |
| KR101594734B1 (ko) * | 2015-08-10 | 2016-02-16 | 고려대학교 산학협력단 | 산화인듐 중공구조 및 산화세륨 나노입자를 포함하는 가스 검출용 복합체, 그 제조방법 및 이를 포함하는 가스센서 |
| CN111883788A (zh) * | 2020-06-24 | 2020-11-03 | 华南理工大学 | 一种氧化铈基中低温固体氧化物燃料电池关键材料的制备方法 |
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| DE102004041746A1 (de) * | 2004-08-28 | 2006-03-02 | Degussa Ag | Kautschukmischung, enthaltend nanoskalige, magnetische Füllstoffe |
| US7704586B2 (en) * | 2005-03-09 | 2010-04-27 | Degussa Ag | Plastic molded bodies having two-dimensional and three-dimensional image structures produced through laser subsurface engraving |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111672524A (zh) * | 2019-06-13 | 2020-09-18 | 河南理工大学 | 一种二氧化铈-氧化锌-卤氧化铋-铁酸钴磁性可见光催化剂制备方法 |
| CN111672524B (zh) * | 2019-06-13 | 2023-03-10 | 河南理工大学 | 一种二氧化铈-氧化锌-卤氧化铋-铁酸钴磁性可见光催化剂制备方法 |
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| Publication number | Publication date |
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| EP1798263A2 (de) | 2007-06-20 |
| US20070149395A1 (en) | 2007-06-28 |
| CN100567409C (zh) | 2009-12-09 |
| EP1798263A3 (de) | 2010-07-28 |
| JP2007161578A (ja) | 2007-06-28 |
| DE102005059405A1 (de) | 2007-06-14 |
| KR20070062921A (ko) | 2007-06-18 |
| KR100797745B1 (ko) | 2008-01-24 |
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