CN86106689A - 球形二氧化硅粒子 - Google Patents
球形二氧化硅粒子 Download PDFInfo
- Publication number
- CN86106689A CN86106689A CN86106689.8A CN86106689A CN86106689A CN 86106689 A CN86106689 A CN 86106689A CN 86106689 A CN86106689 A CN 86106689A CN 86106689 A CN86106689 A CN 86106689A
- Authority
- CN
- China
- Prior art keywords
- particle
- sio
- tetraalkoxysilane
- described method
- alcohol
- 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/32—Bonded phase chromatography
- B01D15/325—Reversed phase
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
- B01J20/287—Non-polar phases; Reversed phases
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3092—Packing of a container, e.g. packing a cartridge or column
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3259—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulfur with at least one silicon atom
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
- B01J20/3261—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such comprising a cyclic structure not containing any of the heteroatoms nitrogen, oxygen or sulfur, e.g. aromatic structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Silicon Compounds (AREA)
- Silicon Polymers (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
本发明是关于高单分散、无孔隙球形SiO2粒子的制备方法,其具有0.05和10μm之间的平均粒径和不超过5%的标准误差。它为在水/醇氨介质中通过对四烷氧基硅烷进行水解缩聚,先制备成初级粒子溶胶,然后由反应程度控制,通过连续定量加入四烷氧基硅烷,使所得的SiO2粒子转换成理想的粒径。使用该SiO2粒子作为色谱中的吸着材料。
Description
本发明涉及到一种制备高单分散、无孔隙的球形SiO2粒子的方法及其所述的粒子。
球形SiO2粒子在科技领域中是具有特殊意义的有价值的工具,也是科学研究中有趣的研究项目。这种粒子的一个重要应用领域,就是用于标准化,特别是当这种粒子具有确定和均匀的直径(主要在nm和μm范围内)情况下,例如用作为决定诸如粉粒或细胞之类微小物体的大小标准。在色谱领域中及由此派生出来的分离技术中,用作吸着材料或载体材料,被认为是这种粒子进一步的应用。在所有应用中,粒径和粒径分布起着相当重要的作用。因此,根据所述的(粒子的)特点,能够以予定的、重复生产的方式来制备这种粒子,是很重要的。
从先有技术,例如从W.STOBER等人在“胶体与界面科学杂志”1968,Vol 62,No26和1969,Vol 568,No 30上发表文章以及从美国专利3,634,588号,已知可通过对四烷氧基硅烷进行水介缩聚得到球形SiO2粒子。上述这些文献并指出了进行此步的基本反应条件,设想将四烷氧基硅烷导入到过量的水/醇氨水解混合物中,同时用合适的手段,如搅拌、振摇或超声波处理等,将其彻底混合。在这种情况下,随着特定实验参数的选择,就能得到不同平均粒径的SiO2粒子和不同的粒径分布。按引用的出版物的数据,研究了在水解混合物中不同的硅酸酯。氨和水的浓度以及不同的醇的影响,获得了平均粒径在0.05和2μm(少数情况下,高达3μm)的SiO2粒子。从未公开的研究证实的结果,可以推断,在某种程度上仅仅在大到2μm的粒径(大小)范围内,可获得单分散球形的粒子,但到目前为止还不具备充分控制重复生产这种粒子的能力。这样,粒径的标准误差通常落在约5~15%之间。在少数情况下,标准误差高达50%。在制备较大直径的单分散粒子上是不成功的;还未见过描述制备直径超过3μm的粒子。根据引用的出版物,仅仅描述和制备以粒子水解形式的粒子,但未在本质上作为粒子本身从水解混合物中分离出。结果,缺乏任何关于其粒子的其他性质的数据,尤其是关于其孔隙性的数据。
在对用STOBER等人的方法制备以及紧接其后的通过淀积或离心干燥而分离出的SiO2粒子所作的未公开的研究中,就体现这样的粒子有显著的微孔性。情况表现在此表面上,这例如可通过气体吸收(例如通过BET方法)来测定;并且这取决于给定的实验条件超过在理论上用10到100的因数来计算的表面。
粒子的微孔性必然会极大地影响粒子的性质。尽管如此,就上述许多应用而言,倘若粒子实质上没有孔隙,即粒子表面是完全封闭的话,就认为是有益的。
从而,本发明是建立在制备得到尽可能的没有孔隙、且具高度单分散性的球形SiO2粒子的目标基础上的。应该尽可能容易地进行制备和供应具有予定的可重复生产的粒径的粒子。若可能的话,甚至其粒径大达10μm。此外,应该可以改良这类粒子,使其在SiO2基质中所包含的有机基,这SiO2基质通常例如用于来改良硅胶。
令人惊奇的是,现已发现,如果先通过在水/醇氨介质中,用已知的方法,对四烷氧基硅烷进行水解缩聚,首先获得一个初级粒子的溶胶,然后通过连续地。定量地加入四烷氧基硅烷。(通过反应程度来控制)将所得到的SiO2粒子转换成希望得到的粒径,那么,就能得到平均粒径在0.05和10μm之间、标准误差不超过5%的无孔隙球形SiO2粒子。在这种情况下,(显然)最终获得的SiO2粒子,作为具有严格的球形状和均匀的粒径,即高度单分散、无孔隙的离散微粒而聚集。
另外,也可以得到同样满足无孔隙、单分散要求的有机改良SiO2粒子。
更进一步发现,由于SiO2粒子的特殊性质,以这种方式制备的SiO2粒子,非常适合在色谱中作为特殊的吸着材料。因此,当有机改良的SiO2用作为高分子量生物分子(如蛋白质)的反相色谱法的吸着材料时,表现出优越性。就这一点来说,用传统的吸着剂,是达不到这种优点的。
因而,本发明的主题是:通过对四烷氧基硅烷在水/醇氨介质中水解缩聚,来制备球形SiO2粒子的方法。在此方法中,首先生产出初级粒子溶胶,然后,通过连续地,定量地加入四烷氧基磕烷(通过反应的程度来,控制),将所得的SiO2粒子转换成希望得到的粒径,从而就得到高单分散、无孔隙、平均粒径在0.05和10μm之间、标准误差不超过5%的粒子。
本发明的主题也是由这样一种具有独特性质的SiO2粒子构成的。
此外,本发明的主题是将按本发明的方法所制备SiO2粒子用作为色谱中的吸着材料,特别是用作为高分子量生物分子(如蛋白质、核酸)反相色谱的吸着材料。
按本发明所述的制备高单分散、无孔隙球形SiO2粒子的方法,是用两步进行的。
第一步,按已知的方法,制备初级粒子溶胶。为此,将四烷氧基硅烷导入水/醇氨水解混合物,并彻底混合。所有可令人满意地被水解的脂族醇原硅酸酯均适合作四烷氧基硅烷。在此情况下主要就考虑含有1-5个碳原子的脂族醇酯,例如,甲醇、乙醇、n-或i-丙醇及同分异构的丁醇和戊醇。它们可单个地使用。也可以混合的使用。最好是C1-C3醇的原硅酸脂,特别是四烷氧基硅烷。除脂族醇外,水解混合物应含有约0.5至约0.8摩尔/升的氨,约1至15摩尔/升的水。适合作醇成分的有脂族C1-C5醇,最佳的为C1-C3醇,如甲醇,乙醇,还有正或异丙醇。这些可单独地出现,也可以在水解混合中以相互之间的混合物形式出现。一批性地加四烷氧基烷硅到水解混合物中,以使反应物在上述醇中以一种纯的或溶液的形式出现。水解混合物中四烷氧基烷硅的浓度约在0.01至1摩尔/升之间,用来作为制备初级粒子。反应物被聚集后,反应立即或几分钟便开始,这可由立刻产生的粒子所造成的反应物的乳白色或混浊(度)显示出来。一般说来,在不超过15至30分钟的时间内反应完成,在不利的情况下,时间甚至更长一点。随着反应物的选择及其反应混合物的浓度的变化,按已知的方法,就能得到平均直径在约0.01和约2μm之间的粒子。
按本发明方法的第一步,最好是使用含3-13摩尔/升的水,0.5至4.5摩尔/升的氨,10至25摩尔/升的醇以及0.1-0.5摩尔/升的四烷氧基烷硅的反应混合物。在此情况下,可得到平均直径在0.01和1μm之间的初级粒子。在这一阶段,可从初级粒子溶胶中取出试样,例如,使用电子显微,来对粒子的粒径、形状的精确性和粒径分布进行研究。通过分离粒子试样,就有可能测出初级粒子的孔隙性(例如通过气体吸收测定)。
已经证明,在高温下进行制备初级粒子的反应是便利的。在这种情况下,35至75℃之间的温度,是有利的。已表明,在高温时,粒径扩张减小,正如平均粒径减小一样。在较低的温度时,即大约在室温下,在其他条件都相同时,得到具有大粒径扩张的较大粒子。另外,在此情况下,还会观察到有增加的、不希望的烧结物形成。
在按本发明所述的方法第二步里,缓慢地、连续定量地将四烷氧基烷硅加到初级粒子溶胶里。在这里,控制定量的加入的速率,以便在粒子存在于溶胶的情况下,能迅速、完全的反应,而不致以新的初级粒子的核的形成过程中产生过量的四烷氧基烷硅这一点是很重要的。用计量加入四烷氧基烷硅的方法(通过反应程度来控制的),在溶胶里可达到粒子的可控的二次生长。所以,获得的最终粒径取决于总的加入四烷氧基烷硅的数量。总的加入的烷基硅烷的数量,在原则上不是最重要的-如果通过可能的进一步加水解混合物,使水解混合物时,没有时间限制;这种加入可持续若干小时至若干天。中间停止和重新开始二次生长,也是允许的,因为粒子在其生长的各个阶段都是稳定的。同样,在二次过程中,最佳的是利用高温(约40℃)。
约0.05μm,即规定的初级粒子的最小粒径,应被定为较低的粒径。按本发明得到的粒子具有均为的球形状,没有任何孔隙。由气体吸收所测定的比表面为理论计算表面的1至1.5倍。这样充其量不过是表面稍微粗糙一些,但排除了气孔的存在。可以这样解释,原来存在于初级粒子的孔隙,被缓慢的、连续的二次生长所封闭,新的孔隙就不会形成。
令人惊奇和出乎意料的是,在初级粒子中出现的广泛的粒径扩张(在那种情况下,标准误差平均为5-10%)现象,在通过二次生长步骤的方法获得的粒子中未发现。这样得到的粒子的标准误差不超过5%,通常在2%左右或以下,因而是高度单分散的,显然,在这第二步,发生了对原有的各种粒径的调整,并且发生了随着相对标准误差的相应减少而出现的所有粒子的均匀的进一步生长。
从而,按本发明的方法,就能使那些本专业领域内的人员制备直径直至10μm,高度单分散、无孔隙的球形SiO2粒子。特别是,在这个范围内,现在可利用这类粒子作为系统尺寸等级的精确的标准,这种标准大致是与“标准尺”一致的。
也可以在专门的实施例中制备这类含有机改良基(即含有共价键有机基)的粒子。制备这类粒子的方法在原则上为已知的。为此,在按本发明的方法里,最好是在二次生长步骤,用一种或多种已知的有机三烷氧基硅烷来取代所用的0.1至100%,最好为1-30%的四烷氧基烷硅,以改良硅胶。这些化合物中的有机基可以是具有1-20个碳原子的脂族基;这类脂族基是可以有选择地通过诸如羟基、硫代、氨基或羧基或囟素)及链烯基而起作用的。将起作用的有机基并入粒子的SiO2基中,就可以用已知的方式,通过共价键连接,容易地使后面的进一步改良变成可能。这类有机三烷氧基硅烷的例子有:
甲基三乙氧基硅烷
乙基三乙氧基硅烷
己基三乙氧基硅烷
辛基三乙氧基硅烷
十二烷基三乙氧基硅烷
十八烷基三乙氧基硅烷
乙烯基三乙氧基硅烷
3-羟基丙基三乙氧基硅烷
3-氯丙基三乙氧基硅烷
3-氨基丙基三乙氧基硅烷
3-glycidoxypropyltriethoxysilane
3-巯基丙基三乙氧基硅烷
3-异硫氰酸根合丙基三乙氧基硅烷
3-(氨基乙氨基)丙基三乙氧基硅烷
3-甲丙烯酰基丙氧三乙氧基硅烷
3-乙酸基丙基三乙氧基硅烷
N-(3-三乙氧基甲硅烷丙基)-N′-(1-苯基-1-羟基异丙基)-硫脲
N-(3-三乙氧基甲基硅烷丙基)-N′-(α-苯乙基)硫脲
就无孔隙性和单分散性而言,粒子的性质是不受这种有机改良的影响的;而在另一些方面,又可以保留改良的硅胶已知的有益性质。根据本发明的方法,自然还可以通过用已知的诸如用于孔隙材料的后处理的方法,来使制备的未径改良的SiO2粒子得到表面的有机改良(例如,在制备反相色谱吸着剂中)。
这种有机改良SiO2粒子,可应用于众多的其他领域,例如作为色谱中的特制吸着剂。
特别是,所述的按本发明方法制备的有机改良SiO2粒子,适用于反相色谱。
所述的粒子的使用,使得高分子量生物分子(如肽、蛋白质或核酸)的分离变成可能。例如,这类分子是:溶菌酶、核糖核酸酶A、脲酶、转铁蛋白、胰岛素、醛缩酶、肌红蛋白、触酶、卵清蛋白、乳酸脱氢酶、吡啶偶氮苯酚、α-糜蛋白酶、过氧化物酶、牛血清清蛋白、铁蛋白、CI-INA、肌酸激酶、碳酸酐酶、戊基葡糖苷酶、血红蛋白、inter-leucin及其他。当本发明的粒子用于这类生物分子的分离时,便体现出这样的优点,即用传统的材料,是不可能取得这种良好的效果的。
这低平均粒径,窄粒径分布以及与孔隙材料相比所缺乏的扩散膜,这些都显著地达到了更高的柱效率,从而也就达到了一个更高的检测极限。进一步的优越性在于缩短了分析次数。与用传统材料所需要的(分析)次数相比,分析次数约减少到原来的五分之一。另外,与用孔隙材料时的情况相比,物质损失也明显地低。
在溶液的选择上,没有任何的限制,所有已知的溶液系统都可使用。
实施例一
制备一个水解混合物,其包含11.9克(0.66摩尔)水,62.7克(1.96摩尔)甲醇,2克(0.12摩尔)氨。把所述的水解混合物调温在40℃,将4.4克(0.02摩尔)同样调温的四烷氧基硅烷,以一批的形式加入该水解混合物里,并彻底混合。得到平均粒径为0.07μm、标准误差为11%的初级粒子溶胶。
将36克(0.17摩尔)四烷氧基硅烷、450克具有上述成分的水解混合物滴状加入到所得的初级粒子溶胶,同时搅拌24小时以上。(离心分离或沉积和干燥后)得到平均粒径为0.145μm、标准误差为5%的球形SiO2粒子。按BET方法,得其比表面为23m2/g(理论计算表面为19m2/g)。
实施例二
制备一个水解混合物,其包含13.5克(0.75摩尔)水,80克(2.5摩尔)甲醇和0.85(0.05摩尔)氨。把这一水解混合物调温在40℃,一批地将4.2克(0.02摩尔)同样调温的四烷氧基硅烷加入该水解混合物里,并彻底混合。得到平均粒径为0.015μm、标准误差为15%的初级粒子溶胶。
将170克(0.82摩尔)四烷氧基硅烷、1.9公升水解混合物滴状加入加到所得到的初级粒子溶胶里,同时搅拌100小时。得到平均粒径为0.05μm、标准误差为5%的球形SiO2粒子。用BET方法得到的比表面为64m2/g(理论计算表面为55m2/g)。
实施例三
制备一个水解混合物,其包含13.5克(0.75摩尔)水,64.4克(14摩尔)乙醇和6.4(0.38摩尔)氨。把这一水解混合物调温在40℃,一批地将4.2克(0.02摩尔)同样调温的四烷氧基硅烷加入该水解混合物里,同时彻底混合。得到平均粒径为0.58μm、标准误差为5%的初级粒子溶胶。比表面:SBET=340m2/g;S理论=4.7m2/g。
将650克(3.1摩尔)四烷氧基硅烷,5.9公斤水解混合物滴状加入到所得到的初级粒子溶胶,同时搅拌5天。得到平均粒径为3.1μm、标准误差为1.3%的球形SiO2粒子。通过BET方法得到的比表面为1.1m2/g(理论计算表面:0.88m2/g)。
实施例四
按例一的方法制备初级粒子溶胶。以相似的方法,进行二次生长步骤,但使用含4克(0.09摩尔)的四烷氧基硅烷、0.4克(1.8毫摩尔)的氨丙基-三氧甲基硅烷的混合物。
得到平均粒径为0.09μm、标准误差为5%的有机改良球形SiO2粒子。比表面为44m2/g(理论计算表面:30m2/g)。所述粒子的碳成份为2.4%。
实施例五至八
制备一种水解混合物,其包含16.2克(0.9摩尔)水,64.8克(1.8摩尔)甲醇和2.7克(0.16摩尔)氨。把这一水解混合物调温在40℃,一批地将4.2克(0.02摩尔)同样调温的四烷氧基硅烷加入该水解混合物中,并彻底混合。得到平均粒径为0.13μm、标准误差为10%的初级粒子溶胶。比表面:SBET=280m2/g;S理论=4.7m2/g。
在2天的过程中,每次滴状加入特定数量的四烷氧基硅烷及水解混合物到原有的100毫升的溶胶里,直到将其加至600毫升为止,在这此步骤果就发生了二次生长。下面的表一说明了每一步加入的硅烷的数量及得到的有关数据。
表一
实施 加入的四 平均粒径/ 比 表 面
例号 烷氧基硅 标准误差No. 烷数量
SBET S理论
5 35克 0.26μm/5% 14m2/g 10.3m2/g
6 54克 0.56μm/3.4% 5.5m2/g 4.9m2/g
7 55.3克 1.15μm/2.6% 2.6m2/g 2.4m2/g
8 55.3克 2.4μm/1.7% 1.5m2/g 1.1m2/g
实施例九
在3公升的含有1摩尔氨/公升、8摩尔水/公升、和乙醇(剩余数量)、且调温在40℃的水解混合物中,有按例三所制备的170克粒径为1.55μm的硅胶粒子。将含有2.4克辛基三甲氧基硅烷和17.6克四烷氧基硅烷的混合物滴状加入到上述溶液中,滴入时间为1.5至2小时。得到有机改良的球形SiO2粒子。所述粒子的碳成份为1.0%。
实施例A
一含有5种蛋的质的混合物,通过填充着按例九制备的1.5μm的无孔隙、单分散的辛基改良SiO2粒子的柱塔(长40cm,直径8cm)而得到分离。
蛋白质混合物包含:
1)核糖核酸酶A (分子量=13,700)
2)细胞色素C (分子量=12,500)
3)醛缩酶 (分子量=156,000)
4)触酶 (分子量=24.000)
5)卵清蛋白 (分子量=45,000)
使用了下列溶剂:
溶剂A:水100%,含HCLO4,PH值调节在2.0
溶剂B:乙腈75%/溶剂A25%。
以1.5毫升/分钟的流速进行分离。
梯度变化:
在所有情况下,起始条件为75%的溶剂A,在3,10,20和40分钟后,达到溶剂B的终值100%。
各蛋白质的洗脱品级比较于表二。
表二
蛋白质 tc (分钟) 3 10 20 40
核糖核酸酶A 3.2 4.2 5.4 7.9te(分钟)
细胞色素C 3.6 5.8 7.6 12.1
醛缩酶 4.2 7.1 10.8 18.8
触酶 4.5 7.6 11.9 20.7
卵清蛋白 4.8 8.2 13.2 23.9
tc=以分钟计的梯度时间
te=以分钟计的的物质洗脱时间
该表表明,即使只用了10分钟的分析时间,仍然可得到令人满意的良好分离,因为在此情况下,洗脱品级相距已足够远。
Claims (10)
1、在水/醇氨介质中,通过对四烷氧基硅烷水解缩聚而制备球形SiO粒子的方法,其特征在于先制备初级粒子溶胶,然后,由反应程度控制,通过连续定量地加入四烷氧基硅烷,使所得到的SiO粒子转换成理想的粒径,得到平均粒径在0.05和10μm之间标准差不超过5%的高单分散、无孔隙的粒子。
2、按权利要求1所述的方法,其特征在于水解缩聚是在35至75℃,最佳的是在40至65℃的温度里进行的。
3、按权利要求1所述的方法,其特征在于用低脂族醇(C-C)的硅酸酯作为所用的四烷氧基硅烷。
4、按权利要求1所述的方法,其特征在于使用四烷氧基硅烷。
5、按权利要求1所述的方法,其特征在于用三烷氧基硅烷取代所用的0.1至100%,最佳的为1-30%的四烷氧基硅烷。
6、球形SiO粒子,其特征在于其平均粒径在0.05和10μm之间,标准误差不超过5%,以高度单分散、无孔隙形式存在。
7、按权利要求6所述的SiO粒子,其特征在于其质中含有用来改良硅胶的共价键合的有机基团。
8、按权利要求1制备的SiO粒子,其中把该SiO粒子用作为色谱中的吸着材料。
9、按权利要求7所述的SiO粒子,其中把该SiO粒子用作为高分子量生物分子特别是蛋白质的反相色谱中的吸附材料。
10、按权利要求1制备的SiO2粒子,其中把该SiO2粒子用作为高分子量生物分子,特别是蛋白质的反相色谱中的吸附材料。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853534143 DE3534143A1 (de) | 1985-09-25 | 1985-09-25 | Kugelfoermige sio(pfeil abwaerts)2(pfeil abwaerts)-partikel |
DEP3534143.2 | 1985-09-25 | ||
DEP353414312 | 1985-09-25 | ||
DE19863616133 DE3616133A1 (de) | 1985-09-25 | 1986-05-14 | Kugelfoermige sio(pfeil abwaerts)2(pfeil abwaerts)-partikel |
DEP361613310 | 1986-05-14 | ||
DEP3616133.0 | 1986-05-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN86106689A true CN86106689A (zh) | 1987-05-27 |
CN1008081B CN1008081B (zh) | 1990-05-23 |
Family
ID=25836353
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN86106689A Expired CN1008081B (zh) | 1985-09-25 | 1986-09-23 | 球形二氧化硅粒子—的制备方法 |
Country Status (7)
Country | Link |
---|---|
US (2) | US4775520A (zh) |
EP (1) | EP0216278B1 (zh) |
JP (1) | JPH0825739B2 (zh) |
CN (1) | CN1008081B (zh) |
AU (1) | AU588363B2 (zh) |
CA (1) | CA1280399C (zh) |
DE (2) | DE3616133A1 (zh) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1051054C (zh) * | 1997-12-30 | 2000-04-05 | 中国科学院感光化学研究所 | 从碱金属的硅酸盐制备纳米二氧化硅颗粒的方法 |
CN1051747C (zh) * | 1994-06-01 | 2000-04-26 | 瓦克化学有限公司 | 二氧化硅的甲硅烷基化方法以及由此制得的产品及其应用 |
CN1305764C (zh) * | 2004-03-31 | 2007-03-21 | 张永 | 一种硅粉的制作方法 |
CN1930082B (zh) * | 2004-03-08 | 2010-09-29 | 默克专利有限公司 | 制造单分散SiO2颗粒的方法 |
CN102099014A (zh) * | 2008-07-15 | 2011-06-15 | 默克专利股份有限公司 | 二氧化硅纳米颗粒及其用于疫苗接种的用途 |
CN102295290A (zh) * | 2010-06-23 | 2011-12-28 | 富士施乐株式会社 | 二氧化硅颗粒的制造方法 |
CN102295292A (zh) * | 2010-06-25 | 2011-12-28 | 富士施乐株式会社 | 二氧化硅颗粒及其制造方法 |
CN102527354A (zh) * | 2012-02-07 | 2012-07-04 | 月旭材料科技(上海)有限公司 | 核壳型颗粒及制备方法 |
CN102862991A (zh) * | 2011-07-06 | 2013-01-09 | 富士施乐株式会社 | 二氧化硅颗粒、二氧化硅颗粒的制造方法和树脂颗粒 |
CN103080008A (zh) * | 2010-11-05 | 2013-05-01 | 松下电器产业株式会社 | 二氧化硅多孔体及使用其的光学麦克风 |
TWI405843B (zh) * | 2006-11-30 | 2013-08-21 | Jgc Catalysts & Chemicals Ltd | 金平糖狀無機氧化物溶膠,其製造方法及含該溶膠之研磨劑 |
CN103328382A (zh) * | 2011-01-21 | 2013-09-25 | Dic株式会社 | 多孔质二氧化硅颗粒的制造方法、防反射膜用树脂组合物、具有防反射膜的物品以及防反射薄膜 |
CN103318899A (zh) * | 2013-06-24 | 2013-09-25 | 哈尔滨工业大学 | 一种单分散二氧化硅微球粒径的控制方法 |
WO2014005272A1 (zh) * | 2012-07-03 | 2014-01-09 | 蚌埠鑫源石英材料有限公司 | 一种二氧化硅粉体材料及其制备方法 |
US8962139B2 (en) | 2011-01-20 | 2015-02-24 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
US9187502B2 (en) | 2010-06-24 | 2015-11-17 | Fuji Xerox Co., Ltd. | Silica particles and method for producing the same |
US9243145B2 (en) | 2013-01-28 | 2016-01-26 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
US9394413B2 (en) | 2011-01-19 | 2016-07-19 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
CN105800625A (zh) * | 2016-02-19 | 2016-07-27 | 江苏和成新材料有限公司 | 一种可控吸水二氧化硅微球的制备方法 |
CN106669589A (zh) * | 2016-12-20 | 2017-05-17 | 常州大学 | 一种基于巯基的高效吸附剂的制备方法及应用 |
US9708191B2 (en) | 2011-12-01 | 2017-07-18 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
CN114229853A (zh) * | 2021-11-29 | 2022-03-25 | 桂林理工大学 | 一种锌掺杂介孔二氧化硅纳米球的制备方法 |
Families Citing this family (150)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3786933T2 (de) * | 1986-02-12 | 1994-01-20 | Catalysta & Chemicals Ind Co | Verfahren zur Herstellung von mono-dispergierten Teilchen. |
JPH0611404B2 (ja) * | 1986-02-25 | 1994-02-16 | 住友セメント株式会社 | 触媒関連材料の作成方法 |
US5304324A (en) * | 1986-03-07 | 1994-04-19 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Monodispersed glycol suspension of fine inorganic oxide particles having excellent dispersion stability |
JPH0770420B2 (ja) * | 1987-06-18 | 1995-07-31 | ダイアホイルヘキスト株式会社 | コンデンサ−用二軸延伸ポリエステルフイルム |
JPS6374911A (ja) * | 1986-09-19 | 1988-04-05 | Shin Etsu Chem Co Ltd | 微細球状シリカの製造法 |
US5236683A (en) * | 1987-01-20 | 1993-08-17 | Mizusawa Industrial Chemicals, Ltd. | Amorphous silica spherical particles |
US5236680A (en) * | 1987-01-20 | 1993-08-17 | Mizusawa Industrial Chemicals, Ltd. | Preparation of amorphous silica-alumina particles by acid-treating spherical P-type zeolite particles crystallized from a sodium aluminosilicate gel |
JPH0684444B2 (ja) * | 1987-07-03 | 1994-10-26 | 東洋紡績株式会社 | 熱可塑性フィルム |
DE3913260A1 (de) * | 1988-05-19 | 1989-11-23 | Degussa | Kugelfoermige, hydrophile kieselsaeure, verfahren zu seiner herstellung und verwendung |
US4902598A (en) * | 1988-07-01 | 1990-02-20 | Xerox Corporation | Process for the preparation of silica containing charge enhancing additives |
JPH02120221A (ja) * | 1988-10-31 | 1990-05-08 | Nippon Steel Chem Co Ltd | シリカ粒子の製造方法 |
EP0369091A1 (en) * | 1988-11-15 | 1990-05-23 | Battelle Memorial Institute | Method for manufacturing amorphous silica objects |
JPH0655828B2 (ja) * | 1988-12-15 | 1994-07-27 | 信越化学工業株式会社 | 表面変性ポリメチルシルセスキオキサン球状微粒子及びその製造方法 |
JPH02188421A (ja) * | 1989-01-13 | 1990-07-24 | Shin Etsu Chem Co Ltd | 非晶質シリカ球状微粒子およびその製造方法 |
US5043062A (en) * | 1989-02-21 | 1991-08-27 | Eastman Kodak Company | High performance affinity chromatography column comprising non-porous, nondisperse polymeric packing material |
KR950001660B1 (ko) * | 1989-04-07 | 1995-02-28 | 니혼 쇼꾸바이 가가꾸 고오교 가부시기가이샤 | 무기산화물 입자의 제조법 |
JPH02296711A (ja) * | 1989-05-12 | 1990-12-07 | Shin Etsu Chem Co Ltd | 球状シリカ微粒子およびその製造方法 |
GB8917456D0 (en) * | 1989-07-31 | 1989-09-13 | British Telecomm | Reflective modulators |
US4983369A (en) * | 1989-11-22 | 1991-01-08 | Allied-Signal Inc. | Process for forming highly uniform silica spheres |
US5409687A (en) * | 1990-02-22 | 1995-04-25 | Vereinigte Aluminum-Werke Aktiengesellschaft | Gallosilicate catalysts and method of making same |
JPH07108989B2 (ja) * | 1990-08-02 | 1995-11-22 | 株式会社コロイドリサーチ | 電気レオロジー流体 |
DE69130322D1 (de) * | 1990-08-16 | 1998-11-12 | Catalysts & Chem Ind Co | Feines, plättchenförmiges pulver, herstellungsverfahren, und kosmetisches produkt |
WO1992003378A1 (en) * | 1990-08-23 | 1992-03-05 | United States Department Of Energy | A METHOD FOR PRODUCING METAL OXIDE AEROGELS HAVING DENSITIES LESS THAN 0.02 g/cm?3¿ |
DE69131902T2 (de) * | 1990-10-02 | 2000-08-17 | Catalysts & Chem Ind Co | Flüssigkristall-anzeigevorrichtung |
JP2624027B2 (ja) * | 1991-05-14 | 1997-06-25 | 富士ゼロックス株式会社 | 表面処理無機微粉末を用いた電子写真現像剤 |
NO912006D0 (no) * | 1991-05-24 | 1991-05-24 | Sinvent As | Fremgangsmaate for fremstilling av et silika-aerogel-lignende materiale. |
US5196267A (en) * | 1991-06-21 | 1993-03-23 | Allied-Signal Inc. | Process for coating silica spheres |
JP3051945B2 (ja) * | 1991-07-22 | 2000-06-12 | 大阪瓦斯株式会社 | 無機質均一微小球体、及びその製造方法 |
IT1251937B (it) * | 1991-10-17 | 1995-05-27 | Donegani Guido Ist | Xerogels di silice ad alta porosita` e processo per la loro preparazione. |
DE4137764A1 (de) * | 1991-11-16 | 1993-05-19 | Merck Patent Gmbh | Eisenoxidpigmente |
WO1993016125A1 (en) * | 1992-02-18 | 1993-08-19 | Matsushita Electric Works, Ltd. | Process for producing hydrophobic aerogel |
DE4218306C2 (de) * | 1992-06-03 | 1995-06-22 | Bayer Ag | Verfahren zur kontinuierlichen Herstellung großpartikulärer Kieselsole |
DE69227448T2 (de) * | 1992-06-19 | 1999-07-01 | Uetikon Chemie Ag | Verfahren zur Herstellung von Pulvern und Suspensionen von amorphen Siliziumdioxidmikrokugeln |
US5399535A (en) * | 1993-08-17 | 1995-03-21 | Rohm And Haas Company | Reticulated ceramic products |
US5425930A (en) * | 1993-09-17 | 1995-06-20 | Alliedsignal Inc. | Process for forming large silica spheres by low temperature nucleation |
JP2725573B2 (ja) * | 1993-11-12 | 1998-03-11 | 松下電工株式会社 | 疎水性エアロゲルの製法 |
DE4422118A1 (de) | 1994-06-24 | 1996-01-04 | Merck Patent Gmbh | Präparationen von monodispersen kugelförmigen Oxidpartikeln |
JP2580537B2 (ja) * | 1994-06-27 | 1997-02-12 | 工業技術院長 | シリカ球状粒子からなる三次元網状構造体 |
DE4439143A1 (de) * | 1994-11-03 | 1996-05-09 | Philips Patentverwaltung | Drehanoden-Röntgenröhre mit einem Gleitlager |
DE19530031A1 (de) * | 1995-08-16 | 1997-02-20 | Merck Patent Gmbh | Poröse monodisperse SiO¶2¶-Partikel |
ES2202511T3 (es) * | 1996-04-22 | 2004-04-01 | Merck Patent Gmbh | Particulas de sio2 recubiertas. |
DE19617931C5 (de) * | 1996-04-26 | 2010-07-22 | Ivoclar Vivadent Ag | Verwendung eines gefüllten und polymerisierbaren Materials als Dentalmaterial |
DE19638591A1 (de) * | 1996-09-20 | 1998-04-02 | Merck Patent Gmbh | Kugelförmige magnetische Partikel |
DE19643781C2 (de) * | 1996-10-29 | 2000-01-27 | Fraunhofer Ges Forschung | Sphärische Partikel auf der Basis von Metalloxiden, Verfahren zu deren Herstellung und deren Verwendung |
US6071486A (en) * | 1997-04-09 | 2000-06-06 | Cabot Corporation | Process for producing metal oxide and organo-metal oxide compositions |
US6172120B1 (en) | 1997-04-09 | 2001-01-09 | Cabot Corporation | Process for producing low density gel compositions |
US6315971B1 (en) | 1997-04-09 | 2001-11-13 | Cabot Corporation | Process for producing low density gel compositions |
AU7147798A (en) | 1997-04-23 | 1998-11-13 | Advanced Chemical Systems International, Inc. | Planarization compositions for cmp of interlayer dielectrics |
US7384680B2 (en) * | 1997-07-21 | 2008-06-10 | Nanogram Corporation | Nanoparticle-based power coatings and corresponding structures |
US6726990B1 (en) * | 1998-05-27 | 2004-04-27 | Nanogram Corporation | Silicon oxide particles |
US6290735B1 (en) | 1997-10-31 | 2001-09-18 | Nanogram Corporation | Abrasive particles for surface polishing |
DE19734547B4 (de) | 1997-08-01 | 2004-08-19 | Lancaster Group Gmbh | Kosmetische Zusammensetzungen mit agglomerierten Substraten |
DE19828231C2 (de) * | 1997-08-16 | 2000-09-07 | Merck Patent Gmbh | Verfahren zur Abscheidung poröser optischer Schichten |
FR2770153B1 (fr) * | 1997-10-29 | 1999-11-19 | Commissariat Energie Atomique | Gels hybrides inorganiques-organiques pour l'extraction d'especes chimiques telles que les lanthanides et les actinides, et leur preparation |
DE19751542A1 (de) * | 1997-11-20 | 1999-07-29 | Siemens Ag | Kunststoffmassen zur Umhüllung eines Metall- oder Halbleiterkörpers |
DE19756887A1 (de) * | 1997-12-19 | 1999-07-01 | Siemens Ag | Kunststoffverbundkörper |
US6360562B1 (en) * | 1998-02-24 | 2002-03-26 | Superior Micropowders Llc | Methods for producing glass powders |
GB9815271D0 (en) | 1998-07-14 | 1998-09-09 | Cambridge Display Tech Ltd | Particles and devices comprising particles |
DE19832965A1 (de) | 1998-07-22 | 2000-02-03 | Fraunhofer Ges Forschung | Sphärische Ionomerpartikel und deren Herstellung |
JP4366735B2 (ja) * | 1998-11-05 | 2009-11-18 | Jsr株式会社 | 重合体粒子を含有する研磨剤 |
US6686035B2 (en) | 1999-02-05 | 2004-02-03 | Waters Investments Limited | Porous inorganic/organic hybrid particles for chromatographic separations and process for their preparation |
DE10046152A1 (de) | 2000-09-15 | 2002-03-28 | Merck Patent Gmbh | Pigmentpräparation in Granulatform |
EP1119068B1 (en) | 1999-06-30 | 2012-11-28 | JGC Catalysts and Chemicals Ltd. | Photoelectric cell |
DE19947175A1 (de) | 1999-10-01 | 2001-04-05 | Merck Patent Gmbh | Pigmentpräparation |
AU2001234893A1 (en) * | 2000-02-08 | 2001-08-20 | The Regents Of The University Of Michigan | Protein mapping |
DE10024466A1 (de) | 2000-05-18 | 2001-11-22 | Merck Patent Gmbh | Pigmente mit Opalstruktur |
JP2004504242A (ja) | 2000-06-15 | 2004-02-12 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | 球型結晶の製造方法 |
JP2002019268A (ja) * | 2000-07-03 | 2002-01-23 | Nippon Aerosil Co Ltd | インクジェット記録媒体のインク吸収層形成用超微粒セラミック粉末凝集体分散水 |
DE10051725A1 (de) * | 2000-10-18 | 2002-05-02 | Merck Patent Gmbh | Wäßrige Beschichtungslösung für abriebfeste SiO2-Antireflexschichten |
WO2002044301A2 (en) | 2000-11-30 | 2002-06-06 | Merck Patent Gmbh | Particles with opalescent effect |
US6528167B2 (en) * | 2001-01-31 | 2003-03-04 | Waters Investments Limited | Porous hybrid particles with organic groups removed from the surface |
JP2002312659A (ja) * | 2001-04-13 | 2002-10-25 | Inter Communications:Kk | シリアルナンバー利用のポイントサーバーシステム |
DE10120856A1 (de) | 2001-04-27 | 2002-10-31 | Merck Patent Gmbh | Pigmentpräparation |
US20090056541A1 (en) * | 2001-08-01 | 2009-03-05 | Davison Dale A | Method and apparatus for high resolution flash chromatography |
JP4216716B2 (ja) * | 2001-08-09 | 2009-01-28 | ウォーターズ・インヴェストメンツ・リミテッド | クロマトグラフィー分離用多孔質有機・無機ハイブリッドモノリス状物質、およびその製造方法 |
EP1464769A1 (de) * | 2001-08-11 | 2004-10-06 | Flabeg Solarglas GmbH & Co. KG | Verwendung eines Sicherheitsglases in einem Fensterelement eines Gewächshauses und Fensterelement mit einem derartigen Sicherheitsglas |
EP1425322B1 (de) * | 2001-09-14 | 2009-10-21 | MERCK PATENT GmbH | Formkörper aus kern-mantel-partikeln |
DE10146687C1 (de) | 2001-09-21 | 2003-06-26 | Flabeg Solarglas Gmbh & Co Kg | Glas mit einer porösen Antireflex-Oberflächenbeschichtung sowie Verfahren zur Herstellung des Glases und Verwendung eines derartigen Glases |
DE10204339A1 (de) * | 2002-02-01 | 2003-08-07 | Merck Patent Gmbh | Dehnungs- und Stauchungssensor |
DE10204338A1 (de) * | 2002-02-01 | 2003-08-14 | Merck Patent Gmbh | Formkörper aus Kern-Mantel-Partikeln |
DE10227071A1 (de) * | 2002-06-17 | 2003-12-24 | Merck Patent Gmbh | Verbundmaterial enthaltend Kern-Mantel-Partikel |
AUPS334902A0 (en) * | 2002-07-03 | 2002-07-25 | Monash University | Purification method |
EP1541115B1 (en) * | 2002-07-11 | 2011-06-01 | JGC Catalysts and Chemicals Ltd. | Cosmetic |
DE10245848A1 (de) * | 2002-09-30 | 2004-04-01 | Merck Patent Gmbh | Verfahren zur Herstellung inverser opalartiger Strukturen |
DE10393599T5 (de) * | 2002-10-30 | 2005-10-27 | Waters Investments Ltd., New Castle | Poröse anorganische/organische Homogene copolymerische Hybridmaterialien für chromatographische Auftrennungen und Verfahren für deren Herstellung |
DE10251534A1 (de) * | 2002-11-04 | 2004-05-19 | Merck Patent Gmbh | Mikrostrukturierte Effektpigmente |
EP1585574A4 (en) * | 2002-12-20 | 2006-04-26 | Cardiac Inv S Unltd Inc | DEVICE AND METHOD FOR IMPLANTING LEFT-VATRICULAR PIPE MACHINE IN KORONARSINUS |
DE10330204A1 (de) * | 2003-07-03 | 2005-02-03 | Universität Tübingen | Verfahren zum Aufbringen von Substanzen auf unporöse Kieselgel-Nanopartikel |
DE102004032799A1 (de) * | 2003-07-21 | 2005-02-17 | Merck Patent Gmbh | Effektpigmente mit einheitlicher Form und Grösse |
EP1526115A1 (de) * | 2003-10-23 | 2005-04-27 | Universität Hannover | Funktionalisierte Kieselsäure-Partikel |
JP4966667B2 (ja) | 2003-12-04 | 2012-07-04 | ディーエスエム アイピー アセッツ ビー.ブイ. | Uvフィルター活性を有するマイクロカプセル、およびそれを製造する方法 |
US7122078B2 (en) * | 2003-12-22 | 2006-10-17 | E. I. Du Pont De Nemours And Company | Ink jet ink composition |
US7111935B2 (en) * | 2004-01-21 | 2006-09-26 | Silverbrook Research Pty Ltd | Digital photofinishing system media cartridge |
US20070215547A1 (en) * | 2004-02-17 | 2007-09-20 | Waters Investments Limited | Porous Hybrid Monolith Materials With Organic Groups Removed From the Surface |
DE102004017124B4 (de) * | 2004-04-07 | 2008-07-10 | Ivoclar Vivadent Ag | Härtbare Dentalmaterialien mit einer einstellbaren Transluzenz und hohen Opaleszenz |
DE102004019575A1 (de) * | 2004-04-20 | 2005-11-24 | Innovent E.V. Technologieentwicklung | Verfahren zur Herstellung von transmissionsverbessernden und/oder reflexionsmindernden optischen Schichten |
US20050261390A1 (en) * | 2004-05-13 | 2005-11-24 | Jean-Marc Frances | Stable cationically crosslinkable/polymerizable dental composition with a high filler content |
DE102004032120A1 (de) * | 2004-07-01 | 2006-02-09 | Merck Patent Gmbh | Beugungsfarbmittel für die Kosmetik |
DE112005001838B4 (de) * | 2004-07-30 | 2018-11-29 | Waters Technologies Corp. (N.D.Ges.D. Staates Delaware) | Poröse anorganische/organische Hybridmaterialien mit geordneten Domänen für chromatographische Auftrennungen, Verfahren für deren Herstellung sowie Auftrennvorrichtung und chromatographische Säule |
US10773186B2 (en) | 2004-07-30 | 2020-09-15 | Waters Technologies Corporation | Porous inorganic/organic hybrid materials with ordered domains for chromatographic separations and processes for their preparation |
WO2006045567A2 (de) | 2004-10-25 | 2006-05-04 | Merck Patent Gmbh | Verwendung von Formkörpern aus Kern-Mantel-Partikeln |
ZA200707903B (en) * | 2005-03-16 | 2008-12-31 | Unilever Plc | Colourant compositions and their use |
US20060288906A1 (en) * | 2005-04-27 | 2006-12-28 | Martin Wulf | Process of preparation of specific color effect pigments |
DE102005041243A1 (de) * | 2005-08-31 | 2007-03-01 | Merck Patent Gmbh | Verfahren zur Herstellung einer strukturierten Sol-Gel-Schicht |
DE102005041242A1 (de) * | 2005-08-31 | 2007-03-01 | Merck Patent Gmbh | Verfahren zur Strukturierung von Oberflächen von Substraten |
DE102005053618A1 (de) * | 2005-11-10 | 2007-05-16 | Merck Patent Gmbh | Nanoskalige Partikel als Kontrastmittel für die Kernspintomographie |
WO2007070673A1 (en) * | 2005-12-15 | 2007-06-21 | Cabot Corporation | Transparent polymer composites |
UA88413C2 (ru) * | 2005-12-16 | 2009-10-12 | Акзо Нобель Н.В. | Органомодифицированный материал на основе кремнезема, способ его изготовления, использования, разделительный материал стационарной фазы, способ его изготовления, использования и разделительная колонка для хроматографии |
US9308520B2 (en) * | 2005-12-16 | 2016-04-12 | Akzo Nobel N.V. | Silica based material |
WO2007095158A2 (en) * | 2006-02-13 | 2007-08-23 | Advanced Materials Technology, Inc. | Process for preparing substrates with porous surface |
WO2007142316A1 (ja) * | 2006-06-08 | 2007-12-13 | The University Of Tokushima | 新規なナノシリカ粒子の製造方法と用途 |
US7470974B2 (en) * | 2006-07-14 | 2008-12-30 | Cabot Corporation | Substantially transparent material for use with light-emitting device |
DE102006046952A1 (de) | 2006-10-04 | 2008-04-10 | Ley, Fritz, Dr. | Dentale, insbesondere remineralisierende und gegen schmerzempfindliche Zähne wirksame Zusammensetzung sowie dentale Partikel, insbesondere für die Zusammensetzung |
JP5137521B2 (ja) * | 2006-10-12 | 2013-02-06 | 日揮触媒化成株式会社 | 金平糖状シリカ系ゾルおよびその製造方法 |
US8697765B2 (en) | 2007-01-12 | 2014-04-15 | Waters Technologies Corporation | Porous carbon-heteroatom-silicon hybrid inorganic/organic materials for chromatographic separations and process for the preparation thereof |
US8580935B2 (en) * | 2007-02-26 | 2013-11-12 | Alltech Associates, Inc. | Ultra-fast chromatography |
CA2690537A1 (en) * | 2007-06-04 | 2008-12-11 | Alltech Associates, Inc. | Silica particles and methods of making and using the same |
DE102007053839B4 (de) | 2007-11-12 | 2009-09-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Verwendung eines beschichteten, transparenten Substrats zur Beeinflussung der menschlichen Psyche |
WO2009072657A1 (ja) * | 2007-12-06 | 2009-06-11 | The University Of Tokushima | ナノ機能性シリカ粒子およびその製造方法 |
WO2009085424A1 (en) * | 2007-12-19 | 2009-07-09 | 3M Innovative Properties Company | Precisely-shaped porous particles |
JP5188175B2 (ja) * | 2007-12-28 | 2013-04-24 | 日揮触媒化成株式会社 | シリカゾルおよびその製造方法 |
KR101259015B1 (ko) * | 2008-02-29 | 2013-04-29 | 삼성전자주식회사 | 재생 방법 및 장치 |
DE102008020440A1 (de) | 2008-04-23 | 2009-10-29 | Merck Patent Gmbh | Reaktiv oberflächenmodifizierte Partikel |
US8178784B1 (en) | 2008-07-20 | 2012-05-15 | Charles Wesley Blackledge | Small pins and microscopic applications thereof |
US9284456B2 (en) | 2008-08-29 | 2016-03-15 | Agilent Technologies, Inc. | Superficially porous metal oxide particles, methods for making them, and separation devices using them |
US8357628B2 (en) | 2008-08-29 | 2013-01-22 | Agilent Technologies, Inc. | Inorganic/organic hybrid totally porous metal oxide particles, methods for making them and separation devices using them |
US8685283B2 (en) | 2008-08-29 | 2014-04-01 | Agilent Technologies, Inc. | Superficially porous metal oxide particles, methods for making them, and separation devices using them |
DE102008045308A1 (de) | 2008-09-02 | 2010-03-04 | Merck Patent Gmbh | Dispersionen |
US11439977B2 (en) | 2009-06-01 | 2022-09-13 | Waters Technologies Corporation | Hybrid material for chromatographic separations comprising a superficially porous core and a surrounding material |
EP2437882A4 (en) | 2009-06-01 | 2016-11-23 | Waters Technologies Corp | HYBRID MATERIAL FOR CHROMATOGRAPHY SEPARATIONS |
DE102010010792A1 (de) | 2010-03-09 | 2011-09-15 | Pss Polymer Standards Service Gmbh | Wahlweise hydrophil oder hydrophob schaltbare Schicht, damit beschichtetes Substrat, Verfahren zur Herstellung sowie Verwendung |
EP2598441B1 (en) | 2010-07-26 | 2021-01-06 | Waters Technologies Corporation | Superficially porous materials comprising a substantially nonporous core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations |
JP5875261B2 (ja) * | 2011-06-28 | 2016-03-02 | 住友ゴム工業株式会社 | 表面が有機修飾された球状シリカ及びその製造方法 |
DE102012009226A1 (de) | 2012-05-07 | 2013-11-07 | Frank Slembeck | Gravitationsgenerator sowie Verfahren zur Energiegewinnung |
CN105358247B (zh) * | 2013-07-02 | 2019-06-18 | 安捷伦科技有限公司 | 具有精确控制的颗粒密度的表面多孔颗粒及其准备和使用方法 |
JP6284443B2 (ja) * | 2014-06-25 | 2018-02-28 | 扶桑化学工業株式会社 | コアシェル型シリカ粒子を含有するコロイダルシリカの製造方法 |
US10471411B2 (en) | 2014-07-03 | 2019-11-12 | Advanced Materials Technology | Porous media compositions and methods for producing the same |
WO2016066249A1 (en) | 2014-10-28 | 2016-05-06 | Merck Patent Gmbh | Preparation of nanoparticles-releasing enteric microparticles |
JP5993079B2 (ja) * | 2015-12-15 | 2016-09-14 | 住友ゴム工業株式会社 | 表面が有機修飾された球状シリカ及びその製造方法 |
US20190015815A1 (en) | 2016-03-06 | 2019-01-17 | Waters Technologies Corporation | Superficially porous materials comprising a coated core having narrow particle size distribution; process for the preparation thereof; and use thereof for chromatographic separations |
US10434496B2 (en) | 2016-03-29 | 2019-10-08 | Agilent Technologies, Inc. | Superficially porous particles with dual pore structure and methods for making the same |
WO2018186468A1 (ja) | 2017-04-06 | 2018-10-11 | 株式会社日本触媒 | シリカ粒子 |
GB201715949D0 (en) | 2017-10-02 | 2017-11-15 | Glaxosmithkline Consumer Healthcare (Uk) Ip Ltd | Novel composition |
WO2019140198A1 (en) | 2018-01-12 | 2019-07-18 | Restek Corporation | Superficially porous particles and methods for forming superficially porous particles |
KR102030601B1 (ko) | 2019-01-04 | 2019-10-10 | 민남기 | 광결정 구조체가 분산된 마이크로 패턴을 포함하는 색약 보정 콘택트 렌즈 |
JP2023518287A (ja) | 2020-03-20 | 2023-04-28 | レステック・コーポレーション | スパイク粒子、表面多孔質スパイク粒子、クロマトグラフィー分離装置、およびスパイク粒子を形成するための方法 |
EP3816123A1 (de) | 2020-03-24 | 2021-05-05 | FRAUNHOFER-GESELLSCHAFT zur Förderung der angewandten Forschung e.V. | Gasochromes glas, verfahren zur herstellung desselben und vorrichtung zur detektion eines zielgases |
EP3909612A1 (en) | 2020-05-12 | 2021-11-17 | Life Science Inkubator Betriebs GmbH & Co. KG | Composition of nanoparticles |
US11964874B2 (en) | 2020-06-09 | 2024-04-23 | Agilent Technologies, Inc. | Etched non-porous particles and method of producing thereof |
EP4291153A1 (en) | 2021-02-11 | 2023-12-20 | Evonik Operations GmbH | Amorphous non-porous silicas |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3453077A (en) * | 1965-05-04 | 1969-07-01 | Grace W R & Co | Process for preparing microspheroidal silica |
GB1211702A (en) * | 1966-12-08 | 1970-11-11 | Unilever Ltd | Fine particles |
US3634588A (en) * | 1970-05-28 | 1972-01-11 | Toledo Engineering Co Inc | Electric glass furnace |
AU505536B2 (en) * | 1975-03-12 | 1979-11-22 | J.M. Huber Corp. | Methods for production and use of siliceous products |
US4422880A (en) * | 1975-03-12 | 1983-12-27 | J. M. Huber Corporation | Precipitated siliceous products |
CS179184B1 (en) * | 1975-07-25 | 1977-10-31 | Stanislav Vozka | Method for preparation of precisely spherical particles of silica gel with controlled size and controled size pores. |
FR2328508A1 (fr) * | 1975-10-22 | 1977-05-20 | Atomic Energy Authority Uk | Gels poreux, leur procede d'obtention et applications |
JPS52138091A (en) * | 1976-05-14 | 1977-11-17 | Riken Piston Ring Ind Co Ltd | Treating process for hydrogen sulfide |
US4202813A (en) * | 1977-05-16 | 1980-05-13 | J. M. Huber Corporation | Rubber containing precipitated siliceous products |
US4190457A (en) * | 1978-06-09 | 1980-02-26 | Phillips Petroleum Co. | Preparation of inorganic xerogels |
SE422045C (sv) * | 1979-04-30 | 1985-03-18 | Guy Von Dardel | Sett att framstella silikaaerogel i form av ett vesentligen sprickfritt, foretredesvis transparent block samt anvendning av detsamma i solpaneler |
JPS58110414A (ja) * | 1981-12-23 | 1983-07-01 | Tokuyama Soda Co Ltd | 無機酸化物及びその製造方法 |
JPS61141604A (ja) * | 1984-12-13 | 1986-06-28 | Tokuyama Soda Co Ltd | 球状無機酸化物の製造方法 |
JPS6252119A (ja) * | 1985-08-29 | 1987-03-06 | Tokuyama Soda Co Ltd | シリカ粒子の製造方法 |
JPH0746948B2 (ja) * | 1989-02-08 | 1995-05-24 | 三菱農機株式会社 | 歩行型移動農機 |
JPH1026523A (ja) * | 1996-07-10 | 1998-01-27 | Toshiba Mach Co Ltd | 直径測定方法、直径加工・測定方法および装置、被加工物の心出し装置 |
-
1986
- 1986-05-14 DE DE19863616133 patent/DE3616133A1/de not_active Withdrawn
- 1986-09-09 AU AU62469/86A patent/AU588363B2/en not_active Ceased
- 1986-09-13 DE DE8686112677T patent/DE3684071D1/de not_active Expired - Fee Related
- 1986-09-13 EP EP86112677A patent/EP0216278B1/de not_active Expired - Lifetime
- 1986-09-23 CN CN86106689A patent/CN1008081B/zh not_active Expired
- 1986-09-24 CA CA000518938A patent/CA1280399C/en not_active Expired - Fee Related
- 1986-09-25 US US06/911,534 patent/US4775520A/en not_active Expired - Lifetime
- 1986-09-25 JP JP61225082A patent/JPH0825739B2/ja not_active Expired - Fee Related
-
1988
- 1988-07-12 US US07/218,000 patent/US4911903A/en not_active Expired - Lifetime
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1051747C (zh) * | 1994-06-01 | 2000-04-26 | 瓦克化学有限公司 | 二氧化硅的甲硅烷基化方法以及由此制得的产品及其应用 |
CN1051054C (zh) * | 1997-12-30 | 2000-04-05 | 中国科学院感光化学研究所 | 从碱金属的硅酸盐制备纳米二氧化硅颗粒的方法 |
CN1930082B (zh) * | 2004-03-08 | 2010-09-29 | 默克专利有限公司 | 制造单分散SiO2颗粒的方法 |
CN1305764C (zh) * | 2004-03-31 | 2007-03-21 | 张永 | 一种硅粉的制作方法 |
TWI405843B (zh) * | 2006-11-30 | 2013-08-21 | Jgc Catalysts & Chemicals Ltd | 金平糖狀無機氧化物溶膠,其製造方法及含該溶膠之研磨劑 |
CN102099014A (zh) * | 2008-07-15 | 2011-06-15 | 默克专利股份有限公司 | 二氧化硅纳米颗粒及其用于疫苗接种的用途 |
CN105126115A (zh) * | 2008-07-15 | 2015-12-09 | 默克专利股份有限公司 | 二氧化硅纳米颗粒及其用于疫苗接种的用途 |
CN102099014B (zh) * | 2008-07-15 | 2015-08-26 | 默克专利股份有限公司 | 二氧化硅纳米颗粒及其用于制备疫苗的用途 |
CN105126115B (zh) * | 2008-07-15 | 2020-11-27 | 默克专利股份有限公司 | 二氧化硅纳米颗粒及其用于疫苗接种的用途 |
CN102295290A (zh) * | 2010-06-23 | 2011-12-28 | 富士施乐株式会社 | 二氧化硅颗粒的制造方法 |
US9416015B2 (en) | 2010-06-23 | 2016-08-16 | Fuji Xerox Co., Ltd. | Method of producing silica particles |
CN102295290B (zh) * | 2010-06-23 | 2014-11-05 | 富士施乐株式会社 | 二氧化硅颗粒的制造方法 |
US9187502B2 (en) | 2010-06-24 | 2015-11-17 | Fuji Xerox Co., Ltd. | Silica particles and method for producing the same |
CN102295292B (zh) * | 2010-06-25 | 2016-01-20 | 富士施乐株式会社 | 二氧化硅颗粒及其制造方法 |
US8871344B2 (en) | 2010-06-25 | 2014-10-28 | Fuji Xerox Co., Ltd. | Hydrophobization treatment of silica particles |
CN102295292A (zh) * | 2010-06-25 | 2011-12-28 | 富士施乐株式会社 | 二氧化硅颗粒及其制造方法 |
CN103080008A (zh) * | 2010-11-05 | 2013-05-01 | 松下电器产业株式会社 | 二氧化硅多孔体及使用其的光学麦克风 |
US9028788B2 (en) | 2010-11-05 | 2015-05-12 | Panasonic Intellectual Property Management Co., Ltd. | Porous silica material and optical microphone using the same |
US9394413B2 (en) | 2011-01-19 | 2016-07-19 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
US8962139B2 (en) | 2011-01-20 | 2015-02-24 | Fuji Xerox Co., Ltd. | Resin particle and method for producing the same |
CN103328382A (zh) * | 2011-01-21 | 2013-09-25 | Dic株式会社 | 多孔质二氧化硅颗粒的制造方法、防反射膜用树脂组合物、具有防反射膜的物品以及防反射薄膜 |
CN102862991A (zh) * | 2011-07-06 | 2013-01-09 | 富士施乐株式会社 | 二氧化硅颗粒、二氧化硅颗粒的制造方法和树脂颗粒 |
CN102862991B (zh) * | 2011-07-06 | 2015-10-28 | 富士施乐株式会社 | 二氧化硅颗粒、二氧化硅颗粒的制造方法和树脂颗粒 |
US9708191B2 (en) | 2011-12-01 | 2017-07-18 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
CN102527354A (zh) * | 2012-02-07 | 2012-07-04 | 月旭材料科技(上海)有限公司 | 核壳型颗粒及制备方法 |
CN102527354B (zh) * | 2012-02-07 | 2013-12-18 | 月旭材料科技(上海)有限公司 | 核壳型颗粒及制备方法 |
WO2014005272A1 (zh) * | 2012-07-03 | 2014-01-09 | 蚌埠鑫源石英材料有限公司 | 一种二氧化硅粉体材料及其制备方法 |
US9243145B2 (en) | 2013-01-28 | 2016-01-26 | Fuji Xerox Co., Ltd. | Silica composite particles and method of preparing the same |
CN103318899A (zh) * | 2013-06-24 | 2013-09-25 | 哈尔滨工业大学 | 一种单分散二氧化硅微球粒径的控制方法 |
CN105800625A (zh) * | 2016-02-19 | 2016-07-27 | 江苏和成新材料有限公司 | 一种可控吸水二氧化硅微球的制备方法 |
CN105800625B (zh) * | 2016-02-19 | 2017-09-12 | 江苏和成新材料有限公司 | 一种可控吸水二氧化硅微球的制备方法 |
CN106669589A (zh) * | 2016-12-20 | 2017-05-17 | 常州大学 | 一种基于巯基的高效吸附剂的制备方法及应用 |
CN106669589B (zh) * | 2016-12-20 | 2019-11-12 | 常州大学 | 一种基于巯基的高效吸附剂的制备方法及应用 |
CN114229853A (zh) * | 2021-11-29 | 2022-03-25 | 桂林理工大学 | 一种锌掺杂介孔二氧化硅纳米球的制备方法 |
CN114229853B (zh) * | 2021-11-29 | 2023-10-13 | 桂林理工大学 | 一种锌掺杂介孔二氧化硅纳米球的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA1280399C (en) | 1991-02-19 |
DE3616133A1 (de) | 1987-11-19 |
CN1008081B (zh) | 1990-05-23 |
EP0216278B1 (de) | 1992-03-04 |
US4775520A (en) | 1988-10-04 |
DE3684071D1 (de) | 1992-04-09 |
AU588363B2 (en) | 1989-09-14 |
EP0216278A2 (de) | 1987-04-01 |
JPH0825739B2 (ja) | 1996-03-13 |
US4911903A (en) | 1990-03-27 |
EP0216278A3 (en) | 1989-01-04 |
AU6246986A (en) | 1987-03-26 |
JPS6272514A (ja) | 1987-04-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN86106689A (zh) | 球形二氧化硅粒子 | |
CN86107584A (zh) | 用於色谱分离的磷酸钙型羟基磷灰石及其生产方法 | |
CA1338492C (en) | Reagent for cell separation | |
CN86107535A (zh) | 磷酸钙型羟(基)磷灰石及其制备方法 | |
JP4901719B2 (ja) | 単分散SiO2粒子の製造方法 | |
CN101246178B (zh) | 用于吸附、分离、检测超微量靶蛋白的系统及其用途 | |
CN1042132A (zh) | 新型可吸性沉淀二氧化硅和以此二氧化硅为基础的组合物 | |
CN104418990B (zh) | 一种有机无机杂化微球颗粒及其制备和应用 | |
CN104069839B (zh) | 一种有序介孔核壳结构硅胶色谱填料及其制备和应用 | |
CN101857675B (zh) | 一种高纯球形全孔硅胶粒子的制备方法 | |
US20100294977A1 (en) | Separation of biomolecules | |
CN1165292C (zh) | 包含一种被吸收在沉淀硅石基载体上的液体的组合物 | |
CN1075166A (zh) | 用酶制备光活性氰醇的方法 | |
CN106477585B (zh) | 一种功能化介孔硅基材料及其制备方法和应用 | |
CN1010746B (zh) | 羟基磷灰石颗粒集合物和制法及用途 | |
Sakai-Kato et al. | Integration of biomolecules into analytical systems by means of silica sol-gel technology | |
JPH1135315A (ja) | 高密度メソ多孔体の製造方法 | |
JP6805538B2 (ja) | シリカ粒子分散体及び表面処理シリカ粒子 | |
JPH02263707A (ja) | 金属酸化物系複合体球状微粒子及びその製法 | |
CN1034700A (zh) | 氧化铝细粒的制备方法以及由此制得的产品 | |
CN111330555A (zh) | 一种具有磁性的核壳式介孔硅胶材料及其制备方法和应用 | |
CN107096504B (zh) | 含有二羟基苯基的化合物修饰的硫化铜纳米材料及其在糖肽富集中的应用 | |
Unger et al. | Spherical SiO2 Particles | |
Li et al. | Synthesis and chromatographic properties of a chiral stationary phase derived from bovine serum albumin immobilized on magnesia‐zirconia using phosphonate spacers | |
CN110498830A (zh) | 一种用于蛋白分离纯化的磁珠的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C13 | Decision | ||
C14 | Grant of patent or utility model | ||
C17 | Cessation of patent right |