CN1042822C - 疏水白炭黑 - Google Patents
疏水白炭黑 Download PDFInfo
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- CN1042822C CN1042822C CN94193657A CN94193657A CN1042822C CN 1042822 C CN1042822 C CN 1042822C CN 94193657 A CN94193657 A CN 94193657A CN 94193657 A CN94193657 A CN 94193657A CN 1042822 C CN1042822 C CN 1042822C
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
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- OBMZMSLWNNWEJA-XNCRXQDQSA-N C1=CC=2C(C[C@@H]3NC(=O)[C@@H](NC(=O)[C@H](NC(=O)N(CC#CCN(CCCC[C@H](NC(=O)[C@@H](CC4=CC=CC=C4)NC3=O)C(=O)N)CC=C)NC(=O)[C@@H](N)C)CC3=CNC4=C3C=CC=C4)C)=CNC=2C=C1 Chemical compound C1=CC=2C(C[C@@H]3NC(=O)[C@@H](NC(=O)[C@H](NC(=O)N(CC#CCN(CCCC[C@H](NC(=O)[C@@H](CC4=CC=CC=C4)NC3=O)C(=O)N)CC=C)NC(=O)[C@@H](N)C)CC3=CNC4=C3C=CC=C4)C)=CNC=2C=C1 OBMZMSLWNNWEJA-XNCRXQDQSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101710176384 Peptide 1 Proteins 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
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- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Structural Engineering (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
可通过下列步骤得到的疏水白炭黑:使水玻璃溶液与酸在pH-值为7.5-11时反应,用水或稀释的无机碱水溶液洗涤基本除去生成的二氧化硅水凝胶中的离子组分,期间维持水凝胶的pH-值在7.5-11范围,用醇置换水凝胶中包含的水相并接着对得到的醇凝胶进行超临界干燥。
Description
本发明有关新的疏水白炭黑(Silica aerogel),它可通过下列步骤得到:使水玻璃溶液与酸在pH-值7.5-11反应、从生成的二氧化硅水凝胶(Silica hydrogel)通过用水或稀释的无机碱水溶液洗涤而基本除去离子组分,其间保持水凝胶的pH-值在7.5-11范围,用异丙醇置换水凝胶中包含的水相,并接着对得到的醇凝胶(alcogel)进行超临界干燥。
此外本发明有关这种白炭黑的制备和作为绝热材料、催化剂载体和橡胶添加剂的应用。
白炭黑由于只有很低的导热能力而极适用作绝热材料。例如已知的有通过用酸将二氧化硅从水玻璃中沉淀出来,从生成的水凝胶中洗出离子组分,用低沸点的水溶性有机液体,特别是醇,如甲醇置换水,将所得到的含醇的“醇凝胶”在超临界压力下加热到有机液体的临界温度以上,并在超临界温度下通过闪蒸蒸发除去有机液体。在必要情况下,可将水溶性的液体在超临界干燥前用非水溶性有机液体或也可用液体二氧化碳置换出来(US-A-2 093454,DE-A-34 29 671)。
在此干燥过程生成的大体积的和大孔的白炭黑可通过研磨转化成粉末状。根据DE-A-21 03 342有一种制造小颗粒白炭黑的特殊方法是将水玻璃和酸从混合喷嘴中喷出,由此得到滴状的小颗粒。
按已知方法生成的白炭黑还必须进行疏水处理,否则由于它很快吸水而使其绝缘性能急剧变坏。为此目的通常采用有机硅化合物、硅烷和氯硅烷,用这些物质对干燥的凝胶在气相中进行处理,或者它也可以存在于沉淀过程或存在于超临界干燥过程。然而这些疏水化剂是很昂贵的,在用氯硅烷时必须将生成的氯化氢除去和进行中和。
本发明的任务是提供可用简单而经济方法生产的疏水白炭黑。
为此,发现疏水白炭黑可通过使水玻璃溶液与酸在pH-值7.5-11下反应、从生成的二氧化硅水凝胶中用水或用稀释的无机碱水溶液洗涤而基本分离出离子组分,在此水凝胶的pH-值维持在7.5-11范围,用异丙醇置换水凝胶中包含的水相,并接着对得到的醇凝胶进行超临界干燥。
此外还发现了生产这些白炭黑的方法。
还已发现这种白炭黑可作为绝热材料、催化剂载体以及橡胶的添加剂使用。
用作白炭黑原料的水凝胶有利地从碱金属-水玻璃,特别是钠水玻璃来生产。其中一般是10-30,优选12-20%(重量)水玻璃溶液与稀酸均匀混合,特别是与无机酸,优选硫酸均匀混合,以使在混合产物中pH-值调节至7.5-11,优选8-11,特别优选8.5-10,更特别优选8.5-9.5。这里特别适当的是,如在DE-A-21 03 243中所说明的,采用混合喷嘴,溶胶由此喷嘴喷出,并在空气中飞行期间固化为水凝胶滴。
当然也可制造水凝胶的模制体,其中将水玻璃和酸一起混合加入一个适当的模子中,接着使之进行凝胶化。
另外如在DE-A-39 14 850中所说明的,水凝胶也可含有颜料,其中特别适用的是能发射、吸收或反射波长在3-10μm红外线的颜料。
优选的是将生成的凝胶用水洗至不含盐,其中水凝胶的pH-值几乎不变,并且几乎相当于在混合产物所调的值。但是,洗涤水也可采用无机碱如苛性钠或氨水,但要注意的是水凝胶在洗涤后的pH-值仍在上述的范围,即7.5-11,优选8.5-10,特别优选9-10。通常在洗涤水中不添加酸。
适当的方法是洗涤至排出的洗涤水的电导率平均为20-300μs/cm,优选50-150μs/cm为止。这相当于在水凝胶中碱金属-(钠)-含量通常为0.1-1.7,优选0.4-1.3%(重量),这是用在80℃水泵真空下干燥的样品测得的。
在水凝胶中含的水相通过异丙醇几乎完全被置换,也就是直至排出的有机相中含水量一般为<0.2,优选为<0.1%(体积)。有利的是这种液体交换在一连续流动设备中进行。也有可能在压力下进行交换,通常在室温中进行交换,但也可将水凝胶和异丙醇的混合物加热至50℃。
接着的超临界干燥可以普通方法进行,其中醇凝胶与过量的异丙醇一起于压力容器中在异丙醇的超临界条件下(例如在温度约为240-280℃和压力约为55-90巴)进行处理,也就是将压力容器在限制压力的同时加热到超临界温度。然后通过卸压,优选的是通过等温卸压,最好是通过慢慢打开压力阀逐步除去异丙醇。
本发明的白炭黑以其良好的性能为特征,特别是它除了有好的绝热性能外还仅显示出微小的吸水倾向。
它们可以按发明的方法简单地生产,在此可以无须采用价格昂贵的疏水化试剂。
因此它特别适用于绝热,它可单独作为绝热材料也可作为基体材料用于隔热的复合材料,并且也可用作例如催化剂的载体材料。
它既可以颗粒(通常粒度大小为1-8mm)也可在预研磨后以粉使用(粒度<1mm)。
特别是当其以粉末存在时,本发明白炭黑更有利于作为热解或高分散硅胶的代用品,后者以复杂的方式通过在氧氢焰中分解四氯硅烷制得。作为适当的应用领域是塑料,特别是天然和合成的橡胶(例如用于汽车轮胎)、粘合剂、染料、油漆、医药、化装品、造纸、纺织、矿物油和纤维工业以及玻璃制造、热解技术和铸造技术,在这些领域中作为分散剂、增强剂、流动性助剂、悬浮剂、填充剂、消泡剂和/或吸收剂表现出多种多样的作用。如果是在有水的条件下使用,则可对白炭黑进行热处理,然后成为亲水化而再使用,当然为此应用目的也可以适当材料形式获得。
A)疏水白炭黑的生产和检测实例1:
在DE-A-21 03 243中所说明的混合喷嘴中,于20℃和2.5巴下加入45.7升/小时13%(重量)水玻璃溶液(用水稀释含有27%(重量)SiO2和8%(重量)Na2O的工业水玻璃溶液来制备)和6升/小时23%(重量)的硫酸。在混合室中连续不断地中和水玻璃溶液,形成不稳定的水溶胶,其pH-值为8.1±0.1,在停留时间为0.1秒后通过直径为2mm的喷嘴喷出,当液体射流飞穿过空气时分散成单个的液滴,它们在到达水池前凝固成透明的机械稳定的水凝胶球。
水凝胶用去离子水洗至排出的洗涤液的电导率≤110μs/cm和pH-值为9.8±0.1为止。在80℃水泵真空干燥的水凝胶样品的钠含量为1.1%(重量)。
然后将在水溶胶中所含的水用异丙醇置换出来。为此将2000g的水凝胶放入5升的容器中,容器中充满异丙醇,在25℃用泵使异丙醇流过容器,直到流出的异丙醇的水含量<0.1%(体积),为此需要8立升异丙醇。
进行超临界干燥时,将得到的醇凝胶与10升异丙醇一起加到一个20立升的压力容器中,在5个小时内加热至270℃,期间压力限制在90巴。然后在60分钟内进行等温卸压。
将冷却的样品取出并经2小时在200毫巴80℃进行干燥。
所得到的白炭黑以颗粒度分布为1-8mm的粒子形式存在。将其一半用玻璃球研磨5小时转化成粉末。
在表1中归纳出粒子和粉末的特征参数。堆积密度ρ[kg/m3](依据ISO3944)、BET比表面积[m2/g]、热导率λ10[W/m.k](按DIN 52 616方法),在25℃相对湿度为95%的干燥器中放置30天测得的吸水率[%(重量)]。对比实例1:
用于比较,按DE-A-39 14 850的实例1制备白炭黑,水凝胶在pH-值为7.1±0.1形成。
这些白炭黑的特征参数同样列于表1
表1
Q[kg/m3] | 比表面积[m2/g] | λ10[W/m·K] | 吸水率[w.-%] | |
颗粒 | 110 | 365 | 0.023 | 1.6 |
粉末 | 110 | 380 | 0.028 | 1.4 |
比较 | 140 | 436 | 0.024 | 38.6 |
B)在天然橡胶中的应用实例2:
研磨实例1制备的白炭黑(平均颗粒大小60μm,粒度分布为1-400μm),然后在60℃双辊磨中添加入天然橡胶中。
混合物组成如下:
100重量份天然橡胶(皱纹烟胶,Weber+Schaer,Hamburg)
1.5重量份聚乙二醇(PluriolE 9000,BASF)
2 重量份PE-抗光腊(Antilux500,Rhein Chemie)
2 重量份酚类防老化剂(VulkanoxBKF,Bayer)
5 重量份氧化锌作为活化剂
1.5重量份硬脂酸作为活化剂
2.5重量份硫(5%Coated;StruktolSu 95,Schill+
Sailacher)
1.25重量份促进剂,巯基苯并噻唑(VulkacitDM/C,Bayer)
0.5重量份二苯基肽1促进剂(Vulkacit D)
30重量份白炭黑粉末
按DIN 53 529测定的混合物特征参数、反应时间(分钟),按DIN 53 504测定的处理后温度[℃]和撕裂强度[N/mm2]、按DIN 53 505测定的肖氏硬度A和按DIN 53 523测定的粘度[Mooney,Units,Mu]归纳在表2中。对比实例2:
类似于实例2,应用BET-表面积为200m2/g的普通热解的二氧化硅制备橡胶混合物。
此混合物的特征参数同样列于表2
表2
实例2 | 比较实例2 | |
反应时间 (分) | 17.4 | 42.8 |
加工温度 (℃) | 80 | >100 |
断裂强度 [N/mm2] | 20.3 | 15.0 |
肖氏硬度 A […] | 57.4 | 59.7 |
粘度 [MU] | 89.9 | 76.1 |
Claims (5)
1.生产疏水白炭黑的方法,包括使水玻璃溶液与酸在pH-值7.5-11时反应,用水或稀释的无机碱水溶液洗涤基本除去生成的二氧化硅水凝胶中的离子组分,期间保持水凝胶的pH-值在7.5-11范围,用异丙醇置换水凝胶中包含的水相,并且接着对得到的醇凝胶进行超临界干燥。
2.按权利要求1的方法生产的疏水白炭黑。
3.权利要求2的白炭黑作为绝热材料的应用。
4.权利要求2的白炭黑作为催化剂载体的应用。
5.权利要求2的白炭黑在橡胶中的应用。
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DE4329294 | 1993-08-31 | ||
DEP4329294.1 | 1993-08-31 |
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US (1) | US5738801A (zh) |
EP (1) | EP0716641B1 (zh) |
JP (1) | JP3712410B2 (zh) |
CN (1) | CN1042822C (zh) |
AU (1) | AU7655594A (zh) |
DE (1) | DE59405045D1 (zh) |
DK (1) | DK0716641T3 (zh) |
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- 1994-08-25 WO PCT/EP1994/002822 patent/WO1995006617A1/de active IP Right Grant
- 1994-08-25 AU AU76555/94A patent/AU7655594A/en not_active Abandoned
- 1994-08-25 CN CN94193657A patent/CN1042822C/zh not_active Expired - Lifetime
- 1994-08-25 EP EP94926888A patent/EP0716641B1/de not_active Expired - Lifetime
- 1994-08-25 US US08/600,929 patent/US5738801A/en not_active Expired - Lifetime
- 1994-08-25 JP JP50792795A patent/JP3712410B2/ja not_active Expired - Lifetime
- 1994-08-25 DK DK94926888.2T patent/DK0716641T3/da active
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NO960820L (no) | 1996-02-28 |
DE59405045D1 (de) | 1998-02-19 |
CN1132500A (zh) | 1996-10-02 |
AU7655594A (en) | 1995-03-22 |
EP0716641B1 (de) | 1998-01-14 |
EP0716641A1 (de) | 1996-06-19 |
JP3712410B2 (ja) | 2005-11-02 |
US5738801A (en) | 1998-04-14 |
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NO315599B1 (no) | 2003-09-29 |
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WO1995006617A1 (de) | 1995-03-09 |
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