CN100386370C - 新颖勃姆石颗粒及掺入这种颗粒的聚合物材料 - Google Patents
新颖勃姆石颗粒及掺入这种颗粒的聚合物材料 Download PDFInfo
- Publication number
- CN100386370C CN100386370C CNB038116642A CN03811664A CN100386370C CN 100386370 C CN100386370 C CN 100386370C CN B038116642 A CNB038116642 A CN B038116642A CN 03811664 A CN03811664 A CN 03811664A CN 100386370 C CN100386370 C CN 100386370C
- Authority
- CN
- China
- Prior art keywords
- polymer
- boehmite particles
- boehmite
- base material
- polymer base
- 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 - Fee Related
Links
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims abstract description 100
- 229910001593 boehmite Inorganic materials 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 title claims abstract description 66
- 239000002861 polymer material Substances 0.000 title abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004677 Nylon Substances 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 229920001778 nylon Polymers 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012438 extruded product Nutrition 0.000 claims 4
- 150000001408 amides Chemical class 0.000 claims 2
- 229920000178 Acrylic resin Polymers 0.000 claims 1
- 239000000523 sample Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000037396 body weight Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Abstract
揭示了一种改性聚合物材料，其包括聚合物基料和在聚合物基料内的勃姆石颗粒。所述勃姆石颗粒主要由各向异性形状的颗粒构成。
Description
发明背景
发明领域
本发明涉及勃姆石颗粒，具体涉及特别适用作热塑树脂填料的。
相关领域的叙述
由于勃姆石粒度细及其分散在聚合物中相对惰性使得它长期以来被认为是热塑树脂的合适填料。它能充分地提高模量和热性能，甚至在美国专利6,143,816提出用它作阻燃剂。
一些美国专利如USP5,360,680和5,401,703所述的较佳方式是认为较佳的细小薄片状，因为早期经研磨法产生的细粒状勃姆石粉会呈球形作为填料效果稍差。用其它方法制造细颗粒勃姆石会引起其它问题。例如热解会产生一系列勃姆石产品的污染物，且常规的水热处理会形成结实的菱形棱柱状颗粒团聚，很不容易分开。如美国专利5,194,243(建立在USPP2,763,620，2,915,475，3,385,663，4,117,105和4,344,928所述的早期研究基础上)提出的氢氧化铝精制水热法引入晶种概念，采用勃姆石晶种转化勃姆石前体。发现为了制得亚微米级各向基本等轴颗粒的勃姆石分散体，需要高含量的，至少15％勃姆石晶种方能有效。
所有一切努力制作的片状或各向等轴的勃姆石颗粒都不容易以各个颗粒分散在聚合物中，除非事先采用表面活性剂处理提高其分散性。所用的典型的表面活性剂包括氨基硅烷，它具有粘附在亲水性表面颗粒的勃姆石的能力，使这些颗粒表面与有机聚合物相容性更好而使颗粒分散其中。这样避免了没有这种处理往往会发生的结块。这种倾向随颗粒变小而增加，因为随着颗粒变小，它的表面能必然增加。
本发明提供了一种新颖的勃姆石，它能容易地以纳米级粒子分散在热塑性聚合物中而无需任何表面处理，与现有技术的勃姆石填料相比，它明显改进了它的混合性能。
发明概述
按照本发明一个方面，提供一种改性的聚合物材料，其包括聚合物基料和聚合物基料中的勃姆石颗粒，所述勃姆石颗粒主要含有长径比至少约3∶1各向异性形状的颗粒。
按照本发明另一个方面，提供一种改性的聚合物材料，其包括聚合物基料和不含表面活性剂，且被分散在聚合物基料中的长径比至少约3∶1。
按照本发明还有一个方面，提供勃姆石材料其主要含有长径比至少约3∶1的勃姆石颗粒。
按照本发明还有一个方面，提供制备一种产品的方法，其包括提供一种改性聚合物材料，该材料聚合物基料和主要含有各向异性形状的长径比至少约3∶1的颗粒的勃石颗粒，并将改性聚合物材料挤出成挤出产物，其中所述勃姆石颗粒分散于所述挤出产物中。
附图简要说明
图1A与图1B所示为现有技术很好分散的勃姆石颗粒(图1A)和本发明针形勃姆石(图1B)。
图2A，2B和2C所示为仅尼龙6和掺入两种不同含量勃姆石的尼龙的UV-可见光谱。
图3A，3B和3C是UV光谱为图2A，2B和2C的三种配方的富里叶变换IR光谱。
图4所示为同样三种配方的相应的N 1s光谱。
图5所示为含有6.62体积％勃姆石的尼龙6的高放大倍数透射电子显微照片。
图6A和图6B所示为仅尼龙6、含3.15体积％常用勃姆石的尼龙以及含3.15体积％本发明针形勃姆石的尼龙的不同物理性能条形图。
图7所示为含有1.86体积％勃姆石的热塑性聚氨酯(陶氏化学公司销售的Isoplast 301)的高放大倍数透射描电子显微照片
图8是条形图，显示氨基硅烷添加剂对提高含有分散于其中的5体积％针形勃姆石颗粒的环氧树脂的储能模量(Storage modulus)的作用。
详细说明
本发明提供勃姆石，它含有针形(或各向异性)晶体，其中最长尺寸至少为50nm，较佳为50-2000nm，更佳为100-1000nm，而与长度垂直的尺寸基本相同，且优选均小于50nm；且长径比定义为最长尺寸与垂直于长度的次最长尺寸之比率，这个比率至少为3∶1，且较佳至少为6∶1。在该描述中，为清楚起见，以下将这些颗粒称之为针形。
出乎意料的是，水热法条件加上低含量的晶种，及混合物酸性pH造成勃姆石优选沿某一晶轴生长，使得水热处理持续时间越长，制成的勃姆石针形颗粒越长。惊人的是这些针形勃姆石颗粒不需要表面处理就能各自均匀分散，也就是说通过常规的配混技术在聚合物内基本上均匀分布，实质上不形成团粒。这种均匀各自分散质量在下文中称之为纳米分散性。
按照本发明针形颗粒经BET法测量，其表面积至少为75m2/g，且优选为100-300m2/g。
本发明还包括通过掺入0.5-20体积％，优选为2-10体积％(以聚合物+勃姆石的总体积计)的本发明针形勃姆石颗粒而改性的聚合物。针形勃姆石颗粒可以分散于其中的聚合物的实例有：聚酰胺(包括例如尼龙6和尼龙12)，热塑性聚氨酯，聚亚烷基二醇，乙烯/乙烯醇聚合物，环氧树脂，丙烯酸酯类树脂等。更一般地说，聚合物优选热塑性聚合物，因为在常规聚合物配混技术中采用高强力混合机、挤出机等，这种聚合物具有很好的分散性。还应认识到采用填料改进聚合物的物理性能是热塑性聚合物中最常见的目的(objective)。本发明产品具有独特性质(可能是颗粒针形所致)使得挤出时勃姆石颗粒会排列一致，使得经这种针形颗料增强的聚合物大大提高了诸如弯曲强度等在挤出方向的物理性能。
可以相信，针形勃姆石颗粒这种独特分散性得自于它们能与聚合物链上极性基团形成氢键，这有利于形成单分散状态。针形勃姆石颗粒也能分散于那些添加如氨基硅烷一类常用分散剂的基本为非极性的其它聚合物之中。
因为诸如酚醛类与丙烯酸酯类热固性树脂也是适当的极性树脂，可以认为针形勃姆石颗粒可以各个颗粒完全分散于这类树脂之中，如果在例如组分形成聚合物的情况下在交联阶段明显进行之前或在空合树脂如酚醛树脂的B阶段完成掺合。
本发明针形勃姆石颗粒可以通过水热处理制备，在该处理中将勃姆石前体分散/悬浮在水中，在压热器中在100-300℃，较佳在150-250℃的温度，自发产生的压力1×105-8.5×106，较佳5×105-1.2×106牛/m2下加热1-24小时，较佳1-3小时。分散体中勃姆石前体固体含量为5-40％，较佳为10-30％。除勃姆石前体之外，分散体还含有2-15重量％，较佳5-10重量％(以前体重量计)的勃姆石颗粒。勃姆石颗粒起晶种作用，在晶种周围由前体转化而成的勃姆石可结晶。由于水热处理的条件与较低晶种含量，勃姆石晶体优先沿单一晶轴生长，并呈现保持各自分散的针形。
勃姆石前体可以是任何一种氢氧化铝，如三羟铝石或三水铝矿，但也可以是磨碎的铝土矿。也可以采用γ-氧化铝作原料。在采用不纯材料如铝土矿生产针形勃姆石颗粒情况下最好在将得到的勃姆石颗粒掺入到聚合物中之前先清洗掉诸如硅或氢氧化钛、以及至少某些在天然铝土矿中存在的常见残留杂质二氧化硅。
除了出乎意料地方便并完全纳米分散在具有极性基团的聚合物之外，勃姆石针形颗粒还可以经诸如氨基硅烷，如购自Aldrich化学公司的A-1100的表面活性剂进行合适表面处理之后也容易分散于其它聚合物中。
由于颗粒的纳米分散性，它们的尺寸很小，将这种颗粒填料掺入聚合物薄膜，则对薄膜的透光率影响很小或实际没有影响，甚至掺入量高达10体积％也是如此。这证实在某些场合下是很有价值的性质。这也意味着得到的薄壁注塑中容易带有颗粒团聚物所造成的表面薄弱或断裂的点的情况将被大大消除。
水热处理之后，分离任何尚未反应的原料与任何硬团聚物往往是有益的。这通常通过简单离心分离，或甚至简单地将胶溶的勃姆石颗粒的液相从沉淀或未反应的固相中倾析出去就可以做到。
针形勃姆石的制备
实施例1
压热器内装上250g从Alcoa公司购得的CV3002三水铝矿，25g从SASOL公司生产的商品名为Catapal B的假勃姆石的勃姆石，1000g去离子水和56g的18％硝酸。所述勃姆石在加入到三水铝矿和其余的水与酸之前，预先在100g水和7g硝酸中分散。
将压热器在45分钟内升温到180℃，在所述温度下保温二小时，并以530rpm速率搅拌。自发产生的压力达到并保持在150psi。然后从压热器内取出勃姆石分散体。在95℃时去除液体部分，将所得固体物料磨碎到小于100目。
得到的勃姆石呈图1B所示针形颗粒。该图连同图1A一起说明了由SASOL生产的C-200勃姆石所代表的现有技术的勃姆石。须指出C-200与工业上最常见的勃姆石粉一样，其颗粒主要呈等轴性(在三个互相垂直方向上等尺寸)，除一些明显的团聚物之外。针形晶体很少。相反本发明颗粒，基本上全部是单独的，而且是针形。直径约为10-20nm，长度约为100-200nm。
实施例2
本实施例说明本发明勃姆石与尼龙6的混合技术，并比较由此得到的两种不同勃姆石掺入量的产品与未改性聚合物的性质。
将颗粒状尼龙6在80℃下干燥过夜，然后与指定量的填料混合。然后将所述混合物通过Werner&Pfleiderer ZSK-30双螺杆排气式挤出机，挤出机机筒保持235-245℃，螺杆转速保持300rpm。将挤出物料冷却，造粒，并在80℃下干燥。
然后试样用温度为250-270℃的挤出料筒与保持70-90℃的模具由造粒材料注塑。
三个试样制成这样：一只试样无填料，一只试样含有3.15体积％本发明针形勃姆石，一只试样含有6.62体积％的同一勃姆石。图2A、2B、2C、3A、3B、3C和图4是这三个试样的UV-VIS光谱，FTIR光谱和XPS，N 1s谱。图2A与图2B和2C的比较说明纳米复合物在400-700nm波长范围基本上无吸收，所述波长范围相当于大部分可见/UV波长范围。图3A与图3B和3C比较表明勃姆石对透过试样薄膜的透光率的影响。目的是表明随着勃姆石含量的增加，在3060cm-1附近遇到的特征位移最小。已知与形成氢键有关，清楚地表明在尼龙与勃姆石之间的氢键键合至少是促进勃姆石在尼龙中纳米分散的一种机理。
图4表示相同现象，随着勃姆石含量的增加，在约400eV处发生N 1s结合能峰值的位移。
图5表示含6.62体积％的勃姆石颗粒的产品的剥离表面。图像是使用放大倍数为×51K的透射电子显微镜摄的。从所述图像可清晰地看到单独针形勃姆石颗粒均匀，并各自分散在聚合物中，无团聚现象。
实施例3
本实施例中，掺常用勃姆石，举例说明掺具有如图1A所示SASOL产的C-200的颗粒，掺入量与本发明勃姆石相似，其颗粒如图1B所示。在每种情况中，被评价试样按实施例2的方法配混。对未经改性的尼龙6，含有常用勃姆石，以及含有本发明勃姆石的同种聚合物样品分别测定弹性模量，弯曲模量，30℃与135℃的储能模量E’，拉伸强度，以及热变形温度。测试结果以条形图方式显示在图6A与6B。从条形图上清楚可见，针形勃姆石性能要比常规勃姆石优越并且往往高许多。
实施例4
在本实施例中，本发明勃姆石分散于环氧树脂中。所选树脂连同固化剂是Buehler的Epo-Kwik。将前一实施例所用的勃姆石与树脂组分混合至均匀，再分成四份样品，其中三个样品加入不同的表面活性剂，加入量为配方中勃姆石重量的0.5％。这些试剂为四乙氧基硅烷(TEOS)，γ-环氧丙氧基丙基三甲氧基硅烷(GPTS)和3-氨丙基三乙氧基硅烷(A-1100)。第四个样品不含添加剂。将混合物在电热板上搅拌过夜，温度设定为40-85℃。然后每一混合物经四次超声探头处理，每次时间为2.5-3分钟，每次处理间歇在冰浴中冷却。然后将样品置于铝盘内，在真空下放置20分钟去除真空气。然后将环氧树脂的固化剂成分以树脂量的五分之一的量加入到混合物内，仔细搅拌然后在室温下固化过夜。当设置定在4#，温度为100℃时，三小时完成固化。然后测试固化样品评价它的储能模量，测量结果以条形图方式显示在图8，并与未改性环氧树脂值进行比较。从条形图可见，仅仅勃姆石储能模量没有大的提高，但掺入表面活性剂后，储能模量提高三分之一。
实施例5
本实施例表示在陶氏化学公司提供的注册商标为ISOPLAST 301的热塑性聚氨酯中添加本发明的勃姆石的作用。
所述聚合物首先在100℃下干燥，按实施例1制得的针形勃姆石颗粒在50℃下干燥，每种情况都干燥过夜。然后采用实施例2所述的设备将勃姆石(1.86体积％)与所述聚合物混合，并将挤出物冷却与造粒。混合粒料在80℃下干燥，然后注塑成评价样品。图7所示为勃姆石颗粒完全分散的透射电子显微照片。
Claims (25)
1.一种改性聚合物材料，其包括：
聚合物基料；以及
聚合物基料中的勃姆石颗粒，所述勃姆石颗粒主要包括长径比至少为3∶1的针形颗粒，其中长径比是最长尺寸与次最长尺寸之比，且最长尺寸在50-2000nm之间。
2.如权利要求1所述的材料，其特征在于所述长径比至少6∶1。
3.如权利要求1所述的材料，其特征在于所述勃姆石颗粒的最长尺寸在100-1000nm之间。
4.如权利要求1所述的材料，其特征在于所述勃姆石颗粒占改性聚合物材料体积的0.5-20％。
5.如权利要求1所述的材料，其特征在于所述勃姆石颗粒占改性聚合物材料体积的2-10％。
6.如权利要求1所述的材料，其特征在于所述勃姆石颗粒不含表面活性剂。
7.如权利要求1所述的材料，其特征在于所述勃姆石颗粒分散在聚合物基料内。
8.如权利要求1所述的材料，其特征在于所述勃姆石颗粒基本上各自均匀地分散在聚合物基料内。
9.如权利要求8所述的材料，其特征在于在聚合物基料中所述勃姆石颗粒基本上没有团聚物。
10.如权利要求1所述的材料，其特征在于所述聚合物基料包含热塑性聚合物。
11.如权利要求10所述的材料，其特征在于所述热塑性聚合物基料包含聚酰胺。
12.如权利要求11所述的材料，其特征在于所述聚合物基料包含尼龙。
13.如权利要求1所述的材料，其特征在于所述聚合物基料包含热固化树脂。
14.如权利要求13所述的材料，其特征在于所述聚合物基料包含酚醛类树脂和丙烯酸酯类树脂中的至少一种。
15.如权利要求1所述的材料，其特征在于所述勃姆石颗粒在聚合物基料内定向排列。
16.如权利要求15所述的材料，其特征在于所述改性聚合物材料包括挤出产品。
17.一种制备产品的方法，其包括：
提供一种改性聚合物材料，其包括聚合物基料和主要包括长径比至少为3∶1的针形勃姆石颗粒，其中长径比是最长尺寸与次长尺寸之比；并
将改性聚合物材料挤出成挤出产品，其中所述的勃姆石颗粒分散在所述的挤出产品中。
18.如权利要求17所述的方法，其特征在于所述勃姆石颗粒在挤出产品内基本上定向排列。
19.如权利要求17所述的方法，其特征在于所述改性聚合物材料被挤出到模具中形成制作。
20.如权利要求17所述的方法，其特征在于所述的聚合物基料包含热塑性聚合物。
21.如权利要求20所述的方法，其特征在于所述热塑性聚合物包括聚酰胺。
22.如权利要求17所述的方法，其特征在于所述长径比至少为6∶1。
23.如权利要求17所述的方法，其特征在于所述勃姆石颗粒的最长尺寸在50-2000nm之间。
24.如权利要求17所述的方法，其特征在于所述勃姆石颗粒占改性聚合物材料体积的0.5-20％。
25.如权利要求17所述的方法，其特征在于所述勃姆石颗粒基本上各自均匀地分散。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US37401402P | 2002-04-19 | 2002-04-19 | |
| US60/374,014 | 2002-04-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1656161A CN1656161A (zh) | 2005-08-17 |
| CN100386370C true CN100386370C (zh) | 2008-05-07 |
Family
ID=29251117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038116642A Expired - Fee Related CN100386370C (zh) | 2002-04-19 | 2003-04-16 | 新颖勃姆石颗粒及掺入这种颗粒的聚合物材料 |
Country Status (24)
| Country | Link |
|---|---|
| US (2) | US7189775B2 (zh) |
| EP (1) | EP1499666B1 (zh) |
| JP (1) | JP4405814B2 (zh) |
| KR (1) | KR100656112B1 (zh) |
| CN (1) | CN100386370C (zh) |
| AT (1) | ATE443100T1 (zh) |
| AU (1) | AU2003228571B2 (zh) |
| BR (1) | BR0309394B1 (zh) |
| CA (1) | CA2481475C (zh) |
| CO (1) | CO5611203A2 (zh) |
| DE (1) | DE60329287D1 (zh) |
| DK (1) | DK1499666T3 (zh) |
| ES (1) | ES2333711T3 (zh) |
| HK (1) | HK1075670A1 (zh) |
| IL (3) | IL164534A (zh) |
| MX (1) | MXPA04010312A (zh) |
| NO (1) | NO20045018L (zh) |
| NZ (1) | NZ535816A (zh) |
| PL (1) | PL372586A1 (zh) |
| RU (1) | RU2271929C2 (zh) |
| TW (1) | TWI302545B (zh) |
| UA (1) | UA75827C2 (zh) |
| WO (1) | WO2003089508A1 (zh) |
| ZA (1) | ZA200408108B (zh) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI302545B (en) | 2002-04-19 | 2008-11-01 | Saint Gobain Ceramics | Boehmite particles and polymer materials incorporating same |
| US20050124745A1 (en) * | 2002-04-19 | 2005-06-09 | Saint-Gobain Ceramics & Plastics, Inc. | Flame retardant composites |
| US20040265219A1 (en) * | 2002-04-19 | 2004-12-30 | Saint-Gobain Ceramics & Plastics, Inc. | Seeded boehmite particulate material and methods for forming same |
| US7582277B2 (en) | 2002-04-19 | 2009-09-01 | Saint-Gobain Ceramics & Plastics, Inc. | Seeded boehmite particulate material and methods for forming same |
| US20050227000A1 (en) * | 2004-04-13 | 2005-10-13 | Saint-Gobain Ceramics & Plastics, Inc. | Surface coating solution |
| WO2005012404A1 (ja) * | 2003-07-31 | 2005-02-10 | Kyoto University | 繊維強化複合材料及びその製造方法と、その利用 |
| DE102004009582A1 (de) * | 2004-02-25 | 2005-09-15 | Sasol Germany Gmbh | Mit böhmitischen Tonerdehydraten gefüllte Polymere |
| EP1580223A1 (de) * | 2004-02-25 | 2005-09-28 | SASOL Germany GmbH | Mit Böhmiten gefüllte Polymere |
| JP4487689B2 (ja) * | 2004-08-26 | 2010-06-23 | 日産自動車株式会社 | アルミナ粒子、アルミナ粒子の製造方法、樹脂組成物、及び樹脂組成物の製造方法 |
| JP4940556B2 (ja) | 2004-09-07 | 2012-05-30 | 日産自動車株式会社 | 樹脂組成物 |
| US20060104895A1 (en) | 2004-11-18 | 2006-05-18 | Saint-Gobain Ceramics & Plastics, Inc. | Transitional alumina particulate materials having controlled morphology and processing for forming same |
| US20060148955A1 (en) * | 2004-12-01 | 2006-07-06 | Saint-Gobain Ceramics & Plastics, Inc. | Rubber formulation and methods for manufacturing same |
| JP2006160541A (ja) * | 2004-12-03 | 2006-06-22 | Sumitomo Chemical Co Ltd | 針状水酸化アルミニウムの製造方法 |
| JP4563448B2 (ja) * | 2005-02-17 | 2010-10-13 | 三井化学株式会社 | シール材樹脂組成物、シール材、シール方法およびエレクトロルミネッセンスディスプレイ |
| JP2006249343A (ja) * | 2005-03-14 | 2006-09-21 | Mitsui Chemicals Inc | エポキシ樹脂組成物および半導体素子収納用パッケージ |
| JP2007031684A (ja) * | 2005-06-22 | 2007-02-08 | Nissan Motor Co Ltd | 樹脂組成物、及び樹脂組成物の製造方法 |
| US7479324B2 (en) * | 2005-11-08 | 2009-01-20 | Saint-Gobain Ceramics & Plastics, Inc. | Pigments comprising alumina hydrate and a dye, and polymer composites formed thereof |
| DE102007032820A1 (de) * | 2006-07-14 | 2008-02-21 | Sumitomo Chemical Co., Ltd. | Nadelförmiges Böhmit und Verfahren zu dessen Herstellung |
| EP2048189A4 (en) | 2006-08-03 | 2009-09-30 | Nissan Motor | ALUMINUM OXIDE NANOPARTICLE WITH COATED SURFACE AND RESIN COMPOSITION THEREOF |
| JP2008106100A (ja) * | 2006-10-24 | 2008-05-08 | Sumitomo Chemical Co Ltd | 結晶性熱可塑性樹脂組成物 |
| JP5233266B2 (ja) * | 2006-12-26 | 2013-07-10 | 住友化学株式会社 | 結晶性熱可塑性重合体組成物 |
| JP2008266613A (ja) * | 2007-03-23 | 2008-11-06 | Sumitomo Chemical Co Ltd | ベーマイト充填ポリプロピレン樹脂組成物およびそれからなる成形体 |
| JP2008266614A (ja) * | 2007-03-23 | 2008-11-06 | Sumitomo Chemical Co Ltd | ベーマイト充填ポリプロピレン樹脂組成物およびそれからなる成形体 |
| WO2009011278A1 (ja) | 2007-07-17 | 2009-01-22 | Mitsubishi Chemical Corporation | ポリカーボネート樹脂組成物及びその製造方法 |
| KR101213791B1 (ko) * | 2007-10-02 | 2012-12-18 | 제일모직주식회사 | 폴리머 필름과 그를 포함하는 광학 장치 |
| ATE515529T1 (de) * | 2007-10-12 | 2011-07-15 | Dow Corning | Folie aus verstärktem silikonharz und nanofasergefüllte silikonzusammensetzung |
| JP5485896B2 (ja) * | 2007-10-12 | 2014-05-07 | ダウ コーニング コーポレーション | 酸化アルミニウム分散物およびこれを調製する方法 |
| US8575255B2 (en) | 2007-10-19 | 2013-11-05 | Saint-Gobain Ceramics & Plastics, Inc. | Applications of shaped nano alumina hydrate as barrier property enhancer in polymers |
| WO2009085870A2 (en) | 2007-12-19 | 2009-07-09 | Saint-Gobain Ceramics & Plastics, Inc. | Aggregates of alumina hydrates |
| US9102690B2 (en) * | 2007-12-28 | 2015-08-11 | 3M Innovative Properties Company | Acicular boehmite nanoparticles |
| US20110301277A1 (en) * | 2008-03-26 | 2011-12-08 | Johnson Sr William L | Boundary breaker paint, coatings and adhesives |
| US8496320B2 (en) | 2008-05-08 | 2013-07-30 | Hewlett-Packard Development Company, L.P. | Ink cartridge having a staked vent sealing member |
| US8460768B2 (en) | 2008-12-17 | 2013-06-11 | Saint-Gobain Ceramics & Plastics, Inc. | Applications of shaped nano alumina hydrate in inkjet paper |
| US20140066551A1 (en) * | 2012-08-30 | 2014-03-06 | Sabic Innovative Plastics Ip B.V. | Glass-filled polyamide composition and article |
| WO2015110913A1 (en) * | 2014-01-21 | 2015-07-30 | Sasol Olefins & Surfactants Gmbh | Alumina compositions and methods for producing same |
| KR20210005140A (ko) | 2018-04-27 | 2021-01-13 | 바스프 코팅스 게엠베하 | 수성 코팅제 조성물의 레올로지 첨가제로서의 표면-개질된 산화수산화알루미늄 입자 |
| CN110090561A (zh) * | 2018-12-13 | 2019-08-06 | 湖北工业大学 | 一种含改性勃姆石多功能膜的制备方法 |
| CN111621150B (zh) * | 2020-06-11 | 2023-02-14 | 绍兴思安阻燃科技有限公司 | 一种阻燃尼龙组合物及其制备方法 |
| CN114456560A (zh) * | 2022-02-17 | 2022-05-10 | 杭州师范大学 | 一种具有高透明度的多功能性聚乳酸纳米复合材料及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401703A (en) * | 1992-03-30 | 1995-03-28 | Yoshida Kogyo K.K. | Fine flaky boehmite particles amd process for the preparation of the same |
| CN1237146A (zh) * | 1996-03-05 | 1999-12-01 | 佐藤护郎 | 氧化铝溶胶、其制备方法、用其制成氧化铝成形制品的方法和从氧化铝成形制品获得的氧化铝作载体的催化剂 |
| JP2001180930A (ja) * | 1999-12-28 | 2001-07-03 | Ykk Corp | 薄片状ベーマイト粒子及びその製造方法 |
| JP2001261976A (ja) * | 2000-03-16 | 2001-09-26 | Otsuka Chem Co Ltd | 樹脂組成物 |
Family Cites Families (109)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2763620A (en) * | 1951-12-05 | 1956-09-18 | Du Pont | Process for preparing alumina sols |
| US2915475A (en) * | 1958-12-29 | 1959-12-01 | Du Pont | Fibrous alumina monohydrate and its production |
| US3108888A (en) | 1960-08-04 | 1963-10-29 | Du Pont | Colloidal, anisodiametric transition aluminas and processes for making them |
| NL302055A (zh) | 1962-12-27 | |||
| US3357791A (en) * | 1964-07-20 | 1967-12-12 | Continental Oil Co | Process for producing colloidal-size particles of alumina monohydrate |
| US3385663A (en) * | 1964-07-31 | 1968-05-28 | Du Pont | Preparation of high surface area, waterdispersible alumina monohydrate from low surface area alumina trihydrate |
| US3387447A (en) * | 1965-12-27 | 1968-06-11 | Celanese Corp | Traveler rings |
| US3814782A (en) | 1968-12-27 | 1974-06-04 | Universal Oil Prod Co | Making alumina fibers from a mixture of alumina sol and hexamethylene-tetramine |
| US3853688A (en) | 1971-06-23 | 1974-12-10 | Du Pont | Continuous filaments and yarns |
| BE787691A (fr) | 1971-08-17 | 1973-02-19 | Degussa | Composes organosiliciques contenant du soufre |
| US3873489A (en) | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| US3978103A (en) | 1971-08-17 | 1976-08-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Sulfur containing organosilicon compounds |
| US3865917A (en) | 1972-02-10 | 1975-02-11 | United Aircraft Corp | Preparation of alumina monofilaments |
| JPS49125298A (zh) * | 1973-04-06 | 1974-11-30 | ||
| SU580840A3 (ru) | 1974-02-07 | 1977-11-15 | Дегусса (Фирма) | Способ получени серосодержащих кремнийорганических соединений |
| US3950180A (en) | 1974-07-02 | 1976-04-13 | Mitsubishi Kinzoku Kabushiki Kaisha | Coloring composites |
| US4002594A (en) | 1975-07-08 | 1977-01-11 | Ppg Industries, Inc. | Scorch retardants for rubber reinforced with siliceous pigment and mercapto-type coupling agent |
| CA1110930A (en) | 1976-09-29 | 1981-10-20 | Union Carbide Corporation | Treated hydrated alumina |
| US4117105A (en) * | 1977-03-21 | 1978-09-26 | Pq Corporation | Process for preparing dispersible boehmite alumina |
| FR2449650A1 (fr) | 1979-02-26 | 1980-09-19 | Rhone Poulenc Ind | Procede de preparation d'alumine au moins partiellement sous forme de boehmite ultra-fine |
| US4377418A (en) | 1980-03-21 | 1983-03-22 | Imperial Chemical Industries Limited | Particulate filler, coated with material bonded thereto and containing a sulfur-containing group which releases sulfur as a curing agent for s-curable unsaturated polymers |
| US4386185A (en) | 1980-05-06 | 1983-05-31 | Phillips Petroleum Company | Phosphonates as silica-to-rubber coupling agents |
| US4525494A (en) | 1981-06-09 | 1985-06-25 | Robert Andy | High strength flame resistant poly-olefins comprising surface coated alumina hydrate plus organic titanate and methods of making the same |
| FR2520722A1 (fr) * | 1982-01-29 | 1983-08-05 | Rhone Poulenc Spec Chim | Boehmites et pseudo- |
| JPS6046923A (ja) * | 1983-08-23 | 1985-03-14 | Mitsubishi Chem Ind Ltd | ベ−マイト |
| JPS58222128A (ja) | 1982-06-18 | 1983-12-23 | Kyowa Chem Ind Co Ltd | ハロゲン含有ゴムの耐水性改良法 |
| JPS59193949A (ja) | 1983-04-18 | 1984-11-02 | Sumitomo Alum Smelt Co Ltd | 光拡散性アクリル系樹脂組成物 |
| US5194243A (en) * | 1983-09-22 | 1993-03-16 | Aluminum Company Of America | Production of aluminum compound |
| US5445807A (en) * | 1983-09-22 | 1995-08-29 | Aluminum Company Of America | Production of aluminum compound |
| US4539365A (en) | 1984-02-21 | 1985-09-03 | The B. F. Goodrich Company | Universal cement for natural and synthetic rubber tire compounds |
| US4623738A (en) | 1985-04-22 | 1986-11-18 | Kenrich Petrochemicals, Inc. | Neoalkoxy organo-titanates and organo-zirconates useful as coupling and polymer processing agents |
| US4632364A (en) | 1985-03-08 | 1986-12-30 | Bethea Electrical Products, Inc. | Bundle conductor stringing block gate |
| GB2174998B (en) | 1985-03-20 | 1989-01-05 | Dainichi Nippon Cables Ltd | Flame-retardant resin compositions |
| DE3512404A1 (de) * | 1985-04-04 | 1986-10-09 | Vereinigte Aluminium-Werke AG, 1000 Berlin und 5300 Bonn | Verfahren zur verminderung der organischen bestandteile in aluminatlaugen |
| US4891127A (en) | 1985-12-31 | 1990-01-02 | Exxon Research And Engineering Company | Preparation and use of catalysts comprising a mixture of tungsten oxide and silica supported on a boehmite-like surface |
| US5302368A (en) | 1987-01-29 | 1994-04-12 | Sumitomo Chemical Company, Limited | Process for preparation of alumina |
| US4797139A (en) * | 1987-08-11 | 1989-01-10 | Norton Company | Boehmite produced by a seeded hydyothermal process and ceramic bodies produced therefrom |
| DE3817251A1 (de) * | 1988-05-20 | 1989-11-23 | Condea Chemie Gmbh | Lackentklebungs- und sedimentationsmittel |
| US5321055A (en) | 1990-01-31 | 1994-06-14 | Slocum Donald H | Process for the preparation of a synthetic quartzite-marble/granite material |
| DE69112514T3 (de) | 1990-06-29 | 1999-10-21 | Sumitomo Chemical Co | Wärmebeständige Übergangsalumina und Verfahren zu deren Herstellung. |
| DE4118564A1 (de) * | 1991-06-06 | 1992-12-17 | Vaw Ver Aluminium Werke Ag | Teilkristalline uebergangsaluminiumoxide, verfahren zu deren herstellung und verwendung zur gewinnung von formkoerpern, die im wesentlichen aus gamma-al(pfeil abwaerts)2(pfeil abwaerts)o(pfeil abwaerts)3(pfeil abwaerts) bestehen |
| DE4131986A1 (de) * | 1991-09-26 | 1993-04-01 | Basf Ag | Unverstaerkte polyamidformmassen |
| US5344489A (en) | 1991-11-15 | 1994-09-06 | Manfred R. Kuehnle | Synthetic, monodispersed color pigments for the coloration of media such as printing inks, and method and apparatus for making same |
| JPH05238729A (ja) | 1991-12-18 | 1993-09-17 | Sumitomo Chem Co Ltd | 遷移アルミナの製造方法 |
| US5286290A (en) | 1992-04-16 | 1994-02-15 | Avonite, Inc. | Filler and artificial stone made therewith |
| CA2122099C (en) | 1993-04-28 | 1999-08-17 | Hitoshi Yoshino | Recording medium, ink-jet recording method using the same, and dispersion of alumina hydrate |
| JP2884990B2 (ja) | 1993-05-14 | 1999-04-19 | 東レ株式会社 | ポリエステル組成物およびフィルム |
| GB9312356D0 (en) | 1993-06-16 | 1993-07-28 | Bp Chem Int Ltd | Stabilised polyketone compositions |
| US5723529A (en) | 1994-12-21 | 1998-03-03 | The Goodyear Tire & Rubber Company | Silica based aggregates, elastomers reinforced therewith and tire tread thereof |
| US5525659A (en) | 1993-09-08 | 1996-06-11 | The Dow Chemical Company | Batch inclusion packages |
| WO1995011270A1 (en) * | 1993-10-21 | 1995-04-27 | Vista Chemical Company | Alumina thickened latex formulations |
| JP2887098B2 (ja) | 1994-10-26 | 1999-04-26 | キヤノン株式会社 | 被記録媒体、その製造方法及び画像形成方法 |
| US5580919A (en) | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
| JP2921785B2 (ja) * | 1995-04-05 | 1999-07-19 | キヤノン株式会社 | 被記録媒体、該媒体の製造方法及び画像形成方法 |
| DE19530200A1 (de) * | 1995-08-17 | 1997-02-20 | Bayer Ag | Feinstteilige anorganische Pulver als Flammschutzmittel in thermoplastischen Formmassen |
| DE19548319A1 (de) | 1995-12-22 | 1997-06-26 | Basf Magnetics Gmbh | Thermoplastische Formmassen zum Spritzgießen von Formteilen und Spritzguß-Formteil daraus |
| US5583245A (en) | 1996-03-06 | 1996-12-10 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| FR2749313A1 (fr) * | 1996-05-28 | 1997-12-05 | Michelin & Cie | Composition de caoutchouc dienique a base d'alumine en tant que charge renforcante et son utilisation pour la fabrication d'enveloppes de pneumatiques |
| US5853886A (en) | 1996-06-17 | 1998-12-29 | Claytec, Inc. | Hybrid nanocomposites comprising layered inorganic material and methods of preparation |
| US5696197A (en) | 1996-06-21 | 1997-12-09 | The Goodyear Tire & Rubber Company | Heterogeneous silica carbon black-filled rubber compound |
| US5989515A (en) * | 1996-07-24 | 1999-11-23 | Nissan Chemical Industries, Ltd. | Process for producing an acidic aqueous alumina sol |
| US5663396A (en) | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| JP2000508021A (ja) | 1996-12-31 | 2000-06-27 | ザ ダウ ケミカル カンパニー | ポリマー―オルガノクレー複合材料およびそれらの調製 |
| US5684171A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
| US5684172A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
| DE19722750C2 (de) * | 1997-05-30 | 2001-07-19 | Rwe Dea Ag | Verwendung einer Zusammensetzung als Lackentklebungs- und Sedimentationsmittel |
| FR2764213B1 (fr) * | 1997-06-10 | 1999-07-16 | Inst Francais Du Petrole | Catalyseur d'hydrotraitement de charges hydrocarbonees dans un reacteur a lit fixe |
| US5973048A (en) | 1997-08-08 | 1999-10-26 | General Electric Company | Melt and color stabilization of aliphatic polyketones |
| AU1876299A (en) * | 1997-11-28 | 1999-06-16 | Compagnie Generale Des Etablissements Michelin - Michelin & Cie | Reinforcing aluminous filler and rubber composition comprising such a iller |
| TW555696B (en) * | 1998-01-08 | 2003-10-01 | Nissan Chemical Ind Ltd | Alumina powder, process for producing the same and polishing composition |
| DE19812279C1 (de) * | 1998-03-20 | 1999-05-12 | Nabaltec Gmbh | Flammwidrige Kunststoffmischung und Verfahren zur Herstellung eines Füllstoffs |
| JP3283475B2 (ja) * | 1998-09-16 | 2002-05-20 | 河合石灰工業株式会社 | 板状ベーマイト及び板状アルミナ並びにそれらの製造方法 |
| MXPA01005691A (es) | 1998-12-07 | 2002-04-24 | Eastman Chem Co | Una composicion colorante, un monocompuesto polimero ique consta de una composicion colorante y articulos producidos de el. |
| JP3616269B2 (ja) | 1999-02-19 | 2005-02-02 | 河合石灰工業株式会社 | 針状ベーマイトの製造方法及び針状ベーマイト |
| KR20010072070A (ko) * | 1999-05-28 | 2001-07-31 | 미첼 롤리에르 | 디엔 탄성중합체 및 강화 산화티탄을 기재로 하는 공기타이어용 고무 조성물 |
| JP2003504493A (ja) | 1999-07-13 | 2003-02-04 | ネーデルランドセ オルガニサティエ フォール トエゲパストナトールヴェテンシャッペリク オンデルゾエク ティエヌオー | ナノコンポジットコーティング |
| KR20010021420A (ko) * | 1999-08-30 | 2001-03-15 | 고사이 아끼오 | 보우마이트 및 자기 기록 매체의 초벌층 |
| US6417286B1 (en) | 1999-09-08 | 2002-07-09 | The Goodyear Tire & Rubber Company | Titanium and zirconium compounds |
| US6413308B1 (en) * | 1999-10-15 | 2002-07-02 | J. M. Huber Corporation | Structured boehmite pigment and method for making same |
| JP2001207077A (ja) | 2000-01-26 | 2001-07-31 | Otsuka Chem Co Ltd | 真珠光沢顔料 |
| EP1120281B1 (en) * | 2000-01-28 | 2006-05-24 | Oji Paper Company Limited | Ink jet recording material |
| DE60133829T2 (de) | 2000-09-06 | 2009-05-20 | Bridgestone Corp. | Verbundstoff aus dienkautschuk und anorganischer verbindung und verfahren zu dessen herstellung und kautschukzusammensetzung |
| US6635700B2 (en) | 2000-12-15 | 2003-10-21 | Crompton Corporation | Mineral-filled elastomer compositions |
| ATE362958T1 (de) | 2001-01-02 | 2007-06-15 | Michelin Soc Tech | Kautschukmischung auf der basis eines dienelastomers und eines verstärkenden siliciumcarbids |
| US6534584B2 (en) | 2001-01-08 | 2003-03-18 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition which contains carbon black supported thioglycerol coupling agent and article of manufacture, including a tire, having at least one component comprised of such rubber composition |
| EP1225200B1 (en) | 2001-01-17 | 2006-09-06 | Bridgestone Corporation | Rubber composition and pneumatic tire |
| AR032424A1 (es) | 2001-01-30 | 2003-11-05 | Procter & Gamble | Composiciones de recubrimiento para modificar superficies. |
| JP2002332381A (ja) | 2001-05-10 | 2002-11-22 | Sumitomo Chem Co Ltd | ゴム組成物およびそれを用いるタイヤ |
| JP3663369B2 (ja) | 2001-06-18 | 2005-06-22 | 河合石灰工業株式会社 | 六角板状ベーマイト及び六角板状アルミナの製造方法 |
| US6858665B2 (en) | 2001-07-02 | 2005-02-22 | The Goodyear Tire & Rubber Company | Preparation of elastomer with exfoliated clay and article with composition thereof |
| JP3930273B2 (ja) | 2001-08-08 | 2007-06-13 | 岐阜県 | 針状ベーマイト及びそれを含有する樹脂組成物 |
| US6653387B2 (en) | 2001-09-26 | 2003-11-25 | The Goodyear Tire & Rubber Company | Alumina reinforced rubber composition which contains tetrathiodipropionic and/or trithiodipropionic acid coupling agent and article of manufacture, including a tire, having at least one component comprised of such rubber composition |
| US6706660B2 (en) * | 2001-12-18 | 2004-03-16 | Caterpillar Inc | Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems |
| US6646026B2 (en) | 2002-02-07 | 2003-11-11 | University Of Massachusetts | Methods of enhancing dyeability of polymers |
| JP4236146B2 (ja) | 2002-02-19 | 2009-03-11 | 河合石灰工業株式会社 | 多孔質ベーマイト成形体及び多孔質アルミナ成形体 |
| JP3686384B2 (ja) | 2002-02-28 | 2005-08-24 | 住友ゴム工業株式会社 | トレッド用ゴム組成物およびそれを用いた空気入りタイヤ |
| US20050124745A1 (en) | 2002-04-19 | 2005-06-09 | Saint-Gobain Ceramics & Plastics, Inc. | Flame retardant composites |
| US20050227000A1 (en) | 2004-04-13 | 2005-10-13 | Saint-Gobain Ceramics & Plastics, Inc. | Surface coating solution |
| US20040265219A1 (en) | 2002-04-19 | 2004-12-30 | Saint-Gobain Ceramics & Plastics, Inc. | Seeded boehmite particulate material and methods for forming same |
| US7582277B2 (en) * | 2002-04-19 | 2009-09-01 | Saint-Gobain Ceramics & Plastics, Inc. | Seeded boehmite particulate material and methods for forming same |
| TWI302545B (en) | 2002-04-19 | 2008-11-01 | Saint Gobain Ceramics | Boehmite particles and polymer materials incorporating same |
| JP2004059643A (ja) * | 2002-07-25 | 2004-02-26 | Mitsubishi Gas Chem Co Inc | プリプレグ及び積層板 |
| US6924011B2 (en) | 2002-08-27 | 2005-08-02 | Agfa Gevaert | Ink jet recording material |
| US6841207B2 (en) | 2002-09-30 | 2005-01-11 | Hewlett-Packard Development Company, L.P. | Porous media coatings having surface-modified alumina particulates |
| US7666410B2 (en) | 2002-12-20 | 2010-02-23 | Kimberly-Clark Worldwide, Inc. | Delivery system for functional compounds |
| US7226647B2 (en) | 2003-10-16 | 2007-06-05 | Hewlett-Packard Development Company, L.P. | Permanent fixation of dyes to surface-modified inorganic particulate-coated media |
| US20060104895A1 (en) * | 2004-11-18 | 2006-05-18 | Saint-Gobain Ceramics & Plastics, Inc. | Transitional alumina particulate materials having controlled morphology and processing for forming same |
| US20060148955A1 (en) * | 2004-12-01 | 2006-07-06 | Saint-Gobain Ceramics & Plastics, Inc. | Rubber formulation and methods for manufacturing same |
| US7479324B2 (en) * | 2005-11-08 | 2009-01-20 | Saint-Gobain Ceramics & Plastics, Inc. | Pigments comprising alumina hydrate and a dye, and polymer composites formed thereof |
-
2003
- 2003-04-16 TW TW092108815A patent/TWI302545B/zh not_active IP Right Cessation
- 2003-04-16 AU AU2003228571A patent/AU2003228571B2/en not_active Ceased
- 2003-04-16 EP EP03726331A patent/EP1499666B1/en not_active Revoked
- 2003-04-16 BR BRPI0309394-8B1A patent/BR0309394B1/pt not_active IP Right Cessation
- 2003-04-16 UA UA20041109464A patent/UA75827C2/uk unknown
- 2003-04-16 US US10/414,590 patent/US7189775B2/en not_active Expired - Fee Related
- 2003-04-16 PL PL03372586A patent/PL372586A1/xx not_active Application Discontinuation
- 2003-04-16 JP JP2003586225A patent/JP4405814B2/ja not_active Expired - Fee Related
- 2003-04-16 AT AT03726331T patent/ATE443100T1/de active
- 2003-04-16 KR KR1020047016705A patent/KR100656112B1/ko not_active IP Right Cessation
- 2003-04-16 DE DE60329287T patent/DE60329287D1/de not_active Expired - Lifetime
- 2003-04-16 DK DK03726331.6T patent/DK1499666T3/da active
- 2003-04-16 WO PCT/US2003/011941 patent/WO2003089508A1/en active Application Filing
- 2003-04-16 CN CNB038116642A patent/CN100386370C/zh not_active Expired - Fee Related
- 2003-04-16 CA CA002481475A patent/CA2481475C/en not_active Expired - Fee Related
- 2003-04-16 RU RU2004133888/04A patent/RU2271929C2/ru not_active IP Right Cessation
- 2003-04-16 NZ NZ535816A patent/NZ535816A/en not_active IP Right Cessation
- 2003-04-16 ES ES03726331T patent/ES2333711T3/es not_active Expired - Lifetime
- 2003-04-16 MX MXPA04010312A patent/MXPA04010312A/es active IP Right Grant
-
2004
- 2004-10-07 ZA ZA2004/08108A patent/ZA200408108B/en unknown
- 2004-10-12 IL IL164534A patent/IL164534A/en not_active IP Right Cessation
- 2004-10-15 CO CO04104127A patent/CO5611203A2/es not_active Application Discontinuation
- 2004-11-18 NO NO20045018A patent/NO20045018L/no not_active Application Discontinuation
-
2005
- 2005-07-26 HK HK05106414.0A patent/HK1075670A1/xx not_active IP Right Cessation
-
2007
- 2007-03-12 US US11/685,000 patent/US7531161B2/en not_active Expired - Fee Related
-
2009
- 2009-04-30 IL IL198456A patent/IL198456A/en not_active IP Right Cessation
- 2009-04-30 IL IL198457A patent/IL198457A/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401703A (en) * | 1992-03-30 | 1995-03-28 | Yoshida Kogyo K.K. | Fine flaky boehmite particles amd process for the preparation of the same |
| CN1237146A (zh) * | 1996-03-05 | 1999-12-01 | 佐藤护郎 | 氧化铝溶胶、其制备方法、用其制成氧化铝成形制品的方法和从氧化铝成形制品获得的氧化铝作载体的催化剂 |
| JP2001180930A (ja) * | 1999-12-28 | 2001-07-03 | Ykk Corp | 薄片状ベーマイト粒子及びその製造方法 |
| JP2001261976A (ja) * | 2000-03-16 | 2001-09-26 | Otsuka Chem Co Ltd | 樹脂組成物 |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100386370C (zh) | 新颖勃姆石颗粒及掺入这种颗粒的聚合物材料 | |
| JP6552008B2 (ja) | ポリマー／窒化ホウ素化合物から生成される構成部品、かかる構成部品を生成するためのポリマー／窒化ホウ素化合物、及びそれらの使用 | |
| US7479324B2 (en) | Pigments comprising alumina hydrate and a dye, and polymer composites formed thereof | |
| JP5418720B2 (ja) | 無機フィラー複合体、熱伝導性樹脂組成物、及び成形体 | |
| US10328620B2 (en) | Component parts produced by thermoplastic processing of polymer/boron nitride compounds, polymer/boron nitride compounds for producing such component parts, method for producing such component parts and use thereof | |
| KR101218366B1 (ko) | 나노카본 고형체의 제조방법, 이를 이용한 나노카본 고형체, 나노카본 분산액, 나노카본 소재의 제조방법 | |
| JP2016522299A (ja) | ポリマー／窒化ホウ素化合物の熱可塑加工によって生成される構成部品、そのような構成部品を生成するためのポリマー／窒化ホウ素化合物、及びその使用 | |
| WO2005065301A2 (en) | Polymer composites containing keratin | |
| KR20060113521A (ko) | 수산화마그네슘 입자 및 그 제조 방법 및 이를 포함하는수지조성물 | |
| JPH08165376A (ja) | 熱可塑性樹脂組成物 | |
| JPH10265630A (ja) | 強化ポリプロピレン組成物 | |
| Verbeek et al. | Thermoplastic protein nano-composites using bloodmeal and bentonite | |
| JPH10265613A (ja) | 樹脂添加用複合フィラー | |
| CN112236468A (zh) | 矿物填料的新应用 | |
| WO2009138256A1 (de) | Verfahren zur einarbeitung keramischer nanopartikel in eine polymerschmelze | |
| CN110408126A (zh) | 一种抗冲共聚聚丙烯/非改性蒙脱土组合物及其制法和其复合材料及应用 | |
| Kadam et al. | Particulate nano-talc reinforced nylon-6: Effect on mechanical, rheological, thermal and morphological properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080507 Termination date: 20170416 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |