CN104169237A - 无机材料在制备复合材料中的用途 - Google Patents
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- CN104169237A CN104169237A CN201380014023.1A CN201380014023A CN104169237A CN 104169237 A CN104169237 A CN 104169237A CN 201380014023 A CN201380014023 A CN 201380014023A CN 104169237 A CN104169237 A CN 104169237A
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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Classifications
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- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
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- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D99/00—Subject matter not provided for in other groups of this subclass
- B29D99/001—Producing wall or panel-like structures, e.g. for hulls, fuselages, or buildings
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
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- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/045—Polyalkenes
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
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- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing halogen
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- 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
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
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- G10—MUSICAL INSTRUMENTS; ACOUSTICS
- G10K—SOUND-PRODUCING DEVICES; METHODS OR DEVICES FOR PROTECTING AGAINST, OR FOR DAMPING, NOISE OR OTHER ACOUSTIC WAVES IN GENERAL; ACOUSTICS NOT OTHERWISE PROVIDED FOR
- G10K11/00—Methods or devices for transmitting, conducting or directing sound in general; Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
- G10K11/16—Methods or devices for protecting against, or for damping, noise or other acoustic waves in general
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- B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
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Abstract
本发明涉及无机材料在制备复合材料中的用途,其特征在于,将包含一种或多种无机细小残余物和一种或多种基于烯键式不饱和单体的聚合物的混合物通过热塑成型技术处理。
Description
本发明涉及无机材料在制备复合材料,尤其是制备板形式的绝缘材料或阻尼材料中的用途。
基于无机材料的复合材料是众所周知的。因而,US2009/0004459描述了基于硅酸盐和乙酸乙烯酯聚合物的建筑纸板。US2008/0115442公开了由石膏层或混凝土层、聚苯乙烯板和玻璃纤维网构成的夹层状复合材料。
在无机材料的处理过程中,每年都形成大量的细小垃圾,例如石膏、混凝土或硅酸盐的研磨粉;迄今它们主要没有任何用途并不得不以昂贵方式被处理掉。因而需要可将这些垃圾材料处理为有价值产品的方法。由于增加的原料成本以及可获得有价值产品而代替垃圾材料的昂贵处理,从经济上这是可取的。原料的更有效管理以及更低能耗,从生态上通常也是迫切需要的。
鉴于该背景,本发明的目的是研制新方法,通过所述新方法可以节省材料以及如果可能节省能源的方式获得基于无机材料的复合材料。
出人意料地,本发明的该目的通过将来自于加工无机材料的各种方法中的细小残留物例如研磨粉或如石灰石的锯屑使用基于烯键式不饱和单体的聚合物进行热塑性处理法而得到复合材料来实现。
本发明提供无机材料在制备复合材料中的用途,其特征在于,将包含一种或多种无机细小残余物和一种或多种基于烯键式不饱和单体的聚合物的混合物通过热塑成型技术来处理。
所述无机细小残余物是基于例如无机材料,如金属或半金属的氧化物、氢氧化物、碳酸盐、硅酸盐、硫酸盐或硫化物。合适的金属或半金属为例如碱金属,如锂、钠或钾;碱土金属如镁、钙、钡;或第三主族的原子,如铝或硼;以及过渡金属如钛。优选的金属或半金属为镁、钙、钡或铝。优选的无机细小残余物是基于石膏、石灰,尤其是碳酸钙或碳酸镁,滑石、二氧化硅、高岭土、硅酸盐或二氧化钛;特别优选基于石膏、石灰或白垩,最优选基于石灰石或石膏。
所述无机细小残余物可以任何形式存在,例如以削屑形式,或者尤其是以粉尘、粉状物或纤维形式存在。
无机细小残余物优选具有0.1μm~2000μm,特别优选0.2μm~1000μm,甚至更优选0.2μm~500μm,最优选0.2μm~250μm的粒径(使用仪器TGVGoulter LS13320通过随机光散射测定)。优选0.1~100体积%,更优选80~100体积%,尤其是90~100体积%的无机细小残余物具有0.5~2000μm,特别优选0.5~500μm,最优选0.5~100μm的粒径(使用仪器TGV Goulter LS13320通过随机光散射测定)。无机细小残留物粒径分布的最大值优选为0.5~200μm,特别优选为5~100μm(使用仪器TGV Goulter LS13320通过随机光散射测定)。如果无机细小残留物基本上不是圆形或球形,粒径所表示的数值优选与具有最小外延的细小残余物的尺寸有关。
纤维或削屑优选具有0.1mm~5mm,特别优选0.5mm~2mm的长度。然而,无机细小残余物通常基本上为圆形或球形。
例如在无机材料的研磨、粉碎、机器碾磨、锯切、钻孔、剥离或切割期间获得无机细小残留物。无机细小残余物还可以是由这些材料的磨损形成的颗粒。无机细小残余物例如在建筑业中、在家具制造中、在石雕、或通常在无机材料的处理中获得。在干地施工中或在楼面料生产中,尤其是在空心楼板或石膏板的生产中在特定程度上形成该无机细小残余物。在上述过程中可获得所需形式的无机细小残留物,或者通过进一步处理,例如通过粉碎、破碎、压榨或沉淀产生所需形式。
基于烯键式不饱和单体的合适的聚合物例如是基于一种或多种选自以下组的单体以及任选存在的可与其共聚合的其他单体的那些:乙烯基酯、(甲基)丙烯酸酯、乙烯基芳烃、烯烃、1,3-二烯和卤乙烯。
合适的乙烯基酯例如是具有1~22个碳原子,尤其是1~12个碳原子的羧酸的那些乙烯基酯。优选乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、2-乙基己酸乙烯酯、月桂酸乙烯酯、豆蔻酸乙烯酯、棕榈酸乙烯酯、硬脂酸乙烯酯、花生四烯酸乙烯酯(vinyl arachinate)、乙酸1-甲基乙烯酯、新戊酸乙烯酯和具有9~11个碳原子的α-支化的一元羧酸的乙烯基酯,例如VeoVa9R或者VeoVa10R(Resolution的商品名)。乙酸乙烯酯是特别优选的。
合适的丙烯酸酯或甲基丙烯酸酯例如是具有1~22个碳原子,尤其是1~15个碳原子的直链或支链醇的酯。优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、丙烯酸2-乙基己酯、丙烯酸十二烷醇酯、丙烯酸十四烷醇酯、丙烯酸十八烷醇酯、丙烯酸十六烷醇酯、甲基丙烯酸十二烷醇酯、甲基丙烯酸十四烷醇酯、甲基丙烯酸十八烷醇酯或甲基丙烯酸十六烷醇酯。特别优选的是丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯或丙烯酸2-乙基己酯。
优选的乙烯基芳族化合物为苯乙烯、甲基苯乙烯和乙烯基甲苯。优选的卤乙烯为氯乙烯。优选的烯烃为乙烯、丙烯,优选的二烯烃为1,3-丁二烯和异戊二烯。
基于单体混合物的总重量,可任选共聚合0.1~10重量%的辅助单体。优选使用0.5~5重量%的辅助单体。辅助单体的实例为烯键式不饱和的一元羧酸和二元羧酸,优选丙烯酸、甲基丙烯酸、富马酸和马来酸;烯键式不饱和甲酰胺和羧基腈,优选丙烯酰胺和丙烯腈;富马酸和马来酸的单酯和二酯,例如二乙基酯和二异丙基酯,以及马来酸酐;烯键式不饱和磺酸或其盐,优选乙烯基磺酸、2-丙烯酰氨基-2-甲基丙烷磺酸。其他实例为预交联的共聚单体,例如多烯键式不饱和共聚单体,如邻苯二甲酸二烯丙酯、己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯;或者后交联的共聚单体,如丙烯酰氨基乙醇酸(AGA)、甲基丙烯酰氨基乙醇酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺、N-羟甲基烯丙基氨基甲酸酯,烷基醚如N-羟甲基丙烯酰胺、N-羟甲基甲基丙烯酰胺和N-羟甲基烯丙基氨基甲酸酯的异丁氧基醚或酯。环氧官能共聚物单体例如甲基丙烯酸缩水甘油酯和丙烯酸缩水甘油酯也是合适的。其他实例为硅官能共聚单体,如丙烯酰氧基丙基三(烷氧基)硅烷和甲基丙烯酰氧基丙基三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷,其中例如乙氧基和乙氧基丙二醇醚基能够作为烷氧基存在。还可提及具有羟基或CO基的单体,例如甲基丙烯酸和丙烯酸的羟烷基酯,如丙烯酸或甲基丙烯酸的羟乙基酯、羟丙基酯或羟丁基酯,以及化合物如双丙酮丙烯酰胺或丙烯酸乙酰基乙酰氧基乙酯或甲基丙烯酸乙酰基乙酰氧基乙酯。
单体的选择或共聚单体的重量份的选择使得玻璃转化温度Tg≤+120℃,优选-50℃~+60℃,甚至更优选-30℃~+40℃,最优选-15℃~+20℃。聚合物的玻璃转化温度Tg可以已知方式通过差示扫描量热法(DSC)测定。Tg还可通过Fox方程预先近似计算。根据Fox T.G.,Bull.Am.PhysicsSoc.1,3,page123(1956):1/Tg=x1/Tg1+x2/Tg2+...+xn/Tgn,其中xn为单体n的质量分数(重量%/100),Tgn为单体n的均聚物以开尔文表示的玻璃转化温度。均聚物的Tg值在聚合物手册(Polymer Handbook),第二版,J.Wiley&Sons,New York(1975)中给出。
优选包含一种或多种选自以下组的单体的均聚物或共聚物:乙酸乙烯酯、具有9~11个碳原子的α-支化的一元羧酸的乙烯基酯、氯乙烯、乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯和苯乙烯。特别优选包含乙酸乙酯和乙烯的共聚物;包含乙酸乙烯酯、乙烯和具有9~11个碳原子的α-支化的一元羧酸的乙烯基酯的共聚物;包含丙烯酸正丁酯和丙烯酸2-乙基己酯和/或甲基丙烯酸甲酯的共聚物;包含苯乙烯和一种或多种选自以下组的单体的共聚物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯;包含乙酸乙烯酯和一种或多种选自以下组的单体的共聚物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯和任选存在的乙烯;包含1,3-丁二烯和苯乙烯和/或甲基丙烯酸甲酯以及任选存在的其他丙烯酸酯的共聚物;其中所述混合物任选还能够包含一种或多种上述辅助单体。
以已知方式在乳化剂或优选在保护胶体的存在下,例如通过乳液聚合法或通过悬浮聚合法进行聚合物的制备,优选通过乳液聚合法,其中聚合温度通常为20℃~100℃,优选为60℃~90℃,并且气态共聚单体例如乙烯的共聚合优选能够在超大气压下,通常为5巴~100巴下进行。对于乳液聚合或悬浮聚合,通常使用水溶性引发剂或单体可溶性引发剂、或氧化还原引发剂组合引发聚合反应。为了控制分子量,在聚合期间可使用调节物质。保护胶体,任选与乳化剂的组合,可用于稳定化。聚合物优选以保护胶体稳定的含水分散体的形式存在。
用于稳定聚合批次的常用保护胶体例如是部分水解或完全水解的聚乙烯醇;聚乙烯吡咯烷酮;聚乙烯缩醛;水溶性多糖,如淀粉(直链淀粉和支链淀粉),纤维素及其羧甲基、甲基、羟乙基、羟丙基衍生物;蛋白质如酪蛋白或酪蛋白酸盐、大豆蛋白、明胶;木质素磺酸盐;合成聚合物如聚(甲基)丙烯酸、(甲基)丙烯酸酯与羧基官能共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物;三聚氰胺-甲醛磺酸盐共聚物、萘-甲醛磺酸盐共聚物、苯乙烯-马来酸共聚物和乙烯基醚-马来酸共聚物。优选部分水解或完全水解的聚乙烯醇。特别优选具有80~95摩尔%的水解度并且在4%浓度的水溶液中具有1~30mPa·s的粘度(法,在20℃下,DIN53015)的部分水解的聚乙烯醇。
合适的乳化剂例如是阴离子型、阳离子型或非离子型乳化剂,如阴离子型表面活性剂,如具有8~18个碳原子链长的烷基硫酸盐,在疏水基上具有8~18个碳原子并且至多具有40个环氧乙烷单元或环氧丙烷单元的烷基醚硫酸盐或烷基芳基醚硫酸盐,具有8~18个碳原子的烷基磺酸盐或烷基芳基磺酸盐,磺基琥珀酸与一元醇或烷基酚的酯和单酯;或非离子型表面活性剂,如具有8~40个环氧乙烷单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚。基于单体的总重量,通常使用1~5重量%的乳化剂。聚合优选在未添加乳化剂的情况下进行。
以该方式可获得的含水分散体具有优选30~75重量%,特别优选50~60重量%的固体含量。
为了将聚合物转变为水可再分散的聚合物粉末,任选在添加其他保护胶体作为干燥助剂之后,可将该分散体干燥,例如通过流化床干燥、冻冻干燥或喷雾干燥。所述分散体优选进行喷雾干燥。所述喷雾干燥可在常规喷干装置中进行,其中能通过单流喷嘴、双流喷嘴或多流喷嘴或通过转盘进行雾化。出口温度通常选择在45℃~120℃,优选60℃~90℃的范围,取决于装置、树脂的Tg和需要的干燥程度。待雾化的物料的粘度通过固体含量来设定,以获得<500mPa·s,优选<250mPa·s的值(在20rpm和23℃下的Brookfield粘度)。待雾化的分散体的固体含量>35%,优选>40%。
基于分散体的聚合物成分,通常使用的干燥助剂的总量为0.5~30重量%。这是指,基于聚合物的比例,在干燥操作之前保护胶体的总量应当优选为至少1重量%至30重量%,特别优选基于分散体的聚合物成分,使用总共5~20重量%的保护胶体。合适的干燥助剂例如是上述保护胶体。
基于基础聚合物,含量至多1.5重量%的消泡剂已被反复发现对雾化是有利的。通过提高结块稳定性来提高存储稳定性,尤其是对于具有低玻璃转化温度的粉末,对获得的粉末可提供基于聚合物成分的总重量优选1~30重量%的抗结块剂。抗结块剂的实例为碳酸钙或碳酸镁、滑石、石膏、二氧化硅、高岭土如偏高岭土、粒径优选为10nm~10μm的硅酸盐。
最优选再分散粉末含有包含乙酸乙烯酯和乙烯的共聚物,或者包含乙酸乙烯酯、乙烯和具有9~11个碳原子的α-支化的一元羧酸的乙烯基酯的共聚物作为基础聚合物,以及部分水解的聚乙烯醇作为保护胶体。
术语水可再分散的聚合物粉末或再分散粉末是指可通过在干燥助剂,尤其是保护胶体的存在下,将聚合物相应的含水分散体干燥而获得的聚合物组合物。由于该制备方法,分散体的高度分散的树脂被足够量的干燥助剂或保护胶体包覆。在干燥期间,干燥助剂或保护胶体就像护套防止颗粒的粘连。在水中再分散时,干燥助剂或保护胶体再一次溶于水中,并获得初始聚合物颗粒的含水分散体(Schulze J.in TIZ,No.9,1985)。
聚合物优选以含水分散体形式或者特别优选以水可再分散的聚合物粉末形式使用。
在每种情况下基于聚合物和无机细小残余物的总重量,复合材料优选是基于5~80重量%,特别优选10~50重量%,最优选20~40%的聚合物;20~95重量%,特别优选50~90重量%,最优选60~80重量%的无机细小残余物。
此外,复合材料可包含一种或多种有机填料,例如基于木材、皮革、椰子材料如椰子纤维、或者其他天然纤维或者尤其是软木的有机填料。所述有机填料通常以微粒形式存在,尤其是高度分散的微粒形式存在。软木使得复合材料具有特别有利的绝缘性质;皮革制备的复合物包含有机材料并且具有有利的燃烧性能。
除了无机细小残余物之外,复合材料可包含一种或多种其他无机填料。所述其他无机填料不是残余物并且不是垃圾材料,而是特别提供作为填料的无机材料。其他无机填料也可是基于在上面描述无机细小残余物中所述的无机材料。
所述其他无机填料通常不同于根据本发明的残余物之处在于更均匀的粒径分布。因此,其他填料的体积分布曲线优选具有≤2的最大值,尤其是只有一个最大值。无机细小残余物的体积分布曲线优选具有≥3的最大值,特别优选具有≥4的最大值。体积分布曲线描述了根据颗粒的粒径,颗粒的总体积分布。
对于无机细小残余物,体积分布曲线的两个最大值的比例优选为1~2.4,特别优选为1~2,最优选为1~1.5。对于其他无机填料,如果存在两个最大值,体积分布曲线的两个最大值的比例优选≥2.5,特别优选≥3,最优选≥3.5。
联合使用纤维形式的其他无机填料或有机填料是优选的。
基于聚合物和无机细小残余物的总重量,有机填料和/或其他无机填料的用量例如可以为0~90重量%,优选10~90重量%,特别优选10~60重量%,最优选15~40重量%。
在制备复合材料中,还可任选使用添加剂例如润滑剂如硬脂酸钙、增塑剂、抗氧化剂、UV稳定剂、抗静电剂、粘结剂、抗结块剂、染料、颜料、填料、加工助剂或者用于后交联的过氧化物如过氧二碳酸盐。这里优选润滑剂。此外,根据本发明除了使用的聚合物之外,还可加入常规的热塑性塑料、弹性体或者热固性塑料。基于聚合物和无机细小残余物的总重量,可以使用常规量如0~2重量%,尤其是0~1重量%,优选0.5~1重量%的添加剂。
将复合材料的各个成分混合,并随后通过常规热塑成型技术处理,以得到复合材料。
混合例如可在加热-冷却混合机中,并且通过例如在挤出机、palltruder、或者团粒机(agglomerator)中直接造粒来进行。混合优选在多螺杆挤出机、行星齿轮挤出机中进行,特别优选在双螺杆挤出机,尤其是反转双螺杆挤出机中进行。
合适的热塑成型技术例如是挤出、注射成型、压制、造粒和压延。优选造粒,并且特别是压制。
优选通过热塑成型技术首先制备颗粒、小球或混合物,随后通过其他热塑成型技术进一步处理它们。所述颗粒、小球或混合物优选具有2~6mm的粒径。
在混合期间,处理温度通常为40℃~120℃,优选为60℃~100℃。在热塑性处理期间,处理温度通常为80℃~220℃,优选为120℃~180℃。所述温度范围是特别有利的,使聚合物尤其是以水可再分散的聚合物粉末形式的聚合物和用于制备复合材料的其他组分亲密混合,并且聚合物显示其粘结剂作用。在更高温度下,复合材料的成分可能遭受损害。
根据本发明的操作方式适于制备各种模制品、木板、片状结构体或卷状制品。为此的实例尤其是板状的绝热材料或隔音材料或阻尼材料。其他实例是用于制鞋业、服装业、家具业、体育业、娱乐业或尤其是建筑业的材料,例如用于制备墙壁、地板或天花板的材料。优选绝缘材料,尤其是墙壁面料或地板面料。所述复合材料可用作地板面料如地毯或天花板系统的背面涂料。这里,复合材料可取代铺的沥青。使用根据本发明的复合材料有利地抑制了室内声音以及脚步声并且导致热绝缘。
根据本发明制备的复合材料,其特征在于高机械强度,即使在高比例无机材料或其他填料情况下,并且甚至可使用细小的或甚至粉尘状的起始材料制备复合材料。还出人意料地是,在根据本发明的用途中可非常容易地处理无机细小残余物,尽管其不均匀的粒径分布,并且此外,得到具有规则外观和同样的用途特性的复合材料。通过使用可再分散的聚合物粉末可进一步提高机械强度。当根据本发明使用具有基础聚合物的玻璃转化温度Tg的聚合物粉末时,获得具有高机械强度和高弹性的模制品。使用含有乙烯的聚合物能够进一步提高复合材料的弹性。复合材料具有无机材料或有机填料如软木的天然特性例如气味、感觉或光学。为此,小比例的聚合物尤其是有利的。特别有利的是,可以增加价值的方式使用无机细小残余物并可取代昂贵的无机或有机填料。
以下实施例用于阐述本发明:
以下材料用于测试:
Vinnex A:购自Wacker Chemie的可再分散的聚合物粉末,具有-7℃的Tg的基于乙酸乙烯酯-乙烯共聚物的聚乙烯醇稳定的聚合物粉末。
Vinnex B:购自Wacker Chemie的可再分散的聚合物粉末,具有-14℃的Tg的基于乙酸乙烯酯-乙烯共聚物的聚乙烯醇稳定的聚合物粉末。
石膏研磨粉:粒径为0.2μm~250μm(通过TGV Coulter LS13320随机光散射法测定);粒径分布的最大值为15μm(通过TGV Coulter LS13320随机光散射法测定)。
购自Amorim的粒径为1~2mm粒径的软木颗粒。
将所述材料根据表中所示比例在加热-冷却混合机中均匀混合至最终混合温度为80℃,并随后冷却至40℃。然后将该混合物在反转双螺杆挤出机Weber DS 48中处理,得到直径为2~6mm的小球。
将该小球在静态压机上在150℃的温度和5N/mm2的压力以及5分钟的压制时间下处理,得到厚度为2mm或6mm的压制板。
根据DIN53505测定压制板的肖氏硬度A以及肖氏硬度D。
根据DIN EN ISO5271-3或DIN53504在拉伸试验中通过测定拉伸应力和断裂伸长率来测定压制板的机械强度。
结果汇总于下表。
表:
配制 | 实施例1 | 实施例2 | 实施例3 |
石膏研磨粉[kg] | 70 | 55 | 70 |
Vinnex A[kg] | 30 | 30 | |
Vinnex B[kg] | 30 | ||
软木颗粒[kg] | 15 | ||
Shore A | 85.1 | 89.8 | 80.7 |
Shore D | 25.4 | 33.8 | 19.8 |
拉伸应力[MPa] | 6.67 | 5,45 | 3.23 |
伸长率[%] | 17.12 | 23.1 | 71.35 |
Claims (11)
1.无机材料在制备复合材料中的用途,其特征在于,将包含一种或多种无机细小残余物和一种或多种基于烯键式不饱和单体的聚合物的混合物通过热塑成型技术处理。
2.权利要求1的无机材料在制备复合材料中的用途,其特征在于,所述无机细小残余物是基于选自以下组的无机材料:金属或半金属的氧化物、金属或半金属的氢氧化物、金属或半金属的碳酸盐、金属或半金属的硅酸盐、金属或半金属的硫酸盐和金属或半金属的硫化物。
3.权利要求1或2的无机材料在制备复合材料中的用途,其特征在于,所述无机细小残余物是基于选自以下组的无机材料:石膏、石灰、滑石、二氧化硅、高岭土、硅酸盐和二氧化钛。
4.权利要求1~3之一的无机材料在制备复合材料中的用途,其特征在于,所述无机细小残余物是在无机材料的研磨、粉碎、机械碾磨、锯削、钻孔、剥离、或切割、或磨损期间获得的。
5.权利要求1~4之一的无机材料在制备复合材料中的用途,其特征在于,所述聚合物是基于一种或多种选自以下组的烯键式不饱和单体:乙烯基酯、(甲基)丙烯酸酯、乙烯基芳烃、烯烃、1,3-二烯和卤乙烯。
6.权利要求1~5之一的无机材料在制备复合材料中的用途,其特征在于,所述一种或多种基于烯键式不饱和单体的聚合物是以含水聚合物分散体的形式或以水可再分散的聚合物粉末的形式使用。
7.权利要求1~6之一的无机材料在制备复合材料中的用途,其特征在于,所述一种或多种基于烯键式不饱和单体的聚合物是以保护胶体稳定的含水聚合物分散体的形式或以保护胶体稳定的水可再分散的聚合物粉末的形式使用。
8.权利要求1~7之一的无机材料在制备复合材料中的用途,其特征在于,以基于烯键式不饱和单体的聚合物和无机细小残余物的总重量计,所述复合材料是基于5~80重量%的基于烯键式不饱和单体的聚合物和20~95重量%的无机细小残余物。
9.权利要求1~8之一的无机材料在制备复合材料中的用途,其特征在于,使用一种或多种有机填料和/或一种或多种与所述无机细小残余物不同的其他无机填料。
10.权利要求1~9之一的无机材料在制备复合材料中的用途,其特征在于,所述混合物通过热塑成型技术进行处理,所述热塑成型技术选自挤出、注射成型、压制、造粒和压延。
11.权利要求1~10之一的无机材料在制备复合材料中的用途,其特征在于,所述复合材料是模制品、板、片状结构体或卷状制品,例如绝热材料、或隔音材料、或阻尼材料,例如用于制鞋业、服装业、家具业、地板业、体育业、娱乐业或建筑业的绝热材料、或隔音材料、或阻尼材料。
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PCT/EP2013/054906 WO2013135641A1 (de) | 2012-03-13 | 2013-03-11 | Verwendung von anorganischen materialien zur herstellung von verbundstoffen |
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EP2825511B1 (de) | 2019-05-08 |
DE102012203881A1 (de) | 2013-09-19 |
US9631766B2 (en) | 2017-04-25 |
CN104169237B (zh) | 2018-02-16 |
US20150069283A1 (en) | 2015-03-12 |
EP2825511A1 (de) | 2015-01-21 |
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