CN103827192A - 基于还原性糖和氢化糖的矿棉用粘合组合物、以及获得的隔离性产品 - Google Patents
基于还原性糖和氢化糖的矿棉用粘合组合物、以及获得的隔离性产品 Download PDFInfo
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- CN103827192A CN103827192A CN201280048787.8A CN201280048787A CN103827192A CN 103827192 A CN103827192 A CN 103827192A CN 201280048787 A CN201280048787 A CN 201280048787A CN 103827192 A CN103827192 A CN 103827192A
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Abstract
本发明涉及用于基于矿棉,尤其是玻璃矿棉或岩矿棉的隔离性产品的粘合组合物,其包含:至少一种还原性糖;至少一种氢化糖;和至少一种多官能交联剂,该氢化糖占该还原性糖和氢化糖的总重量的10至90%。本发明还涉及基于获得的矿物纤维的隔离性产品及其制造方法。
Description
本发明涉及基于矿棉(laine minérale),尤其是玻璃矿棉或岩矿棉,和无甲醛有机粘合剂(liant)的隔热和/或隔音产品的领域。
本发明更特别涉及用于形成所述有机粘合剂的可交联粘合组合物(composition d'encollage
apte à réticuler),其含有还原性糖(saccharide réducteur)、氢化糖(saccharide hydrogéné)和多官能交联剂。
本发明还涉及制备所述粘合组合物(composition d'encollage)的方法,以及所得隔离性产品。
制造基于矿棉的隔离性产品通常包括制造该棉本身,其可以通过各种方法进行,例如根据通过内部或外部离心制造纤维的已知技术。
内部离心包括将熔融的矿物材料(玻璃或岩石)引入到包含多个小孔的离心机中,该材料在离心力的作用下向该设备的外周壁投射并保持为长丝形式。在离心机出口处,该长丝被高温高速气流拉伸并夹带至接收装置,形成纤维(或矿棉)层。
外部离心包括将熔融材料浇铸到称为转子的旋转部件的外周面上,该熔融材料由此在离心力的作用下喷出。还提供了用于通过气流拉伸和用于在接收器上收集的装置。
为了确保纤维聚集在一起并提供具有内聚力的层,在该纤维由离心机出口至接收装置的路径上将含有热固性树脂的粘合组合物喷涂到纤维上。在通常高于100℃的温度下对涂有粘合剂的纤维层施以热处理以实现树脂的缩聚并由此获得具有特定性质——尤其是具有尺寸稳定性、拉伸强度、压缩后厚度恢复与均匀色彩的隔热和/或隔音产品。
涂覆在矿棉上的粘合组合物通常为含有热固性树脂和添加剂如用于该树脂的交联催化剂、附着力促进硅烷、防尘矿物油等等的水溶液形式。通常通过喷涂将该粘合组合物涂覆在该纤维上。
该粘合组合物的性质极大取决于该树脂的特性。从应用的观点看,该粘合组合物必须具有良好的可喷涂性,并且必须能够沉积在纤维表面上以有效地粘接它们。
该树脂在其用于形成该粘合组合物前在给定时期内必须是稳定的,所述组合物通常在使用时通过混合该树脂与上述添加剂来制备。
在监管方面,该树脂必须是无污染的,即其应含有——并且在粘合步骤中或在随后产生——最小可能量的可能对人体健康或对环境有害的化合物。
最常使用的热固性树脂是甲阶酚醛类酚醛树脂(résins phénoliques appartenant à la famille des résols)。除了它们在前述热条件下良好的交联能力外,这些树脂是水溶性的,具有对矿物纤维尤其是玻璃的良好亲和力,并且是相对廉价的。
最常见的甲阶酚醛树脂(résols)由苯酚与甲醛在碱性催化剂存在下的缩合获得。在结束时,这些甲阶酚醛树脂含有一定比例的未反应单体,特别是甲醛,考虑到其已知的有害作用,其存在是不合意的。
出于这个原因,甲阶酚醛-基树脂通常用脲处理,脲与游离甲醛反应,以非挥发性脲-甲醛缩合物形式捕集甲醛。此外,由于其以相对大量引入而不影响树脂的使用品质,尤其是不会不利地影响成品的机械性质,这显著降低了该树脂的总成本,因此在树脂中存在脲因其低成本而具有一定的经济优势。
但是据观察,在对该层施加以获得树脂交联的温度条件下,脲-甲醛缩合物是不稳定的;它们分解再次产生甲醛和脲,后者至少部分降解为氨,并释放到车间气氛中。
环保方面的法规越来越严格,迫使隔离性产品的制造商寻找解决方案,由此更进一步地降低不合意的排放水平,尤其是甲醛的排放水平。
取代粘合组合物中的甲阶酚醛树脂的解决方案是已知的,并基于使用羧酸与醇。
在US 5 340 868中,粘合剂包含多元羧酸聚合物、β-羟基酰胺和至少三官能的单体羧酸。
已经描述了包含含有至少两个羟基的链烷醇胺和多元羧酸聚合物的粘合组合物(US 6 071 994、US 6 099 773、US 6
146 746),其可以与共聚物结合使用(US 6 299 936)。
已经提出了包含多元羧酸聚合物和多元醇的粘合组合物(US 2002/0091185、US 2002/0091185)。这些组合物可以另外含有催化剂,该催化剂可以是含磷化合物(US 5
318 990、US 5 661 213、US 6331 350、US
2003/0008978)、氟硼酸盐(US 5 977 232)或氨腈(cyanamide)、二氨腈或氰基胍(US 5 932 689)或阳离子型、两性或非离子表面活性剂(US 2002/0188055)或硅烷类型的偶联剂(US 2004/0002567)。
WO 2006/120523描述了一种粘合组合物,其包含(a)聚(乙烯醇),(b)选自非聚合的多元酸或其盐、酸酐或非聚合的多元醛的多官能交联剂和(c)任选地催化剂,该(a)/(b)重量比为95:5至35:65且pH至少等于1.25。
由WO 2008/053332,已知一种粘合组合物,其包含(a)糖聚合物和(b)选自单体多元酸或其盐、以及酸酐的多官能交联剂的加合物。其在使得(a)/(b)重量比为95:5至35:65的条件下获得。
此外,已经描述了其中所有或部分的醇被一种或多种糖类取代的粘合组合物。
在US 2005/0215153中,该粘合组合物由含有羧酸与多元醇的聚合物的预粘合剂以及作为助粘合剂的糊精形成。
在US 5 895 804中,该粘合组合物包含具有至少1000的分子量的多元羧酸聚合物和具有至少10 000的分子量的多糖。
在WO 2009/080938中,该粘合组合物包含至少一种分子量小于或等于1000的有机多元羧酸和至少一种单糖和/或多糖。
最后,由WO 2010/029266,包含至少一种氢化糖和多官能交联剂的一种粘合组合物是已知的。
本发明的目的是改善已知粘合组合物,尤其是WO 2009/080938中公开的粘合组合物,以及获自所述组合物的隔热和/或隔音产品。
事实上发现,通过喷涂在矿物纤维上施加所述粘合组合物并不令人满意:液滴中所含一部分水在喷涂后很快被除去,导致该粘合组合物的粘度显著提高。结果,该液滴不那么有效地分布在矿物纤维表面上,并因此不能如所需那样充分分布在该纤维的连接点处。
为了克服该缺陷,必须向粘合组合物中添加附加量的水或在喷涂时单独在纤维上添加。喷涂过程中水量的提高在处理矿物粘合纤维材料生坯以获得粘合剂的交联的窑炉中存在问题。为了除去过量的水,必须提高窑炉中的温度,或通过降低生产线的速度来提高生坯在窑炉中的停留时间。无论选择哪一种解决方案,都会提高隔离性成品的成本。
根据本发明,用氢化糖替换已知粘合组合物中的一部分糖类,这可以将该粘合组合物的粘度降低至一个值,该值低到足以使该粘合组合物适当喷涂在矿物纤维上,而无需进一步添加水。
本发明的另一目的是提出一种粘合组合物,其能够如下文中解释的那样获得高粘合剂生产线效率。
为了实现这些目的,本发明提出了一种基于矿棉,尤其是玻璃矿棉或岩矿棉的隔离性产品用的粘合组合物,其包含:
- 至少一种还原性糖,
- 至少一种氢化糖,和
- 至少一种多官能交联剂,
该氢化糖占该还原性糖和氢化糖的总重量的10至90%。
术语“还原性糖”理解为常规含义,即带有游离半缩醛OH基团的单糖或多糖,所述基团尤其对碱性铜溶液(cupro-alkaline solution)具有还原作用。
作为还原性单糖的实例,我们可以提及含有3至8个碳原子的还原性糖,优选醛糖且有利地为含有5至7个碳原子的醛糖(aldoses)。特别优选的醛糖是天然醛糖(属于D系列),尤其是己糖(hexoses),如葡萄糖、甘露糖和半乳糖。
本发明的还原性多糖选自具有低于100 000、优选低于50 000、有利地低于10 000且更好高于180的重均分子量的还原性多糖。
有利地,该还原性多糖具有小于或等于10的定义为重均分子量对数均分子量的比的多分散性指数(PI)。
优选地,该还原性多糖含有至少一个选自上述醛糖、有利地为葡萄糖的单元。主要(超过50重量%)由葡萄糖单元构成的多糖是特别优选的。
根据一个优选实施方案,本发明使用尤其是获自植物的还原性单糖和/或多糖的混合物,特别是糊精。
糊精是通过淀粉部分水解获得的符合通式(C6H10O5)n的化合物。糊精的制备方法是已知的。例如,糊精可以通过通常在酸催化剂存在下将淀粉加热或干燥至干来制备,这使得构成所述淀粉的直链淀粉与支链淀粉的分子断裂为较低分子量的产物。糊精还可以通过用一种或多种能够水解淀粉键的淀粉酶(尤其是微生物)酶促处理淀粉来获得。该处理(化学或酶促)的性质和水解条件对糊精的平均分子量和分子量分布具有直接的关系。
本发明的糊精可以获自不同植物来源的淀粉或淀粉衍生物,例如衍生自块茎如马铃薯、木薯、竹芋和甘薯,衍生自谷物如小麦、玉米、黑麦、水稻、大麦、小米、燕麦和高粱,衍生自果实如栗子、板栗和榛子,或衍生自豆科植物如豌豆和黄豆。
具有大于或等于5、优选大于或等于10、有利地大于或等于15并且更好小于100的葡糖当量DE的糊精是特别优选的。
通常,葡糖当量DE由下列关系式定义:
“氢化糖”指的是以任何手段还原选自直链、支链或环状的单糖、寡糖、多糖的糖类所获得的所有产物,以及这些产物的混合物,尤其是淀粉水解物。
糖的氢化可以通过已知方法进行,该方法在高氢压力和高温条件下在选自元素周期表第IB、IIB、IVB、VI、VII和VIII族、优选选自镍、铂、钯、钴、钼及其混合物的催化剂的存在下进行。优选的催化剂是雷尼镍。氢化反应将该糖或糖类混合物(例如淀粉水解物)转化为相应的多元醇。
尽管并非优选,氢化可以在不存在氢化催化剂的情况下在除氢气之外的氢源存在下进行,所述氢源例如为碱金属的硼氢化物,如硼氢化钠。
作为氢化糖的实例,我们可以提及赤藓糖醇、阿糖醇、木糖醇、山梨糖醇、甘露醇、艾杜糖醇、麦芽糖醇、异麦芽糖醇、乳糖醇、cellobitol、异麦芽酮糖醇、麦芽三糖醇和淀粉水解物的氢化产物,尤其是Roquette公司以名称Polysorb®销售的。优选使用淀粉水解物的氢化产物,有利地为麦芽糖醇糖浆。
本发明的氢化糖具有低于100 000、优选低于50
000、有利地低于5000、更特别低于1000且更好高于150的数均分子量。
在该粘合组合物中,该氢化糖优选占该还原性糖和氢化糖的总重量的18至80%,有利地为30至70%且更好为40至60%。
如已经提到的那样,除了降低粘合组合物的粘度外,用氢化糖取代一部分糖类对基于矿棉的隔离性产品制造中的粘合剂生产线效率具有正面效果。该效率定义为隔离性成品中粘合剂的量对制造所述产品时使用的粘合组合物的量(排除水)的比。在恒定的糖类含量下,当粘合组合物含有至少一种氢化糖时,该粘合剂效率更高。发明人相信效率的提高是由于以下事实:不同于非氢化糖,氢化糖不会脱水。
该多官能交联剂能够在热的作用下与还原性糖和氢化糖的羟基反应以形成酯键,导致在最终粘合剂中形成聚合物网络。该聚合物网络指的是在矿棉中纤维的接合点处形成键。
该多官能交联剂选自有机多元羧酸或这些酸的盐,酸酐和多元醛。
“有机多元羧酸”指的是包含至少两个羧基官能、优选最多300个、有利地最多70个且更好最多15个羧基官能的有机酸。
该有机多元羧酸可以是非聚合或聚合的酸;其具有通常小于或等于50 000、优选小于或等于10 000和有利地小于或等于5000的数均分子量。
该非聚合有机多元羧酸是直链或支链的、饱和或不饱和的非环状酸、环状酸或芳族酸。
该非聚合有机多元羧酸可以是二羧酸,例如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、苹果酸、酒石酸、丙醇二酸、天冬氨酸、谷氨酸、富马酸、衣康酸、马来酸、愈伤酸、樟脑酸、邻苯二甲酸及其衍生物(尤其是含有至少一个硼或氯原子的衍生物)、四氢化邻苯二甲酸及其衍生物(尤其是含有至少一个氯原子的衍生物,如氯菌酸)、间苯二甲酸、对苯二甲酸、甲基反丁烯二酸和柠康酸;三羧酸,例如柠檬酸、丙三羧酸、1,2,4-丁三羧酸、乌头酸、连苯三酸、偏苯三酸和均苯三酸;四羧酸,例如1,2,3,4-丁四羧酸和均苯四酸。
特别有利地,该非聚合有机多元羧酸含有两个至四个羧基官能。
作为聚合有机多元羧酸的实例,我们可以提及不饱和羧酸如(甲基丙烯酸)、巴豆酸、异巴豆酸、马来酸、肉桂酸、2-甲基马来酸、富马酸、衣康酸、2-甲基衣康酸、α,β-亚甲基戊二酸和不饱和二羧酸单酯如马来酸与富马酸C1-C10烷基酯的均聚物,以及至少一种上面提到的不饱和羧酸与至少一种乙烯基单体如未取代或被烷基、羟基烷基或磺酰基取代或被卤素原子取代的苯乙烯、(甲基)丙烯腈、(甲基)丙烯酰胺,未取代的或被C1-C10烷基取代,(甲基)丙烯酸烷基酯,尤其是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯和(甲基)丙烯酸异丁酯,(甲基)丙烯酸缩水甘油酯、丁二烯和乙烯基酯,尤其是乙酸乙烯酯的共聚物。
该粘合组合物优选包含至少一种具有小于或等于1000、优选小于或等于750和有利地小于或等于500的数均分子量的非聚合有机多元羧酸,任选与至少一种聚合有机酸混合。
该多官能交联剂还可以是酸酐,尤其是马来酸酐、琥珀酸酐或邻苯二甲酸酐。但是,向粘合组合物中添加酸酐引起pH的快速降低,导致在氢化糖的制造与水解的生产线中腐蚀设备的问题。通过添加碱可以充分提高该粘合组合物的pH以避免这些问题。与额外添加的碱相关的成本意味着使用酸酐是不优选的。
该多官能交联剂还可以是多元醛。
“多元醛”指的是包含至少两个醛官能的醛。
优选地,该多元醛是非聚合二醛,例如乙二醛、戊二醛、1,6-己二醛或1,4-对苯二醛。
该多元醛具有相对于还原性糖和氢化糖的羟基的极高反应性,但通常对羟基均具有极高反应性,这会产生问题,尤其是在热交联处理前该粘合组合物的稳定性降低和/或预胶凝。为了防止这些问题,有利地阻断该多元醛的醛官能,以便在矿棉进入窑炉前防止与粘合组合物中存在的组分的反应。作为阻断醛官能的试剂的实例,我们可以提及脲和环脲。
在前述多官能交联剂中,有机多元羧酸是优选的。
在该粘合组合物中,该还原性糖和氢化糖占由该还原性糖、该氢化糖和该多官能交联剂组成的混合物重量的10至90%,优选20至85%、有利地为30至80%、更好40至65%且特别有利地为45至65%。
通常,本发明的粘合组合物不含有单烷基胺、二烷基胺和链烷醇胺。实际上,不希望这些组分(其能够与粘合组合物的其它成分反应)混入最终粘合剂中的聚合物网络。
该粘合组合物可以进一步包含酸催化剂或碱性催化剂,其尤其具有调节交联起始温度的作用。
该催化剂可以选自路易斯碱和酸,如粘土、非胶态二氧化硅或胶态二氧化硅、有机胺、季胺、金属氧化物、金属硫酸盐、金属氯化物、脲硫酸盐、脲氯化物和硅酸盐-基催化剂。
该催化剂还可以是含有磷的化合物,例如碱金属的次磷酸盐、碱金属亚磷酸盐、碱金属多磷酸盐、碱金属磷酸氢盐、磷酸或烷基膦酸。该碱金属优选为钠或钾。
该催化剂还可以是含有氟和硼的化合物,例如四氟硼酸或该酸的盐,尤其是碱金属如钠或钾的四氟硼酸盐,碱土金属如钙或镁的四氟硼酸盐、锌的四氟硼酸盐和铵的四氟硼酸盐。
该催化剂优选为次磷酸钠、亚磷酸钠和这些化合物的混合物。
添加到该粘合组合物中的催化剂的量可以占该还原性糖、该氢化糖和该多官能交联剂的总重量的最多20%,优选最多10%,并且其有利地至少等于1%。
本发明的粘合组合物可以以基于100重量份还原性糖、氢化糖与多官能交联剂计算的下列比例进一步包含下列常规添加剂:
- 0至2份的硅烷,特别是氨基硅烷或环氧硅烷,
- 0至20份的油,优选4至15份,
- 0至30份的脲,优选0至20份,
- 0至5份的有机硅,
- 0至20份不同于前述糖类的多元醇,
- 0至30份“增量剂”,选自木质素衍生物如木质素磺酸铵(ALS)或木质素磺酸钠,以及动物或植物蛋白质。
添加剂的作用是已知的,并简要重述如下:硅烷是纤维与粘合剂之间的偶联剂,也起抗老化剂的作用;油是防尘和疏水剂;脲和甘油充当增塑剂并可以防止粘合组合物的预胶凝;有机硅是疏水剂,具有减少隔离性产物吸附水的作用;“增量剂”是可溶于或可分散于该水性粘合组合物中的有机填料,尤其能够降低粘合组合物的成本。
作为添加剂添加的多元醇必须不同于该还原性糖与氢化糖。该多元醇尤其是甘油,二醇类如乙二醇、丙二醇、丁二醇和基于这些二醇的聚(亚烷基)二醇,或乙烯基醇的均聚物与共聚物。
当该多官能交联剂是有机多元羧酸时,取决于所用酸类型,该粘合组合物具有大约1至5、优选大于或等于1.0的酸性pH。通过添加不能与还原性糖和氢化糖反应的胺化合物,例如叔胺,尤其是三乙醇胺,该pH有利地保持在至少等于1.5的值以限制粘合组合物不稳定性的问题和生产线的腐蚀问题。胺化合物的量可以占该还原性糖和氢化糖和有机多元羧酸的总重量的最多30重量份。
该粘合组合物意在施加到矿物纤维上,尤其是玻璃纤维或岩石纤维。
常规上,该粘合组合物在离心机出口处和在以纤维层形式在接收装置上收集纤维之前喷射到矿物纤维上,并随后在允许粘合组合物交联并形成不熔性粘合剂的温度下进行处理。本发明的粘合组合物的交联在相当于常规酚醛树脂的温度下,在大于或等于110℃、优选大于或等于130℃和有利地大于或等于140℃的温度下进行。
由这些粘合的纤维获得的隔音和/或隔热产品也构成本发明的主题。
这些产品通常为玻璃矿棉或岩矿棉的毯或毡,或玻璃或岩石的矿物纤维的垫(尤其是意在形成所述毯或所述毡的表面覆层的垫)的形式。
下列实施例描述本发明但是不限制本发明。
在这些实施例中,测量下列参数:
- 通过动态机械分析(DMA)分析交联开始时的温度(TR),其表征聚合物材料的粘弹性行为。程序如下:将Whatman纸的试样用该粘合组合物(有机固含量为大约40%)浸渍并随后水平固定在两个夹爪之间。装有测量随施加形变而改变的应力的装置的振荡元件配置在试样的上表面上。该装置能够计算弹性模量E’。将该试样以4℃/分钟的速率加热至20至250℃不等的温度。测量用于绘制弹性模量E’(以MPa为单位)随温度(以℃为单位)改变的的曲线,其一般形式显示在图1中。对应于以℃为单位的交联开始温度(TR)的值由该曲线测定。
- 粘度,单位为mPa.s,使用板-板旋转型流变仪以100 s-1的剪切在20℃下测得。
- 根据标准ASTM C 686-71T在从该隔离性产品上通过冲压切割的样品上测量的抗张强度。样品具有长度为122毫米、宽度为46毫米。外缘切割曲率半径等于38毫米且内缘切割曲率半径等于12.5毫米的环面形状。
将样品放置在试验机的两个圆柱心轴之间,其中一个心轴是可移动的并以恒定速率移动。测量该样品的断裂力F(以牛顿为单位)并计算抗张强度,所述抗张强度定义为断裂力F对样品质量的比。
在制造后(称为TSfab的初始抗张强度)和在105℃的温度和100%相对湿度下在高压釜中加速老化15分钟后(TS15)测量该抗张强度。
- 隔离性产品的初始厚度,以及以等于4.8/1(实施例7至12和15至17)和8/1(实施例13和14)的压缩度(定义为标称厚度对压缩下厚度的比)在不同时间下压缩后的厚度。该厚度测量能够评价该产品的良好的尺寸行为。
- 在标准EN 1609的条件下的吸水率,表示为每平方米隔离性产品吸收的水的千克数。表现出小于1千克/平方米的吸水率的隔离性产品被视为具有低的短期吸水率(24小时);它们根据ACERMI认证属于“WS”类别。
实施例1至6
制备包含表1中以重量份为单位给出的成分的粘合组合物。
该粘合组合物通过连续向含有水的容器中添加还原性糖、氢化糖、柠檬酸和次磷酸钠(催化剂),剧烈搅拌直到成分已经完全溶解来制备。
与根据WO 01/96254 A1的实施例2,试验1制备的含有酚醛树脂和脲的常规粘合组合物(参比)比较和与不含氢化糖的组合物(对比例6)比较来评价表1中给出的粘合组合物的性质。
实施例1至5的粘合组合物具有可与对比例6和参比相比的交联起始温度(TR)。
本发明的粘合组合物的pH类似于对比例6的pH。
实施例1至5的粘度(不考虑干提取物)低于对比例6。尤其是具有70和75%干提取物的实施例4的组合物具有大约1/3的粘度。
实施例7至14
这些实施例描述了在工业生产线中制造隔离性产品。
玻璃棉在2.4米宽的生产线上通过内部离心技术以连续方式制造,其中熔融玻璃组合物借助称为离心盘的工具转化为纤维,该工具包含形成用于接收熔融组合物的室的篮和穿刺大量小孔的外周带:该盘围绕其垂直设置的对称轴旋转,该组合物在离心力的作用下经该小孔喷出,由该小孔漏出的材料在拉制气流的帮助下拉伸成纤维。
通常,施胶喷雾环位于成纤盘下方以便在刚刚成形的玻璃棉上均匀分布该施胶组合物。
在装有内部吸气箱的带式输送机上收集由此施胶的矿棉,该内部吸气箱使矿棉在输送机表面上保持为网辐或毡的形式。该输送机连续穿过保持在270℃的烘箱,在烘箱中该施胶剂聚合形成粘合剂。
在烘箱末端获得的隔离性产品具有17.5 kg/m3的标称密度和75 mm的标称厚度(实施例7至12)或10.6 kg/m3的标称密度和80 mm的标称厚度(实施例13和14)。
所用粘合组合物在表2中给出,量以重量份为单位。它们仅通过在剧烈搅拌下将成分混合到水中直到成分已经完全分散或溶解来制备。
对比于下列粘合组合物评估该隔离性产品的性质:
- 实施例6(对比)的粘合组合物,向其中加入添加剂(硅烷和矿物油):实施例11;
-包含实施例1至6中提及的酚醛树脂和脲、硫酸铵和上述添加剂的粘合组合物(参比):实施例12和14。
通过使用具有6.0%在喷雾环处的干提取物(高于对比例11中,等于5.1%)的粘合组合物获得本发明的实施例7至10的产品。实施例7至10的产品的抗张强度与压缩后厚度类似于实施例11。
实施例7至10和13的产品的厚度也分别类似于使用酚醛树脂的对比例12和14的产品的那些。该抗张强度,虽然对于对比例12和14,但也可接受。
实施例15至17
在实施例7至12中公开的条件下制造具有17.5 kg/m3的标称密度和75 mm的标称厚度的隔离性产品,改进之处在于将烧灼损失降低至5.2%。
所用粘合组合物以及由此获得的隔离性产品的性质在表3中给出。
实施例15和16的产品具有非常类似于对比例17的产品的压缩后厚度。这些实施例的抗张强度几乎与实施例17一样高。
吸水率低,并保持在1 kg/m²的最大限度下。
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Claims (25)
1.基于矿棉,尤其是岩矿棉或玻璃矿棉的隔离性产品用的粘合组合物,其特征在于其包含:
- 至少一种还原性糖,
- 至少一种氢化糖,和
- 至少一种多官能交联剂,
该氢化糖占该还原性糖和氢化糖的总重量的10至90%。
2.如权利要求1所述的组合物,其特征在于该还原性糖选自含有3至8个、优选5至7个碳原子的还原性单糖。
3.如权利要求2所述的组合物,其特征在于该还原性单糖是醛糖。
4.如权利要求3所述的组合物,其特征在于该醛糖是己糖如葡萄糖、甘露糖和半乳糖。
5.如权利要求1所述的组合物,其特征在于该还原性糖是具有低于100 000、优选低于50 000、有利地低于10 000且更好高于180的重均分子量的还原性多糖。
6.如权利要求5所述的组合物,其特征在于该还原性多糖由超过50重量%的葡萄糖单元构成。
7.如权利要求1至6之一所述的组合物,其特征在于该还原性糖是还原性单糖和/或还原性多糖的混合物,特别是糊精。
8.如权利要求7所述的组合物,其特征在于该糊精具有大于或等于5、优选大于或等于10、有利地大于或等于15并且更好小于100的葡糖当量。
9.如权利要求1至8之一所述的组合物,其特征在于该氢化糖选自赤藓糖醇、阿糖醇、木糖醇、山梨糖醇、甘露醇、艾杜糖醇、麦芽糖醇、异麦芽糖醇、乳糖醇、cellobitol、异麦芽酮糖醇、麦芽三糖醇和淀粉水解物的氢化产物。
10.如权利要求9所述的组合物,其特征在于该氢化糖是淀粉水解物的氢化产物,优选为麦芽糖醇糖浆。
11.如权利要求9或10所述的组合物,其特征在于该氢化糖具有低于100 000、优选低于50 000、有利地低于5000、更特别低于1000且更好高于150的数均分子量。
12.如权利要求1至11之一所述的组合物,其特征在于该氢化糖占该还原性糖和氢化糖的总重量的18至80%,优选30至70%且有利地为40至60%。
13.如权利要求1至12之一所述的组合物,其特征在于该多官能交联剂选自有机多元羧酸或这些酸的盐、酸酐和多元醛。
14.如权利要求13所述的组合物,其特征在于该有机多元羧酸包含至少两个羧基官能、优选最多300个、有利地最多70个且更好最多15个羧基官能。
15.如权利要求14所述的组合物,其特征在于该有机多元羧酸是非聚合或聚合的酸,并且其特征在于其具有通常小于或等于50 000、优选小于或等于10 000和有利地小于或等于5000的数均分子量。
16.如权利要求14或15所述的组合物,其特征在于该有机多元羧酸是非聚合的,并含有两个至四个羧基官能。
17.如权利要求13所述的组合物,其特征在于该酸酐是马来酸酐、琥珀酸酐或邻苯二甲酸酐。
18.如权利要求13所述的组合物,其特征在于该多元醛是非聚合二醛,如乙二醛、戊二醛、1,6-己二醛或1,4-对苯二醛。
19.如权利要求1至18之一所述的组合物,其特征在于该还原性糖和氢化糖占由该还原性糖、该氢化糖和该多官能交联剂组成的混合物重量的10至90%,优选20至85%、有利地为30至80%、更好40至65%且特别有利地为45至65%。
20.如权利要求1至19之一所述的组合物,其特征在于其进一步包含选自路易斯酸和碱、含磷化合物和含氟与硼的化合物的催化剂。
21.如权利要求20所述的组合物,其特征在于该催化剂占该还原性糖、该氢化糖和该多官能交联剂的总重量的最多20%,优选最多10%,并且其有利地至少等于1%。
22.如权利要求1至21所述的组合物,其特征在于其以基于100重量份还原性糖、氢化糖与多官能交联剂计算的下列比例进一步包含下列添加剂:
- 0至2份的硅烷,特别是氨基硅烷或环氧硅烷,
- 0至20份的油,优选4至15份,
- 0至30份的脲,优选0至20份,
- 0至5份的有机硅,
- 0至20份不同于前述糖类的多元醇,
- 0至30份“增量剂”,选自木质素衍生物如木质素磺酸铵(ALS)或木质素磺酸钠,以及动物或植物蛋白质。
23.通过如权利要求1至22之一的粘合组合物粘接的基于矿棉,尤其是玻璃矿棉或岩矿棉的隔音和/或隔热产品。
24.通过通过如权利要求1至22之一的粘合组合物粘接的矿物纤维,尤其是玻璃或岩石的矿物纤维的垫。
25.制造如权利要求23所述的基于矿棉的隔音和/或隔热产品或如权利要求24所述的矿物纤维垫的方法,由此制造矿棉或矿物纤维,将粘合组合物喷射到所述矿棉或所述纤维上,并在允许该粘合组合物交联并形成不熔性粘合剂的温度下处理所述矿棉或所述纤维,其特征在于该粘合组合物包含:
- 至少一种还原性糖,
- 至少一种氢化糖,和
- 至少一种多官能交联剂,
该氢化糖占该还原性糖和氢化糖的总重量的10至90%。
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