CN108350193A - 改进的粘合剂组合物及其用途 - Google Patents
改进的粘合剂组合物及其用途 Download PDFInfo
- Publication number
- CN108350193A CN108350193A CN201680062342.3A CN201680062342A CN108350193A CN 108350193 A CN108350193 A CN 108350193A CN 201680062342 A CN201680062342 A CN 201680062342A CN 108350193 A CN108350193 A CN 108350193A
- Authority
- CN
- China
- Prior art keywords
- crosslinking agent
- adhesive composition
- azetidin
- acid
- polysaccharide
- 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.)
- Granted
Links
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- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 claims abstract description 33
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
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- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
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- 239000003784 tall oil Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- PNWOTXLVRDKNJA-UHFFFAOYSA-N tert-butylperoxybenzene Chemical compound CC(C)(C)OOC1=CC=CC=C1 PNWOTXLVRDKNJA-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J103/00—Adhesives based on starch, amylose or amylopectin or on their derivatives or degradation products
- C09J103/04—Starch derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
- B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/003—Crosslinking of starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract
本发明涉及一种物质组装件,它包括通过含单糖和/或多糖,和氮杂环丁交联剂,和可能地由多糖与氮杂环丁交联剂之间交联得到的反应产物的可固化粘合剂组合物或者通过将含单糖和/或多糖,和氮杂环丁交联剂,和可能地由多糖与氮杂环丁交联剂之间交联得到的反应产物的水性可固化粘合剂组合物置于固化条件下获得的粘合剂粘结在一起的矿物纤维,合成纤维或天然纤维,纤维素颗粒或片材材料。该粘合剂组合物可进一步包括能经历自由基聚合的交联剂。还公开了粘合剂组合物和制造所述物质组装件的方法。
Description
本发明涉及新型的改进粘合剂组合物,更具体地,在由非组装或松散组装的物质的集合体来制造产品中使用的可固化的粘合剂组合物。例如,这些粘合剂组合物可用于制造纤维产品,所述纤维产品可由织造或非织造纤维制造。在一个示意性的实施方案中,该粘合剂组合物用于粘结玻璃纤维,以制造玻璃纤维。在另一示意性实施方案中,该粘合剂组合物用于在毡制层,例如绝缘产品内粘结岩棉纤维,例如玻璃棉或岩棉。在进一步的实施方案中,该粘合剂用于制造例如具有所需物理性能(例如,机械强度)的木纤维板,刨花板或定向刨花板(OSB)。进一步地,该粘合剂可用于组装纤维素材料的片材,例如木材片,以制造胶合板。本发明进一步延伸到使用所述粘合剂组合物粘结松散组装的物质的方法,和由通过本发明的粘合剂粘结的松散组装的物质制造的产品。
最近开发了若干种无甲醛的粘合剂组合物。一种这样的可固化的粘合剂组合物牵涉可持续的材料,且基于聚酯化学品,更特别地含多酸组分或酸酐或其盐衍生物和多羟基组分,可能地与含硅化合物一起的可固化的水性粘合剂组合物。另一种这样的组合物牵涉缩合无机酸或多羧酸的铵盐或胺,优选多胺与还原糖作为热固性树脂。与现有技术的甲醛基技术相比,这些化学品显示出优点,但导致显示出变色的固化树脂,而变色在某些应用中可能是非所需的。因此,仍然需要改进的粘合剂化学品。进一步对改进所使用的粘合剂组合物的粘结强度,进而提供显示出改进的性能的改进的最终产品,和/或在更加有利的成本下具有降低的粘合剂含量的最终产品存在持续的兴趣。
本发明寻求提供包括矿物纤维,合成纤维和天然纤维,纤维素粒子或片材材料的物质的组装件,其显示出改进的性能,其中包括不那么非所需的变色和可能地改进的机械性能。
本发明的另一目的是提供此处以上定义的物质组装件的制备方法。
本发明另一目的是提供适合于生产的成本合算的方法。
另一目的是提供基于可再生和/或可持续资源的改进的粘合剂组合物。
进一步地,本发明寻求提供快速固化成牢固粘合剂的粘合剂组合物。
本发明现在提供根据所附权利要求的产品,方法和粘合剂组合物。
本发明的产品在于物质的组装件,它包括通过粘合剂粘结在一起的矿物纤维,合成纤维或天然纤维,纤维素粒子或片材材料,所述粘合剂通过将含单糖或多糖和氮杂环丁交联剂的水性可固化粘合剂组合物置于固化条件下而获得。所述粘合剂组合物也可包括由糖和氮杂环丁交联剂之间交联得到的一些反应产物。
单糖可有利地为5碳或6碳单糖,优选右旋糖。多糖包括至少两个,优选至少四个糖单元和最多106个糖单元,优选最多10000个糖单元,更优选最多5000或甚至3000个糖单元。它可有利地选自天然淀粉和淀粉衍生物。淀粉包括D-吡喃型葡萄糖的两种不同聚合物:直链淀粉和支链淀粉。直链淀粉是一种直链多糖,而支链淀粉是一种高度支化的多糖。直链淀粉具有聚合度范围为1000至10000个葡萄糖单元且Mw>106g/mol的相对低分子量,而支链淀粉是聚合度超过105且Mw>107g/mol的较大支化的多糖。淀粉衍生物包括,但不限于,淀粉醚,例如羧甲基淀粉,羟烷基淀粉,阳离子淀粉,两性淀粉,淀粉酯,例如淀粉乙酸酯,淀粉磷酸酯,淀粉辛烯基琥珀酸酯,酸改性淀粉,氧化改性淀粉,和部分水解的淀粉,其中包括,但不限于,糊精。多糖也可衍生于纤维素或其他天然或合成来源,例如甲壳素。淀粉衍生物包括糊精和麦芽糊精,它们由含2-20个葡萄糖单元的可变链长连接的D-葡萄糖单元组成。
氮杂环丁交联剂是本领域已知的。可使用有具不同比值的不同偶联剂和胺官能的单体,制造多官能氮杂环丁交联剂,所述胺官能的单体含有至少一个取代或未取代的四元含氮杂环。氮杂环丁基团与均聚物或共聚物链一起化学键合,所述均聚物或共聚物链包括在该聚合物结构内掺入的一个或多个非-氮杂环丁单体单元。适合于使用的优选的氮杂环丁基材料包括在链内至少两个氮杂环丁基。根据本发明的优选的氮杂环丁聚合物显示出下述通式结构:
其中n是整数,一般地n≥1,R1可以是C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,它们可能地被羟基,羧基官能团或胺取代;
R2可以独立地为R1或-R3-NH-C(O)-R4-,其中R3和R4独立地为C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,
Y1和Y3是H或C1-C5烷基,它可能被羟基,胺或羧基取代,
Y2是OH或独立地为Y1,
X-是卤素抗衡离子。
氮杂环丁官能化的聚合物具有高度反应性的季铵基,它可改进最终产品的性能,且因存在阳离子氮杂环丁基团导致可提供抗微生物活性。氮杂环丁官能团因角张力导致具有反应性,且可与许多亲核物反应。氮杂环丁交联剂在高温下和/或通过自由基引发而聚合。
在有利的实施方案中,以干重为基础,单糖和/或多糖对氮杂环丁交联剂的重量比包括99/1至60/40,优选98/2至70/30,更优选95/5至75/25。
已发现,当以上定义的水性粘合剂组合物施加到玻璃纤维薄毡上时,一旦固化,则它显示出高的粘结强度,甚至在气候老化之后。与现有技术的热固性粘合剂相比,在气候老化之后粘结强度的损失显著减少。
用本发明的粘合剂组合物粘结的薄毡产品的粘结强度可受到组合物pH的轻微影响,尤其在较低的相对氮杂环丁含量下。更特别地,在较高淀粉/氮杂环丁之比下,粘合剂组合物的碱性pH倾向于轻微降低粘结强度(干和湿),而酸性pH推高粘结强度。
根据优选的实施方案,该水性粘合剂组合物包括通过氮杂环丁交联剂交联的单糖和/或多糖,和进一步包括能经历自由基聚合的交联剂。这种交联剂可选自多羧酸,丙烯酰胺和甲基丙烯酰胺,丙烯酸类及其盐,丙烯腈,双酚丙烯酸类,碳水化合物单体,氟化丙烯酸类,马来酰亚胺,多官能丙烯酸类,及其混合物。在通过自由基引发剂引发自由基聚合情况下,该组合物可进一步包括一种或多种自由基引发剂以供引发糖残基和交联剂之间的进一步的交联反应。这种反应机理是本领域公知的。可通过提供能量,其中包括热和/或合适的辐射,引发反应。一旦固化,则这种粘合剂组合物产生高度交联的树脂,所述高度交联的树脂赋予本发明的物质组装件进一步改进的粘结强度。已发现,两段聚合提供显示出高聚合密度的高度聚合的树脂,所述两段聚合包括特征在于自由基聚合的第二步。这种树脂赋予基底,例如纤维和纤维素粒状物或片材材料高的粘结强度。
本发明的粘合剂组合物尤其适合于粘结纤维和纤维素粒状物或片材材料,因为固化很少或者没有释放水,因此降低蒸发在最终产品内包含的水所要求的能量。
多羧酸可有利地选自单体和聚合的多羧酸。示意性地,单体多羧酸可以是二羧酸,其中包括,但不限于,不饱和脂族二羧酸,饱和脂族二羧酸,芳族二羧酸,不饱和环状二羧酸,饱和环状二羧酸,其任选地被例如羟基、卤素、氨基、烷基、羧基、烷氧基、酸酐、盐、酯及其混合物取代。有利地,单体多羧酸选自苹果酸,谷氨酸,戊烯二酸,3-富马酰基丙酮酸,2,5-呋喃二羧酸,中康酸,丙酮二酸,戊二酸,奈多罗米,4-(γ-谷氨酰基氨基)丁酸,neoglutyl和琥珀酸。其他合适的多羧酸考虑包括,但不限于,乌头酸,己二酸,壬二酸,丁四羧酸二酐,丁三羧酸,氯菌酸,柠康酸,二环戊二烯-马来酸加合物,二亚乙基三胺五乙酸,二戊烯和马来酸的加合物,乙二胺四乙酸(EDTA),完全马来酸化的松香,马来酸化妥尔油脂肪酸,富马酸,戊二酸,间苯二甲酸,衣康酸,用过氧化钾氧化成醇,然后借助与二氧化碳的KOLBE-Schmidt反应而反应的羧酸,马来酸,苹果酸,中康酸,双酚A或双酚F,以引入3-4个羧基的马来酸化松香;草酸,邻苯二甲酸,癸二酸,琥珀酸,酒石酸,对苯二甲酸,四溴邻苯二甲酸,四氯邻苯二甲酸,四氢邻苯二甲酸,偏苯三酸,均苯三酸和类似物,和酸酐,及其组合。示意性地,聚合的多羧酸可以是酸,例如聚丙烯酸,聚甲基丙烯酸,聚马来酸,和类似的聚合多羧酸,其共聚物,其酸酐,及其混合物。可商购的聚丙烯酸的实例包括AQUASET-529(Rohm&Haas,Philadelphia,PA,USA),CRITERION 2000(Kemira,Helsinki,Finland,欧洲),NF1(H.B.Fuller,St.Paul,MN,USA),和SOKALAN(BASF,Ludwigshafen,欧洲德国)。关于SOKALAN,它是分子量为约4000的水溶性丙烯酸和马来酸的聚丙烯酸共聚物。AQUASET-529是含用甘油交联的聚丙烯酸,还含有次磷酸钠作为催化剂的组合物。CRITERION 2000是分子量为约2000的聚丙烯酸的部分盐的酸性溶液。关于NF1,它是一种含羧酸官能度和羟基官能度,以及不具有任意这两个官能度的单元的共聚物;NF1还含有链转移剂,例如次磷酸钠或有机基磷酸酯(organophosphate)催化剂。聚合的多羧酸可以是由不饱和羧酸制备的均聚物或共聚物,所述不饱和羧酸包括,但不一定限于,丙烯酸,甲基丙烯酸,巴豆酸,异巴豆酸,马来酸,肉桂酸,2-甲基马来酸,衣康酸,2-甲基衣康酸,α,β-亚甲基戊二酸,和类似物。或者,聚合的多羧酸可以由不饱和酸酐制备,所述不饱和酸酐包括,但不一定限于,马来酸酐,衣康酸酐,丙烯酸酐,甲基丙烯酸酐,和类似物,以及它们的混合物。聚合这些酸和酸酐的方法是化学领域公知的。聚合的多羧酸可另外包括一种或多种前述不饱和羧酸或酸酐和一种或多种乙烯基化合物的共聚物,所述乙烯基化合物包括,但不一定限于苯乙烯,α-甲基苯乙烯,丙烯腈,甲基丙烯腈,丙烯酸甲酯,丙烯酸乙酯,丙烯酸正丁酯,丙烯酸异丁酯,甲基丙烯酸甲酯,甲基丙烯酸正丁酯,甲基丙烯酸异丁酯,甲基丙烯酸缩水甘油酯,乙烯基甲醚,乙酸乙烯酯,和类似物。聚合的多羧酸和尤其聚丙烯酸聚合物的分子量可以小于10000道尔顿(Da),小于5000Da,或小于或等于约3000Da。例如,分子量可以是2000Da。
丙烯酰胺和甲基丙烯酰胺单体的合适的实例包括烷基丙烯酰胺,N-叔丁基丙烯酰胺,双丙酮丙烯酰胺,N,N-二乙基丙烯酰胺,N,N-二乙基甲基丙烯酰胺,N,N-二甲基丙烯酰胺,N-[3-(二甲基氨基)丙基]甲基丙烯酰胺,N-二苯基甲基丙烯酰胺,N-乙基丙烯酰胺,N,N'-六亚甲基双(甲基丙烯酰胺),N-羟乙基丙烯酰胺,N-(羟甲基)丙烯酰胺,N-(2-羟丙基)-2-甲基-丙-2-烯酰胺,N-(异丁氧基甲基)-丙烯酰胺,N-异丙基丙烯酰胺,N-异丙基甲基丙烯酰胺,甲基丙烯酰胺,N-(3-甲氧基丙基)丙烯酰胺,N-苯基丙烯酰胺,2-丙烯酰胺基-2-甲基-1-丙磺酸及其盐,3-(丙烯酰胺即)苯基硼酸,N-丙烯酰基酰胺基乙氧基乙醇,N-(三苯基甲基)-甲基丙烯酰胺和N-[三(羟甲基)甲基]-丙烯酰胺。
合适的丙烯酸酯单体的实例包括丙烯酸4-乙酰氧基苯乙酯,4-丙烯酰基吗啉,丙烯酸丁酯,丙烯酸2-(4-苯甲酰基-3-羟基苯氧基)乙酯,2-丙基丙烯酸苄酯,丙烯酸叔丁酯,丙烯酸2-[[(丁基氨基)羰基]氧基]乙酯,丙烯酸4-叔丁基环己酯,丙烯酸2-羧乙酯,丙烯酸2-(二乙基氨基)乙酯,二(乙二醇)乙醚丙烯酸酯,二(乙二醇)2-乙基己基醚丙烯酸酯,丙烯酸2-(二甲基氨基)乙酯,丙烯酸3-(二甲基氨基)丙酯,二季戊四醇五-/六-丙烯酸酯,丙烯酸乙酯,顺式-(β-氰基)丙烯酸乙酯,乙二醇二环戊烯基醚丙烯酸酯,乙二醇甲醚丙烯酸酯,乙二醇苯醚丙烯酸酯,2-乙基丙烯酸乙酯,丙烯酸2-乙基己酯,2-丙基丙烯酸乙酯,2-(三甲基甲硅烷基甲基)丙烯酸乙酯,丙烯酸己酯,丙烯酸4-羟丁酯,丙烯酸2-羟乙酯,丙烯酸2-氰基-3-苯氧基丙酯,丙烯酸羟丙酯,丙烯酸异丁酯,丙烯酸异癸酯,丙烯酸异辛酯,丙烯酸月桂酯,2-乙酰胺基丙烯酸甲酯,丙烯酸甲酯,3-羟基-2-亚甲基丁酸甲酯,丙烯酸十八烷酯,聚(乙二醇)丙烯酸酯,聚(乙二醇)二丙烯酸酯,聚(乙二醇)甲醚丙烯酸酯,聚(丙二醇)丙烯酸酯,丙烯酸3-磺基丙酯和盐,丙烯酸四氢糠酯,丙烯酸2-四氢吡喃酯,丙烯酸3-(三甲氧基甲硅烷基)丙酯,丙烯酸3,5,5-三甲基己酯,丙烯酸10-十一碳烯基酯,和氨基甲酸酯丙烯酸酯甲基丙烯酸酯。
优选的甲基丙烯酸酯单体可包括甲基丙烯酸烯丙酯,甲基丙烯酸氨乙酯,甲基丙烯酸2-[3-(2H-苯并三唑-2-基)-4-羟苯基]乙酯,甲基丙烯酸苄酯,双(2-甲基丙烯酰基)氧基乙基二硫化物,双(2-甲基丙烯酰基)氧基乙基二硫化物,甲基丙烯酸2-(2-溴异丁酰基氧基)乙酯,甲基丙烯酸2-(叔丁基氨基)乙酯,甲基丙烯酸丁酯,甲基丙烯酸叔丁酯,甲基丙烯酸咔唑-9-乙酯,甲基丙烯酸3-氯-2-羟丙酯,甲基丙烯酸环己酯,甲基丙烯酸2-(二乙基氨基)乙酯,乙二醇丁醚甲基丙烯酸酯,二(乙二醇)甲醚甲基丙烯酸酯,甲基丙烯酸2-(二异丙基氨基)乙酯,甲基丙烯酸2-(二甲基氨基)乙酯,甲基丙烯酸2-乙氧基乙酯,乙二醇二环戊烯基醚甲基丙烯酸酯,乙二醇甲基丙烯酸酯磷酸酯,乙二醇甲醚甲基丙烯酸酯,乙二醇苯醚甲基丙烯酸酯,甲基丙烯酸乙基己酯,甲基丙烯酸乙酯,甲基丙烯酸糠酯,甲基丙烯酸缩水甘油酯,甲基丙烯酸糖基氧基乙酯,甲基丙烯酸己酯,甲基丙烯酸羟丁酯,甲基丙烯酸羟乙酯,甲基丙烯酸羟丙酯,甲基丙烯酸羟丙酯,邻苯二甲酸2-羟丙基2-(甲基丙烯酰氧基)乙酯,甲基丙烯酸2-羟基-3-{3-[2,4,6,8-四甲基-4,6,8-三(丙基缩水甘油基醚)-2-环四硅氧烷基]丙氧基}丙酯,甲基丙烯酸异丁酯,甲基丙烯酸2-异氰酸根合乙酯,甲基丙烯酸异癸酯,甲基丙烯酸月桂酯,甲基丙烯酸N-羟基琥珀酰亚胺酯,甲基丙烯酸甲酯,甲基丙烯酸2-(甲硫基)乙酯,马来酸单-2-(甲基丙烯酰氧基)乙酯,琥珀酸单-2-(甲基丙烯酰氧基)乙酯,甲基丙烯酸2-N-吗啉基乙酯,甲基丙烯酸萘酯,甲基丙烯酸2-(2-氧代-1-咪唑烷基)乙酯,甲基丙烯酸五溴苯酯,1,4-亚苯基二甲基丙烯酸酯,甲基丙烯酸苯酯,磷酸2-羟乙基甲基丙烯酸酯,聚(乙二醇)二十二烷基醚甲基丙烯酸酯,聚(丙二醇)甲基丙烯酸酯,甲基丙烯酸丙酯,甲基丙烯酸1-芘甲酯,甲基丙烯酸硬脂酯,甲基丙烯酸3-磺基丙酯和盐,甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯,甲基丙烯酸3,3,5-三甲基环己酯,甲基丙烯酸(三甲基甲硅烷酯),氨基甲酸酯丙烯酸酯甲基丙烯酸酯,氨基甲酸酯环氧基甲基丙烯酸酯和甲基丙烯酸乙烯酯。
原则上,多官能丙烯酸类用作交联剂,和最优选多官能丙烯酸类化合物选自甲基丙烯酸3-(丙烯酰氧基)-2-羟丙酯,磷酸双[2-(甲基丙烯酰氧基)乙酯],双酚A丙氧基化二丙烯酸酯,1,3-或4-丁二醇二丙烯酸酯,1,3或4-丁二醇二甲基丙烯酸酯,N,N'-(1,2-二羟基亚乙基)双丙烯酰胺,二(乙二醇)二甲基丙烯酸酯,二(三羟甲基丙烷)四丙烯酸酯,二氨基甲酸酯二甲基丙烯酸酯,N,N'-亚乙基双(丙烯酰胺),乙二醇二甲基丙烯酸酯,甘油1,3-双甘油化(diglycerolate)二丙烯酸酯,甘油二甲基丙烯酸酯,甘油丙氧基化三丙烯酸酯,1,6-己二醇二丙烯酸酯,1,6-己二醇二甲基丙烯酸酯,1,6-己二醇乙氧基化二丙烯酸酯,1,6-己二基双[氧基(2-羟基-3,1-丙二基)]双丙烯酸酯,羟基新戊酰基羟基新戊酸酯双[6-(丙烯酰氧基)己酸酯],新戊二醇二丙烯酸酯,新戊二醇丙氧基化二丙烯酸酯,季戊四醇二丙烯酸酯单硬脂酸酯,季戊四醇四丙烯酸酯,季戊四醇三丙烯酸酯,聚(丙二醇)二丙烯酸酯,聚(丙二醇)二甲基丙烯酸酯,1,3,5-三丙烯酰基六氢-1,3,5-三嗪,三环癸烷二甲醇二丙烯酸酯,三羟甲基丙烷乙氧基化甲醚二丙烯酸酯,三羟甲基丙烷乙氧基化三丙烯酸酯,三羟甲基丙烷乙氧基化三丙烯酸酯,三羟甲基丙烷乙氧基化三丙烯酸酯,三羟甲基丙烷丙氧基化三丙烯酸酯,三羟甲基丙烷三丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,三(丙二醇)二丙烯酸酯和三[2-(丙烯酰氧基)乙基]异氰脲酸酯。
以干重为基础,能经历自由基聚合的交联剂和用于引发糖残基与交联剂之间进一步的交联反应的自由基引发剂的重量比可以在2/0.5至20/1之间变化,优选5/1至10/1。以干重为基础,在粘合剂组合物中交联剂的质量分数可以有利地从2变化到30w%,优选从5到20w%,更优选从5到15w%。
自由基引发剂可包括无机过氧化物,其有利地选自过氧化氢或过氧二硫酸盐,例如过氧二硫酸的单-或二-碱金属盐或铵盐,例如它们的单-和二-钠盐与铵盐。优选的无机过氧化物可以是过硫酸铵或钾或钠或其混合物。
自由基引发剂可进一步包括有机过氧化物,其有利地选自氢过氧化烷基,例如氢过氧化叔丁基,氢过氧化枯基,氢过氧化枯烯,和过氧化二烷基或二芳基,例如二叔丁基或二枯基,过氧化二叔戊基,过氧化苄基,过氧化丁酮,过氧化月桂酰,2,5-双(过氧叔丁基)-2,5-二甲基己烷,1,1-双(过氧叔丁基)-3,3,5-三甲基-环己烷,1,1-双(过氧叔戊基)环己烷,叔丁基过氧苯,和碳酸过氧叔丁基2-乙基己酯。
偶氮化合物也可用作自由基引发剂,且可一般地选自偶氮双(异丁腈)(AIBN),2,2'-偶氮双(2-甲基丙腈),4,4'-偶氮双(4-氰基戊酸),1,1'-偶氮双(环己烷碳腈),2,2-偶氮双(2,4-二甲基戊腈)和2,2'-偶氮双(脒基丙基)二盐酸盐(AIBA)。
用于氧化还原引发剂的合适氧化剂可以选自以上提及的过氧化物。相应的还原剂可选自具有低氧化态的硫化合物,例如碱金属亚硫酸盐,例如亚硫酸钾和/或亚硫酸钠,碱金属,亚硫酸碱金属氢盐,例如亚硫酸氢钾和/或亚硫酸氢钠,焦亚硫酸碱金属盐,例如焦亚硫酸钾和/或焦亚硫酸钠,脂族亚磺酸的钾和/或钠盐,碱金属盐,特别地钾和/或钠盐,和碱金属硫氢化物,例如硫氢化钾和/或硫氢化钠,多价金属的盐,例如硫酸铁(II),硫酸铵铁(II),磷酸铁(II)和铈离子,例如硝酸铵铈。
已发现,本发明的粘合剂组合物显示出形成暗褐色粘合剂树脂的较低倾向(例如,Champagne,Tapioca,Vanilla custard,Papyrus,Nude,Wheat等),该倾向对于碳水化合物基粘合剂化学来说是典型的。
根据优选的实施方案,该水性粘合剂组合物包括通过含至少两个氮杂环丁基团的氮杂环丁交联剂交联的多糖,且进一步包括多糖和引发糖残基与多羧酸之间进一步的交联反应的自由基引发剂。一旦固化,这种粘合剂组合物产生显示出进一步改进的粘结强度的高度交联的树脂。
本发明的粘合剂组合物和由其生产的粘合剂基本上无甲醛(也就是说含小于约1ppm甲醛,基于组合物的重量),且没有释放显著量的甲醛。
本发明的组合物显然可进一步包括偶联剂,染料,抗真菌剂,抗细菌剂,疏水物和本领域已知的用于这种粘合剂应用的其他添加剂,如果适当的话。含硅偶联剂典型地通常以约0.1至约1wt%的范围存在于这种粘合剂内,基于粘合剂组合物内的固体重量。显然选择这些添加剂,例如没有抵消粘合剂的粘合性能,也没有抵消含这种粘合剂组合物的最终产品或由其生产的粘合剂的机械和其他所需性能,且有利地符合严格的环境和健康有关的要求。
在没有束缚于理论的情况下,认为固化产生高度交联的高分子量聚合物。这些可以通过本领域通常已知的技术,其中包括测定分子量和其他已知技术来分析。
根据本发明,术语“粘合剂组合物”没有特别限制,且通常包括或者原样或者固化时,能粘结松散组装物质的任何组合物。该粘合剂组合物优选是水性的非固化组合物,其包括形成热固性粘合剂树脂的起始材料,和可能地由至少一部分相关起始材料反应或部分反应得到的反应产物,和可能地添加剂。
本文中所使用的术语“水性”没有特别限制且通常涉及基于水作为溶剂的溶液和/或分散体。所述术语进一步包括含有水和一种或多种额外溶剂的组合物或混合物。本发明的“水性粘合剂组合物”可以是一种或多种所述粘合剂组分的溶液或部分溶液,或者可以是分散体,例如乳液或悬浮液。
本发明的水性粘合剂组合物中的固体含量范围可以是5至95w%,有利地8至90w%,优选10至85w%,基于全部水性粘合剂组合物的重量。更具体地,当用作矿棉绝热的粘合剂时,该水性粘合剂组合物的固体含量范围可以是5至25w%,优选8至20w%,更优选10至20w%或甚至12至18w%,基于全部水性粘合剂组合物的重量。当在木板,例如胶合板,刨花板,纤维板中用作粘合剂时,该水性粘合剂组合物的固体含量范围可以是50至95w%,优选50至90w%,更优选55至85w%或甚至60至80w%,基于全部水性粘合剂组合物的重量。
本发明的粘合剂组合物可进一步包括由无机材料,例如金属氧化物,优选MgO,CaO,Al2O3和CaCO4衍生的纳米颗粒。此外,纳米粘土可掺入到粘合剂配方内。这种纳米粘土没有限制地包括蒙脱土,膨润土,高岭石,水辉石和埃洛石和其他有机改性纳米粘土,和/或其混合物。这种无机材料的存在量范围可以是0.1至10w%,优选0.1至5w%全部组合物的固体含量。
本发明粘合剂组合物中的组分可以独立地运输并在相关制造装置中使用之前立即结合。也可原样运输粘合剂组合物。在备选的实施方案中,预反应的交联淀粉可以独立于进一步的交联剂和可能地自由基引发剂运输;然后在根据本发明使用之前,立即结合相关组分。
可使用本发明的粘合剂粘结非组装或松散组装的物质的集合体。该物质集合体包括含选自矿物纤维,其中包括但不限于矿渣棉纤维,岩棉纤维,玻璃纤维,芳族聚酰胺纤维,陶瓷纤维,金属纤维,碳纤维,聚酰亚胺纤维,聚酯纤维,人造丝纤维和纤维素纤维中的纤维的任何物质集合体。物质集合体的进一步的实例包括粒状物,例如煤,纤维素纤维,刨花,锯屑,木浆,粉碎木材,碎木片,木材刨花,木层,其他天然纤维,例如黄麻,亚麻,大麻,稻草,薄木片,夹心面板和其他颗粒,织造或非织造材料。根据本发明的具体实施方案,物质集合体选自木材颗粒和矿物纤维。
在一个示意性的实施方案中,可使用本发明的粘合剂组合物制造含矿物纤维的绝缘产品。在这一应用中,纤维粘结在一起,使得它们在玻璃纤维毡内组织化,然后可将其加工成绝缘产品。在这一应用中,通常存在用量范围为70至99%的纤维。
根据本发明的另一实施方案,可使用该粘合剂粘结纤维素颗粒,例如纤维素纤维,木材刨花,木层或片材,木浆和常用于制造复合木板,其中包括纤维板,刨花板,定向刨花板,胶合板等的其他材料。这种木板显示出范围为6至30mm的标称厚度和至少约1000N/mm2的弹性模量,至少约5N/mm2的弯曲强度和/或至少0.10N/mm2的内部粘结强度。在这一应用中,在最终木板内的粘合剂含量范围可以是约5至30wt%,相对于木板的总重量,尤其9至20%。
根据本发明,可按照本身已知的方式,将该水性粘合剂组合物施加到纤维或粒状材料或片材材料上。可优选通过喷洒施加,施加粘合剂组合物。其他技术包括辊施加或与粘合剂组合物一起混合和/或翻滚物质集合体。当水蒸发时,粘合剂组合物形成将粒状材料粘结在一起的凝胶,当在所需的组装件内排列时,正如本文中以下进一步详述的。当固化时,引起反应性粘合剂组分反应,形成基本上水不溶的大分子粘合剂树脂。与未固化的粘合剂相比,固化因此赋予增加的粘合性,耐久性和耐水性。可在环境温度(约10至25℃)和一直到280℃之间的温度下进行固化。
根据另一方面,本发明覆盖通过施加根据本发明的水性粘合剂组合物,固化和水蒸发,制备纤维状材料或粒状材料或片材材料的粘结组装件的方法。然后可在合适的工艺步骤中进一步加工所得产品,制造中间体或最终产品,其中包括,但不限于,绝缘产品或木板。更具体地,纤维或纤维素颗粒或片材的组装件的制造方法可包括(i)提供(a)单糖或多糖,(ii)提供适量(b)氮杂环丁交联剂,(iii)接续或同时施加(a)和(b),可能地作为含(a)和(b)的水性组合物,和可能地通过(b)交联的(a)到纤维或粒状材料或片材材料上,生产树脂化材料,和(v)将所得树脂化材料置于固化条件下和允许过量水蒸发。
根据本发明的方法的一个特别的实施方案,纤维或纤维素颗粒或片材材料的制造方法可包括接续或同时施加水性组合物到纤维或纤维素粒状物或片材材料上,所述水性组合物包括用(b)和(c)进一步的交联剂,和(d)自由基引发剂交联的(a),可能地作为单一水性组合物,生产树脂化材料,可能地允许发生交联,和将所得水性组合物置于固化条件下并允许蒸发过量水。
可在范围为从环境温度(10至25℃)到200℃,优选40-95℃的温度下进行单体(b)与(a)的共聚反应。可能地,在(d)存在下,用(c)进一步交联可在相同的温度范围内进行。聚合反应也可同时在相同温度范围内进行。
在范围为90-200℃,优选高于140℃,更优选低于190℃,典型地160℃至180℃的温度下进行固化。在木板的制造中,在材料进行挤压的同时进行固化。
以下在实施例中,参考附图更详细地解释本发明,其中:
图1示出了对于70%T&L Stadex79+20%CA1025+10%DEGDMA+1%偶氮双(环己烷碳腈)(ABCN)的粘合剂配方来说,在160℃下测定的固化的动力学评价;和
图2示出了对于70%T&L Stadex79+20%CA1025+10%HEMA+1%偶氮双(环己烷碳腈)的粘合剂配方来说,在160℃下测定的固化的动力学评价。
图3A和3B示出了根据DMA方法,作为温度的函数,两种不同的粘合剂组合物在两种不同频率(1Hz和10Hz)下测量的模量。
图4A和4B示出了根据DMA方法,作为温度的函数,两种其他粘合剂组合物在两种不同频率(1Hz和10Hz)下测量的模量。
粘合剂配方的材料
淀粉聚合物79购自Tate&Lyle。氮杂环丁交联剂CA1025获自SOLENIS。甲基丙烯酸羟乙酯(HEMA),二甘醇二甲基丙烯酸酯(DEGDMA),和1,1'-偶氮双(环己烷腈)(ABCN)购自Aldrich。
制备粘合剂溶液组合物
在室温下,将所需量的糖溶解在水中并恒定地搅拌充足的时间段(在淀粉情况下45分钟)。视需要,可升温到最多80℃,以便在水中溶解糖。对于交联反应来说,添加要求量的氮杂环丁交联剂到糖溶液中。通过在高温下搅拌,和/或通过添加小量自由基引发剂,允许糖交联。然后在玻璃薄毡上浸渍所得混合物,对其进行固化。由固化的薄毡制备样品并进行如下所述的不同试验。
保留以上获得的含氮杂环丁交联剂的一部分糖混合物,然后与HEMA或DEGDMA和自由基引发剂ABCN结合。在预定温度下,进一步连续搅拌所得水性组合物,获得复杂交联的聚合物网络。
可在各种分子之间,例如直链淀粉对直链淀粉,直链淀粉对支链淀粉,或者支链淀粉或支链淀粉之间发生用氮杂环丁交联剂交联淀粉。当形成这些化学键时,可使用自由基引发剂,采用多羧基交联剂进行进一步的交联和/或共聚物反应。可通过增加温度,诱导(adduce)自由基引发所要求的能量。其他方式也可获得,例如IR,RF或UV辐射。施加所得水性组合物到玻璃薄毡上,然后对其进行固化。由固化的薄毡制备样品并如下所述进行不同试验。
固化动力学评价
在各种时间点在设定温度下固化之前,用以上制备的粘合剂溶液浸渍玻璃微纤维(WhatmanTM)GF/A过滤器。将样品保持在烘箱内的顶部支架上,以避免固化期间烘箱内部的高含湿量。对于每一粘合剂溶液来说,固化样品3分钟至20分钟。在固化之后,切割每一固化样品成长度(150mm)和宽度(20mm)的合适尺寸,然后针对劲度和粘结强度分析,进行机械测试。在图1和2中列出了动力学研究或固化速率研究的结果。
使用薄毡方法的粘结强度分析
在600℃下,将商业PF(酚醛树脂)浸渍的(A4大小)玻璃纤维薄毡置于马弗炉烘箱内30分钟,以便烧掉PF粘合剂,然后允许冷却30分钟。称重所得薄毡样品。
将约400g粘合剂样品倾倒在浸没托盘(dip tray)内,并将所得薄毡样品仔细地完全浸没在相关粘合剂溶液内。浸渍的薄毡在所需温度下固化所需的时间段。然后如下所述测量粘合剂含量并测定粘结强度。
借助机械测试仪器(M350-10CT),测定相关固化的粘合剂浸渍的薄毡的粘结强度。对于每一试验来说,将固化粘合剂浸渍的A4薄毡切割成8个同样的长条。使用50Kg的负载池(DBBMTCL-50kg),在由winTest分析软件控制的10mm/min的自动化试验速度下,独立地测试每一长条。将玻璃薄毡的拉伸板固定到测试机上,以确保板之间100mm的间隙。将样品垂直置于夹持器内,并扣除皮重后的力为0。通过软件,评价各种参数,例如峰值最大负载,峰值应力和峰值模量,并作为8个样品的平均值形式列出数据和标准偏差。平均最大峰值负载或峰值应力被定义为粘结强度。
气候老化稳定性的评价
使用电控制的高压釜系统(蒸汽压力容器),灭菌固化的粘合剂薄毡样品以供随后的强度测试。将固化的粘合剂浸渍的薄毡置于高压釜(J8341,容器:具有相关安全阀,门锁装置和一体化的管道构件的PVO2626)系统内。
在90%湿度下和在范围为40℃至110℃的温度下(全循环),在最多2.62bar的压力下处理样品3小时。完全干燥样品,以便确保在薄毡上没有残留湿气。借助本文以上描述的测试机(M350-10CT),测试高压釜处理过的样品的粘结强度,并比较该结果与未处理过的样品。
动态机械分析(DMA)
采用100g 20%固体的预混水性粘合剂溶液,制备尺寸为35mm x10mm x 0.36mm的粘合剂浸渍的WhatmanTM滤纸3(CatalogNo.1003-150)。将粘合剂浸渍的滤纸条保持在环境温度(约22℃)下约1小时以供起始干燥。然后将每一长条仔细地安装在DMA样品保持器上。在双悬臂模式下,使用两个频率(例如1Hz和10Hz),在1℃/min下进行DMA试验。作为扫描温度的函数,测量模量,并在图3-4中列出了结果。
实施例1:
正如表1中所列出的,测定在140℃下固化2小时时粘合剂固体的重量损失。使以上制备的水性粘合剂组合物(溶液)达到22.5%的固体含量。将约12g溶液置于铝培养皿内并在烘箱中在140℃下保持2小时。测定理论和实验固体并计算固体损失。粘合剂组合物包括淀粉作为多糖,氮杂环丁化合物作为交联剂,丙烯酸酯类(HEMA:甲基丙烯酸2-羟乙酯,或DEGDMA:二(乙二醇)二甲基丙烯酸酯)作为进一步的交联剂,和ABCN(1,1-偶氮双(环己烷碳腈)作为自由基引发剂。
表1
粘合剂材料 | 组合物 | 固体损失(%) |
Stadex79/CA1025 | 90/10 | 2.4 |
Stadex79/CA1025/HEMA/ABCN | 80/10/10/1 | 0.12 |
Stadex79/CA1025 | 85/15 | 1.7 |
Stadex79/CA1025/HEMA/ABCN | 75/15/10/1 | 0.003 |
Stadex79/CA1025 | 80/20 | 3.49 |
Stadex79/CA1025/HEMA/ABCN | 70/20/10/1 | 3.49 |
Stadex79/CA1025/DEGDMA/ABCN | 70/20/10/1 | 10.04 |
实施例2:
如图1中所列出的,在160℃下测定Stadex79/CA1025/DEGDMA/ABCN:70/20/10/1的粘合剂配方的固化动力学评价和五个复制品的标准偏差。根据前一部分中描述的工序,制备粘合剂组合物并测量相应样品的劲度。
实施例3:
如图2中所列出的,在160℃下测定Stadex79/CA1025/HEMA/ABCN:70/20/10/1的粘合剂配方的固化动力学评价和五个复制品的标准偏差。根据前一部分中给出的说明,制备粘合剂组合物。
在实施例2和3中,将一些样品暴露于额外的步骤,例如UV辐射下5分钟,以便提高固化,并比较该结果与相应未暴露的样品。似乎该粘合剂显示出范围为3-5分钟的良好的固化时间。进一步地,在温度固化之前,通过UV辐射提高固化。
实施例4:
列出了在有或无ABCN情况下,单糖(例如,一水合右旋糖,DMH),二糖(一水合麦芽糖,麦芽糖MH)和多糖(麦芽糊精,3至19个糖单元),以及它们与淀粉(stadex 79),CA1025,HEMA的组合的各种粘合剂配方的粘结强度分析。在固化(180℃下15分钟)的薄毡样品上,在干燥条件下针对未气候老化和气候老化处理过的薄毡二者进行机械试验,并基于8个复制品,列出该结果和标准偏差,如表2所示。
表2
实施例5:
进行各种粘合剂配方的粘结强度分析,所述粘合剂配方包括淀粉,氮杂环丁交联剂(CA1025),且在组合物中有和无丙烯酸酯(HEMA)和自由基引发剂(ABCN或Ce4+)。粘结强度定义为薄毡浸渍的固化样品断裂时的最大负载。针对未气候老化和气候老化处理的薄毡样品示出了结果。这些浸渍的薄毡在所需温度(例如180℃)下固化15分钟,并在干燥条件下进行机械试验。基于16个复制品,列出了结果与标准偏差,如表3所示。本发明的组合物对所有样品显示出高的粘结强度。注意粘结强度或者保持在统计偏差以内的相同范围内或者在气候老化处理之后得到改进。
表3
实施例6:
正如图3A和图3B中分别列出的,对含Stadex79/CA1025:85/15,Stadex79/CA1025/HEMA/ABCN:75/15/10/1的粘合剂配方进行通过DMA的模量分析。结果表明,与第一配方(图3A)相比,在第二配方(图3B)情况下,显著较高的模量。与比例为80/20的Stadex79/CA1025的组合物(参见图4A)相比,对于含比例为70/20/10/1的Stadex79/CA1025/HEMA/ABCN的组合物(图4B)来说,获得类似结果。
实施例7:
采用不同淀粉反复实施例5的实验,所不同的是固化温度为190℃,和固化时间为10分钟。在下表中示出了所得数据。
上述实施例利用以上提及的可商购的淀粉。正如以下通过粘度测量所显示的,Stadex淀粉是低分子量淀粉,Ethylex 2040和2095淀粉是较高分子量的淀粉。
表6:改性淀粉的粘度测量
使用DV-II+Pro Viscometer Brookfield LV,测量粘度。所有测量在恒温下进行。
Claims (22)
1.一种物质组装件,它包括通过含有单糖和/或多糖、氮杂环丁交联剂、和可能地由多糖与氮杂环丁交联剂之间交联得到的反应产物的可固化粘合剂组合物,或者通过将含有单糖和/或多糖、氮杂环丁交联剂、和可能地由多糖与氮杂环丁交联剂之间交联得到的反应产物的水性可固化粘合剂组合物置于固化条件下获得的粘合剂而粘结在一起的矿物纤维,合成纤维或天然纤维,纤维素颗粒或片材材料。
2.权利要求1的物质组装件,其中多糖包括至少两个,优选至少四个糖单元,至最多106个糖单元,优选最多10000个糖单元,更优选最多5000或甚至3000个糖单元,且可选自包括但不限于下述的天然资源:部分水解或完全水解的纤维素,其衍生物,甲壳素,粗淀粉和淀粉衍生物。
3.权利要求1或2的物质组装件,其中氮杂环丁交联剂由至少两个单体单元,优选下式的聚氮杂环丁构成:
其中R1可以是C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,它们可以被羟基,羧基官能团或胺取代;
R2可以独立地为R1或-R3-NH-C(O)-R4-,其中R3和R4独立地为C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,
Y1和Y3是H或C1-C5烷基,它可以被羟基,胺或羧基取代,
Y2是OH或独立地为Y1,
X-是卤素抗衡离子;
更特别地,该产品编码为CA1025。
4.权利要求1-3任何一项的物质组装件,其中以干重为基础,单糖和/或多糖对氮杂环丁交联剂的重量比包括99/1至60/40,优选98/2至70/30,更优选95/5至75/25。
5.权利要求1-4任何一项的物质组装件,其中粘合剂组合物包括用氮杂环丁交联剂交联的单糖和/或多糖,且进一步包括能经历自由基聚合的交联剂和可能地自由基引发剂。
6.权利要求1-5任何一项的物质组装件,其中能经历自由基聚合的交联剂选自多羧酸,丙烯酰胺,甲基丙烯酰胺,丙烯酸酯,丙烯酸类和它们的盐,丙烯腈,双酚丙烯酸类,碳水化合物单体,氟化丙烯酸类,马来酰亚胺及其混合物以供引发糖残基和交联剂之间进一步的交联反应。
7.权利要求1-6任何一项的物质组装件,其中进一步的交联剂的存在范围为粘合剂组合物总干重的1-40wt%。
8.权利要求5或7的物质组装件,其中引发剂选自无机过氧化物,有机过氧化物,还原剂,偶氮化合物,氧化还原引发剂,光引发剂,及其混合物,且以范围为0.05-5wt%,优选高于1%,优选低于2wt%包含在粘合剂组合物内,基于粘合剂组合物的干重。
9.前述任何一项权利要求的物质组装件,进一步包括偶联剂,染料,抗真菌剂,抗细菌剂,疏水物和本领域已知的用于这种粘合剂应用的其他添加剂,例如,由诸如金属氧化物,优选MgO,CaO,Al2O3和CaCO4之类的无机材料或诸如蒙脱土,膨润土,高岭石,水辉石和埃洛石和其他有机改性的纳米粘土之类的纳米粘土衍生的纳米颗粒,及其混合物。
10.一种制造产品的方法,该产品包括纤维材料或纤维素颗粒或片材材料的粘结组装件,所述方法包括(i)提供(a)单体和/或多糖,(ii)提供适量(b)氮杂环丁交联剂,(iii)接续或同时施加(a)和(b)可能地作为含(a)和(b)的水性组合物,和可能地通过(b)交联的(a)到纤维或纤维素粒状物或片材材料上,产生树脂化材料,和(v)将所得树脂化材料置于固化条件下,并允许蒸发过量水。
11.权利要求10的方法,该方法包括接续或同时施加水性组合物到纤维或纤维素粒状物或片材材料上,所述水性组合物包括用(b)和(c)能经历自由基聚合的交联剂和可能地(d)自由基引发剂交联的(a)可能地作为单一水性组合物,以生产树脂化材料,可允许发生交联,和将所得水性组合物置于固化条件下并允许蒸发过量水。
12.权利要求10或11的方法,其中可能地在(d)存在下,(a)和(b)之间的交联和可能地用(c)进一步的交联可在范围从环境温度(10至25℃)-200℃,优选40-95℃的温度下进行所要求的时间段,以生成所需的交联材料。
13.权利要求10,11或12的方法,其中可通过自由基引发来进行(a)和(b)之间的交联。
14.权利要求10-13任何一项的方法,其中将所得树脂化材料进行辐射,接着温度固化。
15.权利要求10-14任何一项的方法,其中可在范围为90-200℃,优选高于140℃,更优选低于190℃,典型地160至180℃的温度下进行温度固化。
16.一种水性粘合剂组合物,它包括用氮杂环丁交联剂交联的单糖和/或多糖,和能经历自由基聚合的交联剂,和可能地自由基引发剂。
17.权利要求16的水性粘合剂组合物,其中能经历自由基聚合的交联剂选自多羧酸,丙烯酰胺,甲基丙烯酰胺,丙烯酸酯,丙烯酸类和它们的盐,丙烯腈,双酚丙烯酸类,碳水化合物单体,氟化丙烯酸类,马来酰亚胺及其混合物。
18.权利要求16或17的水性粘合剂组合物,其中多糖包括至少两个,优选至少四个糖单元,至最多106个糖单元,优选最多10000个糖单元,更优选最多5000或甚至3000个糖单元,且可选自包括但不限于下述的天然资源:部分水解或完全水解的纤维素,其衍生物,甲壳素,粗淀粉和淀粉衍生物。
19.权利要求16-18任何一项的水性粘合剂组合物,其中氮杂环丁交联剂由至少两个单体单元,优选下式的聚氮杂环丁构成:
其中R1可以是C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,它们可以被羟基,羧基官能团或胺取代;
R2可以独立地为R1或-R3-NH-C(O)-R4-,其中R3和R4独立地为C1-C25烷二基,优选C1-C10烷二基或C1-C5烷二基,
Y1和Y3是H或C1-C5烷基,它可以被羟基,胺或羧基取代,
Y2是OH或独立地为Y1,
X-是卤素抗衡离子;
更特别地,该产品编码为CA1025。
20.权利要求16-19任何一项的水性粘合剂组合物,其中引发剂选自无机过氧化物,有机过氧化物,还原剂,偶氮化合物,氧化还原引发剂,光引发剂,及其混合物,且以范围为0.05-5wt%,优选高于1%,优选低于2wt%包含在粘合剂组合物内,基于粘合剂组合物的干重。
21.权利要求1-9任何一项的纤维材料的组装件,它是绝缘产品,例如矿棉垫。
22.权利要求1-9任何一项的颗粒的组装件,它是复合木板,例如木纤维板,刨花板或胶合板。
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GBGB1519187.7A GB201519187D0 (en) | 2015-10-30 | 2015-10-30 | Improved binder compositions and uses thereof |
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PCT/EP2016/075823 WO2017072184A1 (en) | 2015-10-30 | 2016-10-26 | Improved binder compositions and uses thereof |
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US20180340104A1 (en) | 2018-11-29 |
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US11384264B2 (en) | 2022-07-12 |
MX2018005368A (es) | 2018-08-15 |
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US11802223B2 (en) | 2023-10-31 |
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