CN1404520A - 固化速率提高的粘合剂组合物 - Google Patents
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Abstract
含游离甲醛类化合物的氨基塑料树脂组成的粘合剂组合物。特别是，在由蜜胺－脲－甲醛树脂组成的粘合剂组合物中加入游离甲醛类化合物使得F/(NH2)2的值为0.8－1.6。粘合剂尤其适合制造板材，即通过将含纤维的材料和本发明的粘合剂在压机中结合，并在该压机中在高温和加压下制造板材。
Description
本发明涉及一种粘合剂组合物及其制备方法，其中粘合剂组合物是以固化速率提高的含甲醛的氨基塑料树脂为基础的。此外，本发明还涉及一种使用获得的粘合剂组合物制得板材的制备方法。
EP-A-436485公开了固化速率提高的粘合剂组合物及其制备方法，其中粘合剂组合物以含甲醛的氨基塑料树脂为基础。在此专利文献中，公开了一种加速固化氨基塑料粘合剂的方法和由此制造的木基材料。为了加速氨基塑料粘合剂的固化，使用促进剂—接受器(accelerator-catcher)系统，其中将作为促进剂的脲甲醛混合物和甲醛清除剂加入粘合剂中。加入甲醛清除剂是为了为避免甲醛释放量的增长。同样地，在EP-A-436485中已经使用了甲醛清除剂脲。在脲甲醛促进剂中，脲与甲醛的摩尔比在1∶3到1∶6之间。所使用促进剂相对于粘合剂的量为0.1-5wt.％。甲醛清除剂相对于粘合剂的量最高可达到10wt.％。
实际上，随后加入脲以结合甲醛的方法的不利之处在于使方法不必要地复杂化。随后加入脲带来的另一个缺点是该树脂必须在较低温度下固化，以防止脲的分解以及在固化过程中产生烟雾。随后加入脲对树脂的稳定性也有不利的影响。
现已发现，在由氨基塑料制得的粘合剂组合物中，游离甲醛类化合物也存在，并且游离甲醛类化合物的含量相对于粘合剂制备中使用的甲醛总量为1到50wt％，则氨基塑料粘合剂的固化速率将显著提高。甲醛类化合物表示能作为甲醛参加反应的化合物。如果将甲醛作为游离甲醛类化合物，优选含量相对于在粘合剂制备过程中加入的甲醛总量为2到15wt.％之间。
现已特别发现用由氨基塑料树脂组成的其中也包含游离甲醛类化合物和总粘合剂组合物的F/(NH2)2比例在0.8到1.6之间的粘合剂组合物，明显提高粘合剂的固化速率。F/(NH2)2的比例为甲醛当量与NH2基团的摩尔比。
优选总粘合剂组合物中F/(NH2)2的比例为0.9到1.5。
用于本发明的氨基塑料树脂为氨基化合物和游离甲醛类化合物的缩聚产物。
可使用的氨基化合物为脲、蜜胺、蜜白胺、蜜勒胺、脲基蜜胺和它们的混合物。优选使用脲和/或蜜胺，更特别是脲和蜜胺的混合物，其中蜜胺和脲的摩尔比在0.01到2之间变化，特别是在0.02到1之间。
作为可作为甲醛类化合物可使用可作为甲醛参加反应的化合物。例如：甲醛和低聚甲醛。低聚甲醛为多聚体或低聚物形式的甲醛，其在解聚作用中分解出甲醛。聚合度为n的低聚甲醛能够产生n个甲醛分子，因此相当于n个甲醛当量。
令人惊讶的发现是，在粘合剂的制备过程中尽管加入了甲醛类化合物，制备出的最终产品板材的甲醛排放量仍然在国际适用的标准内。
本发明还涉及一种固化速率提高的氨基塑料粘合剂的制备方法：通过将氨基化合物与甲醛类化合物反应形成树脂，通过加入甲醛类化合物和催化剂将树脂转化为氨基塑料粘合剂，直到获得F/(NH2)2的比为0.8-1.6。
和树脂形成粘合剂的催化剂为金属盐，优选钠盐、钾盐、铵盐、铝盐、镁盐和锌盐。合适的盐的例子为：硝酸钠、硫酸铝、磷酸氢胺、过硫酸铵、氯化铵、硫酸铵和硝酸铵。优选使用铵盐，特别是氯化铵或硫酸铵。
此外，本发明还涉及板材的制造方法，通过将含纤维素的材料和粘合剂在压机上结合，并在压机中将这些物质在高温和加压下加工为板材，其中用作粘合剂的粘合剂组合物由氨基树脂组成，在该粘合剂组合物中还存在甲醛类化合物以使总粘合剂组合物的F/(NH2)2比为0.8-1.6。
该方法优选用于生产复合板(multiplex)、颗粒板(particle board)、MDF板(中等密度纤维板)、HDF板(高密度纤维板)或OSB板(定向线板(oriented-strand board))。
在通过将甲醛类化合物和催化剂加入树脂中制备本发明粘合剂之后，立刻生产板材。这两种组份加入树脂的顺序并不重要。催化剂和甲醛类化合物也能够同时加入到树脂中。该树脂有足够的室温稳定性，能够储存数天。加入甲醛类化合物和催化剂之后，在10秒到1小时之内使用粘合剂用于制备板材，优选30秒到30分钟。
在制备板材过程中，压制的条件视板材的情况而定。因此，复合板的生产适用压力为1-2MPa，颗粒板适用的压力为1-5MPa，优选2-4MPa，MDF适用的压力为2-7MPa，优选3-6MPa。制造板材的温度通常是，对复合板为100-140℃，对颗粒板和OSB情况下为180-230℃，对MDF情况下为170-230℃。在复合板的情况下，板在所述的条件下保持5-10分钟(加压时间)。适用于颗粒板、MDF和OSB的加压时间，用s/mm板厚表示。适用于OSB板的加压时间为4-12s/mm，优选6-10s/mm。颗粒板的加压时间通常采用4-12s/mm，优选5-10s/mm。制造MDF板的加压时间为5-17s/mm，特别是8-14s/mm。
发现得到的固化速率的增长最高达到40％。
在粘合剂的制备过程中，为了使最终的板材具有更好的抗吸湿性，通常在粘合剂组合物中加入蜡。该蜡通常为乳液状蜡或固体蜡，例如来自于石油工业。
通过下述实施例，将对本发明进行进一步的说明。
实施例I
室温下，在反应器中加入269.2g甲醛/脲(F/U)摩尔比为5.0和固含量为80％的脲-甲醛预缩聚物，然后加入99.6g水。升温至65℃，然后用2N的NaOH中和溶液，直至PH值达到7.3。然后加入91.5g脲，获得甲醛/脲(F/U)的摩尔比为2.0。在10分钟内，温度逐渐地由65℃升至100℃，然后将其羟甲基化5分钟。接着加入2N的乙酸，直至PH值达到5.5。将获得的混合物在100℃浓缩，直至粘度值达到450MPa.s。加入2.5ml 2N的NaOH，使得PH值为8。然后将温度降为90℃，接着加入240g蜜胺(m)，然后加入166g福尔马林(50wt.％甲醛的水溶液)，得到F/(NH2)2为1.452。此后，在每10分钟加入1ml 2N的NaOH的情况下，将缩聚反应进行58分钟。然后将获得的树脂组合物降温至25℃。当温度达到60℃时，开始加入120g脲，后来得到1000gF/(NH2)2为1.6的蜜胺-脲-甲醛(MUF)树脂。通过加入2mol％的硫酸铵溶液(20wt％的水溶液)和18g福尔马林(50wt.％的水溶液)，将MUF树脂转化为最终F/(NH2)2为1.10的MUF粘合剂。获得的粘合剂含有24wt.％蜜胺和27wt.％脲。
测定最终的MUF粘合剂的凝胶时间。凝胶时间为粘合剂固化速率的量度。
凝胶时间按如下进行测定。将树脂用水稀释至固含量为50％，然后在室温下加入催化剂。将5g树脂和催化剂的混合物倒入试管中，将试管置于100℃的水浴中。凝胶时间为将试管放入水浴中和在试管中出现凝胶之间的时间。反应的最终点非常明确，并且是可重复的。
在表1中，列出了在粘合剂中使用的蜜胺的量、加入甲醛类化合物(FH)前后F/(NH2)2的比例、催化剂的量和凝胶时间。
实施例II-XVII
改变蜜胺的量、在树脂中额外加入甲醛的量和催化剂的量，制备与实施例I相似的粘合剂组合物，并且测定其凝胶时间。将组合物和测定的时间显示在表1中。
对比实施例IA-XVIIA
与实施例1类似，通过将催化剂加入到树脂，但不在树脂中加入额外的甲醛，制备粘合剂组合物。将组合物和凝胶时间显示在表1中。
表1
| 实施例 | 蜜胺wt.％ | 加入F前F/(NH2)2比例 | 加入F后F/(NH2)2比例 | 催化剂以mol.％计 | 凝胶时间以秒计 |
| IA | 24 | 1.10 | - | 2.0 | 78 |
| I | 24 | 1.06 | 1.10 | 2.0 | 70 |
| IIA | 24 | 1.10 | - | 2.0 | 81 |
| II | 24 | 1.00 | 1.10 | 2.0 | 70 |
| IIIA | 24 | 1.10 | I | 3.0 | 74 |
| III | 24 | 1.00 | 1.10 | 3.0 | 62 |
| IVA | 24 | 1.10 | - | 5.0 | 70 |
| IV | 24 | 1.00 | 1.10 | 5.0 | 60 |
| VA | 24 | 1.10 | - | 2.0 | 80 |
| V | 24 | 0.90 | 1.10 | 2.0 | 67 |
| VIA | 24 | 1.10 | - | 3.0 | 73 |
| VI | 24 | 0.90 | 1.10 | 3.0 | 60 |
| VIIA | 24 | 1.10 | - | 5.0 | 70 |
| VII | 24 | 0.90 | 1.10 | 5.0 | 57 |
| VIIIA | 24 | 1.10 | - | 3.0 | 72 |
| VIII | 24 | 1.06 | 1.10 | 3.0 | 65 |
| IXA | 24 | 1.10 | - | 5.0 | 69 |
| IX | 24 | 1.06 | 1.10 | 5.0 | 62 |
| XA | 24 | 1.20 | - | 2.0 | 74 |
| X | 24 | 1.10 | 1.20 | 2.0 | 66 |
| XIA | 24 | 1.20 | - | 3.0 | 69 |
| XI | 24 | 1.10 | 1.20 | 3.0 | 58 |
| XIIA | 24 | 1.20 | - | 5.0 | 64 |
| XII | 24 | 1.10 | 1.20 | 5.0 | 53 |
| XIIIA | 24 | 1.00 | - | 2.0 | 94 |
| XIII | 24 | 0.90 | 1.00 | 2.0 | 82 |
| XIVA | 24 | 1.00 | - | 3.0 | 86 |
| XIV | 24 | 0.90 | 1.00 | 3.0 | 73 |
| XVA | 24 | 1.00 | - | 5.0 | 83 |
| XV | 24 | 0.90 | 1.00 | 5.0 | 71 |
| XVIA | 12 | 1.10 | - | 3 | 98 |
| XVI | 12 | 1.00 | 1.10 | 3 | 72 |
| XVIIA | 0 | 1.12 | - | 2 | 79 |
| XVII | 0 | 1.08 | 1.12 | 2 | 47 |
Claims (9)
1.由含甲醛的氨基塑料树脂制备的粘合剂组合物，其特征在于存在游离甲醛类化合物，并且游离甲醛类化合物的量相对于在粘合剂制备过程中的甲醛总加入量为1到50wt.％。
2.根据权利要求1的粘合剂组合物，其特征在于在粘合剂的制备过程中，将甲醛作为游离甲醛类化合物使用，甲醛的加入量相对于甲醛总加入量为2到15wt.％。
3.根据权利要求1-2的粘合剂组合物，其特征在于存在游离甲醛类化合物，使得全部粘合剂组合物中F/(NH2)2比为0.8-1.6。
4.根据权利要求3的粘合剂组合物，其特征在于全部粘合剂组合物中F/(NH2)2比为0.9-1.5。
5.根据权利要求1-4的粘合剂组合物，其特征在于将脲和蜜胺的混合物用作氨基塑料树脂中的氨基化合物。
6.根据权利要求5的粘合剂组合物，其特征在于蜜胺/脲的摩尔比为0.01-2。
7.通过氨基化合物与甲醛类化合物的反应形成树脂，制备固化速率提高的氨基塑料粘合剂的方法，其特征在于通过加入甲醛类化合物和催化剂直至达到F/(NH2)2比为0.8-1.6为止，将该树脂转化为氨基塑料粘合剂。
8.通过将含纤维的材料和粘合剂在压机中结合，并在该压机中将这些物质在高温和加压下加工为板材而制备板材的方法，其特征在于作为粘合剂使用的粘合剂组合物由氨基塑料树脂组成，在该粘合剂组合物中还存在游离甲醛类化合物，且全部粘合剂组合物中的F/(NH2)2比例为0.8-1.6。
9.如说明书和实施例中的粘合剂组合物、方法和板材。
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| NL1014433 | 2000-02-18 | ||
| NL1014433A NL1014433C2 (nl) | 2000-02-18 | 2000-02-18 | Lijmsamenstelling met verhoogde uithardingssnelheid. |
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| US (1) | US6881817B2 (zh) |
| EP (1) | EP1263914B1 (zh) |
| CN (1) | CN1202194C (zh) |
| AR (1) | AR027413A1 (zh) |
| AT (1) | ATE464363T1 (zh) |
| AU (2) | AU2001237802B2 (zh) |
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| BR (1) | BR0108479B1 (zh) |
| CO (1) | CO5231259A1 (zh) |
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| DK (1) | DK1263914T3 (zh) |
| ES (1) | ES2342712T3 (zh) |
| HU (1) | HUP0300021A2 (zh) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061196B (zh) * | 2004-07-27 | 2010-10-27 | 澳大利亚澳瑞凯有限公司 | 用于提供粉末涂布的再生纤维素基材的系统 |
| CN106999832A (zh) * | 2014-11-13 | 2017-08-01 | Fp创新研究中心 | 用于使用多功能清除剂对具有脲‑甲醛树脂的木制复合物产品清除游离甲醛的方法 |
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| EP1681147A1 (en) * | 2005-01-13 | 2006-07-19 | DSM IP Assets B.V. | Oriented strand board |
| CA2594398A1 (en) * | 2005-01-13 | 2006-08-31 | Dsm Ip Assets B.V. | Oriented strand board |
| US20080000581A1 (en) * | 2006-06-28 | 2008-01-03 | Gilles Leon Nison | Preparation of laminated composite substrates using coated oriented polymeric film |
| US8809477B2 (en) | 2010-02-01 | 2014-08-19 | Johns Manville | Formaldehyde-free protein-containing binder compositions |
| WO2012064800A2 (en) | 2010-11-10 | 2012-05-18 | Georgia-Pacific Chemicals Llc | Methods for making and using amino-aldehyde resins |
| US9346926B2 (en) | 2013-03-14 | 2016-05-24 | Georgia-Pacific Chemicals Llc | High flow urea-formaldehyde powders for particleboard and fiberboard manufacture |
| CN103832870B (zh) * | 2014-03-19 | 2016-04-13 | 上海福耀客车玻璃有限公司 | 一种快速安装及自动断胶条装置 |
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| CH188327A (de) * | 1934-07-02 | 1936-12-31 | Chem Ind Basel | Haltbares Trockenleimpräparat. |
| DE2747830A1 (de) * | 1977-10-26 | 1979-05-10 | Basf Ag | Verfahren zur herstellung von holzleimen |
| FR2625207B1 (fr) * | 1987-12-23 | 1991-12-06 | Charbonnages Ste Chimique | Nouveau procede de preparation de resines aminoplastes a tres faible degagement de formol |
| AT395014B (de) * | 1989-12-15 | 1992-08-25 | Krems Chemie Gmbh | Verfahren zur beschleunigten aushaertung von aminoplastleimen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101061196B (zh) * | 2004-07-27 | 2010-10-27 | 澳大利亚澳瑞凯有限公司 | 用于提供粉末涂布的再生纤维素基材的系统 |
| CN106999832A (zh) * | 2014-11-13 | 2017-08-01 | Fp创新研究中心 | 用于使用多功能清除剂对具有脲‑甲醛树脂的木制复合物产品清除游离甲醛的方法 |
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| Publication number | Publication date |
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| BG107110A (bg) | 2003-10-31 |
| EP1263914A1 (en) | 2002-12-11 |
| AR027413A1 (es) | 2003-03-26 |
| MY140746A (en) | 2010-01-15 |
| HUP0300021A2 (en) | 2003-08-28 |
| BR0108479A (pt) | 2003-04-22 |
| DE60141818D1 (de) | 2010-05-27 |
| NL1014433C2 (nl) | 2001-08-22 |
| AU3780201A (en) | 2001-08-27 |
| NZ520843A (en) | 2003-07-25 |
| CO5231259A1 (es) | 2002-12-27 |
| CN1202194C (zh) | 2005-05-18 |
| SK11842002A3 (sk) | 2002-12-03 |
| PL357439A1 (en) | 2004-07-26 |
| US6881817B2 (en) | 2005-04-19 |
| ATE464363T1 (de) | 2010-04-15 |
| PL207012B1 (pl) | 2010-10-29 |
| EP1263914B1 (en) | 2010-04-14 |
| TWI229118B (en) | 2005-03-11 |
| DK1263914T3 (da) | 2010-06-28 |
| PT1263914E (pt) | 2010-06-07 |
| WO2001060937A1 (en) | 2001-08-23 |
| ES2342712T3 (es) | 2010-07-13 |
| BR0108479B1 (pt) | 2010-11-30 |
| AU2001237802B2 (en) | 2004-11-25 |
| SK287450B6 (sk) | 2010-10-07 |
| US20030065127A1 (en) | 2003-04-03 |
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