CN114845548B - 木材防腐剂 - Google Patents

木材防腐剂 Download PDF

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CN114845548B
CN114845548B CN201980070153.4A CN201980070153A CN114845548B CN 114845548 B CN114845548 B CN 114845548B CN 201980070153 A CN201980070153 A CN 201980070153A CN 114845548 B CN114845548 B CN 114845548B
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S·阿鲁穆加姆
D·拉根艾拉
R·W·史蒂芬斯
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Abstract

一种木材防腐组合物以及用于通过使木材与所述组合物接触来保存木材的方法，所述组合物包含聚氨酯聚合物、非水溶剂和木材防腐活性物。

Description

木材防腐剂
本发明涉及一种木材防腐组合物以及用于保存木材以给予针对木材腐烂有机体的保护的方法。
在木材投入使用的时间之前，有许多方法和组合物用于保存木材。此外，用于就地处理木材的防腐剂在市场上是可获得的，包括油基产品和水基产品两者。油基产品通常由含有五氯酚或杂酚油的石油组成。US7,959,723描述了一种用于木材的使用油溶性防腐剂的此种组合物。从毒性和环境污染的角度来看，这些活性成分是不太希望的。
本发明解决的问题是对一种更环境友好的木材处理组合物的需要，所述组合物能够有效地提供活性成分。
本发明涉及一种用于保存木材的方法，所述方法包括使木材与木材防腐组合物接触，所述组合物包含：由包含>95％聚-氧化丙烯的多元醇和异氰酸酯合成的聚氨酯聚合物；有机溶剂；和至少一种木材防腐活性物，其选自卤化异噻唑酮杀生物剂、卤化氨基甲酸酯杀真菌剂和唑类杀真菌剂；其中所述聚氨酯聚合物的异氰酸酯与多元醇的摩尔比是小于或等于0.8至大于或等于0.1。
本发明进一步涉及一种木材防腐组合物，其包含a)由包含>95％聚-氧化丙烯的多元醇；和异氰酸酯合成的聚氨酯聚合物，b)有机溶剂；和c)至少一种木材防腐活性物，其选自卤化异噻唑酮杀生物剂、卤化氨基甲酸酯杀真菌剂和唑类杀真菌剂；其中所述聚氨酯聚合物的异氰酸酯与多元醇的摩尔比是小于或等于0.8至大于或等于0.1。
除非另外指出，否则所有百分比和百万分率(ppm)值均是基于组合物的总重量。术语“一个/种(a/an)”是指单数情况和其中存在多于一个/种的情况两者。所有范围端点都是包括端值的和可组合的。如本文所包含，所有分子量均为数均分子量并且通过凝胶渗透色谱法(GPC)确定。设想到本领域技术人员可以选择和/或组合本发明中的多个合适的和/或优选的实施例。
本发明的木材防腐组合物包含由化学计量过量的双羟基封端的聚氧化丙烯大分子单体(多元醇)和异氰酸酯合成的聚氨酯聚合物。如本文使用的，聚氨酯聚合物可以含有由异氰酸酯与其他单体反应衍生的其他官能团，例如衍生自羧酸的酰胺基团和衍生自胺(例如乙二胺(EDA))的脲，或其他聚合物，如聚酯，例如衍生自己二酸和1,6-己二醇、1,4-丁二醇和/或新戊二醇的聚酯，或聚碳酸酯，例如衍生自聚1,6-己二醇碳酸酯的聚碳酸酯。合适的异氰酸酯包括，例如亚甲基双(4-环己基异氰酸酯)(MCI)、亚甲基双(4-苯基异氰酸酯)(MDI)、多亚甲基多元酚异氰酸酯(pMDI)、六亚甲基二异氰酸酯(HDI)、异佛尔酮二异氰酸酯(IPDI)和甲苯二异氰酸酯(TDI)及其组合。优选地，本发明的异氰酸酯是二异氰酸酯。合适的二异氰酸酯的实例包括IPDI、pMDI、MDI及其组合。更优选地，二异氰酸酯是MDI和IPDI。在本发明中用于制备聚氨酯的多元醇是>95％聚-氧化丙烯。合适地，聚氨酯聚合物的异氰酸酯与多元醇的摩尔比是小于或等于0.8至大于或等于0.1。
聚氨酯聚合物在非水溶剂或非水溶剂的混合物中合成。优选地，溶剂的量是60％至90％，更优选地70％至90％，并且最优选地75％至90％。合适的溶剂包括具有至少150℃的沸点，并且优选至少60℃的闪点的酯和醚溶剂。此类溶剂的实例包括烷烃、支链烷烃、芳烃，例如矿物油精、甲苯、苯甲醇、二甲苯和烷基苯。可用于本发明的合适的非水溶剂的混合物是Aromatic 200，CAS号64742-94-5。
本发明的木材处理组合物，除了聚氨酯聚合物之外，还包含木材防腐活性物。木材防腐活性物可以选自卤化异噻唑啉酮杀生物剂、卤化氨基甲酸酯杀真菌剂、环烷酸的金属盐和唑类杀真菌剂的类别。当木材防腐活性物是卤化异噻唑啉酮杀生物剂时，其优选包含具有C4-C12 N-烷基取代基的3-异噻唑酮，更优选氯化的3-异噻唑酮,并且最优选4,5-二氯-2-正辛基-4-异噻唑啉-3-酮(“DCOIT”)。可以使用木材防腐活性物的混合物。当聚氨酯聚合物与DCOIT组合时，合适的组合物包含23％的聚氨酯聚合物固体、23％的DCOIT、和54％的Aromatic 200。
用于处理木材的组合物优选包含100ppm至40,000ppm、更优选200ppm至30,000ppm、并且最优选300ppm至25,000ppm的木材防腐剂。优选地，组合物的聚合物固体含量为10％至40％、更优选10％至30％、并且最优选15％至30％。优选地，聚合物固体与杀生物剂的比率是2:1至1:2，更优选2:1至1:1。
木材防腐组合物的另一个关键要素是有机溶剂。聚氨酯聚合物用有机溶剂稀释。合适地，有机溶剂是柴油，然而可以使用本领域技术人员已知的其他有机溶剂。在一些实施例中，有机溶剂不是与本发明的非水溶剂相同的化合物。如本文使用的，柴油被定义为在200℃(392°F)至350℃(662°F)下在大气压下对原油分馏，得到每分子典型地含有8至21个碳原子的碳链的混合物或从植物油或动物脂肪(生物脂质)获得的生物柴油，其已经与甲醇(脂肪酸甲酯(FAME))及其混合物进行了酯交换。
本发明中使用的组合物可以任选地包含额外的组分，包括但不限于稳定剂、染料、防水剂、其他木材杀生物剂、杀真菌剂和杀虫剂、抗氧化剂、金属螯合剂、自由基清除剂等。稳定剂包括，例如，有机和无机UV稳定剂，如氧化铜或耐浸出的其他铜盐或络合物；氧化锌；铁盐、氧化铁、铁络合物、透明氧化铁和纳米颗粒氧化铁；二氧化钛；二苯甲酮和取代的二苯甲酮；肉桂酸及其酯和酰胺；取代的三嗪，如三苯基三嗪和取代的苯基三嗪UV吸收剂、苯并三唑和取代的苯并三唑UV吸收剂；受阻胺光稳定剂，单独使用或组合使用。防水剂包括，例如各种蜡型防水剂，例如石蜡、巴西棕榈蜡和聚乙烯蜡；以及硅酮。其他木材杀生物剂、杀真菌剂，如铜金属、百杀辛(bethoxazin)和环丙唑醇、百菌清、戊唑醇、丙环唑、五氯酚、杂酚油、环烷酸铜、二烷基二甲基季铵碳酸盐/碳酸氢盐，和杀虫剂，包括例如美国专利号6,610,282中列出的那些，例如吡虫啉、噻虫啉、苄氯菊酯和醚菊酯。抗氧化剂包括任何可商购的抗氧化剂化合物，例如亚磷酸酯抗氧化剂(如IRGAFOS)；内酯抗氧化剂；酚类抗氧化剂如BHT；抗坏血酸；以及IRGANOX等。金属螯合剂包括，例如，EDTA、NTA、1,10-菲咯啉、ACUMER 3100、DEQUEST、TAMOL 731、三聚磷酸盐和可用于螯合或分散金属盐的其他无机和有机化合物以及聚合物。自由基清除剂包括，例如TEMPO。
木材的防腐是通过使木材与本文所述的木材防腐组合物接触来进行的，优选在符合AWPA标准T1-16并且满足U1-16中规定的使用条件的条件下进行。为了提供长期保护，防腐剂需要“固定”在木材中并且不会通过挥发或通过在木材变湿时浸出而过快损耗。可以预期的是，在处理过程中防腐剂深入木材的增强的渗透或增强的移动也可能导致有机木材防腐活性物的减少的固定。
实例
聚氨酯聚合物的合成：
以下聚氨酯是由化学计量过量的双羟基封端的聚氧化丙烯(多元醇)和异氰酸酯合成的。将150mL在aromatic 200(溶剂，10-30wt％溶液)中的无水聚氧化丙烯和异氰酸酯(相对于羟基0.8摩尔当量的异氰酸酯)与0.003％的锡催化剂(二月桂酸二丁基锡)一起装入反应器中。在架空搅拌下将反应器加热至90℃。将反应混合物在90℃下保持3h，并且在该时间点，当用SWYPE(TM)测试条测试时，没有观察到游离异氰酸酯。PU溶液的聚合物固体由用于反应的反应物的转化率和量估算。聚合物固体计算为在聚合物合成中反应性组分的总和。
除了改变NCO/OH摩尔比以外，对比样品1至6和实例2-4按照以上样品程序合成。除了使用MDI代替IPDI和改变NCO/OH摩尔比以外，对比样品7至9和实例5-8按照样品程序合成。
确定柴油相容性的程序：
在透明的1盎司小瓶中，用9.9克的柴油燃料(重量/重量)将0.1克聚合物(基于100％聚合物固体)稀释至1％聚合物溶液。将样品在室温下维持48小时。48小时后，检查溶液的不相容性，定义为相分离、聚合物以固体形式沉淀和/或混浊。
表1.具有100％p-iPO和IPDI的PU聚合物的柴油相容性
表2.具有100％p-iPO和MDI的PU聚合物的柴油相容性

Claims (10)

1.一种用于保存木材的方法，所述方法包括：
使木材与非水基木材防腐组合物接触，所述组合物包含：
a)聚氨酯聚合物，其由以下合成：
i)包含>95％聚-氧化丙烯的多元醇，和
ii)异氰酸酯；
b)有机溶剂，所述有机溶剂包括柴油；和
c)至少一种木材防腐活性物，其选自卤化异噻唑酮杀生物剂、卤化氨基甲酸酯杀真菌剂和唑类杀真菌剂；
其中所述聚氨酯聚合物的异氰酸酯与多元醇的摩尔比是小于或等于0.8至大于或等于0.1。
2.如权利要求1所述的方法，其中，所述木材防腐活性物是4,5-二氯-2-正辛基-4-异噻唑啉-3-酮。
3.如权利要求1所述的方法，其中，所述多元醇包含100％聚-氧化丙烯。
4.如权利要求1所述的方法，其中，所述异氰酸酯是亚甲基双(4-苯基异氰酸酯)。
5.如权利要求1所述的方法，其中，所述异氰酸酯是异佛尔酮二异氰酸酯。
6.一种非水基木材防腐组合物，所述组合物包含：
a)聚氨酯聚合物，其由以下合成：
i)包含>95％聚-氧化丙烯的多元醇，和
ii)异氰酸酯；
b)有机溶剂，所述有机溶剂包括柴油；和
c)至少一种木材防腐活性物，其选自卤化异噻唑酮杀生物剂、卤化氨基甲酸酯杀真菌剂和唑类杀真菌剂；
其中所述聚氨酯聚合物的异氰酸酯与多元醇的摩尔比是小于或等于0.8至大于或等于0.1。
7.如权利要求6所述的组合物，其中，所述木材防腐活性物是4,5-二氯-2-正辛基-4-异噻唑啉-3-酮。
8.如权利要求6所述的组合物，其中，所述多元醇包含100％聚-氧化丙烯。
9.如权利要求6所述的组合物，其中，所述异氰酸酯是亚甲基双(4-苯基异氰酸酯)。
10.如权利要求6所述的组合物，其中，所述异氰酸酯是异佛尔酮二异氰酸酯。
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