CN1007499B - 木材防腐的改进方法 - Google Patents
木材防腐的改进方法Info
- Publication number
- CN1007499B CN1007499B CN86106533A CN86104657A CN1007499B CN 1007499 B CN1007499 B CN 1007499B CN 86106533 A CN86106533 A CN 86106533A CN 86104657 A CN86104657 A CN 86104657A CN 1007499 B CN1007499 B CN 1007499B
- Authority
- CN
- China
- Prior art keywords
- solution
- timber
- acid
- pressure
- metal
- 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.)
- Expired
Links
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Abstract
叙述了一种用金属盐浸渍木材进行防腐处理的改进方法。更详细地说,该改进方法由以下工序组成:(A)在足够的时间、温度和压力条件下,使容器内木材同含有至少一种的可溶性有机羧酸金属盐的溶液接触;(B)降低容器内压力,至少从木材内排出一些溶液,该溶液与容器中的多余处理液相混,且该混合物可被用作热递介质或用作下一批木材的处理液;(C)随后将木材加热到足以使金属固定在木材内的温度。
Description
本发明涉及木材防腐方法。更详细地说,在控制时间、温度和压力条件下,尤其是控制温度的条件下,本发明方法包括一系列工序。本发明也涉及按照本发明方法所处理的木材。
为了防止木材和原木朽烂并延长使用寿命,通常的作法是,用诸如杂酚油、溶解或分散于水中的无机化合物混合物、或某些溶解于石油馏份物中的有机化合物一类的防腐剂浸渍木材或原木。这些防腐物质提供的防护能力取决于它们渗入木材或原木的深度和合适均匀性。
在题为“木材损蚀及其防腐处理预防”(1973年纽约州锡拉丘兹市锡拉丘兹大学出版社锡拉丘兹木材科学丛书5Darrel D.Nicholas编著)(Darrel D.Nicholas,Editor,Syracuse Wood Scicnce Series5.Syracuse Vniversity Press,Syracuse,N,Y.,1973)的两卷论文中,较详细地讨论了木材处理和木材防腐的问题。各种杂酚油组合剂、五氯苯酚、环烷酸铜、8-羟基喹啉铜、有机锡化合物、有机汞化合物、环烷酸锌、氯化烃、加氨亚砷酸铜(ACA)、酸式铬酸铜(ACC)、诸如氯化锌、氧化锌和硫酸锌一类的锌盐、铬酸盐化了的砷酸铜(CCA)等等都在上述文章所提木材防腐剂的实例之中。
在第Ⅱ卷第3章279页~298页中讨论了木材处理的各种方法和设备。压力处理方法是作为木材防腐、防虫和防火等最有效的方法加以叙述的。本章也讨论了各种非压力处理方法。尽管观察到了某些渗透现象,还是首先提出浸渍法作为一种令人满意的表面处理方法。另一种非压力技术是用于未干新伐木材的扩散方法。文章作者指出,由于扩散速率慢,该方法需要很长的处理时间。
上述那些木材防腐剂是以溶液,乳剂,糊剂或分散在液态烃和/或水体系中应用于木材。在许多应用中,由于液态烃有气味、易燃和经常有毒性的缺点,优先考虑使用水体系中的防腐剂。美国专利4,507,152叙述了能够在木材处理中使用的具有灭菌和杀虫性能的水溶组合剂。水溶组合剂包括可溶解于油的有机羧酸金属盐、卤化吡啶磷酸盐和表面活化剂。这种组合剂可以用来渗透干木材和未干新伐木材,用这种水溶体系处理过的木材能够抗菌防虫。
在美国专利4,001,400中叙述了用脂肪酸盐氨水溶液作为木材防腐剂,在美国专利4,193,993中叙述了羧酸金属盐及氨和/或铵化合物的水溶液。氨和/或铵化合物用来把金属盐保持在溶液中。英国专利说明书GB2049430叙述了水基灭菌组合剂,它包括C1-4一元羧酸铜氨配合物和选自于碱土金属、锌和锰的C1-4一元羧酸金属盐。该组合剂对于处理诸如葡萄、咖啡、茶、苹果、梨一类的作物是有效的,并且该组合剂可能用作生物杀伤剂涂料和木材防腐剂。
在美国专利4,090,000中叙述了应用多卤代苯酚水溶体系的技术。简单地说,该方法包括使用含有可溶于水的多卤代苯酚盐的水溶液和酸生成物质,该物质在溶液浸入到木材后在溶液中发生反应,释放出一种能把多卤代苯酚从盐中置换出来的酸。
不管用什么样的化学体系浸渍,浸渍木材的最普通的工业方法包括在150~200磅/英寸2较高压力下使木材进行长时间的,例如1~24小时的防腐处理。该方法也可以要求约75℃到约90~95℃的较高温度。此外,使用压力会造成木材外层的压缩,特别是由于水蒸汽的作用使木材强度降低和变软以后。很可能发生木材细胞皱缩特别是在处理较软的低比重未干木材时。在木材皱缩处,形成阻止甚至完全阻断防腐剂流入木材内部的较难渗透层。
还提出过首先对木材进行真空处理改进压力处理的方法。叙述先用真空技术随后加压浸渍木材各种方法的先有技术实例的专利有美国专利2,668,779;3.200,003和3,968,276。
美国专利3,677,805叙述一种改进型压力处理方法。在此方法中,木材浸泡在压力容器内的处理液中,压力升高到操作压力,于是容器内东西经受脉动泵的作用,该脉动泵在容器内产生正弦波压力脉冲。换句话说,用调制幅度的方式重复应用各种压力脉冲,产生使压力容器内保持高于或低于环境压力的各种压力峰值。这种方法需要在装有压力释放设备的压力装置内工作的脉动泵。
如上所述,浸渍木材最普通的工业方法包括在较高压力下,有时候在较高温度对木材进行防腐处
理。通常,该方法包括将木材放入容器内、使容器内充满防腐剂混合物、并使容器内压力升高到所要求的水平,使溶液渗入木材。有时候,将容器内液体温度升至高温。在所需时间内使木材经受浸渍体系的处理以后,通常把压力降到大气压力,随着压力降低,由于木材内的空气随着外界压力降低发生膨胀,木材内的某些浸渍液被压出木材。这种随着外界压力降低从木材内释放和回收的浸渍溶液在该已知技术中一般称为“回出液”(Kickback)。在本申请中使用该术语时,它应该具有同样的意义。在浸渍溶液含有羧酸金属盐时,我们在处理过程中已经观察到,回出液常常比初始浸渍溶液含有较少的金属和较多的酸。因为回出液通常同容器内初始溶液混合,从而导致总金属含量减少和酸增加,所以回出液成分变化是一个问题。尽管可以补加金属盐来控制溶液内金属浓度的降低,但很难去除溶液内增加的游离酸,随着处理过程的继续,酸浓度也继续增长。除了酸增加引起的释放效应以外,混合物内存在的多余酸会导致潮湿体系内低碳钢的腐蚀。
上述先有技术是代表了小部分的建议,提出这些建议是为了用水和/或防腐剂材料处理木材以预防朽烂。尽管在先有技术中提出许多这样的建议,仍然继续需要有效的和能使防腐蚀与其它化学物质均匀渗入木材芯的廉价、安全、无毒和无腐蚀的处理方法。
叙述了一种用金属盐浸渍木材进行防腐处理的改进方法。更详细地说,改进的方法由以下工序组成:
(A)在一定的时间、温度和压力条件下,在容器内使木材同含有至少一种可溶性的有机羧酸金属盐溶液接触,该时间、温度和压力条件足以
(ⅰ)使溶液渗入木材内,而且
(ⅱ)使工序(B)中从木材内排出溶液内的金属与酸之比同工序(A)中浸渍木材所用溶液内的金属与酸之比基本上保持相同,
(B)降低容器内压力,至少从木材内排出一些溶液,而且
(C)随后将木材加热到足以使金属固定在木材内的温度。
在上述方法中所用的溶液可以是水溶液或是烃溶液,这些溶液除了含有金属盐诸如杀虫剂、阻燃剂、防水剂等以外,还可以含有其它所需成分,在一个最佳实施方案中,该方法中所用有机羧酸金属盐是一种杀菌剂。
本发明是一种在压力状态下用金属盐浸渍木材进行防腐处理的改进方法。该改进方法在控制时间、温度和压力的条件下进行一系列的处理工序,这些条件足以使溶液渗入木材,同时使回出液内金属与酸之比同初始浸渍液内金属与酸之比基本上保持相同。
更具体地说,本发明改进方法由以下工序组成:
(A)在一定的时间、温度和压力条件下,使容器内木材同含有至少一种可溶性有机羧酸金属盐溶液接触,这些条件足以
(ⅰ)使溶液渗入木材内,而且
(ⅱ)使工序(B)中从木材内排出溶液内的金属与酸之比同工序(A)中浸渍木材所用溶液内的金属与酸之比基本上保持相同,
(B)降低容器内压力,至少从木材内排出一些溶液,而且
(C)随后将木材加热到足以使金属固定在木材内的温度。
在本说明书和附加的权利要求书中使用的术语“溶液”不仅是指真溶液,而且也是指乳化液、微乳化液等等。在使用这些乳化液、微乳化液时,术语“可溶性金属盐”是指该金属盐至少可溶于这种乳化液、微乳化液等中一种相内。
本发明改进方法的一个重要点是确定为工序(A)步的第一步。我们已经看出,如果在工序(A)中所用溶液的温度保持在不足以“使金属固定在木材内”的温度,就可以得到所需的改进结果。“使金属固定在木材内”这一说法是指,在木材持续在水和/或烃溶剂中时,用本发明方法渗入木材内的金属盐不会从木材中浸出。关于金属盐固定在木材内,是由于金属盐与木材内纤维素结构或木质素或其它反应物质内的官能团发生化学反应的结果,还是一种由于升高温度而加速的物理现象,这在熟知本行技术的人中也不完全清楚,存在相当大的推测。因为在某些情况下,从排空细胞过程得到的回出液比处理液含有较少的金属和较多的酸,此现象支持这一理论:即金属固定于木材内和游离酸的释放,是起因于金属盐中金属同木材纤维素结构内含氢活性基团之间的化学交换,从而释放出游离酸。
在本方法中,要控制好工序(A)中保持的温度和压力条件,使随后工序(B)中从木材内排出回出液内金属与酸之比同工序(A)中浸渍木材所用溶液内金属与酸之比基本上保持相同。在最佳实施方案中,使工序(A)中浸渍液温度保持低于金属固定在木材内时的温度,以得到工序(A)中所需结果。在一个实施方案中,一般使工序(A)所用溶液温度保持在20°~80℃之间。只要由回出液内金属浓度降低而酸浓度增高证明,金属盐没有稠合在木材内,对于某些金属盐就可以应用较高的温度。工序(A)中容器内压力可以在很大范围内变化,该压力一般将大于0~14.06公斤/平方厘米(表压)。容器内的压力值控制溶液渗入木材的速率,如果施加的压力较低,工序(A)会持续较长时间,直到溶液达到所需渗入量为止。同样,如果工序(A)的温度在20°~80℃范围的较低段,则工序(A)也会进行较长时间。
在浸渍液渗入木材达到所要求的程度后,由于降低容器内压力,会从木材内至少排出一些浸渍液。在此第二步〔工序(B)〕中,由于容器内压力降低,木材内的空气膨胀,至少从木材内释放和压出一些浸渍液。这种释放出来的溶液是回出液,它将同初始处理溶液混合。
然后浸渍过的木材经过第三步〔工序(C)〕处理,它包括将木材加热到足以使金属固定在木材内的温度。尽管工序(C)中温度可以随处理中所用金属盐的性质而变化,一般足以使金属固定在木材内的温度在约90°直到木材分解温度即约120℃的范围内。
在处理溶液和工序(B)中排出的回出液混合物存在的情况下,可以进行工序(C)中木材的加热,在这种情况下,混合物用作容器内的热传导介质。当混合液用作热传导介质时,最好在可以是大气压力或稍高压力的恒压下进行工序(C)中的加热。为了使从木材到包括因金属固定于木材内而产生任何游离酸的溶液的进一步的传质减至最小,最好在工序(C)中使用恒压。显然,精确不变的压力是不切实际的也不需要,仅仅要求基本上使压力保持恒定,该压力可以变化约±0.14公斤/平方厘米。
在另一个可行的实施方案中,在对木材进行工序(C)的加热以前,可以从容器内排出由于工序(B)产生的混合溶液,用诸如矿物油一类的惰性液体物质代替。在此实施方案中,该矿物油用作热传导介质,从工序(B)排出和回收的混合溶液可以用于随后的木材处理过程。当来自工序(B)的混合物呈乳化液形式,并且在工序(C)使用的温度很可能引起相分离时,这方案可作为最佳实施方案使用。
在另一个实施方案中,在工序(B)的末了可以从容器内排出工序(B)产生的混合溶液,例如在工序(C)中可以用水蒸汽作为热传导介质加热木材,因为水蒸汽作为热传导介质不如混合溶液或矿物油那样有效,而且在已浸渍的金属盐固定在木材内以前,使用水蒸汽会引起金属盐的浸出,所以此实施方案不如上述实施方案好。然而,当从工序(B)产生的混合溶液呈乳化液形式,并且在工序(C)所用温度很可能引起相分离时,这个实施方案也是一个较佳的实施方案。
在本发明工序(A)中用作浸渍液的溶液可以是烃溶液,或是水溶液。如上所指,这些溶液也可以是乳化液或者微乳化液。这些乳化液和微乳化液的连续相可以是烃或是水溶液。一般在工序(A)中所用溶液内金属盐量足以在溶液内提供0.1~5%(按以溶液重量为基础的金属重量)的金属含量。
在一个最佳实施方案中,该溶液是金属盐溶于烃溶剂的溶液。有效的烃溶剂实例为芳香和脂族烃溶剂,以及芳香和脂族烃溶剂的混合物。特殊的烃的例子为溶剂油、石脑油、轻矿物油、二甲苯、甲苯和诸如石油烃一类的工业烃溶剂的混合物。诸如各种醇、酮、醚和酯一类氧化了的烃作为烃溶剂也是有效的。
当本发明方法中使用烃液时,金属盐最好是可溶于油或可溶于烃溶剂的盐类。可认为本发明中各种金属盐的油溶解性有助于得到有利和所需结果。由于有机化合物可溶于油,基本上是疏水的,因而,甚至在很长时间内,不存在从已处理的木材内被萃取和浸出的可能性。
在本发明水溶体系中有效的最佳类型的可溶于油的金属盐是有机羧酸的酸式、中性和碱式盐。这些盐作为“皂类”在该技术中也是众所周知的。
对盐中所含金属的选择,将取决于想使处理木材得到什么样的性能、可获得性、成本和有效性。
在本发明方法中较常用的某些金属包括铜、锌、锆、铬、铁、锑、铅和汞。也可以使用含有这些两个或多个金属离子的混合物的盐。
如上所述,这些盐可以是酸式、中性或碱式的。酸式盐含有使酸中和不充分的金属阳离子。中性盐含有的金属阳离子量正好足以使盐阴离子中存在的酸性基团中和。碱式盐含有过量的金属阳离子,经常称为高碱性的、过碱性的或超碱性的盐。这些酸式、中性和碱式盐最好是可溶于油的有机羧酸盐及其混合物。
可以制取合适的酸式、中性和碱性盐的羧酸包括脂族、环脂族和芳香族的一元和多元羧酸。这些有机羧酸可以是天然的,或是合成的,或是它们的混合物。一般要进行提纯的天然酸的实例包括直链和支链羧酸和诸如妥尔油酸和环状羧酸如环烷酸的混合物。各种合成羧酸,特别是脂族羧酸及其混合物是有效的,这些酸通常含有6个或更多的碳原子。
可以通过熔融或沉淀法制取各种金属盐或肥皂。通常用诸如烃油或溶剂一类的惰性液体介质制取皂。各种有机羧酸通常至少含有6个碳原子和30个之多的碳原子,但当使用多于一种的羧酸时,作为混合物羧酸中的一种酸可以使用含有仅仅有两个碳原子的羧酸。各种有效有机羧酸的例子包括醋酸、丙酸、丁酸、异戊酸、己酸、2-乙基丁酸、壬酸、癸酸、2-乙基己酸、异辛酸、异壬酸、新癸酸、月桂酸、棕榈酸、硬脂酸、油酸、亚油酸、环烷酸,以及诸如市售的环烷酸、妥尔油酸、松香酸等一类两种或多种羧酸的混合物。
酸式盐的各种例子是含有比铜化学计算当量/(酸克当量)少的各种酸式铜盐。对于除铜以外的各种金属,因为碱式盐或肥皂含有较高的金属含量,所以最好使用它们。例如,诸如新癸酸一类的一元羧酸正锌盐溶液,含有约6%(重量)锌,而碱式新癸酸锌溶液可以含有高达约16%(重量)或更多的锌。
用技术上众所周知的方法,也可以制取羧酸碱金属盐或羧酸的皂。例如,可以在美国专利2,251,798;2,955,949;3,723,152和3,941,606内找到中性和碱式盐的各种实例,以及金属盐配合物及其制取方法的各种实例,因此可以参考采用它们的公开内容。因为某些碱式盐不是简单盐,所以它们称为配合物。例如,在美国专利3,941,606中叙述的碱性组合物称为“金属羧酸盐-烷氧基醇盐”配合物。对于本发明来说,在说明书和权利要求书中,这种碱式配合物是以金属盐或皂的词出现的。
在本发明中有效的各种盐或肥皂的具体实例包括下表1叙述的那些实例和以后的具体实例。
表1
金属羧酸盐
组分 金属 金属含量(重量%) 酸
S-1 Cu 16 新癸酸
S-2 Cu 11 新癸酸
S-3 Cu 10 环烷酸
S-4 Zn 18 2-乙基己酸
S-5 Zn 8 环烷酸
S-6 Zn 10 C8-C13混合物
用以下各种实例说明上述各种盐的制取方法,其中各部分和百分数按重量计算,除非另有说明。
实例S-1
制取260份粗新癸酸、103份丙酸、400份溶剂油、172份铜粉、91份甲基溶纤剂、14份双丙甘醇、70份水、10份辛基-苯氧基聚乙氧基乙醇(Rohm和Haas公司的triton X-15)和3份Santoflex-77的混合物,并用空气搅动,同时加热到约80℃温度。在这些条件下,反应持续约6小时。添加少量(7份)硼酸,用空气搅动,在80℃继续加热。在此温度下,该反应一直持续到180%的酸达到中和为止(全部,14小时)。在温度约为150℃,将混合物再加热2小时直到190%的酸达到中和。停止鼓入空气,充入惰性氮气,同时慢慢地在8小时内将混合物加热到约150℃,并将过量的水除去。
在3小时间隔内,大致按四等份添加总量为176份的磷酸戊酯,同时保持约145℃温度和氮气氛。然后使混合物冷却到约125℃,静放去除过剩的铜并且过滤。
在真空下使过滤的产品加热到约150℃,以便去除溶剂油得到所需浓度的金属盐的产品。
可以通过上述S-1类似的方法或在技术上众所周知的另一种可行的方法,制取表1中S-2到S-6各种实例的混合物。
实例S-7
将840份蒸馏的环烷酸、176份2-乙基己酸、512份溶剂油、48份卡必醇(联合碳化物公司的商用二甘醇乙醚)、4.8份醋酸、1.6份水和10.9份阻泡剂加入反应器内,将混合物搅动加热到约65℃。用二氧化碳搅动混合物,并将214.4份氧化锌加入到混合物里,然后混合物加热到约105℃。在此温度下保持反应,同时定期检查锌的百分比、酸值和水的百分比。如果需要,在锌含量为10%时将酸值调节到-33~-38。如果水含量超过0.4%,使混合物脱水。
将约100份助滤剂搅拌加入混合物内,然后过滤混合物。滤液是一透明液体,用溶剂油将液体调节到锌含量为10%,得到所要求的产品。
上述类型的金属羧酸盐在市场上可以买到,例如美国俄亥州克利夫兰市穆尼化学公司通用商标号44113的TEN-CEM、CEM-ALL、NAP-ALL、HEX-CEM、LIN-ALL和NEO-NAP。这些溶剂油溶液可以用于制取本发明的浸渍溶液,只要将上述溶剂油溶液同另加的溶剂油或烃溶剂混合就可以。
按照本发明方法很容易制取和使用表1所列的那些羧酸盐混合物。例如,从各等份的S-1和S-6组分制取本发明的混合物,生成含8%铜和5%锌的混合物。2份S-1组分同1份S-6组分的混合物将含有10.7%铜和3.3%锌。
也可以通过例如使金属铜或铜盐与环烷酸反应的普通方法制取在本发明溶液中所用的金属盐。当酸为液体时,一般不需要溶剂。用这种方法制取的金属盐可以是上述的酸式盐或是上述的中性盐,并能溶解在烃溶剂内,在本发明中使用。
其它中性或碱式盐的各种实例包括环烷酸铅、新癸酸铅、2-乙基己酸铅、树脂酸铅、树脂酸锌、2-乙基己酸铬、树脂酸铬、油酸铬、辛酸锑、油酸锑、环烷酸铁、树脂酸铁、油酸苯汞、二油酸汞等等。尽管在本发明方法中可以利用多种多样的金属盐,通常,本发明方法中所用的金属盐最好为杀菌剂,因此,金属盐的金属通常将至少是锌、铜、铬、铁、锑、铅或汞中的一种。除了上述金属盐以外,在该技术中众所周知的其它金属盐,也可以按照本发明方法用于处理木材。例如,在美国专利4,374,854中叙述了各金属盐组成,它是饱和无环羧酸一代和/或二代和饱和无环羧酸三代盐同锌或铜的混合物。这种盐在本发明方法中是有效的。
在另一个实施方案中,在本发明方法中使用的溶液可以是水溶液。在这种情况下,最好是该金属盐是一种可溶于水的金属盐,在先有技术中已经叙述过这种盐。使金属盐溶解在氨水溶液中和/或在氨水中制取金属盐,可以将许多不溶于水的金属盐变成可溶于水的盐。例如美国专利4,001,400和美国专利4,193,993技术中叙述过这种盐,可以参考采用这两种专利有关制取这种可溶于水的盐的公开内容。此外,美国专利4,193,993叙述了使用诸如碳酸铵、碳酸氢铵和这种铵盐同氨的混合物一类的铵盐制取各种可溶于水的金属盐。
可以通过在技术上众所周知的技术制取在本发明工序(A)中使用的溶液,例如使固体金属盐溶解在所要的溶剂内,该溶剂可以是烃溶剂或是水。另一方面,如果得到的金属盐是浓缩溶液,可以用合适的溶剂稀释浓缩物,生成含有所需金属盐量的处理溶液或浸渍溶液。
在本发明中使用的溶液也可以包括使处理的木材具有所需性能的其它添加剂。例如,该溶液可以包含阻泡剂、表面活化剂、抗氧剂、阻燃组合剂、染色剂、杀虫剂、添味剂、祛霉剂、木材稳定剂等等。当添加剂包含在水可分散的组合物中时,这种添加剂的数量范围可以从约0.01到约20~30%。尽管上述成分的数量从约0.01到约5%一般是令人满意的,在本发明溶液中包含的这种添加剂的数量可以在相当大的范围内变化。
无机阻燃组合剂在本发明溶液中特别有效。各种无机材料的实例包括在该技术中众所周知的金属氧化物,例如氧化锑等等。各种有机阻燃剂的实例包括许多可以分散在溶液中的卤化物和有机磷化合物。
尽管按照本发明方法可处理的木材对于大多数用途具有令人满意的外观,如果要求具有不同的彩色外表,也可以改变外观。本发明期望在本发明溶液中包含染色剂。可以使用众所周知的可溶于油或可分散于水中的染色剂。这些染色剂同上述金属盐浓缩物混合,或是同溶液混合,当木材浸渍在含有染色剂的溶液中时,染色剂同金属盐一起渗入木材内,可以得到所需彩色外表,在许多情况下使木材纹理更加明显。根据所需结果可以使用的各种染色
剂的实例包括:可从Bruce化学公司买到的Bruco Creosote Brown RGY,可从穆尼化学公司买到的Iron Cem-All以及可从Pylam染料公司买到的Pylaklor Red Brown Lx-6249。
在本发明溶液中也可以包含杀虫剂,最好,杀虫剂可溶于油或是可溶于水。这种杀虫剂的各种实例包括可从Dow化学公司买到的Dursban Tc和可从BFC化学公司买到的Fican76WP。
在本发明方法中使用的溶液中可以包含添味剂,一种较好的添味剂是松油。在该溶液内也可以包含具有所需气味的其它化合物。
在本发明中使用的溶液内可以包含木材稳定剂,使木材提高形稳性。当木材被干燥时,这种稳定剂滞留在细胞壁内,这种堆积作用可以防止木材皱缩。在木材处理技术中已经提出各种各样的化学药品用于这个目的。一组有效的稳定剂是聚二醇,更具体地说,是聚乙二醇。必须选择好乙二醇的分子量,以便该乙二醇可溶于水。分子量约达6000的聚乙二醇是合乎要求的,因为它们通常是水溶性的。各种聚乙二醇在市场上可以买到。
本发明方法由以下工序组成:
(A)在一定的时间、温度和压力条件下,使木材在反应容器内同至少一种可溶性的有机羧酸金属盐溶液接触,该条件足以
(ⅰ)使溶液渗入木材内,而且
(ⅱ)使工序(B)中从木材内排出溶液内的金属与酸之比同工序(A)中浸渍木材所用溶液内的金属与酸之比基本上保持相同。
(B)降低反应容器内压力,至少从木材内排出一些溶液,而且
(C)随后将木材加热到足以使金属固定于木材内的温度。
如上所述,金属溶液可以是烃溶液或是水溶液。
除非在以下各实例中以及说明书和附加权利要求书中别处另有说明,所有百分数都是重量百分数,所有温度都是摄氏温度。
实例1
将环烷酸铜溶解在定名为p9,A型油的工业石油烃中,制取含有1%铜的环烷酸铜烃溶液(其它沸点相当的烃溶剂可以代替石油烃)。
工序A
将已风干的木材原木放入钢制压力容器内。施加的初始压力。并将环烷酸铜烃溶液在压力为2.11公斤/平方厘米(表压)、温度为75°F(24℃)时泵入,一直到容器内流体静压装满为止。将流体静压增加到9.14公斤/平方厘米(表压),并将此压力保持4小时。
工序B
将静压降低到2.81~4.22公斤/平方厘米(表压),至少使已渗入木材内的一些溶液释放出来。这种释放出来的溶液(回出液)同容器内的初始溶液混合。如果要求从木材内去除更多的溶液,例如,可以将压力进一步降低到0~1.05公斤/平方厘米(表压),同时将容器内溶液温度保持在约75°F(24℃)或更低。
工序C
当已经得到所需量的回出液时,在大致恒压例如0.07公斤/平方厘米(表压)下,将容器内溶液温度升到200°F(94℃),使铜固定在木材内。在此温度下,将木材保持在足以使铜固定的时间内。一般此时间为约1小时到24小时,更一般地说,是从4小时到12小时。使用上述特殊的环烷酸铜溶液,木材从浓厚的黄绿色变成棕褐色,就证明铜固定在木材内了。
实例2
除了按照美国专利4,193,993实例11的方法,在室温下,使56.6份碳酸铜(53%铜)、38.8份碳酸铵、74份比重为0.88的氨水溶液和405.1份水混合制取的水溶液代替环烷酸铜烃溶液以外,重复本实例1的方法。
按照本发明方法处理的风干木材例如上述例子中所示出的木材显示出改进了的耐霉性,而当改变溶液添加有杀虫剂时,用按照本发明方法溶液处理的木材是耐霉防虫的。
对比实例A
重复实例1工序(A)的方法,在完成工序(A)以后,在2.81~4.22公斤/平方厘米的表压力下将环烷酸铜处理溶液从容器内抽出来。然后仍在75°F(24℃)下,将压力进一步降低到-0.98公斤/平方厘米表压,得到回出液。对以这种方式得到的回出液进行分析,发现含有1%铜,并且溶液中金属与酸之比约为0.9,它同初始溶液中金属与酸之比大致相同。
对比实例B
除了在工序(A)期间将容器内溶液温度保持在约200°F(94℃)以外,重复对比实例A的方法。在本实例中得到的回出液仅含有0.5%铜,并且金属与酸之比仅为0.5。这表明在回出液中铜减少、酸增加。
从上述各实例可见,当工序(A)中容器内溶液温度保持在约75°F(24℃)时,同初始溶液比较,回出液中的铜含量以及金属与酸之比基本上无变化。然而,当浸渍液温度很高时,例如200°F(94℃),回出液的铜浓度以及金属与酸之比发生变化,这可能是由金属盐同木材活性基团之间的反应引起的。金属与酸之比的减少表明酸的增长使浸渍溶液发生了不希望有的稀释。况且,因为环烷酸腐蚀金属,所以环烷酸数量增加不受欢迎。
本发明方法可以应用于许多类型的木材。木材同工序(A)中溶液接触的实际时间将随许多因寺而变化,例如,(1)容器内压力水平,(2)进入木材内的金属盐数量,(3)渗入被处理的特殊类型木材的困难性,(4)木材是新伐木材还是风干木材。任何类型的木材,干燥的还是新伐的,都能用本发明溶液处理。一般把新伐木材规定为含有30%(重量)或更多的水的木材。干燥或风干木材规定为含有少于30%(重量)水(以极干燥木材为基础的木材)。可按照本发明方法处理的各种木材种类的实例包括南部黄松、美国侧柏、美国枞、云杉、铁杉、糖槭、槐梣、胡桃、樱桃、白松、红松、桦树、红栎、榆树、山核桃、菩提、山毛榉、美国梧桐,等等。
根据专利法,虽然已经详细叙述了最佳实施方案和最好方法,本发明的范围并不局限于此,而是要根据所附的权利要求书的范围。
Claims (25)
1、一种用金属盐浸渍木材进行防腐处理的改进了的方法,它由以下工序组成:
(A)在一定的时间、温度和压力条件下,使容器内木材同含有至少为一种的可溶性有机羧酸金属盐的溶液接触,该时间、温度和压力条件足以
(i)使溶液渗入木材内,而且
(ii)使工序(B)中从木材内排出溶液内的金属与酸之比同工序(A)中浸渍木材所用溶液内的金属与酸之比基本上保持相同,
(B)降低容器内压力,至少从木材内排出一些溶液,该溶液与容器中的多余的处理液相混,且该混合液可用作热传递介质或用作下一批木材的处理液,
(C)随后将木材加热到足以使金属固定在木材内的温度。
2、权利要求1的方法,其特征在于,工序(A)中的压力大于0到14.06公斤/平方厘米(表压)。
3、权利要求1的方法,其特征在于,工序(A)中的温度在20℃~80℃之间。
4、权利要求1的方法,其特征在于,在工序(C)中,将木材加热到90℃~120℃。
5、权利要求1的方法,其特征在于,
(a)工序(B)中从木材内排出的溶液同槽内溶液混合,
(b)混合溶液用作热传导介质,
(c)在基本上是恒压下进行木材加热。
6、权利要求1的方法,其特征在于,该溶液是烃溶液。
7、权利要求1的方法,其特征在于,该溶液是水溶液。
8、权利要求1的方法,其特征在于,工序(A)中所用溶液内的金属含量从0.1到5%(重量)。
9、权利要求1的方法,其特征在于,金属盐中的金属是锌、铜、铬、铁、锑、铅或汞,或者它们的混合物。
10、权利要求1的方法,其特征在于,该酸是含有6到30个碳原子的脂族或环脂族一元羧酸。
11、权利要求1的方法,其特征在于,该盐是铜或锌盐。
12、一种用有机羧酸铜或锌盐浸渍木材进行防腐处理的改进了的方法,它由以下工序组成:
(A)在14.06公斤/平方厘米的表压力下,在一定时间和温度下,使容器内木材同含有至少一种可溶性的有机羧酸铜或锌盐的溶液接触,该时间和温度足以
(ⅰ)使溶液渗入木材内,而且
(ⅱ)使工序(B)中排出溶液内的金属与酸之比同工序(A)中浸渍木材所用溶液内的金属与酸之比基本上保持相同,
(B)降低容器内压力,至少从木材内排出一些溶液,使上述排出的溶液同槽内溶液混合,
(C)随后将木材加热到足以使金属固定在木材内的温度,将工序(B)中所得混合溶液用作热传导介质。
13、权利要求12的方法,其特征在于,该溶液是烃溶液。
14、权利要求12的方法,其特征在于,该溶液是水溶液。
15、权利要求12的方法,其特征在于,该盐是铜盐。
16、权利要求12的方法,其特征在于,在温度为80℃和压力为10.55公斤/平方厘米的表压下,使木材同工序(A)中的溶液接触。
17、权利要求12的方法,其特征在于,在工序(C)中将已浸渍的木材加热到120℃。
18、权利要求12的方法,其特征在于,工序(A)中所用溶液内的铜含量为0.1到5%(重量)。
19、权利要求12的方法,其特征在于,该羧酸是至少一种含有6到30个碳原子的脂族或环脂族一元羧酸。
20、权利要求12的方法,其特征在于,该溶液是烃溶液,而盐是铜盐。
21、权利要求12的方法,其特征在于,该铜盐是一种杀菌剂。
22、权利要求12的方法,其特征在于,该溶液还含有杀虫剂。
23、权利要求12的方法,其特征在于,该溶液还含有阻燃剂。
24、根据权利要求1的方法所处理的木材。
25、根据权利要求12的方法所处理的木材。
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-
1985
- 1985-07-08 US US06/752,881 patent/US4649065A/en not_active Expired - Fee Related
-
1986
- 1986-05-27 NZ NZ21631886A patent/NZ216318A/xx unknown
- 1986-05-29 FI FI862275A patent/FI88686C/fi not_active IP Right Cessation
- 1986-06-25 AU AU59228/86A patent/AU580502B2/en not_active Ceased
- 1986-07-01 DE DE8686305096T patent/DE3679355D1/de not_active Expired - Fee Related
- 1986-07-01 EP EP19860305096 patent/EP0209293B1/en not_active Expired - Lifetime
- 1986-07-01 AT AT86305096T patent/ATE63714T1/de not_active IP Right Cessation
- 1986-07-02 JP JP15426286A patent/JPH074805B2/ja not_active Expired - Lifetime
- 1986-07-07 NO NO862733A patent/NO170875C/no unknown
- 1986-07-07 CN CN86106533A patent/CN1007499B/zh not_active Expired
- 1986-07-07 DK DK322786A patent/DK322786A/da not_active Application Discontinuation
- 1986-07-08 CA CA000513321A patent/CA1255977A/en not_active Expired
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CN1300013C (zh) * | 2004-09-21 | 2007-02-14 | 华南理工大学 | 水溶性无机金属盐的固定化方法 |
Also Published As
Publication number | Publication date |
---|---|
AU5922886A (en) | 1987-01-15 |
AU580502B2 (en) | 1989-01-12 |
EP0209293A1 (en) | 1987-01-21 |
US4649065A (en) | 1987-03-10 |
NO862733L (no) | 1987-01-09 |
JPH074805B2 (ja) | 1995-01-25 |
DE3679355D1 (de) | 1991-06-27 |
EP0209293B1 (en) | 1991-05-22 |
DK322786A (da) | 1987-01-09 |
FI88686B (fi) | 1993-03-15 |
ATE63714T1 (de) | 1991-06-15 |
FI88686C (fi) | 1993-06-28 |
FI862275A0 (fi) | 1986-05-29 |
NZ216318A (en) | 1989-02-24 |
DK322786D0 (da) | 1986-07-07 |
NO170875C (no) | 1992-12-23 |
CN86104657A (zh) | 1987-01-07 |
NO862733D0 (no) | 1986-07-07 |
NO170875B (no) | 1992-09-14 |
CA1255977A (en) | 1989-06-20 |
FI862275A (fi) | 1987-01-09 |
JPS629905A (ja) | 1987-01-17 |
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