CN106281104A - 用于微胶囊化聚合促进剂的方法 - Google Patents
用于微胶囊化聚合促进剂的方法 Download PDFInfo
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- CN106281104A CN106281104A CN201610659862.4A CN201610659862A CN106281104A CN 106281104 A CN106281104 A CN 106281104A CN 201610659862 A CN201610659862 A CN 201610659862A CN 106281104 A CN106281104 A CN 106281104A
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- B01J13/02—Making microcapsules or microballoons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/41—Compounds containing sulfur bound to oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/10—Encapsulated ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
描述了用于微胶囊化聚合促进剂的方法。所述密封制剂包含至少一种丙烯酸树脂和苯氧基‑聚乙氧基硫酸盐。自锁制剂包含至少一种二丙烯酸酯、丙烯酸树脂、微胶囊化的聚合引发剂和微胶囊化的聚合促进剂。描述了用于包覆聚合促进剂以获得微胶囊化的聚合促进剂的方法。
Description
本申请是分案申请,其原申请的国际申请号为PCT/IB2012/000968,国际申请日是2012年05月18日,中国国家申请号为201280073262.X,进入中国的日期为2014年11月18日,发明名称为“用于密封和封闭螺栓和螺母的厌氧固化制剂”。
技术领域
本发明涉及基于水性乳剂中的丙烯酸树脂的厌氧固化/可交联制剂(formulations)。基于这些制剂的组合物,可以调节它们的反应产品的特性,以使它们特别适合于作为密封和/或封闭剂(blocking agents)使用,用于螺钉、螺母、螺栓以及螺帽或密封帽的连接。
背景技术
在市场上可以获得各种适合用于密封和封闭螺母和螺栓的制剂。以下简要地论述这些已知的专利出版物中的一些。
国际专利申请WO 00/01767涉及用于将螺母密封和自锁在螺钉上的组合物。该组合物是以下组分的乳剂或水性分散体系(dispersion):
a)至少一种以组合物总重的4wt%-15wt%的量存在的可聚合的(甲基)丙烯酸单体,
b)在水中可溶的或可分散的粘合剂(binding agent)(反应性单体)以及
c)有效量的微胶囊形式的自由基聚合引发剂(过氧化苯甲酰)。
诸如对苯二酚等阻聚剂的添加为聚合的组合物(polymeric composition)提供了稳定性。可以向该组合物中添加聚合促进剂(polymerization accelerator),例如含有二茂铁部分(fraction)的有机金属化合物。通过添加碱性溶液来控制pH值。该组合物对由热引起的老化显示了高的耐性,且在铜和青铜的表面上是非常稳定的。
美国专利US 4,417,028描述了粘合涂覆组合物(adhesive coatingcomposition),该粘合涂覆组合物包括可聚合的单体、粘合体系(binding system)和聚合引发剂和促进剂(二茂铁)。在该组合物中使用的可聚合的单体被描述为多官能的和单官能的丙烯酸的酯类(它们包括氨基甲酸乙酯丙烯酸酯(urethane acrylates);甲基丙烯酸羟丙酯;甲基丙烯酸羟乙基酯)的混合物。粘合体系包括酸酐和选自亚芳基、亚烷基、亚烷氧基(alkoxylene)、芳基亚烷基(arylalkylene)等的化合物的共聚物。优选的粘合剂是乙烯/马来酸酐。这些粘合剂形成稳定的悬浮液或分散体系,且利用酸酐环的水解还有助于预先涂在衬底上的薄膜的粘附。碱(NH4OH、NaOH)用于控制组合物的pH值,以获得预先涂到衬底上的组合物的最佳的粘附。该组合物具有长的保质期、改善的耐热老化性、以及螺栓和螺钉之间的更大的自锁。
美国专利US 4,546,125涉及粘合固化组合物(adhesive curing composition),该组合物具有改善的强度和粘附速度。该组合物包含厌氧可聚合的单体,该厌氧可聚合的单体包括至少10wt%的能够溶解(dissolving)多于0.5wt%的水的厌氧可聚合的单体;邻苯甲酸磺酰胺(o-benzoic sulfonamide)(聚合促进剂);来改善耐热性的杂环叔胺和/或芳香胺;自由基聚合引发剂和水。氨基甲酸乙酯聚(甲基)丙烯酸酯(Urethane poly(meth)acrylate)被描述为可聚合的单体。
US 4,048,259描述了粘合密封组合物,该组合物在厌氧条件下硬化。该组合物包含可聚合的丙烯酸酯、过氧化物聚合引发剂和丙烯酸的酯。该组合物可以包含稳定剂(对苯二酚)、促进剂(脂肪族或芳香族季胺)、增稠剂、染料和填料(CaCO3、TiO2和可溶性染料)。可用于该组合物的增稠剂是聚(烷基)丙烯酸酯类和甲基丙烯酸酯类。该组合物是无腐蚀性的粘合混合物且产生非常强的固定(fixing)。
US 4,007,322描述了厌氧密封组合物,该组合物包括一个以上的非氧化的(non-oxygenated)丙烯酸单体、聚合引发剂(有机过氧化物)、阻聚剂(对苯二酚)和聚合促进剂(苯甲酸磺酰胺(benzoic sulfonamide))。在与空气接触的情况下,阻聚剂赋予组合物长的保质期。如果没有一个表面是金属的,至少一个接触表面必须用底漆(primer)预处理。
US 3,855,040涉及厌氧组合物,该厌氧组合物迅速地聚合且包含丙烯酸酯单体、聚合引发剂(有机过氧化物)、强酸和活化剂(activator)(含二茂铁部分)。选择所述活化剂来控制固化速度。
US 3,970,505描述了厌氧组合物,该厌氧组合物包含多官能的丙烯酸酯单体、过氧化物聚合引发剂、取代的硫脲和酸性物质。该组合物迅速地固化,同时保持诸如坚固性、柔韧性和密封性能等良好的机械性能。所使用的单体产生粘合性和持久的密封剂。聚丙烯酸酯类的实例为:二和四甘醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、双甘油二丙烯酸酯等。
US 4,410,644描述了厌氧密封组合物,该厌氧密封组合物包含可聚合的丙烯酸酯单体、聚合引发剂(氢过氧化物)、阻聚剂(醌)、有机磺酰胺类的促进剂、增稠剂(聚乙二醇)、着色剂、诸如硅粉等粘度控制剂(=流变改性剂);抗磨剂[(针对金属接触部件之间的摩擦所引起的金属磨损),即防磨损剂,诸如四氟乙烯等]和至少一种增塑剂(甘油脂)。
所有的这些已知的制剂是均基于与不同类型添加剂、聚合物引发剂和促进剂结合的(甲基)丙烯酸酯化合物、以获得具有期望的物理、机械和化学特性的固化的反应产品。然而,存在厌氧固化/可交联的制剂的需求,所述厌氧固化/可交联的制剂能够满足要求更宽的固化强度范围的应用,而不需要使用底漆和阻聚剂,且所述厌氧固化/可交联的制剂具有优于已知技术的那些的物理、机械和化学特性。
发明内容
本发明提供了水性乳剂中的厌氧可聚合的和固化/可交联的制剂和它们的反应产品,所述水性乳剂中的厌氧可聚合的和固化/可交联的制剂在相对较短的时间内固化/交联,它们的反应产品显示出提高的封闭力(blocking force)(由提高的剥离强度(detachment)表示)、提高的耐油性和高耐热性。
本发明的制剂是糊剂(paste)的形式,可以很容易地涂到螺钉和螺栓的螺纹,以保证密封和封闭效果;它们不需要使用底漆和阻聚剂。
本发明的一个方面包括新的制剂,所述新的制剂在厌氧条件下是可聚合和可固化的,且对于应用于螺钉和螺栓的螺纹上以产生相对于使用已知技术的产品所能够获得的结果的提高的密封力,所述新的制剂是特别有用的。所述制剂包括与已知技术中所常用的其它添加剂结合的至少一种丙烯酸树脂和苯氧基-聚乙氧基硫酸盐(phenoxy-polyethoxysulphate)。根据本发明,以下将该制剂称为“密封制剂”。
本发明的另一个方面包括新的制剂,所述新的制剂在厌氧条件下是可聚合和可固化的,且对于应用于螺钉和螺栓的螺纹上以产生相对于使用根据已知技术的产品所能够获得的结果的提高的密封力,所述新的制剂是特别有用的。所述制剂包含至少一种二甲基丙烯酸酯、丙烯酸树脂、聚合和固化引发剂、促进剂和已知技术中所常用的其他添加剂。引发剂和促进剂两者均以微胶囊化的形式使用。根据本发明,该制剂被称为“自锁制剂(self-locking formulation)”。
这些制剂的反应产品能够执行所需的螺栓密封和封闭作用,根据它们预定的应用类型,所述密封和封闭作用可以更强或更弱以及更快或更慢。
利用现有技术中已知的设备使所述制剂沉积在螺钉的螺纹的内部并随后烘干,在该过程中拧紧螺母并引发聚合,从而得到产生上述结果的反应产品。
这些制剂的反应产品的特征是优良的耐振性、耐热性和耐化学品侵蚀性。它们尤其是用于密封和封闭螺钉和机械装置的螺纹,防止松动和渗漏。
具体实施方式
所述密封制剂包含4wt%-8wt%的丙烯酸树脂和40wt%-70wt%的苯氧基-聚乙氧基硫酸盐。根据本发明,优选使用的苯氧基-聚乙氧基硫酸盐是浓度为40%-45%的壬基苯氧基聚乙氧基支化的硫酸铵(nonylphenoxy polyethoxy branched ammonium sulphate)和0.1%-0.2%的氨的水性溶液的水性混合物。
所述密封制剂包含20wt%-35wt%的量的水。可以向所述密封剂中添加其他添加剂,例如增塑剂、染料、填料、缓蚀剂等。
以下是根据本发明的密封制剂的实例:
在本发明中以wt%表示的量是参照所述制剂的总重。
所述自锁制剂包含30wt%至60wt%的量的二甲基丙烯酸酯。部分的二甲基丙烯酸酯可以用二脲烷二甲基丙烯酸酯(diurethanedimethacrylate)代替,在这种情况下,所述自锁制剂优选包含15wt%至30wt%的量的二甲基丙烯酸酯,同时使用15wt%至30wt%的量的二脲烷二甲基丙烯酸酯。
所述自锁制剂此外还包含5wt%-9wt%的丙烯酸树脂、2wt%-4wt%的引发剂和0.3wt%-1.5wt%的促进剂。所述引发剂和所述促进剂两者均以微胶囊化的形式使用。
以下是根据本发明的自锁制剂的实例:
在本发明中以wt%表示的量是参照所述制剂的总重。
根据本发明的优选的实施方案,所述密封和自锁制剂的pH值保持在5至10的范围,更优选保持在6至8的范围。
通过在本发明的制剂中加入有效量的有机或无机碱可以调节pH值,所述有机或无机碱不干扰所述丙烯酸树脂和所述二甲基丙烯酸酯的聚合。优选地,通过添加NH4OH或NaOH来调节pH值,以获得所述密封和自锁制剂的良好的固化特性。
可以用于本发明的制剂的丙烯酸树脂选自ACRYSOLTM ASE 20、ACRYSOLTM ASE 60和ACRYSOLTM ASE 75、优选ACRYSOLTM ASE 60的固化的共聚物的水性乳剂。
可以用于根据本发明的自锁制剂的二甲基丙烯酸酯是二苯酚A乙氧酸二甲基丙烯酸。
本发明的所述密封制剂不包含催化剂,因此螺栓的固定作用不像所述包含聚合引发剂和促进剂的自锁制剂那样强。
所述密封制剂使用与苯氧基聚乙氧基硫酸盐结合的丙烯酸树脂,所述苯氧基聚乙氧基硫酸盐的存在对反应产品的性能的具有出乎意料的效果。根据本发明的密封制剂中的苯氧基聚乙氧基硫酸盐的引入,赋予所述反应产品相当大的耐化学试剂性和对化学试剂的稳定性,同时也提高了它的密封能力。
此外,出乎意料地是,如此配制的密封剂不需要在它的施用之前用底漆在金属和塑料表面上进行预处理。对于允许使已知技术的其它产品锚固在其所施用到的部件上,所述预处理是必不可少的。
本发明的所述自锁制剂包含微胶囊形式的聚合引发剂和促进剂,当螺母在预先用所述自锁制剂处理的螺钉上被拧紧时,所述微胶囊形式的聚合引发剂和促进剂被激活。在厌氧条件下,引发聚合和固化,且该化学反应立即在螺母和螺钉之间产生封闭效果。
不像已知的技术,根据本发明的自锁制剂不包含产生较短的聚合物链的阻聚剂,因为它们不仅钝化初级自由基(primary radical)和次级自由基(secondary radical),而且还钝化负责聚合物增长的那些自由基。因阻聚剂的作用所形成的短链产生更小的“胶合”效果,因此产生较差的螺栓封闭力。此外,没有阻聚剂(inhibitors)意味着沉积在螺钉上的产品的聚合在螺栓被拧紧之前发生。这种预聚合现象负面地影响了所述反应产品的封闭能力。为了避免所述缺点,本发明的自锁制剂的特征是一方面没有阻聚剂,另一方面是包含微胶囊化的聚合促进剂。根据本发明,优选使用二茂铁作为聚合促进剂。
此外,出乎意料地是,以这种方式组成的封闭制剂不需要在它的施用之前用底漆在表面上进行预处理,而对于允许使已知技术的其它产品锚固在其所施用到的部件上,所述预处理是必不可少的。
二茂铁利用创新的方法包覆防护材料薄膜,在螺栓被拧紧之前,所述防护材料薄膜防止二茂铁与聚合引发剂的反应。根据本发明,当螺栓被拧紧时,所述保护膜由于摩擦而破裂,从而为所述聚合提供二茂铁。
根据本发明,用于包覆所述聚合促进剂的方法包括以下步骤:制备水性明胶溶液,调节所述水性溶液的pH值至4-7之间的值,将促进剂引入到所述水性明胶溶液中,添加所述包覆促进剂的薄膜的硬化剂和防结块物质,自水性部分中分离固体部分,用水洗涤所述固体部分和干燥最终产品。
有利地,所述聚合促进剂是二茂铁,所述硬化剂是戊二醛,且所述防结块物质是二氧化硅(SiO2)。
在本发明的制剂中使用微胶囊化的聚合促进剂避免了导致上述的负面效果的聚合稳定剂和阻聚剂的使用,并允许长期的保存产品,而不改变其封闭特性。
附图说明
从以下参照附图、作为非限定性实施例所提供的描述中,本发明进一步的特征和优势将变得明显,其中:
图1是产品Multicor(车用发动机润滑油)的红外光谱;
图2显示了用根据本发明的密封制剂处理的、浸入油中和没有浸入油中的螺钉的两个重叠的红外光谱;
图3是产品Torma Prot(车用发动机润滑油)的红外光谱;
图4显示了用根据本发明的密封制剂处理的、浸入油中和没有浸入油中的螺钉的两个重叠的红外光谱。
优选的实施方案的描述
然后通过将经处理的螺钉浸入两种不同类型的车用发动机润滑油:Multicor和TormaProt中,来对所述密封制剂进行耐油性测试。
以下在实施例中提供了所述密封制剂的制备方法以及耐油性和剥离力(detachment force)测试的结果,所述实施例仅作为本发明的非限定性实例在此进行描述。
实施例1
在搅拌下将下列化合物添加到叶轮式混合器(turbo-mixer):30g去离子水、4g乙二醇丁醚、0.1g颜料蓝ID 30466565和0.2g的28%的氨的水性溶液,以获得pH6.5的混合物。以1400rpm的速度混合所述化合物,然后在搅拌下向所述混合物中添加2g二氧化钛、0.7g苯甲酸铵和4g的丙烯酸树脂ACRYSOLTMASE 60。将所获得的混合物置于0.6巴的真空中并搅拌5分钟。然后使所述混合物处于常压下,并在搅拌下加入16g同时添加60g苯氧基-聚氧乙基硫酸盐。所获得的混合物在搅拌下在0.8巴保持25分钟。
为了获得具有最佳的诸如粘度和密封性能等特性的最终产品,必须保持如实施例中的反应时间和压力。
在将具有经实施例1的产品处理的表面的螺钉浸入后,对在该实施例中所获得的产品进行耐油性测试。记录Multicor产品的红外光谱(车用发动机润滑油),并获得了图1中所示的红外光谱。螺钉的外表面用根据实施例1所获得的产品处理,并将所述螺钉浸入在Multicor产品中。图2中对比地显示了所记录的红外光谱,并突出地显示了浸入油中的螺钉1的表面和没有浸入油中的螺钉2的表面的两个红外光谱的重叠。最后,发现图2中的两个红外光谱没有显示相关差异,仅是浸入油中的样品的一些吸收带显示略有增大,这可以归因于存在于密封产品中的苯甲酸盐迁移了到所述表面。不存在新的吸收带,因此在用实施例1的产品所处理的螺钉浸入油中之后,在所述密封产品中没有发生化学改性。
使用以Torma Prot的名称销售的另一种类型的车用发动机润滑油重复相同的测试。
图3显示了Torma Prot油的红外光谱,而图4显示了经实施例1的密封产品处理的浸入油中的螺钉1的外表面的红外光谱和没有浸入油中的螺钉2的外表面的红外光谱。浸入过和没有浸入过的螺钉的表面的红外光谱没有显示相关差异。在浸入油中的样品的一些吸收带中记录有略微的增大,这可以归因于存在于密封剂中的苯甲酸盐迁移了到所述表面。不存在新的吸收带,因此在浸入Torma Prot油中之后,在所述密封产品中没有发生化学改性。
实施例2
将55克去离子水置于叶轮式混合器中,并在搅拌下加入以下物质:0.6克颜料红ID 1996500、0.4g的28%的氨的水性溶液、2g的二氧化钛、0.8g滑石粉、1g苯甲酸铵、0.1g磷酸铵、6g丙烯酸树脂ACRYSOLTMASE 60和18g二苯酚A乙氧酸二甲基丙烯酸。所述混合物的pH值是6.5。使所获得的混合物处于室温,并将所述混合物置于0.6巴的真空中、在搅拌下在真空中保持5分钟。然后将混合物的压力调到常压,并加入21g二苯酚A乙氧酸二甲基丙烯酸。将所获得的混合物放置在0.8巴的真空中,并在搅拌下保持20分钟。向如此获得的产品中添加3g的微胶囊化的过氧化苯甲酰和0.9g微胶囊化的二茂铁,并对该混合物搅拌5分钟。
根据现有技术中已知的方法,过氧化苯甲酰引发剂是微胶囊化的,而二茂铁促进剂经由下面的方法被胶囊化。
向混合器中添加80g的去离子水,并在搅拌下引入0.2g六偏磷酸钠和4g明胶。当引入明胶完毕时,保持搅拌几分钟,然后使混合物静置30分钟。在搅拌下,将混合物的温度调到45℃-70℃,并添加氢氧化钠,然后将混合物冷却到43℃,添加0.2g醋酸,最后加入15g的二茂铁。将混合物的温度冷却到室温。然后将所获得的产品的温度快速冷却到10℃-18℃,并添加2g的戊二醛和1g的二氧化硅(SiO2)。
将所获得的产品沉淀,然后除去水性溶液,并用去离子水洗涤固体部分。重复三次该操作。然后将所获得的产品过滤,并在40℃的干燥机中放置48小时。最终产品是微胶囊化的二茂铁。
出乎意料地,如此配制的产品与在用的产品相比,具有更高的剥离值,且该值是非常一致的。在以下的表1中给出了根据DIN 267/27标准在M10螺钉上所测定的剥离值。
表1
实施例3
将55克去离子水置于叶轮式混合器中,然后在搅拌下加入以下物质:0.6克颜料绿ID 30267548、0.4g的28%的氨的水性溶液、1g的二氧化钛、1g苯甲酸铵、0.1g磷酸铵、7g的ACRYSOLTMASE 60(用作丙烯酸树脂)。将所获得的混合物调到室温,并将所述混合物置于0.6巴的真空下。在真空下保持搅拌混合物5分钟。然后将混合物调到常压,并加入25g二苯酚A乙氧酸二甲基丙烯酸。将其放置在0.8巴的真空下,并在搅拌下保持20分钟。
向如此获得的产品中添加2g的微胶囊化的过氧化苯甲酰和0.4g的微胶囊化的二茂铁。搅拌该混合物5分钟。
出乎意料地,如此配制的产品显示非常一致的剥离值。在以下的表2中给出了根据DIN 267/27标准在M10螺钉上所测定的值。
表2
Claims (3)
1.用于微胶囊化聚合促进剂的方法,其特征在于,制备水性明胶溶液,调节所述水性溶液的pH值至4-7之间的值,将聚合促进剂引入到所述水性明胶溶液中,添加硬化所述明胶的试剂和防结块物质,自水性部分中分离固体部分,用水洗涤所述固体部分和干燥最终产品。
2.根据权利要求1所述的方法,其特征在于,所述聚合促进剂是二茂铁,所述硬化剂是戊二醛,且所述防结块物质是二氧化硅。
3.权利要求1或2得到的微胶囊化的聚合促进剂的用于制备自锁厌氧固化制剂的用途。
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