CN86108237A - 包含改进了分散性的粘土的树脂组合物 - Google Patents
包含改进了分散性的粘土的树脂组合物 Download PDFInfo
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
含树脂的组合物,例如不饱和聚酯或环氧树脂的组合物,是采用一种改进了分散性的有机粘土制备的。该有机粘土的制备工序如下:使一种蒙脱石粘土在水中悬浮,形成一种流体悬浮液;用一种无机盐的溶液处理此悬浮液,该盐的阳离子至少为二价,该盐的浓度应能使蒙脱石粘土基本上完全絮凝;使絮凝的蒙脱石粘土悬浮液与一种季铵化合物混合,后者的四个烷基中至少有一个具有10~24个碳原子;将所得到的产物脱水。
Description
本发明是关于在有机介质中改进了分散性的有机粘土及其在树脂组组合物中的应用,尤其是用于涂料和成形。
有机粘土是一种从粘土矿,通常为蒙脱石类如膨润土、蒙脱石、锂蒙脱石,皂石或类似物衍生的亲有机物质的阳离子改性粘土,通过用有机阳离子(每个含有至少一种足够碳原子数的烃基)置换存在于天然粘土矿中的无机可交换阳离子,使得阳离子交换粘土表面疏水。
已经发现,有机粘土在有机介质中,例如润滑油,油基钻井液,油漆、清漆、瓷漆及印刷油墨,作为触变剂非常有用。但是,一般地说,有机粘土在有机介质中难于分散成均匀的凝胶结构,后者用来增稠有机介质或提高其粘度。因此,已经使用各种措施改善有机介质中有机粘土的分散性,包括使用极性有机物质,例如低分子量的醇或酮作为分散剂,以及在制备有机粘土时使用过量的经过特别选择的有机阳离子。
在美国专利4,105,578(Finlayson等人)中公开了一种具有提高有机体系分散性的亲有机粘土的胶凝剂,它包括甲基苄基二烷基铵化合物的反应产物,其中该化合物含有20~35%的16个碳原子的烷基,60~75%的18个碳原子的烷基,以及阳离子交换容量为每100克所述粘土至少75毫克当量的蒙脱石类粘土;其中所述铵化合物的量以100%活性粘土为基准,每100克所述粘土为100~120毫克当量。
在美国专利4,412,018(Finlayson等人)中公开了一种亲有机粘土胶凝剂及其使用和制备方法,它包括有机阳离子,有机阴离子和阳离子交换容量为每100克所述粘土至少75毫克当量的蒙脱石类粘土的反应产物;由此,有机阳离子-有机阴离子复合物与蒙脱石类粘土夹杂,蒙脱石类粘土的阳离子交换部位被有机阳离子所取代。该专利的实例说明了在触变的不饱和聚酯组合物和在触变的涂料组合物中亲有机粘土的使用。
含各种胶凝剂的不饱和聚酯组合物广为人知。除此之外,还知道在制备不饱和聚酯等玻璃纤维层压板中使用触变的胶凝剂是考虑到在高剪切速率下这些树脂易于混合和涂布。但在低剪切速率下,这些胶凝剂大大增加了聚酯的粘度,从而避免了在竖直表面上树脂的逐渐流淌。
最广泛地用于不饱和聚酯的一种胶凝剂是石棉纤维,它有助于生产触变的聚酯而不会明显地影响树脂透明度。尽管如此,在过去几年里已经逐渐确认,在普通生产条件下使用石棉是要不得的,这是由于当人体吸入石棉后它对健康造成长期的有害影响。出于此原因,石棉胶凝剂被一种硅石空气凝胶所代替。当大约1%的硅石分散在树脂中时,它提供了有效的触变性。但是,这种产品比较昂贵,且由于低的松密度,因此存在着贮藏和处理问题。
鉴于此,该项技术已转向使用有机粘土作为胶凝剂。常用的有机粘土不能分散在不饱和聚酯溶液中。它们必须预先分散在单体苯乙烯中。随后凝胶与聚酯共混。这种额外阶段很不经济且很不方便。它还限制了要掺混的有机粘土的量,到一定程度就要在苯乙烯中用物理方法处理;高于约时%(重量),凝胶即硬得无法处理。因此就需要象熔融硅石那样将有机粘土直接搅入聚酯溶液。这就是在本发明中所要表明的。
本发明中所使用的有机粘土是按美国专利4,631,091(1986年12月23日颁布)所描述的一种方法制备的,它包括以下步骤:
(a)使一种蒙脱石粘土悬浮在水中;形成一种流体悬浮液;
(b)用一种无机盐熔液处理所述的蒙脱石粘土水悬浮液,该盐的阳离子至少为2价,盐的浓度应能使蒙脱石粘土基本上完全絮凝。
(c)使絮凝的蒙脱石粘土悬浮液与季铵化合物混合,后者的四个烷基之中至少有一个具有10~24个碳原子;以及
(d)使步骤(c)的产物脱水。
在步骤(b)中,阳离子的价数最好为3,最佳阳离子是铝。如果阳离子为3价,含该阳离子的盐溶液的浓度最好是0.001M~0.02M的范围。但是如果阳离子为2价,则含该阳离子的盐溶液的浓度必须较大,最好在大约0.2M~2M的范围。
絮凝的粘土悬浮液最好按一定比例与季铵化合物混合,使每100克干粘土有95~140毫克当量的季铵阳离子。
在步骤(c)中,絮凝的蒙脱石粘土的水悬浮液最好与熔融季铵化合物混合。季铵化合物最好具有以下通式:
式中R1是10~24个碳原子的饱和或不饱和的烷基,R2和R3可相同或不同,每个为1~24个碳原子的饱和或不饱和的烷基或7~10个碳原子的芳烷基,R4是1~6个碳原子的烷基或7~10个碳原子的芳烷基,X是OH、Cl、Br、I、NO2、CH3SO4或CH3COO。
这类化合物的例子是苄基甲基二烷基氯化铵类、二甲基二烷基氯化铵类,苄基二甲基氯化铵类,苄基三烷基氯化铵类和甲基三烷基氯化铵类;其中一个或一个以上的烷基代表一种从14~20个碳原子的,但最好为C18基团占优势的动物脂衍生的烃基混合物(这种包含在动物脂中的烃基混合物的典型分析为O142.0%;C150.5%;C1619.0%;C171.5%;C1866.0%和C201.0%)。烃基可以部分不饱和,如在天然动物脂中,或基本上完全饱和,如在适宜的催化剂存在下用氢处理动物脂。
业已发现,这些有机粘土可易于混入含不饱和聚酯树脂或环氧树脂的树脂组合物中。
对于不饱和聚酯/苯乙烯体系和极性有机溶剂体系,这些有机粘土是自分散产物。
利用本发明,可提供一种新型触变的能交联的不饱和聚酯组合物它具有极好的流变特性,例如特别高的触变指数。
不需要苯乙烯预凝胶体就可使用本发明的亲有机粘土。具体地说聚酯组合物可通过将亲有机粘土与从液体不饱和聚酯和不饱和芳香单体制备的最终的液体聚酯混合物混合而制备。然后最终的聚酯组合物可采用本技术领域中所熟知的方法交联,以制备涂料或玻璃纤维增强的层压板。
在典型的工序中,液体不饱和聚酯树脂在常规装置中与一种不饱和芳香单体混合,制备一种固体含量大约为30~80%重量聚酯的溶液。然后,可将本发明的亲有机粘土添加到液体层压树脂中。
本发明的不饱和芳香单体是芳族化合物,该化合物上键合着一个或多个烯类不饱和基团,例如乙烯基,取代乙烯基或烯丙基。适宜的单体包括苯乙烯。α-甲基苯乙烯,二乙烯基苯和烯丙基苯。最好是苯乙烯,因为它效率高,用途广,而且容易得到。这些单体用于聚酯的交联,并且还作为稀释剂以降低粘度。
用于制备本发明的触变组合物的不饱和聚酯是一种二羧酸和一种主要量为不饱和烯烃的二醇,最好为每100酯基10~75烯烃基。虽然二醇可以是不饱和的,但不饱和烯烃最好是从羧酸衍生的。有代表性的二醇是乙二醇和丙二醇。有代表性的不饱和酸包括马来酸,富马酸。通常还使用这些酸的酸酐。这类聚酯是采用本技术领域中所熟知的常规的酯化技术制备的。一般地说,分子量从大约400~10000,酸值为每克树脂0~50毫克KOH的聚酯对于制备本发明的触变组合物是有效的。
用于聚酯层压树脂的亲有机粘土胶凝剂的量可在0.25%~10%的范围,最好0.5%~4%。也可以用量大于10%,但这不经济。
下面通过实施例说明本发明的实施,但它只是用来说明本发明,而并不是限定其范围。
下面实施例所涉及的Hegman仪是用于测定有机液体介质中固体颗粒分散的质量,它由一块抛光金属板装配成一个矩型凹陷所组成,其深度从一端为零均匀变化到另一端为100微米。将液体有机组合物涂层均匀地涂布在该板上,并对组合物中最粗颗粒进行目测。
在组合物中,如果比较粗的颗粒(10~100微米)数目很大,与凹陷并排的刻度比较,则观察到明显的“前沿”(front),指示出最大粒径,如果在上述粒径范围只出现少量颗粒,则它们在凹陷中显示出斑点,并可以计数。颗粒状固体在油漆组合物中应分散成这样一种程度,即当油漆试样涂布在Hegman仪上时,观察不到“前沿”,要说有的话,也仅有很少数目的斑点可以看到。
实施例1
按下述方法制备有机粘土样品。
膨润土的水悬浮液的制备是在搅拌器中使怀俄明(Wyoming)的钠膨润土原料与足够的水混合,以形成含10%(重量)干粘土的悬浮液。然后将制成的悬浮液通过300目英国标准筛(标称孔径0.053毫米),筛下物用水稀释到大约4%固体(重量),并在间歇排放中进行颗粒大小的分离,在每分钟1升的流速下进行连续离心处理。然后,细粒级通过均化器作预处理以降低粒径,提高均匀性。向500克均化细粒级样品加入足够的水,使有机粘土反应固体为2.3%(重量)。然后向其中加入计算量的氯化铝(Alcl3·6H2O),而要求后者在悬浮液中给出所希望的氯化铝的浓度。然后用一台桨叶式混合器搅拌悬浮液15分钟,同时将悬浮液加热到65℃。此后,向加热过的悬浮液中加入计算量的季铵化合物和水以及异丙醇的混合物(季铵化合物市售),要求加在干燥膨润土上的该混合物给出季铵化合物所希望的载荷(重量)。然后,所得混合物在桨叶式混合器中搅拌30分钟,在瓷漏斗上过滤,用热水洗,并在流体床干燥器中于60℃干燥1 1/2 小时。然后,将干燥产品研磨成所希望的粒径。
按上述工序制备不同的有机粘土,所使用的季铵化合物的混合物含有75摩尔二甲基苯基氢化动物脂氯化铵(2MBHT)和25摩尔%二甲基二(氢化动物脂)氯化铵(2M2HT),不同浓度的氯化铝可用于制备膨润土水悬浮液。
将每种有机粘土研磨成粒径小于0.250毫米。将1.5%(重量)的每种干有机粘土组合物掺入一种不饱和聚酯树脂组合物中,用一台实验室搅拌器以3500r、p、m搅拌15分钟。这种树脂是迅速固化的,通用的不饱和聚酯树脂,商标为“CRYSTIC196”(SCOtt Bader有限公司销售)。据信,它是邻苯二甲酸、富马酸和丙二醇的共聚物,数均分子量约为3000。混合结束时以0.01%(重量)加入辛酸钴速滤剂。从SCOtt Bader得到的Crystic 196是聚酯树脂在苯乙烯中的70%(重量)%的溶液。使用前,将这种溶液用额外的苯乙烯稀释到54%(重量)的聚酯。
含有机粘土作为胶凝剂的聚酯树脂组合物的粘度用Brookfield RVT粘度计从0.5r、p、m。5r、p、m和50r、p、m的心轴速度测量。数据示于表1中,还给出了触变指数比。
实施例2
将按实例1描述的方法制备的每种有机粘土研磨成粒径小于0.080毫米并掺入双填充(TWO-Pack)环氧瓷漆的组分A中。
这种19%颜料体积浓度的白漆由两个组分,即A和B组成。A是含有环氧树脂的基体;B是聚酰胺固化剂溶液。配料按其加入顺序列出。
为制备组分A,按下述顺序混合:
配料 说明/功能 货源 克
环氧树脂 环氧树脂在二 壳牌化 157°
1001-X-75 甲苯中的75% 学公司
(重量)溶液
溶剂混合物 65%(重量)乙 47.5
二醇单***乙酸
乙酯:15%(重
量)甲基异丁基酮;
20%(重量)=甲苯
脲醛树脂 脲甲醛树脂, 英国工 7.0
640 一种流量控制剂 业塑料
公司(BIP)
Nuosperse 分散剂 Durham 3.5
657 原料公司
二氧化钛 149.0
在一个水冷却槽中用Cowles桨叶以4000r、p、m混合上面的配料,直到得到Hegman仪读数小于10微米。将搅拌速度降到2000r、p、m,接着将下面的配料单独加入混合物中。配料按其加入顺序列出:
配料 说明/功能 克
溶剂混合物 如上所述 42.5
有机粘土 3.07
将搅拌速度提高到4000r.p.m,配料混合30分钟,这时记录Hegman仪读数。
通过混合下述可混的配料单独制备组分B。
配料 说明/功能 货源 克
Versamide 聚酰胺液体 Cray Valley 56.0
115 产品公司
固化剂(胺值
210-220mg
KOH/g)
二甲苯 35.0
使含有有机粘土和溶剂的组分A的样品放置15分钟,然后用Brookfield RVT粘度计以1r、P、m、10r、p、m和100r、p、m测定粘度。
以相同方法制备的但不含有机粘土的组分A的样品,同样进行粘度测定,结果示于表2。
从实施例1和表1中可以看出,能交联的不饱和聚酯组合物可通过主题发明得到,它具有约大于2.5的未曾预料的高触变指数,更好的约大于3.0,最佳者至少约4.0。从实例2中也可以看出,在极性有机溶剂体系中有机粘土易于分散。
Claims (14)
1、包含一种选自不饱和聚酯树脂和环氧树脂的树脂以及一种易分分散的有机粘土的树脂组合物,所述的有机粘土是通过包括下述步骤的方法制备的:
(a)使蒙脱石粘土在水中悬浮,形成水悬浮液;
(b)用一种无机盐溶液处理所述的蒙脱石粘土水悬浮液,其中所述无机盐的阳离子至少为2价,盐的浓度应能使蒙脱石粘土基本上完全絮凝;
(c)使絮凝的蒙脱石粘土悬浮液与季铵化合物混合,后者的四个烷基中至少有一个具有10~24个碳原子;以及
(d)使步骤(c)的产物脱水。
2、根据权利要求1的组合物,其中所述阳离子为3价。
3、根据权利要求2的组合物,其中所述阳离子是铝。
4、根据权利要求2的组合物,其中含阳离子的盐溶液浓度是在0.001m~0.02m。
5、根据权利要求1的组合物,其中所述阳离子为2价,而含阳离子的盐的浓度是在大约0.2~2m的范围。
6、根据权利要求1的组合物,其中步骤(c)的脱水产物是经干燥和研磨的。
7、根据权利要求1的组合物,其中与蒙脱石粘土的水悬浮液混合的季铵化合物是熔融的。
9、根据权利要求8的组合物,其中季铵化合物选自苄基甲基二烷基氯化铵类、二甲基二烷基氯化铵类、苄基二甲基烷基氯化铵类、苄基三烷基氯化铵类和甲基三烷基氯化铵类,其中一个或一个以上的烷基代表从14~20个碳原子的动物脂衍生的烃基混合物。
10、根据权利要求1的组合物,其中蒙脱石粘土与季胺化合物按一定比例混合,以使每100克干粘土有95~140毫克当量的季铵阳离子。
11、根据权利要求1的树脂组合物,其中树脂是一种不饱和聚酯树脂。
12、根据权利要求11的树脂组合物,它是涂料配方。
13、根据权利要求12的树脂组合物,其中树脂是作为一种不饱和聚酯/苯乙烯体系使用。
14、一种分散在极性有机溶剂体系中的有机粘土,它用于制备按照权利要求1的树脂组合物,所述有机粘土是通过包括下述步骤的方法制备的:
(a)使蒙脱石粘土在水中悬浮,形成水悬浮液;
(b)用一种无机盐溶液处理所述蒙脱石粘土水悬浮液,其中所述无机盐的阳离子至少为2价,盐的浓度应能使蒙脱石粘土基本上完全絮凝;
(c)使絮凝的蒙脱石粘土悬浮液与季铵化合物混合,后者的四个烷基中至少有一个具有10~24个碳原子;
(d)使步骤(c)的产物脱水。
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US4558075A (en) * | 1984-03-30 | 1985-12-10 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing organo-modified clay |
TR22515A (tr) * | 1984-04-27 | 1987-09-17 | English Clays Lovering Pochin | Bir organik vasat icinde kolayca dispersiyon hale getirilebilir bir organo-kilin hazirlanmasi |
US4631091A (en) * | 1985-08-13 | 1986-12-23 | English China Clays Lovering Pochin & Co. Ltd. | Method for improving the dispersibility of organoclays |
AT384668B (de) * | 1985-11-28 | 1987-12-28 | Welz Franz Transporte | Transportabler kuehlcontainer |
-
1986
- 1986-11-07 US US06/928,847 patent/US4683259A/en not_active Expired - Fee Related
- 1986-12-16 EP EP86309796A patent/EP0267341B1/en not_active Expired - Lifetime
- 1986-12-16 GB GB8629967A patent/GB2196970B/en not_active Expired - Lifetime
- 1986-12-16 AT AT86309796T patent/ATE68800T1/de not_active IP Right Cessation
- 1986-12-16 DE DE8686309796T patent/DE3682203D1/de not_active Expired - Fee Related
- 1986-12-22 TR TR43475A patent/TR22832A/xx unknown
- 1986-12-22 CN CN86108237.0A patent/CN1007985B/zh not_active Expired
- 1986-12-22 JP JP61306167A patent/JPH07100607B2/ja not_active Expired - Lifetime
- 1986-12-23 MX MX4771A patent/MX164723B/es unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108147419A (zh) * | 2016-12-06 | 2018-06-12 | 赢创有限公司 | 亲有机物质粘土和包含它们的钻井液 |
CN108147419B (zh) * | 2016-12-06 | 2023-01-10 | 赢创有限公司 | 亲有机物质粘土和包含它们的钻井液 |
Also Published As
Publication number | Publication date |
---|---|
ATE68800T1 (de) | 1991-11-15 |
GB8629967D0 (en) | 1987-01-28 |
JPH07100607B2 (ja) | 1995-11-01 |
TR22832A (tr) | 1988-08-18 |
EP0267341A1 (en) | 1988-05-18 |
EP0267341B1 (en) | 1991-10-23 |
GB2196970B (en) | 1990-08-22 |
DE3682203D1 (de) | 1991-11-28 |
US4683259A (en) | 1987-07-28 |
JPS63128906A (ja) | 1988-06-01 |
MX164723B (es) | 1992-09-21 |
CN1007985B (zh) | 1990-05-16 |
GB2196970A (en) | 1988-05-11 |
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