CN101454364B - 基于聚氧化烯和乙烯基酯的两亲性接枝聚合物 - Google Patents
基于聚氧化烯和乙烯基酯的两亲性接枝聚合物 Download PDFInfo
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- CN101454364B CN101454364B CN2007800198078A CN200780019807A CN101454364B CN 101454364 B CN101454364 B CN 101454364B CN 2007800198078 A CN2007800198078 A CN 2007800198078A CN 200780019807 A CN200780019807 A CN 200780019807A CN 101454364 B CN101454364 B CN 101454364B
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
- C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
Abstract
本发明涉及基于作为接枝基质的水溶性聚氧化烯(A)和通过聚合乙烯基酯组分(B)形成的侧链的两亲性接枝聚合物,所述聚合物具有平均≤1个接枝点/50个氧化烯单元并且具有的平均摩尔质量Mw为3000-100000。
Description
本发明涉及基于作为接枝基质的水溶性聚氧化烯(A)和通过聚合乙烯基酯组分(B)形成的侧链的新型两亲性接枝聚合物,所述聚合物具有平均≤1个接枝点/50个氧化烯单元并且具有的平均摩尔质量Mw为3000-100 000。
本发明还涉及这些接枝聚合物的制备。
基于聚氧化烯和乙烯基酯,特别是乙酸乙烯酯的接枝聚合物可由DE-B-10 77 430和GB-B-922 457获知。它们通过在聚氧化烯存在下聚合乙烯基酯制备,所用引发剂为过氧化二苯甲酰、过氧化二月桂酰或过氧化二乙酰。在这些文献的实施例中,程序为由所有反应物制备溶液。将该溶液直接加热到聚合温度或首先仅加入一部分并加热,然后计量加入大部分。在第一个变型中,也可以存在较大量溶剂如乙酸甲酯或甲醇(基于聚亚烷基二醇、乙烯基酯的量为100%或72%)。其他程序在GB-B-922 457中仅提到但未在制备接枝聚合物的实施例中使用。
根据EP-A-219 048和285 037,基于聚氧化烯和乙烯基酯的接枝聚合物适合作为包含合成纤维的织物的洗涤和后处理中的发灰抑制剂。为此,EP-A-285 935和285 038也推荐了包含作为额外接枝单体的呈共聚形式的丙烯酸甲酯或N-乙烯吡咯烷酮的接枝聚合物。对于实施例中所用接枝聚合物的制备,没有给出具体数据;仅一般参考DE-B-10 77 430和GB-B-922457。
相对于本发明接枝聚合物,根据DE-B-10 77 430和GB-B-922 57中说明书制备的接枝聚合物为较高度支化的(>1个接枝点/50个氧化烯单元)并具有宽摩尔质量分布(多分散性>3)。
本发明目的是提供适合作为洗涤和清洁组合物,尤其从织物和硬质表面上除去疏水性污物的添加剂的聚合物。
因此我们已找到基于作为接枝基质的水溶性聚氧化烯(A)和通过聚合乙烯基酯组分(B)形成的侧链的两亲性接枝聚合物,所述聚合物具有平均≤1个接枝点/50个氧化烯单元并且具有的平均摩尔质量Mw为3000-100 000。
我们还发现一种制备接枝聚合物的方法,其包括在水溶性聚氧化烯(A),形成自由基的引发剂(C)以及需要的话基于组分(A)、(B)和(C)总量为至多40重量%的有机溶剂(D)的存在下,在引发剂(C)分解半衰期为40-500分钟的平均聚合温度下,以使反应混合物中未转化的接枝单体(B)和引发剂(C)的分数相对于聚氧化烯(A)恒定维持定量不足的方式聚合包含乙酸乙烯酯和/或丙酸乙烯酯(B1)以及需要的话其他烯属不饱和单体(B2)的乙烯基酯组分(B)。
本发明接枝聚合物的特征在于它们低的支化度(接枝度)。基于所得反应混合物,它们具有平均不大于1个,优选不大于0.6个,更优选不大于0.5个,最优选不大于0.4个接枝点/50个氧化烯单元。基于所得反应混合物,它们优选包含平均至少0.05个,特别是0.1个接枝点/50个氧化烯单元。支化度例如可借助13C NMR波谱由接枝点和聚氧化烯的-CH2-基团的信号积分测定。
根据它们的低支化度,本发明接枝聚合物中接枝与未接枝氧化烯单元的摩尔比为0.002-0.05,优选0.002-0.035,更优选0.003-0.025,最优选0.004-0.02。
本发明接枝聚合物的特征为窄的摩尔质量分布以及由此通常≤3,优选≤2.5,更优选≤2.3的多分散性Mw/Mn。其多分散性Mw/Mn最优选为1.5-2.2。所述接枝聚合物的多分散性例如可通过凝胶渗透色谱法使用窄分布聚甲基丙烯酸甲酯作为标准测定。
本发明接枝聚合物的平均分子量Mw为3000-100 000,优选6000-45000,更优选8000-30 000。
本发明接枝聚合物的两亲性特征和嵌段聚合物结构因其低支化度和低多分散性而特别显著。
本发明接枝聚合物还具有仅呈低含量的未接枝聚乙烯基酯(B)。它们通常包含≤10重量%,优选≤7.5重量%,更优选≤5重量%的未接枝聚乙烯基酯(B)。
本发明接枝聚合物因低的未接枝聚乙烯基酯含量和组分(A)和(B)的平衡比例而可溶于水或水/醇的混合物(例如25重量%的二甘醇单丁基醚水溶液)中。它们已显示低的浊点,在最高50℃水中溶解的接枝聚合物的浊点通常≤95℃,优选≤85℃,更优选≤75℃,另外在25重量%二甘醇单丁基醚水溶液中溶解的接枝聚合物的浊点通常≤90℃,优选为45-85℃。
本发明两亲性接枝聚合物优选具有:
(A)20-70重量%作为接枝基质的水溶性聚氧化烯,和
(B)通过在(A)存在下自由基聚合30-80重量%包含下列物质的乙烯基酯组分所形成的侧链:
(B1)70-100重量%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)0-30重量%的其他烯属不饱和单体。
它们更优选包含25-60重量%的接枝基质(A)和40-75重量%的聚乙烯基酯组分(B)。
适合形成接枝基质(A)的水溶性聚氧化烯原则上为基于C2-C4氧化烯的包含呈共聚形式的至少50重量%,优选至少60重量%,更优选至少75重量%的氧化乙烯的所有聚合物。
聚氧化烯(A)优选具有低的多分散性Mw/Mn。其多分散性优选≤1.5。
聚氧化烯(A)可以为相应的呈游离形式的聚亚烷基二醇,即带有端羟基,但它们还可以在一个端基或两个端基封端。合适的端基例如为C1-C25烷基、苯基和C1-C14烷基苯基。
特别合适的聚氧化烯(A)的具体实例包括:
(A1)可以在一个端基或两个端基,尤其通过C1-C25烷基(但优选未醚化的)封端并且平均摩尔质量Mn优选为1500-20 000,更优选2500-15 000的聚乙二醇;
(A2)同样可以在一个端基或两个端基,尤其通过C1-C25烷基(但优选未醚化的)封端并且平均摩尔质量Mn优选为1500-20 000,更优选2500-15000的氧化乙烯和氧化丙烯和/或氧化丁烯在氧化乙烯含量为至少50重量%下的共聚物;
(A3)可通过使平均摩尔质量Mn为200-5000的聚乙二醇(A1)或平均摩尔质量Mn为200-5000的共聚物(A2)与C2-C12二羧酸或-二羧酸酯或C6-C18二异氰酸酯反应获得的平均摩尔质量特别为2500-20000的链增长产物。
优选接枝基质(A)为聚乙二醇(A1)。
本发明接枝聚合物的侧链通过在接枝基质(A)存在下聚合乙烯基酯组分(B)形成。
乙烯基酯组分(B)可有利地由(B1)乙酸乙烯酯或丙酸乙烯酯或乙酸乙烯酯与丙酸乙烯酯的混合物组成,特别优选乙酸乙烯酯作为乙烯基酯组分(B)。
然而,该接枝聚合物的侧链还可以通过共聚乙酸乙烯酯和/或丙酸乙烯酯(B1)和其他烯属不饱和单体(B2)形成。乙烯基酯组分(B)中单体(B2)的分数可以为至多30重量%,这对应于(B2)在接枝聚合物中的24重量%含量。
合适的共聚单体(B2)例如为单烯属不饱和羧酸和二羧酸及其衍生物(例如酯、酰胺和酸酐)和苯乙烯。当然还可以使用不同共聚单体的混合物。
具体实例包括:(甲基)丙烯酸、(甲基)丙烯酸的C1-C12烷基酯和羟基C2-C12烷基酯、(甲基)丙烯酰胺、N-C1-C12烷基(甲基)丙烯酰胺、N,N-二(C1-C6烷基)(甲基)丙烯酰胺、马来酸、马来酸酐和马来酸的单(C1-C12烷基)酯。
优选单体(B2)为(甲基)丙烯酸的C1-C8烷基酯和丙烯酸羟乙基酯,特别优选(甲基)丙烯酸的C1-C4烷基酯。
非常特别优选单体(B2)为丙烯酸甲酯、丙烯酸乙酯,特别是丙烯酸正丁酯。
当本发明接枝聚合物包含单体(B2)作为乙烯基酯组分(B)的成分时,接枝聚合物以(B2)计的含量优选为0.5-20重量%,更优选1-15重量%,最优选2-10重量%。
本发明接枝聚合物可有利地同样通过本发明方法通过在水溶性聚氧化烯(A),形成自由基的引发剂(C)以及需要的话基于组分(A)、(B)和(C)总量为至多40重量%的有机溶剂(D)的存在下,在引发剂(C)分解半衰期为40-500分钟的平均聚合温度下,以使反应混合物中未转化的接枝单体(B)和引发剂(C)的分数相对于聚氧化烯(A)恒定维持定量不足的方式聚合包含乙酸乙烯酯和/或丙酸乙烯酯(B1)以及需要的话其他烯属不饱和单体(B2)的乙烯基酯组分(B)获得。
在该方法中,优选使用30-80重量%包含下列物质的乙烯基酯组分(B):
(B1)70-100重量%乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)0-30%重量其他烯属不饱和单体
和20-70重量%的平均摩尔质量Mn为1500-20 000的水溶性聚氧化烯(A)。
引发剂(C)的量在每种情况下基于组分(B)优选为0.2-5重量%,特别是0.5-3.5重量%。
对于本发明方法必要的是在平均聚合温度下存在的自由基的稳态浓度基本上是恒定的并且接枝单体(B)在反应混合物中仅恒定地以低浓度(例如不大于5重量%)存在。这使得反应得以控制并且接枝聚合物可在所需低支化度和所需低多分散性下以可控方式制备。
术语“平均聚合温度”在这里指虽然该方法基本上为等温,但因反应放热性而存在优选维持在+/-10℃,更优选+/-5℃范围内的温度变化。
根据本发明,形成自由基的引发剂(C)在平均聚合温度下的分解半衰期应为40-500分钟,优选50-400分钟,更优选60-300分钟。
根据本发明,引发剂(C)和接枝单体(B)有利地以使得在反应混合物中存在低的并基本上恒定浓度的未分解引发剂和接枝单体(B)的方式添加。在全部反应混合物中未分解引发剂的比例基于在单体加成过程中计量加入引发剂的总量优选≤15重量%,特别≤10重量%。
平均聚合温度适当地为50-140℃,优选60-120℃,更优选65-110℃。
在50-140℃下分解半衰期为20-500分钟的合适引发剂(C)的实例为:
-叔-C4-C12烷基氢过氧化物和叔-(C9-C12芳烷基)氢过氧化物的O-C2-C12丙烯酸化衍生物如过乙酸叔丁基酯、过单马来酸叔丁基酯、过异丁酸叔丁基酯、过新戊酸叔丁基酯、过新庚酸叔丁基酯、过-2-乙基己酸叔丁基酯、过-3,5,5-三甲基己酸叔丁基酯、过新癸酸叔丁基酯、过新戊酸叔戊基酯、过-2-乙基己酸叔戊基酯、过新癸酸叔戊基酯、过新癸酸1,1,3,3-四甲基丁基酯、过新癸酸枯基酯、过苯甲酸叔丁基酯、过苯甲酸叔戊基酯和过二邻苯二甲酸二叔丁基酯。
-叔-C8-C14亚烷基双过氧化物的二-O-C4-C12丙烯酸化的衍生物如2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷、2,5-二甲基-2,5-二(苯甲酰过氧)己烷和1,3-二(2-新癸酰基过氧异丙基)苯;
-二(C2-C12烷酰)和二苯甲酰过氧化物如过氧化二乙酰、过氧化二丙酰、过氧化二琥珀酰、过氧化二辛酰、过氧化二(3,5,5-三甲基己酰)、过氧化二癸酰、过氧化二月桂酰、过氧化二苯甲酰、过氧化二(4-甲基苯甲酰)、过氧化二(4-氯苯甲酰)和过氧化二(2,4-二氯苯甲酰);
-过(C4-C12烷基)碳酸叔-C4-C5烷基酯如过(2-乙基己基)碳酸叔戊基酯;
-过二碳酸二(C2-C12烷基)酯如过二碳酸二(正丁基)酯和过二碳酸二(2-乙基己基)酯。
取决于平均聚合温度,特别合适引发剂(C)的实例为:
-在50-60℃的平均聚合温度下:
过新庚酸叔丁基酯、过新癸酸叔丁基酯、过新戊酸叔戊基酯、过新癸酸叔戊基酯、过新癸酸1,1,3,3-四甲基丁基酯、过新癸酸枯基酯、1,3-二(2-新癸酰基过氧异丙基)苯、过二碳酸二(正丁基)酯和过二碳酸二(2-乙基己基)酯。
-在60-70℃的平均聚合温度下:
过新戊酸叔丁基酯、过新庚酸叔丁基酯、过新癸酸叔丁基酯、过新戊酸叔戊基酯和过氧化二(2,4-二氯苯甲酰);
-在70-80℃的平均聚合温度下:
过新戊酸叔丁基酯、过新庚酸叔丁基酯、过新戊酸叔戊基酯、过氧化二丙酰、过氧化二辛酰、过氧化二癸酰、过氧化二月桂酰、过氧化二(2,4-二二氯苯甲酰)和2,5-二甲基-2,5-二(2-乙基己酰基过氧)己烷;
-在80-90℃的平均聚合温度下:
过异丁酸叔丁基酯、过-2-乙基己酸叔丁基酯、过-2-乙基己酸叔戊基酯、过氧化二丙酰、过氧化二辛酰、过氧化二癸酰、过氧化二月桂酰、过氧化二(3,5,5-三甲基己酰)、过氧化二苯甲酰和过氧化二(4-甲基苯甲酰);
-在90-100℃的平均聚合温度下:
过异丁酸叔丁基酯、过-2-乙基己酸叔丁基酯、过单马来酸叔丁基酯、过-2-乙基己酸叔戊基酯、过氧化二苯甲酰和过氧化二(4-甲基苯甲酰);
-在100-110℃的平均聚合温度下:
过单马来酸叔丁基酯、过异丁酸叔丁基酯和过(2-乙基己基)碳酸叔戊基酯;
-在110-120℃的平均聚合温度下:
过单马来酸叔丁基酯、过-3,5,5-三甲基己酸叔丁基酯和过(2-乙基己基)碳酸叔戊基酯。
优选引发剂(C)为叔-C4-C5烷基氢过氧化物的O-C4-C12丙烯酸化衍生物,特别优选过新戊酸叔丁基酯和过-2-乙基己酸叔丁基酯。
特别有利的聚合条件可通过准确调节引发剂(C)和聚合温度容易地确定。例如,优选平均聚合温度在使用新戊酸叔丁基酯情况下为60-80℃,在使用过-2-乙基己酸叔丁基酯情况下为80-100℃。
本发明聚合反应可在少量有机溶剂(D)存在下进行。当然还可以使用不同溶剂(D)的混合物。优选使用水溶性或水混溶性溶剂。
当溶剂(D)用作稀释剂时,在每种情况下基于组分(A)、(B)和(C)的总量通常使用1-40重量%,优选1-35重量%,更优选1.5-30重量%,最优选2-25重量%。
合适溶剂(D)的实例包括:
-一元醇,优选脂族C1-C16醇,更优选脂族C2-C12醇,最优选C2-C4醇如乙醇、丙醇、异丙醇、丁醇、仲丁醇和叔丁醇;
-多元醇,优选C2-C10二醇,更优选C2-C6二醇,最优选C2-C4亚烷基二醇如乙二醇和丙二醇;
-亚烷基二醇醚,优选亚烷基二醇单(C1-C12烷基)醚和亚烷基二醇二(C1-C6烷基)醚,更优选亚烷基二醇单-和二(C1-C2烷基)醚,最优选亚烷基二醇单(C1-C2烷基)醚如乙二醇单甲基和-乙基醚和丙二醇单甲基和-乙基醚;
-聚亚烷基二醇,优选具有2-20个C2-C4亚烷基二醇单元的聚(C2-C4亚烷基)二醇,更优选具有2-20个乙二醇单元的聚乙二醇和具有2-10个丙二醇单元的聚丙二醇,最优选具有2-15个乙二醇单元的聚乙二醇和具有2-4个丙二醇单元的聚丙二醇如二甘醇、三甘醇,双丙甘醇和三丙二醇;
-聚亚烷基二醇单醚,优选具有2-20个亚烷基二醇单元的聚(C2-C4亚烷基)二醇单(C1-C25烷基)醚,更优选具有2-20个亚烷基二醇单元的聚(C2-C4亚烷基)二醇单(C1-C20)烷基醚,最优选具有3-20个亚烷基二醇单元的聚(C2-C3亚烷基)二醇单(C1-C16烷基)醚;
-羧酸酯,优选C1-C6羧酸的C1-C8烷基酯,更优选C1-C3羧酸的C1-C4烷基酯,最优选C2-C3羧酸的C2-C4烷基酯如乙酸乙酯和丙酸乙酯;
-优选具有3-10个碳原子的脂族酮如丙酮、甲基乙基酮、二乙基酮和环己酮;
-环状醚,特别是四氢呋喃和二噁烷。
所述溶剂(D)有利地为那些还用于由于应用(例如在洗涤和清洁组合物中)而配制本发明所用接枝聚合物并由此可保留在聚合产物中的溶剂。
这些溶剂的优选实例是具有2-15个乙二醇单元的聚乙二醇、具有2-6个丙二醇单元的聚丙二醇,特别是C6-C8醇的烷氧基化产物(亚烷基二醇单烷基醚和聚亚烷基二醇单烷基醚)。
这里特别优选高支化度的C8-C16醇的烷氧基化产物,其允许配制在40-70℃下自由流动的并且在较低粘度下具有极低聚合物含量的聚合物混合物。支链可以在该醇的烷基链和/或聚烷氧基化结构部分(至少一个氧化丙烯、氧化丁烯或氧化异丁烯单元的共聚)中存在。这些烷氧基化产物特别合适的实例为用1-15摩尔氧化乙烯烷氧基化的2-乙基己醇或2-丙基庚醇,用1-15摩尔氧化乙烯和1-3摩尔氧化丙烯烷氧基化的C13/C15羰基合成醇或C12/C14或C16/C18脂肪族醇,优选用1-15摩尔氧化乙烯和1-3摩尔氧化丙烯烷氧基化的2-丙基庚醇。
在本发明方法中,将聚氧化烯(A)、接枝单体(B1)以及合适的话(B2)、引发剂(C)以及合适的话溶剂(D)在反应器中加热到所选平均聚合温度。
根据本发明,聚合以在反应器中恒定存在过量聚合物(聚氧化烯(A)和形成的接枝聚合物)的方式进行。聚合物与未接枝单体和引发剂的定量比通常≥10:1,优选≥15:1,更优选≥20:1。
本发明聚合方法原则上可在各种反应器类型中进行。
所用反应器优选为搅拌釜,将聚氧化烯(A)合适的话与特定全部量的接枝单体(B)、引发剂(C)和溶剂(D)中通常至多15重量%部分一起首先全部或部分供入釜中并加热到聚合温度,然后将余量的(B)、(C)以及合适的话(D)优选分开计量加入。优选将余量的(B)、(C)以及合适的话(D)在≥2小时,更优选≥4小时,最优选≥5小时内计量加入。
在特别优选的基本上不含溶剂的方法变型的情况下,将全部量的聚氧化烯(A)首先以熔体供入并将优选在一种溶剂(D)中以10-50重量%溶液形式存在的接枝单体(B1)以及合适的话(B2)以及引发剂(C)计量加入,控制温度以使在聚合过程中所选的平均聚合温度尤其维持在尤其是+/-10℃,特别是+/-5℃的范围内。
在另一特别优选的低溶剂方法变型中,程序如上所述,不同之处在于将溶剂(D)在聚合过程中计量加入以限制反应混合物的粘度。还可以仅在预先聚合后的时间开始计量加入溶剂,或可分批添加溶剂。
聚合可在标准压力下或在减压或升高压力下进行。当单体(B)或所用任何稀释剂(D)的沸点在该选定压力下超过时,聚合在回流冷却下进行。
本发明接枝聚合物因其显著的两亲性特性而具有极好的界面性能。它们可有利地用于洗涤和清洁组合物,其中它们通过表面活性剂帮助除去织物或硬质表面上的疏水性污物并由此改进配制剂的洗涤和清洁性能。此外,它们使除去的污物更好地分散在洗涤或清洁液体中并防止污物在洗涤或清洁过的材料表面上再沉积。
衣用洗涤剂和清洁组合物
本发明新的衣用洗涤剂和清洁组合物基于特定全部组合物通常包含0.05-10重量%,优选0.1-5重量%,更优选0.25-2.5重量%的本发明两亲性接枝聚合物。
此外,衣用洗涤剂和清洁组合物通常包含表面活性剂以及合适的话其他聚合物作为洗涤物质、助洗剂和其他常用成分,例如共助洗剂、配位剂、漂白剂、标度剂(standardizer)、发灰抑制剂、染料转移抑制剂、酶和香料。
本发明的两亲性接枝聚合物可用于包含表面活性剂体系的衣用洗涤剂或清洁组合物,该体系包含C10-C15烷基苯磺酸盐(LAS)和一种或多种选自非离子、阳离子、阴离子或其混合物的辅助表面活性剂。辅助表面活性剂的选择可取决于所需的益处。在一实施方案中,辅助表面活性剂选择为非离子表面活性剂,优选C12-C18烷基乙氧基化物。在另一实施方案中,辅助表面活性剂选择为阴离子表面活性剂,优选C10-C18烷基烷氧基硫酸盐(AExS)(其中x为1-30)。在又一实施方案中,辅助表面活性剂选定为阳离子表面活性剂,优选二甲基羟乙基月桂基氯化铵。如果该表面活性剂体系包含C10-C15烷基苯磺酸盐(LAS),则LAS以组合物的约9重量%至约25重量%或约13重量%至约25重量%或约15重量%至约23重量%的量使用。
该表面活性剂体系可以包含组合物的0重量%至约7重量%或约0.1重量%至约5重量%或约1重量%至约4重量%的选自非离子辅助表面活性剂、阳离子辅助表面活性剂、阴离子辅助表面活性剂及其任何混合物的辅助表面活性剂。
非离子辅助表面活性剂的非限制性实例包括:C12-C18烷基乙氧基化物如购于Shell的非离子表面活性剂;其中烷氧基化单元为亚乙氧基和亚丙氧基单元的混合物的C6-C12烷基酚烷氧基化物;具有氧化乙烯/氧化丙烯嵌段烷基多元胺乙氧基化物的C12-C18醇和C6-C12烷基酚缩合物如购于BASF的;如US 6,150,322中所述的C14-C22中链支化醇,BA;如US 6,153,577、US 6,020,303和US 6,093,856中所述的C14-C22中链支化烷基烷氧基化物,BAEx(其中x为1-30);如1986年1月26日公开的U.S.4,565,647Llenado中所述的烷基多糖;特别是如US 4,483,780和US 4,483,779中所述的烷基聚糖苷;如US 5,332,528中所述的多羟基脂肪酸酰胺;以及如US 6,482,994和WO 01/42408中所述的醚封端的聚(烷氧基化)醇表面活性剂。
半极性非离子辅助表面活性剂的非限制性实例包括:包含一个约10至约18个碳原子的烷基结构部分和2个选自由烷基结构部分和包含约1至约3个碳原子的羟烷基结构部分组成的组的结构部分的水溶性胺氧化物;包含一个约10至约18个碳原子的烷基结构部分和2个选自由烷基结构部分和包含约1至约3个碳原子的羟烷基结构部分组成的组的结构部分的水溶性膦氧化物;以及包含一个约10至约18个碳原子的烷基结构部分和1个选自由烷基结构部分和包含约1至约3个碳原子的羟烷基结构部分组成的组的结构部分的水溶性亚砜。参见WO 01/32816、US 4,681,704和US 4,133,779。
阳离子辅助表面活性剂的非限制性实例包括:可具有至多26个碳原子的季铵盐表面活性剂,其包括:如US 6,136,769中所述的烷氧基化季铵盐(AQA)表面活性剂;如6,004,922中所述的二甲基羟乙基季铵盐;二甲基羟乙基月桂基氯化铵;如WO 98/35002、WO 98/35003、WO 98/35004、WO98/35005和WO 98/35006中所述的多元胺阳离子表面活性剂;如美国专利号4,228,042、4,239,660、4,260,529和US 6,022,844中所述的阳离子酯表面活性剂;以及如US 6,221,825和WO 00/47708中所述的氨基表面活性剂,特别是酰胺基丙基二甲基胺(APA)。
这里使用的阴离子辅助表面活性剂的非限制性实例包括:C10-C20伯、支链和无规烷基硫酸盐(AS);C10-C18仲(2,3)烷基硫酸盐;C10-C18烷基烷氧基硫酸盐(AExS)(其中x为1-30);包含1-5个乙氧基单元的C10-C18烷基烷氧基碳酸盐;如US 6,020,303和US 6,060,443中所述的中链支化烷基硫酸盐;如US 6,008,181和US 6,020,303中所述的中链支化烷基烷氧基硫酸盐;如WO 99/05243、WO 99/05242和WO 99/05244中所述的改性烷基苯磺酸盐(MLAS);脂肪酸甲酯磺酸盐(MES);以及α-烯烃磺酸盐(AOS)。
本发明还涉及包含本发明两亲性接枝聚合物和含有C8-C18线性烷基磺酸盐表面活性剂和辅助表面活性剂的表面活性剂体系的组合物。组合物可以呈任何形式,即呈液体;固体如粉末、细粒、附聚物、糊、片、袋、条、凝胶;乳液;以双隔容器分配的类型;喷雾或泡沫洗涤剂;湿巾(即如US6,121,165,Mackey等所述的与非织造材料结合的清洁组合物);消费者用水活化的干巾(即如US 5,980,931,Fowler等所述的与非织造材料结合的清洁组合物)形式;以及其他均相或多相清洁消费产品形式。
在一实施方案中,本发明清洁组合物为液体或固体衣用洗涤剂组合物。在另一实施方案中,本发明清洁组合物为硬质表面清洁组合物,优选其中硬质表面清洁组合物浸渍非织造基材。这里使用的“浸渍”指将硬质表面清洁组合物与非织造基材接触使该硬质表面清洁组合物渗入至少部分非织造基材中,优选该硬质表面清洁组合物饱和非织造基材。该清洁组合物还可以用于汽车护理组合物来清洁各种表面如硬质木材、砖、陶瓷、塑料、皮革、金属、玻璃。该清洁组合物还可设计用于个人护理和宠物护理组合物如洗发水组合物、浴液、液体或固体皂和其中表面活性剂无硬度接触的其他清洁组合物以及用于需要容许硬度的表面活性剂体系的所有组合物如石油钻井组合物。
在又一实施方案中,该清洁组合物为洗碗用组合物如液体人工洗碗用组合物、固体自动洗碗用组合物、液体自动洗碗用组合物和薄片/单元形式的自动洗碗用组合物。
一般而言,在这里清洁组合物如衣用洗涤剂,衣用洗涤剂添加剂,硬质表面清洁剂,合成和皂基洗衣条,织物软化剂和织物处理液体、固体和各类处理产品将需要数种助剂,但是某些简单配制的产品如漂白添加剂可例如仅需要氧漂白剂和如这里所述的表面活性剂。合适的洗衣或清洁助剂材料的综合清单可在WO 99/05242中找到。
常规清洁助剂包括助洗剂、酶、非上文讨论的聚合物、漂白剂、漂白活化剂、催化剂材料等,单除了上文定义的任何材料。其他清洁助剂在这里可以包括增泡剂、抑泡剂(消泡剂)等、反向活化成分或特定材料(除了上述的那些)如分散剂聚合物(例如购于BASF Corp.或Rohm & Haas)、除斑(color speckle)、银护、防锈和/或防腐蚀剂,染料填料,杀菌剂,碱性源,水溶助长剂,抗氧化剂,酶稳定剂,香料前体,香料,增溶剂,载体,加工助剂,颜料和用于液体配制剂的溶剂、螯合剂、染料转移抑制剂、分散剂、增白剂、抑泡剂、染料、结构增弹剂、织物软化剂、耐磨剂、水溶助长剂、加工助剂和其他织物护理剂、表面和皮肤护理剂。这些其他清洁助剂的合适实例和用量在美国专利号5,576,282、6,306,812 B1和6,326,348 B1中找到。
使用方法
本发明包括一种纯洁目标表面的方法。这里使用的“目标表面”可以包括这些表面如织物、碗碟、玻璃和其他厨用表面、硬质表面、头发或皮肤。这里使用的“硬质表面”包括在一般家里找到的硬质表面如硬质木材、砖、陶瓷、塑料、皮革、金属、玻璃。该方法包括使包含改性多元醇化合物的呈洁净形式或在洗涤液中稀释的组合物与至少一部分目标表面接触,然后任选漂洗该目标表面的步骤。优选使该目标表面在上述任选漂洗步骤之前进行洗涤步骤。对于本发明,洗涤包括但不限于擦洗、擦拭和机械搅拌。
如本领域熟练技术人员所理解,本发明清洁组合物可理想地适合用于家庭护理(硬质表面清洁组合物)和/或洗衣应用。
选择该组合物溶液pH为约5至约11的跨度范围以最符合待清洁目标表面。对于个人护理如皮肤和头发清洁,该组合物pH优选具有约5至约8的pH,对于衣用清洁组合物,pH为约8至约10。所述组合物优选以约200ppm至约10,000ppm的浓度以溶液应用。水温优选为约5℃至约100℃。
对于用于衣用清洁组合物,所述组合物优选以约200ppm至约10000ppm的浓度以溶液(洗涤液)应用。水温优选为约5℃至约60℃。水与织物的比例优选为约1:1至约20:1。
该方法可以包括使浸渍的非织造基材与本发明实施方案的组合物接触的步骤。这里使用的“非织造基材”可包括任何常用流行的具有合适的定量、厚度(厚)、吸收率和强度特性的非织造片或网。合适市售非织造基材的实例包括DuPont市售的商品名为和James River Corp市售的商品名为的那些。
如本领域熟练技术人员所理解,本发明清洁组合物可理想地适合用于液体洗碗用组合物。使用本发明液体洗碗用组合物的方法包括使脏碗碟与有效量(一般为约0.5ml至约20ml(每处理25个碗碟))的用水稀释的本发明液体洗碗用组合物接触的步骤。
实施例
制备本发明接枝聚合物
下文记录的K值以在23℃下3重量%的NaCl水溶液和1重量%的聚合物浓度测得。
平均摩尔质量和多分散性通过凝胶渗透色谱法使用0.5重量%在二甲基乙酰胺中的LiBr溶液作为洗脱剂及聚甲基丙烯酸甲基(PMMA)作为标准测定。
支化度通过13C NMR波谱在氘代二甲基亚砜中由接枝点和聚乙二醇的-CH2-基团的信号的积分测定。记录值涉及产物中存在的所有聚乙二醇,即包括未接枝聚乙二醇并对应于平均每个聚乙二醇上存在的侧链数。
接枝聚合物1
在氮气气氛下在装有搅拌器和回流冷凝器的聚合容器中首先加入480g聚乙二醇(Mn12 000)并在70℃下熔化。
在加入16.0g乙酸乙烯酯和在0.9g双丙甘醇中溶解的0.2g过新戊酸叔丁基酯并继续搅拌5分钟之后,将304g乙酸乙烯酯在6小时内(进料1)和18g双丙甘醇中溶解的4.0g过新戊酸叔丁基酯在7小时内(进料2)在搅拌下在70℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料2供完并将该混合物在70℃下继续搅拌1小时后,将9.0g双丙甘醇中溶解的4.8g过新戊酸叔丁基酯在70℃下分三次加入,每种情况下继续搅拌2小时。此外,加入73g双丙甘醇来降低粘度。
残余量的乙酸乙烯酯通过在70℃下真空蒸馏除去。然后通过添加水达到24.3重量%的固体含量。
所得接枝聚合物具有28.4的K值、1.8的多分散性(Mw36 900,Mn21000)和0.8%的支化度(对应于0.15个接枝点/50个EO单元)。
接枝聚合物2
在氮气气氛下在装有搅拌器和回流冷凝器的聚合容器中首先加入400g聚乙二醇(Mn9000)并在85℃下熔化。
在加入20.0g乙酸乙烯酯和在0.9g双丙甘醇中溶解的0.25g过-2-乙基己酸叔丁基酯并继续搅拌5分钟之后,将380g乙酸乙烯酯在6小时内(进料1)和18g双丙甘醇中溶解的5.0g过-2-乙基己酸叔丁基酯在7小时内(进料2)在搅拌下在85℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料2供完并将该混合物在85℃下继续搅拌1小时后,将9.0g双丙甘醇中溶解的6.0g过-2-乙基己酸叔丁基酯在85℃下分三次加入,每种情况下继续搅拌2小时。此外,加入73g双丙甘醇来降低粘度。
残余量的乙酸乙烯酯通过在85℃下真空蒸馏除去。然后通过添加水达到23.2重量%的固体含量。
所得接枝聚合物具有24.0的K值、1.9的多分散性(Mw37 000,Mn19500)和0.8%的支化度(对应于0.20个接枝点/50个EO单元)。
接枝聚合物3
在氮气气氛下在装有搅拌器和回流冷凝器的聚合压力容器中首先加入1000g聚乙二醇(Mn6000)并在90℃下熔化。
然后,将1500g乙酸乙烯酯在6小时内(进料1)和60.5g三丙二醇中溶解的14.5g过-2-乙基己酸叔丁基酯在7小时内(进料2)在搅拌下在90℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料2供完并将该混合物在90℃下继续搅拌1小时后,将22.6g三丙二醇中溶解的17.1g过-2-乙基己酸叔丁基酯在90℃下分三次加入,每种情况下继续搅拌2小时。此外,加入73g双丙甘醇来降低粘度。
残余量的乙酸乙烯酯通过在90℃下真空蒸馏除去。然后通过添加水达到22.8重量%的固体含量。
所得接枝聚合物具有19.6的K值、1.9的多分散性(Mw35 700,Mn18800)和0.9%的支化度(对应于0.33个接枝点/50个EO单元)。
接枝聚合物4
在氮气气氛下在装有搅拌器和回流冷凝器的聚合容器中首先加入480g聚乙二醇(Mn12 000)并在70℃下熔化。
在加入14.0g乙酸乙烯酯、1.6g丙烯酸丁酯和在0.9g双丙甘醇中溶解的0.3g过新戊酸叔丁基酯并继续搅拌5分钟之后,将274g乙酸乙烯酯在6小时内(进料1)、30.4g丙烯酸丁酯在6小时内(进料2)和18g双丙甘醇中溶解的6.0g过新戊酸叔丁基酯在7小时内(进料3)在搅拌下在70℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料3供完并将该混合物在70℃下继续搅拌1小时后,将9.0g双丙甘醇中溶解的7.2g过新戊酸叔丁基酯在70℃下分三次加入,每种情况下继续搅拌2小时。此外,加入73g双丙甘醇来降低粘度。
残余量的单体通过在70℃下真空蒸馏除去。然后通过添加水达到19.8重量%的固体含量。
所得接枝聚合物具有29.1的K值、1.9的多分散性(Mw35 500,Mn18400)和0.7%的支化度(对应于0.13个接枝点/50个EO单元)。
接枝聚合物5
在氮气气氛下在装有搅拌器和回流冷凝器的聚合压力容器中首先加入1175g聚乙二醇(Mn4000)并在90℃下熔化。
在加入88.0g乙酸乙烯酯和在3.5g三丙二醇中溶解的0.85g过-2-乙基己酸叔丁基酯并继续搅拌5分钟之后,将1674g乙酸乙烯酯在6小时内(进料1)和71g三丙二醇中溶解的17.0g过-2-乙基己酸叔丁基酯在7小时内(进料2)在搅拌下在90℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料2供完并将混合物在90℃下继续搅拌1小时后,将21.0g三丙二醇中溶解的39.0g过-2-乙基己酸叔丁基酯在70℃下分三次加入,每种情况下继续搅拌2小时。此外,加入73g双丙甘醇来降低粘度。
残余量的乙酸乙烯酯通过在90℃下真空蒸馏除去。然后通过添加水达到23.4重量%的固体含量。
所得接枝聚合物具有17.9的K值、2.3的多分散性(Mw26 800,Mn11700)和0.6%的支化度(对应于0.33个接枝点/50个EO单元)。
接枝聚合物6
在氮气气氛下在装有搅拌器和回流冷凝器的聚合压力容器中首先加入444g聚乙二醇(Mn6000)并在90℃下熔化。
在加入1.7g三丙二醇中溶解的0.55g过-2-乙基己酸叔丁基酯并继续搅拌15分钟之后,将666g乙酸乙烯酯在6小时内(进料1)和21.6g三丙二醇中溶解的7.22g过-2-乙基己酸叔丁基酯在6.5小时内(进料2)以及在进料1开始后3小时开始将233g烷氧基化2-丙基庚醇(1摩尔PO和10摩尔EO/摩尔)在3.5小时内(进料3)在搅拌下在90℃的内部温度下以恒定流动速率连续平行地计量加入。
在进料2和3供完,随后在90℃下继续搅拌1小时后,将18.25g三丙二醇中溶解的6.1g过-2-乙基己酸叔丁基酯在90℃下分三次加入,每种情况下继续搅拌2小时。
残余量的乙酸乙烯酯通过在90℃下真空蒸馏除去。然后通过添加水达到86.9重量%的固体含量。
所得接枝聚合物具有17.6的K值、1.8的多分散性(Mw35 700,Mn20000)和0.9%的支化度(对应于0.33个接枝点/50个EO单元)。
组合物配制剂
实施例 7-粒状衣用洗涤剂
A | B | C | D | E | |
重量% | 重量% | 重量% | 重量% | 重量% | |
C11-12线性烷基苯磺酸盐 | 13-25 | 13-25 | 13-25 | 13-25 | 9-25 |
C12-18乙氧基化硫酸盐 | --- | --- | 0-3 | --- | 0-1 |
C14-15烷基乙氧基化物(EO=7) | 0-3 | 0-3 | --- | 0-5 | 0-3 |
二甲基羟乙基月桂基氯化铵 | --- | --- | 0-2 | 0-2 | 0-2 |
三聚磷酸钠 | 20-40 | --- | 18-33 | 12-22 | 0-15 |
沸石 | 0-10 | 20-40 | 0-3 | -- | -- |
硅酸盐助洗剂 | 0-10 | 0-10 | 0-10 | 0-10 | 0-10 |
碳酸盐 | 0-30 | 0-30 | 0-30 | 5-25 | 0-20 |
二亚乙基三胺五乙酸盐 | 0-1 | 0-1 | 0-1 | 0-1 | 0-1 |
聚丙烯酸盐 | 0-3 | 0-3 | 0-3 | 0-3 | 0-3 |
羧甲基纤维素 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 | 0.2-0.8 |
聚合物1 | 0.05-10 | 0.05-10 | 5.0 | 2.5 | 1.0 |
过碳酸盐 | 0-10 | 0-10 | 0-10 | 0-10 | 0-10 |
壬酰氧基苯磺酸盐 | --- | --- | 0-2 | 0-2 | 0-2 |
四乙酰基乙二胺 | --- | --- | 0-0.6 | 0-0.6 | 0-0.6 |
锌酞菁四磺酸盐 | --- | --- | 0-0.005 | 0-0.005 | 0-0.005 |
增白剂 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 | 0.05-0.2 |
MgSO4 | --- | --- | 0-0.5 | 0-0.5 | 0-0.5 |
酶 | 0-0.5 | 0-0.5 | 0-0.5 | 0-0.5 | 0-0.5 |
少量(香料、染料、泡沫稳定剂) | 平衡 | 平衡 | 平衡 | 平衡 | 平衡 |
1根据实施例1、2、3、4、5或6中任一个的两亲性接枝聚合物或这些聚合物的任何混合物
实施例 8-粒状衣用洗涤剂
水浆组合物
组分 | 重量%水浆 |
具有下列通用结构的化合物:二((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-二((C2H5O)(C2H4O)n),其中n=20-30,x=3-8,或其硫酸化 | 1.23 |
或磺酸化变体 | |
乙二胺二琥珀酸 | 0.35 |
增白剂 | 0.12 |
硫酸镁 | 0.72 |
丙烯酸盐/马来酸盐共聚物 | 6.45 |
聚合物1 | 1.60 |
线性烷基苯磺酸盐 | 11.92 |
羟基乙烷二(亚甲基膦酸) | 0.32 |
碳酸钠 | 4.32 |
硫酸钠 | 47.49 |
皂 | 0.78 |
水 | 24.29 |
其他 | 0.42 |
总份数 | 100.00 |
1根据实施例1、2、3、4、5或6中任一个的两亲性接枝聚合物或这些聚合物的任何混合物
制备喷雾干燥粉末
制备含湿量为25.89%的含有上述组成的水浆。将该水浆加热到72℃并在高压(5.5×106Nm-2至6.0×106Nm-2)下泵入空气入口温度为270-300℃的逆流喷雾干燥塔中。将该水浆雾化并将雾化浆干燥产生固体混合物,然后使其冷却并过筛除去过大尺寸材料(>1.8mm)而形成自由流动的喷雾干燥粉末。细物质(<0.15mm)在喷雾干燥塔中用排放空气来排气淘洗并在立式塔容器体系中收集。该喷雾干燥粉末具有1.0重量%的含湿量、427g/l的堆密度和95.2重量%的喷雾干燥粉末具有150-710微米粒度的粒度分布。下文给出该喷雾干燥粉末组成。
喷雾干燥粉末组成
组分 | 重量%喷雾干燥粉末 |
具有下列通用结构的化合物:二((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)-二((C2H5O)(C2H4O)n),其中n=20-30,和x=3-8,或其硫酸化或磺酸化变体 | 1.65 |
乙二胺二琥珀酸 | 0.47 |
增白剂 | 0.16 |
硫酸镁 | 0.96 |
丙烯酸盐/马来酸盐共聚物 | 8.62 |
线性烷基苯磺酸盐 | 15.92 |
羟基乙烷二(亚甲基膦酸) | 0.43 |
碳酸钠 | 5.77 |
硫酸钠 | 63.43 |
皂 | 1.04 |
水 | 1.00 |
其他 | 0.55 |
总份数 | 100.00 |
制备阴离子表面活性剂颗粒1
阴离子洗涤表面活性剂颗粒1使用Tilt-A-Pin混合器,然后使用Tilt-A-Plow混合器(两者都由Processall制造)以520g的批料定量制得。将供给的108g硫酸钠与244g碳酸钠一起加入Tilt-A-Pin混合器中。将168g70重量%的活性C25E3S糊(基于C12/15醇和氧化乙烯的乙氧基硫酸钠)加入Tilt-A-Pin混合器中。然后将所述组分在1200rpm下混合10秒。然后将所得粉末转移到Tilt-A-Plow混合器中并在200rpm下混合2分钟而形成颗粒。然后将所述颗粒在流化床干燥器中在2500l/min的速率下在120℃下干燥直到颗粒的平衡相对湿度小于15%。然后,将干燥的颗粒过筛并且保留1180-250μm的级分。该阴离子洗涤表面活性剂颗粒1的组成如下:
25.0重量%C25E3S乙氧基硫酸钠
18.0重量%硫酸钠
57.0重量%碳酸钠
制备阳离子洗涤表面活性剂颗粒1
阳离子表面活性剂颗粒1在Morton FM-50 Loedige混合器上以14.6g批料定量制得。将4.5kg微粉化硫酸钠和4.5kg微粉化碳酸钠在MortonFM-50 Loedige混合器中预混合。将4.6kg 40%活性单-C12-14烷基单-羟乙基二甲基季铵盐氯化物(阳离子表面活性剂)水溶液加入Morton FM-50Loedige混合器中,同时操作主驱动和切碎。在混合约2分钟后,将1.0kg重量比为1:1的微粉化硫酸钠和微粉化碳酸钠混合物加入该混合器中。收集所得附聚物并使用流化床干燥器基于2500l/min的空气在100-140℃下干燥30分钟。将所得粉末过筛并收集通过1400μm的级分作为阳离子表面活性剂颗粒1。该阳离子表面活性剂颗粒1的组成如下:
15重量%单-C12-14烷基单-羟乙基二甲基季铵盐氯化物
40.76重量%碳酸钠
40.76重量%硫酸钠
3.48重量%水分和其他
制备粒状衣用洗涤剂组合物
将10.84kg实施例1的喷雾干燥粉末、4.76kg阴离子洗涤表面活性剂颗粒1、1.57kg阳离子洗涤表面活性剂颗粒1和7.83kg(总量)其他各个剂量的干物质计量加入在24rpm下运行的1m直径的混凝土分批混合器中。一旦所有物质计量加入该混合器中,就将该混合物混合5分钟而形成粒状衣用洗涤剂组合物。该粒状衣用洗涤剂组合物的配方如下所述:
粒状衣用洗涤剂组合物
实施例 9-液体衣用洗涤剂
成分 | A | B | C | D | E | F5 |
重量% | 重量% | 重量% | 重量% | 重量% | 重量% | |
烷基醚硫酸钠 | 14.4% | 14.4% | 9.2% | 5.4% | ||
线性烷基苯磺酸 | 4.4% | 4.4% | 12.2% | 5.7% | 1.3% | |
烷基乙氧基化物 | 2.2% | 2.2% | 8.8% | 8.1% | 3.4% | |
胺氧化物 | 0.7% | 0.7% | 1.5% | |||
柠檬酸 | 2.0% | 2.0% | 3.4% | 1.9% | 1.0% | 1.6% |
脂肪酸 | 3.0% | 3.0% | 8.3% | 16.0% | ||
蛋白酶 | 1.0% | 1.0% | 0.7% | 1.0% | 2.5% | |
淀粉酶 | 0.2% | 0.2% | 0.2% | 0.3% | ||
脂肪酶 | 0.2% | |||||
硼砂 | 1.5% | 1.5% | 2.4% | 2.9% | ||
甲酸钙和甲酸钠 | 0.2% | 0.2% | ||||
甲酸 | 1.1% | |||||
聚合物1 | 1.8% | 1.8% | 2.1% | 3.2% | ||
聚丙烯酸钠 | 0.2% | |||||
聚丙烯酸钠共聚物 | 0.6% | |||||
DTPA2 | 0.1% | 0.1% | 0.9% | |||
DTPMP3 | 0.3% | |||||
EDTA4 | 0.1% | |||||
荧光增白剂 | 0.15% | 0.15% | 0.2% | 0.12% | 0.12% | 0.2% |
乙醇 | 2.5% | 2.5% | 1.4% | 1.5% | ||
丙二醇 | 6.6% | 6.6% | 4.9% | 4.0% | 15.7% | |
山梨糖醇 | 4.0% | |||||
乙醇胺 | 1.5% | 1.5% | 0.8% | 0.1% | 11.0% | |
氢氧化钠 | 3.0% | 3.0% | 4.9% | 1.9% | 1.0% | |
异丙苯磺酸钠 | 2.0% | |||||
聚硅氧烷抑泡剂 | 0.01% | |||||
香料 | 0.3% | 0.3% | 0.7% | 0.3% | 0.4% | 0.6% |
遮光剂5 | 0.30% | 0.20% | 0.50% | |||
水 | 平衡 | 平衡 | 平衡 | 平衡 | 平衡 | 平衡 |
100.0% | 100.0% | 100.0% | 100.0% | 100.0% | 100.0% |
1根据实施例1、2、3、4、5或6中任一个的两亲性接枝聚合物或这些聚合物的任何混合物
2二亚乙基三胺五乙酸,钠盐
3二亚乙基三胺五亚甲基膦酸,钠盐
4乙二胺四乙酸,钠盐
5Acusol OP 301
实施例 10-液体人工洗碗用洗涤剂
1根据实施例1、2、3、4、5或6中任一个的两亲性接枝聚合物或这些聚合物的任何混合物。
2非离子可以为包含9个乙氧基基团的C11烷基乙氧基化表面活性剂。
31,3BAC为1,3二(甲基胺)-环己烷。
4甲基丙烯酸(N,N-二甲基氨基)乙酯均聚物
实施例 11-自动洗碗机用洗涤剂
A | B | C | D | E | |
聚合物分散剂2碳酸盐三聚磷酸钠硅酸盐固体漂白剂和漂白活化剂聚合物1酶二水柠檬酸二钠非离子表面活性剂3水、硫酸盐、香料、染料和其他添加剂 | 0.5350640.05-100.3-0.600平衡到100% | 54066410.3-0.600平衡到100% | 64010642.50.3-0.600平衡到100% | 535-400-106450.3-0.62-200平衡到100% | 535-400-1064100.3-0.600.8-5平衡到100% |
1根据实施例1、2、3、4、5或6中任一个的两亲性接枝聚合物或这些聚合物的任何混合物。
3如购于Olin Corporation的SLF-18 POLY TERGENT。
除非注明,所有组分或组成含量参照该组分或组成的活性含量,并且不包括杂质如可在市售来源中存在的残留溶剂或副产物。
所有百分数和比例除非另有说明都以重量计算。所有百分数和比例除非另有说明都基于全部组成计算。
Claims (10)
1.一种基于作为接枝基质的水溶性聚氧化烯(A)和通过聚合乙烯基酯组分(B)形成的侧链的两亲性接枝聚合物,所述聚合物具有平均≤1个接枝点/50个氧化烯单元、具有的平均摩尔质量Mw为3000-100000、具有的多分散性Mw/Mn≤3,并且具有:
(A)20-70重量%作为接枝基质的水溶性聚氧化烯,和
(B)通过在(A)存在下自由基聚合30-80重量%包含下列物质的乙烯基酯组分所形成的侧链:
(B1)70-100重量%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)0-30重量%的其他烯属不饱和单体。
2.根据权利要求1的接枝聚合物,其包含≤10重量%呈未接枝形式的聚乙烯基酯(B)。
3.根据权利要求1的接枝聚合物,其包含25-60重量%的接枝基质(A)和40-75重量%的乙烯基酯组分(B)。
4.根据权利要求1的接枝聚合物,其中所述乙烯基酯组分(B)包含70-100重量%的乙酸乙烯酯(B1)和0-30重量%的丙烯酸C1-C8烷基酯(B2)。
5.一种可通过在下列物质存在下:
(A)20-70重量%平均摩尔质量Mn为1500-20000的水溶性聚氧化烯,
(C)基于组分(B)为0.25-5重量%形成自由基的引发剂,以及
(D)基于组分(A)、(B)和(C)总量为0-40重量%的有机溶剂
在引发剂(C)分解半衰期为40-500分钟的平均聚合温度下自由基聚合下列物质获得的两亲性接枝聚合物:
(B)30-80重量%包含下列物质的乙烯基酯组分:
(B1)70-100重量%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)0-30重量%的其他烯属不饱和单体,
其中以使反应混合物中未转化的接枝单体(B)和引发剂(C)的分数相对于聚氧化烯(A)恒定维持定量不足的方式聚合,
其中接枝单体(B)在反应混合物中恒定地以不大于5重量%的低浓度存在,在全部反应混合物中未分解引发剂的比例基于在单体加成过程中计量加入引发剂的总量≤15重量%。
6.一种制备根据权利要求1-5中任一项的接枝聚合物的方法,其包括在水溶性聚氧化烯(A),形成自由基的引发剂(C)以及需要的话基于组分(A)、(B)和(C)总量为至多40重量%的有机溶剂(D)的存在下,在引发剂(C)分解半衰期为40-500分钟的平均聚合温度下,以使反应混合物中未转化的接枝单体(B)和引发剂(C)的分数相对于聚氧化烯(A)恒定维持定量不足的方式聚合包含乙酸乙烯酯和/或丙酸乙烯酯(B1)以及需要的话其他烯属不饱和单体(B2)的乙烯基酯组分(B),其中接枝单体(B)在反应混合物中恒定地以不大于5重量%的低浓度存在,在全部反应混合物中未分解引发剂的比例基于在单体加成过程中计量加入引发剂的总量≤15重量%。
7.根据权利要求6的方法,其中在下列物质存在下:
(A)20-70重量%平均摩尔质量Mn为1500-20000的水溶性聚氧化烯,
(C)基于组分(B)为0.25-5重量%形成自由基的引发剂,以及
(D)基于组分(A)、(B)和(C)总量为0-40重量%的有机溶剂聚合
(B)30-80重量%包含下列物质的乙烯基酯组分:
(B1)70-100重量%的乙酸乙烯酯和/或丙酸乙烯酯,和
(B2)0-30重量%的其他烯属不饱和单体。
8.根据权利要求6或7的方法,其中将乙酸乙烯酯和/或丙酸乙烯酯(B1)以及需要的话其他烯属不饱和单体(B2)和引发剂(C)计量加入聚氧化烯(A)熔体中。
9.根据权利要求6或7的方法,其中所述聚合在60-120℃下进行。
10.根据权利要求6或7的方法,其中所用引发剂(C)为脂族过C4-C12羧酸的叔-C4-C5烷基酯。
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