CN1203962A - 水垢抑制剂 - Google Patents
水垢抑制剂 Download PDFInfo
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- CN1203962A CN1203962A CN98109802A CN98109802A CN1203962A CN 1203962 A CN1203962 A CN 1203962A CN 98109802 A CN98109802 A CN 98109802A CN 98109802 A CN98109802 A CN 98109802A CN 1203962 A CN1203962 A CN 1203962A
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- 229910000394 calcium triphosphate Inorganic materials 0.000 description 13
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- 238000006386 neutralization reaction Methods 0.000 description 1
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Images
Classifications
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及在水系统中对(多)磷酸盐水垢的抑制,包括使用至少一种含有以聚合形式存在的下列单体的共聚物:(Ⅰ)50%—98%重量的一种或多种弱酸;(Ⅱ)2—50%重量的一种或多种强酸;(Ⅲ)0—30%重量的一种或多种单烯属不饱和C4－C8二羧酸;和(Ⅳ)0—30%重量的一种或多种可与(Ⅰ),(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体;其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100%重量的共聚物。本发明尤其适合于使用含少量磷酸盐(STPP)的洗涤制品时对磷酸盐水垢的抑制。
Description
本发明涉及水体系中多磷酸盐水垢的抑制。
已知在硬水地区高浓度的镁和钙盐能导致在所洗涤的器皿中形成不溶解的碳酸钙和碳酸镁沉淀(水垢)。作为白色沉淀，它是可见的，当玻璃器皿在自动洗碗机中洗涤时白色沉淀在这种器皿上尤其明显，并且在机器部件的特殊加热元件上也尤其明显。相似的沉淀问题也在洗衣中存在，这些将引起纤维变得摸起来僵硬粗糙并褪色。相对的高水硬度的自来水和不充分的水软化制品的使用加剧了问题。引起水垢的其它因素是温度(在较高温度发生更多的水垢)和pH(较高的pH也增加水垢)。从二十世纪六十年代中期，三磷酸钠(STPP)在大多数洗涤剂中大量使用作为助洗剂；它能在洗涤溶液中螯合正离子如镁离子和钙离子并阻止它们在需洗涤物品上形成盐(碳酸盐，硅酸盐，等)沉淀。
可是，现在已知磷酸盐的存在，例如以STPP的形式，在湖或河中可作为营养剂有利于藻类生长并且这种结果对水质有害。这些环境问题导致了在洗涤制品中去除STPP并用其它螯合化合物代替。不幸的是，在洗涤过程中不用磷酸盐发生的变化比由于洗涤制品螯合能力的简单下降所预料的更复杂。STPP的多种能力即油状颗粒乳化，固体土壤悬浮液的稳定，土壤混合物的胶溶化，酸性土壤的中和，等对得到优良洗涤结果都是关键。
为了尽可能保持STPP许多可取的性质，并同时限制其环境压力，应减少STPP使用量。但是，这本身将带来新的水垢问题。当大量STPP在洗碗和洗衣机的水浴中使用时，在水系统中形成的大量的物质是水可溶的1∶1金属离子：STPP复合物(例如CaP3O-3 10)。当STPP量减少时，形成水不溶的钙和镁的三磷酸盐(例如Ca5(P3O10)2)和焦磷酸盐(例如Ca2P2O7)并从水系统中沉淀。
现有技术已知，例如美国3806367，US3928196和US3898037中，阐述了在没有STPP的系统中控制水垢的问题。可是，没有任何有效的方法控制使用少量STPP形成的多磷酸水垢(即通过使用Ultra或Compact洗涤制品)，在水浴中其STPP浓度例如低于1500ppm。观察到的精确的水垢量将依据在水浴中二价离子的浓度。作为比较，商业可得的一般的高STPP水浴浓度为大于2000ppm的STPP。
这里所用的术语多磷酸水垢指全部磷酸盐，三磷酸盐和焦磷酸盐水垢。所用的术语共聚物指包括以聚合形式的两种或多种不同的单体单元的聚合物。因此术语共聚物具体包括术语三聚物。
因此本发明提出的问题是提供一种在水系统中控制多磷酸盐水垢的方法，并且也提供洗涤制品，其用于洗碗洗涤剂时有良好的抗薄膜性能，用于洗衣洗涤剂时有良好的抗结壳和抗沉淀性能。
据此，本发明提供了一种控制多磷酸水垢的方法，其包括用至少一种共聚物处理水系统，所述的共聚物含有以聚合形式存在的下列单体：(Ⅰ)50％-98％重量的一种或多种弱酸；(Ⅱ)2-50％重量的一种或多种强酸；(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的聚合物。
本发明进一步提供了一种在水系统中控制多磷酸水垢的方法，其包括用至少一种共聚物处理水系统，所述的共聚物含有以聚合形式存在的下列单体：(Ⅰ)50％-98％重量的一种或多种单烯属不饱和的C3至C6单羧酸；(Ⅱ)2-50％重量的一种或多种不饱和磺酸；(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的聚合物。
优选共聚物含有下列单体的聚合单元：
(Ⅰ)50-90％重量的一种或多种单烯属不饱和C3-C6单羧酸；
(Ⅱ)10-50％重量的不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种能与(Ⅰ)(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体，
单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总和等于100％重量的共聚物。
有利的是，本发明的共聚物包括下列单体的聚合单元：
(Ⅰ)60-90％重量的一种或多种单烯属不饱和C3-C6单羧酸；
(Ⅱ)10-40％重量的不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种能与(Ⅰ)(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体
单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总和等于100％重量的共聚物。
具有尤其优良的多磷酸水垢抑制性能的共聚物包括下列单体的聚合单元：(Ⅰ)77％重量的一种或多种单烯属不饱和C3-C6单羧酸，
(Ⅱ)23％重量的一种或多种不饱和磺酸。
单烯属不饱和C3-C6单羧酸优选(甲基)丙烯酸。
不饱和磺酸单体优选下列中的一种：2-丙烯酰胺基甲基-1-丙基磺酸，2-甲基丙烯酰胺基-2-甲基-1-丙基磺酸，3-甲基丙烯酰胺基-2-羟基-丙基磺酸，烯丙磺酸，甲基烯丙磺酸，烯丙氧苯磺酸，甲基烯丙氧苯磺酸，2-羟基-3-(2-丙烯氧基)丙基磺酸，2-甲基-2-丙烯基-1-磺酸，苯乙烯硫酸，乙烯磺酸，丙烯酸3-磺基丙酯，甲基丙烯酸3-磺基丙酯，磺基甲基丙烯酰胺，磺基甲基异丁烯酰胺，和其水可溶盐。
单烯属不饱和C4-C8二羧酸优选马来酸，能与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体优选一种或多种(甲基)丙烯酸C1-C4烷基酯；(甲基)丙烯酸C1-C4羟烷酯；丙烯酰胺；烷基取代的丙烯酰胺；N，N-二烷基取代的丙烯酰胺；丙烯酰胺的磺化的烷基酯；乙烯基膦酸；乙酸乙烯酯；烯丙醇；磺化的烯丙醇；苯乙烯和相似的单体；丙烯腈；N-乙烯基吡咯烷酮；N-乙烯基甲酰胺；N-乙烯基咪唑；和N-乙烯基吡啶。
根据本发明的共聚物平均分子量是3，000至50，000优选4，500至35，000。
本发明也提供一种洗涤剂，其包括至少一种共聚物，其含有下列单体的聚合单元：(Ⅰ)50％-98％重量的一种或多种单烯属不饱和的C3至C6单羧酸；(Ⅱ)2-50％重量的一种或多种不饱和磺酸；(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的聚合物。
图1表示以AMPS共聚用单体浓度／水硬度的函数关系表示的对三磷酸钙的抑制。
图2表示以AMPS共聚用单体浓度，分子量和水硬度的函数关系表示的对三磷酸钙的抑制。
图3表示以马来酸共聚用单体浓度，分子量和水硬度的函数关系表示的对三磷酸钙的抑制。
图4表示以疏水共聚用单体的函数关系表示的含AMPS的三聚体对三磷酸钙的抑制。
图5表示以分子量的函数关系表示的含AMPS的三聚体对三磷酸钙的抑制。
图6表示各种多羧酸类对成膜抑制的效果。
本发明将进一步通过下列实施例描述：一般筛选方法
根据本发明的聚合物用于评价在含有磷酸盐的自动洗碗机洗涤制品中对三磷酸钙沉淀的抑制，其在提高的温度(55℃)和一个固定的聚合物浓度(100ppm)下通过用增量的水硬度(2／1 Ca++／Mg++)滴定750ppmSTPP溶液。使用Brinkmann PC701探针颜色测定计(520nm)，测定混浊的开始，实验包括使用可见沉淀的观测方法。洗涤制品
表1-洗涤制品
*TAED是四乙酰基乙二胺
| 组分 | 洗涤制品1的浓度(％) | 洗涤制品2的浓度(％) |
| STPP | 20．0 | 35．0 |
| 苏打粉 | 30．0 | 22．0 |
| 焦硅酸钠(Britesil H20) | 12．0 | 12．0 |
| 柠檬酸钠二水合物 | 10．0 | |
| 过硼酸钠·4H2O | 7．5 | 7．5 |
| 漂白活化剂(TAED)* | 2．5 | 2．5 |
| 表面活性剂(SLF-18) | 3．5 | 3．5 |
| 蛋白酶 | 1．0 | 1．0 |
| 液化酶 | 0．5 | 0．5 |
| 硫酸钠 | 9．0 | 14．0 |
| 聚合物 | 4．0 | 2．0 |
洗涤制品1是含低STPP量的制品，而洗涤制品2含有高百分数的STPP。这里所用的首字母大写的意义是：Mw=重均分子量。除非另外说明所引用的所有分子量都是重均分子量。AA=丙烯酸Mal=马来酸AMPS=2-丙烯胺基-2-丙基磺酸TBAM=叔丁基丙烯酰胺TOAM=叔辛基丙烯酰胺DMAM=二甲基丙烯酰胺EA=丙烯酸乙酯HPA=丙烯酸羟丙酯STY=苯乙烯SMAS=甲基烯丙基磺酸钠MAA=丙烯酸甲酯。洗碗条件
在下列的任一条件(A)或(B)下，使用传统方法测定根据本发明的应用于洗碗的聚合物的抗成膜性能：(A)美国洗碗条件洗碗机：Whirlpool model DU 940水硬度：300ppm的碳酸钙(Ca／Mg=3．5∶1)没有食物污垢标准程序(50℃)没有漂清助剂清洗器皿：玻璃循环次数：5成膜标准：
0．0=无可见薄膜 2=中等
0．5=几乎观察不到 3=一般
1．0=轻微 4=严重(B)欧洲洗涤条件洗碗机：Miele Deluxe model G590 SC水硬度：600ppm的碳酸钙(Ca／Mg=3．5∶1)没有食物污垢标准程序(65℃)没有漂清助剂清洗器皿：玻璃循环次数：5成膜等级：
0．0=无可见薄膜 2=中等
0．5=几乎观察不到 3=一般
1．0=轻微 4=严重实施例1含AMPS的共聚物对三磷酸钙的抑制效果
根据上述的一般筛选方法评估含共聚物的溶液得到图1所示的结果。一般来说，当共聚物中AMPS量增加至50％时抗三磷酸钙沉淀性提高；当AMPS大于50％时，对三磷酸钙水垢的抑制开始减低。实施例2含AMPS的共聚物对薄膜的影响
在各种自动洗碗洗涤制品中包括根据实施例1的共聚物，其在条件A下测试。表2所示是得到的玻璃成膜等级；其与AMPS量增至50％则增加对多磷酸水垢的抑制的观察一致。
表2
实施例3含AMPS的共聚物分子量对三磷酸钙的抑制
| 聚合物 | 分子量 | 成膜等级洗涤制品1 | 成膜等级洗涤制品2 |
| 没有聚合物 | 3．5 | 3．0 | |
| 100AA(比较例) | 2，000 | 1．5 | 1．75 |
| 100AA(比较例) | 4，500 | 1．1 | 2．0 |
| 90AA／1 0Mal(比较例) | 3，200 | 1．3 | 1．75 |
| 80AA／20Mal(比较例) | 16，000 | 1．2 | 1．3 |
| 70AA／30Mal(比较例) | 30，000 | 1．0 | 2．0 |
| 50AA／50Mal(比较例) | 3，500 | 1．1 | 1．2 |
| 50AA／50Mal(比较例) | 25，000 | 1．1 | 2 |
| 30AA／70Mal(比较例) | 5，500 | 1．4 | 1．2 |
| 95AA／5EA(比较例) | 2，500 | 1．75 | 2．5 |
| 80AA／20EA(比较例) | 4，300 | 1．25 | 1．1 |
| 70AA／30MAA(比较例) | 3，500 | 1．1 | 1．0 |
| 77AA／23AMPS | 4，500 | 0．5 | 0．6 |
| 60AA／40AMPS | 10，000 | 0．5 | 0．3 |
| 77AA／23SMAS | 6，600 | 0．8 | 0．9 |
| 60AA／40SMAS | 3，870 | 0．3 |
根据上述的一般筛选方法评估含共聚物的溶液得到图2所示的结果。此实施例主要研究两种不同的AA／AMPS摩尔比的共聚物分子量的影响。在两种情况下，增加共聚物的分子量明显地增加共聚物抗三磷酸盐沉淀性能。沉淀的水垢颗粒大小与较高的分子量类似物相比肉眼观察是较小的(高透射比)。实施例4含AMPS的三聚物对三磷酸钙的抑制
将含AA／AMPS／X三聚物的溶液(其中X是不是AA或AMPS的另外一种单体)使用上述的一般的筛选方法测试。结果如图3所示并由此观察到AA／AMPS／X三聚物，在大约稳定的分子量下，对多磷酸盐水垢的抑制随着AMPS量增加而增加。实施例5AA／AMPS／疏水物三聚物对三磷酸钙的抑制
将AA／AMPS／疏水物三聚物使用上述的一般的筛选方法测试，结果如图4。可以观察到AA／AMPS／疏水物三聚物与对照和比较样品相比表现出良好的对多磷酸盐水垢的抑制。实施例6AA／AMPS／疏水三聚物对成膜的影响
在洗涤条件A下使用洗涤剂DF1和DF2测试AA／AMPS／疏水物三聚物。结果如下的表3所示；可以发现AA／AMPS／疏水物三聚物与对照和比较样品相比表现出良好的对多磷酸盐成膜的抑制。
表3
实施例7AA／AMPS／疏水物三聚物的分子量对三磷酸钙的抑制
| 聚合物 | 分子量 | 成膜等级洗涤制品1 | 成膜等级洗涤制品2 |
| 没有聚合物 | 3．5 | 3．0 | |
| 100AA(比较例) | 4，500 | 1．1 | 2．0 |
| 90AA／10Mal(比较例) | 3，200 | 1．3 | 1．75 |
| 70AA／30Mal(比较例) | 30，000 | 1．0 | 2．0 |
| 50AA／50Mal(比较例) | 25，000 | 1．1 | 2 |
| 30AA／70Mal(比较例) | 5，500 | 1．4 | 1．2 |
| 95AA／5EA(比较例) | 2，500 | 1．75 | 2．5 |
| 70AA／30MAA(比较例) | 3，500 | 1．1 | 1．0 |
| 62AA／23AMPS／15TBAM | 24，800 | 0．4 | 0．5 |
| 64．5AA／27SMAS／8．5TBAM | 5，130 | 0．8 | |
| 64．5AA／27SMAS／8．5TBAM | 4，120 | 1．1 |
将含AA／AMPS／疏水物三聚物的溶液使用上述的一般的筛选方法测试；结果如图5所示。可观察到当含AMPS的共聚物分子量增加时对多磷酸盐水垢的抑制增加。实施例8使用条件B时各种多羧酸盐对多磷酸盐成膜抑制的效果
含15g／洗涤剂量的77AA／23AMPS(Mw4500)共聚物的溶液的多磷酸成膜行为与没有聚合物的对照溶液相比，两种比较溶液，一种含70AA／30MAL(Mw30000)的溶液，一种含100％pAA(Mw4500)。在所有情况下，使用洗涤条件B。结果如图6所示，其表明使用含77AA／23AMPS的共聚物与对照和比较样品相比具有对多磷酸盐水垢明显增大的抑制。
Claims (12)
1．一种在水系统中控制多磷酸水垢的方法，其包括用至少一种共聚物处理水系统，所述的共聚物含有以聚合形式的下列单体：(Ⅰ)50％-98％重量的一种或多种弱酸；(Ⅱ)2-50％重量的一种或多种强酸；(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的共聚物。
2．根据权利要求1所述的方法，其中至少一种共聚物含有以聚合形式的下列单体：
(Ⅰ)50％-98％重量的一种或多种单烯属不饱和的C3至C6单羧酸；
(Ⅱ)2-50％重量的一种或多种不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的共聚物。
3．根据权利要求1或2的方法，其中共聚物含有以聚合形式的下列单体：
(Ⅰ)50-90％重量的一种或多种单烯属不饱和C3-C6单羧酸；
(Ⅱ)10-50％重量的不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种能与(Ⅰ)(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总和等于100％重量的共聚物。
4．根据权利要求1，2或3的方法，其中共聚物含有以聚合形式的下列单体：
(Ⅰ)60-90％重量的一种或多种单烯属不饱和C3-C6单羧酸；
(Ⅱ)10-40％重量的不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种能与(Ⅰ)(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总和等于100％重量的共聚物。
5．根据前述任一权利要求的方法，其中单烯属不饱和C3-C6单羧酸是一种或多种(甲基)丙烯酸。
6．根据前述任一权利要求的方法，其中不饱和磺酸单体是一种或多种下列物质：2-丙烯酰胺基甲基-1-丙基磺酸，2-甲基丙烯酰胺基-2-甲基-1-丙基磺酸，3-甲基丙烯酰胺基-2-羟基-丙基磺酸，烯丙磺酸，甲基烯丙磺酸，烯丙氧苯基磺酸，甲基烯丙氧苯基磺酸，2-羟基-3-(2-丙烯氧基)丙基磺酸，2-甲基-2-丙烯基-1-磺酸，苯乙烯硫酸，乙烯磺酸，丙烯酸3-磺基丙酯，甲基丙烯酸3-磺基丙酯，磺基甲基丙烯酰胺，磺基甲基异丁烯酰胺，和其水可溶盐。
7．根据前述任一权利要求的方法，其中单烯属不饱和C4-C8二羧酸优选马来酸，能与(Ⅰ)(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体选自一种或多种(甲基)丙烯酸C1-C4烷基酯；(甲基)丙烯酸C1-C4羟烷酯；丙烯酰胺；烷基取代的丙烯酰胺；N，N二烷基取代的丙烯酰胺；丙烯酰胺的磺化的烷基酯；乙烯基膦酸；乙酸乙烯酯；烯丙醇；磺化的烯丙醇；苯乙烯和相似的单体；丙烯腈；N-乙烯基吡咯烷酮；N-乙烯基甲酰胺；N-乙烯基咪唑；和N-乙烯基吡啶。
8．根据权利要求1-7中任一的方法，其中根据本发明的平均分子量是3，000至50，000优选4，500至35，000。
9．一种洗涤制品，其含有至少一种共聚物，所述共聚物含有下列单体的聚合单元：
(Ⅰ)50％-98％重量的一种或多种单烯属不饱和的C3至C6单羧酸；
(Ⅱ)2-50％重量的一种或多种不饱和磺酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的共聚物。
10．一种共聚物在洗涤制品中作为助洗剂的用途，该共聚物包括：以聚合形式的下列单体：
(Ⅰ)50％-98％重量的一种或多种弱酸；
(Ⅱ)2-50％重量的一种或多种强酸；
(Ⅲ)0-30％重量的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的共聚物。
11．一种共聚物在洗碗机和／或洗衣机洗涤制品中的用途，该共聚物包括使用以聚合形式的一种或多种下列单体：
(Ⅰ)50％-98％重量的一种或多种弱酸；
(Ⅱ)2-50％重量的一种或多种强酸；
(Ⅲ) 0-30％重量的一种或多种单乙烯化的未饱合C4-C8二羧酸；和
(Ⅳ)0-30％重量的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单乙烯化的未饱合单体；
其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于的100％重量的共聚物。
12．根据任一前述权利要求的方法、洗涤制品或用途，其中共聚物含有：
(Ⅰ)77重量份数的(甲基)丙烯酸共聚物；和
(Ⅱ)23重量份数的2-丙烯酸胺基-2-丙基磺酸共聚物；
(Ⅲ)0-30重量份数的一种或多种单烯属不饱和C4-C8二羧酸；和
(Ⅳ)0-30重量份数的一种或多种可与(Ⅰ)，(Ⅱ)和(Ⅲ)聚合的单烯属不饱和单体；其中单体(Ⅰ)(Ⅱ)(Ⅲ)和(Ⅳ)总量等于100％重量的共聚物。
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002236605A CA2236605A1 (en) | 1997-05-09 | 1998-04-30 | Scale inhibitors |
| DE69809329T DE69809329T2 (de) | 1997-05-09 | 1998-05-01 | Verfahren zur Verhinderung von Ablagerungen von (Poly)phosphaten |
| US09/071,025 US6114294A (en) | 1997-05-09 | 1998-05-01 | Copolymeric scale inhibitors for (Poly)phosphate scale control |
| EP98303438A EP0877002B1 (en) | 1997-05-09 | 1998-05-01 | Method for the inhibition of (poly)phosphate scale |
| NO982048A NO982048D0 (no) | 1997-05-09 | 1998-05-06 | FremgangsmÕte til regulering av fosfatavleiring i vandige systemer |
| MX9803623A MX202707B (en) | 1997-05-09 | 1998-05-07 | Scale inhibitors |
| JP12594998A JP4236299B2 (ja) | 1997-05-09 | 1998-05-08 | スケール抑制剤 |
| TW087107170A TW440546B (en) | 1997-05-09 | 1998-05-08 | Method of controlling scale in aqueous systems |
| AU64774/98A AU6477498A (en) | 1997-05-09 | 1998-05-08 | Scale inhibitors |
| KR1019980016553A KR19980086890A (ko) | 1997-05-09 | 1998-05-08 | 스케일 제거제 |
| BR9803305-0A BR9803305A (pt) | 1997-05-09 | 1998-05-08 | Processo de controle de escama de (poli) fosfato em sistemas aquosos, formulação detergente, e, uso de um copolímero |
| PL98326215A PL326215A1 (en) | 1997-05-09 | 1998-05-08 | Method of controlling formation of (poly)phosphate scale in water carrying systems, detergent composition therefor and application of a colopymer in such method t |
| CNB981098029A CN1192127C (zh) | 1997-05-09 | 1998-05-08 | 水垢抑制方法、洗涤制品及其中共聚物在洗涤制品中的用途 |
| US09/612,684 US6395185B1 (en) | 1997-05-09 | 2000-07-10 | Scale inhibitors |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR05739/97 | 1997-05-09 | ||
| FR05739/1997 | 1997-05-09 | ||
| FR9705739 | 1997-05-09 | ||
| CNB981098029A CN1192127C (zh) | 1997-05-09 | 1998-05-08 | 水垢抑制方法、洗涤制品及其中共聚物在洗涤制品中的用途 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1203962A true CN1203962A (zh) | 1999-01-06 |
| CN1192127C CN1192127C (zh) | 2005-03-09 |
Family
ID=27805964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB981098029A Expired - Lifetime CN1192127C (zh) | 1997-05-09 | 1998-05-08 | 水垢抑制方法、洗涤制品及其中共聚物在洗涤制品中的用途 |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US6114294A (zh) |
| EP (1) | EP0877002B1 (zh) |
| JP (1) | JP4236299B2 (zh) |
| KR (1) | KR19980086890A (zh) |
| CN (1) | CN1192127C (zh) |
| AU (1) | AU6477498A (zh) |
| BR (1) | BR9803305A (zh) |
| CA (1) | CA2236605A1 (zh) |
| DE (1) | DE69809329T2 (zh) |
| MX (1) | MX202707B (zh) |
| NO (1) | NO982048D0 (zh) |
| PL (1) | PL326215A1 (zh) |
| TW (1) | TW440546B (zh) |
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| CN103890022A (zh) * | 2011-08-10 | 2014-06-25 | 巴斯夫欧洲公司 | 异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物，其生产方法及其在含水体系中作为沉积物抑制剂的用途 |
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- 1998-05-01 EP EP98303438A patent/EP0877002B1/en not_active Expired - Lifetime
- 1998-05-01 DE DE69809329T patent/DE69809329T2/de not_active Expired - Lifetime
- 1998-05-06 NO NO982048A patent/NO982048D0/no unknown
- 1998-05-07 MX MX9803623A patent/MX202707B/es not_active IP Right Cessation
- 1998-05-08 JP JP12594998A patent/JP4236299B2/ja not_active Expired - Lifetime
- 1998-05-08 PL PL98326215A patent/PL326215A1/xx unknown
- 1998-05-08 BR BR9803305-0A patent/BR9803305A/pt not_active IP Right Cessation
- 1998-05-08 CN CNB981098029A patent/CN1192127C/zh not_active Expired - Lifetime
- 1998-05-08 AU AU64774/98A patent/AU6477498A/en not_active Abandoned
- 1998-05-08 TW TW087107170A patent/TW440546B/zh not_active IP Right Cessation
- 1998-05-08 KR KR1019980016553A patent/KR19980086890A/ko not_active Abandoned
-
2000
- 2000-07-10 US US09/612,684 patent/US6395185B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890022A (zh) * | 2011-08-10 | 2014-06-25 | 巴斯夫欧洲公司 | 异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物，其生产方法及其在含水体系中作为沉积物抑制剂的用途 |
| CN103890022B (zh) * | 2011-08-10 | 2016-10-12 | 巴斯夫欧洲公司 | 异戊二烯醇、单烯属不饱和一元羧酸和磺酸的共聚物及其生产方法和用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO982048D0 (no) | 1998-05-06 |
| US6114294A (en) | 2000-09-05 |
| CA2236605A1 (en) | 1998-11-09 |
| DE69809329D1 (de) | 2002-12-19 |
| AU6477498A (en) | 1998-11-12 |
| CN1192127C (zh) | 2005-03-09 |
| JPH10314793A (ja) | 1998-12-02 |
| KR19980086890A (ko) | 1998-12-05 |
| MX9803623A (en) | 1999-02-28 |
| MX202707B (en) | 2001-06-27 |
| JP4236299B2 (ja) | 2009-03-11 |
| US6395185B1 (en) | 2002-05-28 |
| DE69809329T2 (de) | 2003-08-21 |
| EP0877002B1 (en) | 2002-11-13 |
| BR9803305A (pt) | 1999-10-05 |
| PL326215A1 (en) | 1998-11-23 |
| EP0877002A2 (en) | 1998-11-11 |
| EP0877002A3 (en) | 1999-03-24 |
| TW440546B (en) | 2001-06-16 |
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