CN1234272C - 邻苯基苯酚盐浓缩物 - Google Patents
邻苯基苯酚盐浓缩物 Download PDFInfo
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- CN1234272C CN1234272C CNB011339616A CN01133961A CN1234272C CN 1234272 C CN1234272 C CN 1234272C CN B011339616 A CNB011339616 A CN B011339616A CN 01133961 A CN01133961 A CN 01133961A CN 1234272 C CN1234272 C CN 1234272C
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- opp
- solution
- mixture
- phenyl
- potassium hydroxide
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
本发明涉及严寒下稳定的高浓缩邻苯基苯酚的碱性水溶液及其作为防腐剂的应用。
Description
技术领域
本发明涉及严寒下稳定的高浓缩邻苯基苯酚的碱性水溶液及其作为防腐剂的应用。
背景技术
邻苯基苯酚(OPP)是一种重要的用于制备保护工业材料、特别是例如胶水或粘合剂、混凝土添加剂、冷却润滑剂、颜料浆的防腐剂的活性化合物。保护被处理产品免于微生物降解是工业材料防腐剂的期望功能。为此，防腐剂必须主要存在于水相以到达存活在那里的微生物。因此，防腐剂有效的先决条件是它们具有足够的水溶性。但是，对于基于酚类活性化合物的防腐剂，情况并不总是能达到所要求的程度。因此，例如，活性化合物邻苯基苯酚(参见例如W.Paulus的“用于保护材料的杀微生物剂”，Chapman & Hall，1993，170页及此后各页)在中性水中的溶解度只有约0.02wt％。为了毫无困难地将该活性化合物引入到工业材料中，因此必需首先将微生物活性化合物预溶解以将其转化为更适于进一步加工的形式。实际上，这通常可通过制备在碱溶液(氢氧化钠水溶液、氢氧化钾水溶液)、醇、二醇等中的溶液，然后向待保护产品中加入所需量所得液体杀微生物剂产品而实现。从应用的角度考虑，通过用碱(例如LiOH，NaOH，KOH，Ca(OH)2)中和将OPP转化成相应的苯酚盐是特别有利的，因为OPP的碱金属盐或碱土金属盐比游离OPP具有好得多的水中溶解性。
在氢氧化钠水溶液中形成预溶液的方法是早已已知并广泛使用的方法，但伴随下列问题：随着活性化合物含量(以OPP计算)的增加，即使是在较低OPP浓度下，所得溶液的结晶点对于实际应用而言也太高。由于结晶，在某些情况下甚至发生在0℃以上，在工业实践中难以以可控方式使用这种溶液，特别是在一年的寒冷季节，此时杀菌剂产品在储罐、管道和泵中可能发生不希望的固化。这一过程需要耗时和昂贵的方法来重新液化杀微生物剂产品并可能导致生产停工。此外，在管道和泵中不可控的固化可能导致压力和泄漏增加，从操作安全角度考虑，这是危险的。
邻苯基苯酚(OPP)在水性NaOH中的水溶液的结晶倾向示于下表中：
| OPP(wt％) | 开始结晶温度℃ |
| 18.8 | -7 |
| 21.8 | -3 |
| 25.0 | 3.5 |
| 28.1 | 10 |
为了提供更高浓缩的OPP在碱性介质中的溶液，除了上述在氢氧化钠水溶液中的溶液外，还描述了在氢化钾水溶液中的溶液。但是，目前只制备出最高浓度为30wt％OPP的混合物并用在工业上。除了已知的30％浓度OPP溶液的碱过量(对于许多应用这已经太高了)外，该配方的活性化合物含量相对最佳输给系统还太低，因为航运和国内公司输给系统需要运输大量水，这带来不经济的运作，而且从生态学角度考虑看来也值得改进。
发明内容
因此，本发明的目的是提供不具有上述已知溶液的缺点的OPP碱性水溶液。
特别地，本发明的目的是提供OPP在水性碱性介质如LiOH，NaOH，KOH，Ca(OH)2的水溶液及这些碱性介质的二元混合物中的更高浓缩的溶液(＞30wt％OPP)，它们在即使低于0℃的温度下在储存和使用期间也能保持稳定而不发生任何结晶。
现已令人惊讶地发现，当以一定比例混合各组分时可获得即使在低温下也是对结晶稳定的OPP盐在水中的浓溶液。
因此，根据本发明的溶液是通过以一定比例混合水、OPP以及形成OPP盐所需的碱而制备的。
适于制备根据本发明的OPP浓缩物的碱特别为碱金属氢氧化物和碱土金属氢氧化物。氢氧化锂(LiOH)、氢氧化钠(NaOH)、氢氧化钾(KOH)和氢氧化钙(Ca(OH)2)可以例举被提到。
优选使用NaOH或KOH。还可以使用所述氢氧化物的混合物，例如KOH/NaOH混合物。特别优选的氢氧化物为氢氧化钾。
已令人惊讶地发现，所述目的可通过以预定比例混合OPP和氢氧化钾或OPP和氢氧化钾/氢氧化钠混合物并将OPP在溶液中的浓度调节至达到所述目的所需的浓度而实现。
令人惊讶的是，可以制备浓度大于30wt％OPP的溶液，特别是即使在低温也是对结晶稳定的高浓缩OPP-K或OPP-K/Na溶液。
根据本发明的OPP浓缩物特别由(a)氢氧化钾或氢氧化钾/氢氧化钠混合物、(b)OPP和(c)水制备。
邻苯基苯酚与氢氧化钾或与氢氧化钾/氢氧化钠混合物摩尔之和的摩尔比为1∶1.01-1∶1.5，优选1∶1.02-1∶1.10。
OPP含量为30-55wt％，特别为40-50wt％。在一个特别优选的实施方案中，OPP含量为45wt％。它是用下式计算的：
根据本发明的OPP浓缩物用作工业材料的防腐剂(参见例如W.Paulus的“用于保护材料的杀微生物剂”，Chapman&Hall，1993，170页及此后各页)以保护其免受微生物降解。可提到的工业材料的实例为胶水、粘合剂、混凝土添加剂、密封材料、冷却润滑剂、印刷增稠剂、聚合物分散液、洗涤剂和表面活性剂、蜡乳状液和抛光剂、钻孔液体、油漆、沥青乳液和颜料浆液。
具体实施方式
实施例：严寒下稳定的邻苯基苯酚/钾浓缩物
a)在20℃搅拌下将500.0g邻苯基苯酚(＝50wt％OPP)加入到312.0g去矿化水和188.0g KOH(纯度91.9％)的溶液中，并搅拌混合物直到获得透明的溶液。然后搅拌下冷却该溶液直至开始结晶。结晶结束后，再缓慢加热混合物。最后晶体溶解的温度为溶解温度。对于此组成的溶液，发现其溶解温度为+4℃，即该溶液不能满足本发明目的。
b)在20℃搅拌下将450.0g邻苯基苯酚(＝45wt％OPP)加入到380.8g去矿化水和169.2g KOH(纯度91.9％)的溶液中，并搅拌混合物直到获得透明的溶液。然后搅拌下冷却该溶液直至开始结晶。结晶结束后，再缓慢加热混合物。最后晶体溶解的温度为溶解温度。对于此组成的溶液，测定其溶解温度＜-20℃，即该溶液比现有技术溶液含有含量高得多的OPP，同时即使在低温下也可安全地操作。
Claims (4)
1.混合物，包含水、邻苯基苯酚和氢氧化钾，其特征在于邻苯基苯酚与氢氧化钾的摩尔比为1∶1.02-1∶1.10，并且混合物中邻苯基苯酚的比例为45wt％。
2.制备根据权利要求1的混合物的方法，其特征在于以所述比例将水、邻苯基苯酚和氢氧化钾彼此混合。
3.权利要求1的混合物作为工业材料防腐剂的应用。
4.保护工业材料的方法，其特征在于用权利要求1的混合物处理它们。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10040165A DE10040165A1 (de) | 2000-08-17 | 2000-08-17 | ortho-Phenylphenolat-Konzentrate |
| DE10040165.1 | 2000-08-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1339253A CN1339253A (zh) | 2002-03-13 |
| CN1234272C true CN1234272C (zh) | 2006-01-04 |
Family
ID=7652713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011339616A Expired - Fee Related CN1234272C (zh) | 2000-08-17 | 2001-08-16 | 邻苯基苯酚盐浓缩物 |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US6544441B2 (zh) |
| EP (1) | EP1180326B1 (zh) |
| JP (1) | JP2002060303A (zh) |
| KR (1) | KR100733104B1 (zh) |
| CN (1) | CN1234272C (zh) |
| AR (1) | AR030004A1 (zh) |
| AT (1) | ATE305217T1 (zh) |
| AU (1) | AU782681B2 (zh) |
| BR (1) | BR0103352A (zh) |
| CA (1) | CA2355031C (zh) |
| CO (1) | CO5251481A1 (zh) |
| DE (2) | DE10040165A1 (zh) |
| DK (1) | DK1180326T3 (zh) |
| ES (1) | ES2246969T3 (zh) |
| MX (1) | MXPA01008240A (zh) |
| MY (1) | MY129761A (zh) |
| NO (1) | NO20013985L (zh) |
| NZ (1) | NZ513554A (zh) |
| TW (1) | TWI241885B (zh) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2578967C (en) * | 2004-09-03 | 2011-06-21 | Microban Products Company | Antimicrobial cementitious compositions |
| DE102005008184A1 (de) * | 2005-02-23 | 2006-08-31 | Lanxess Deutschland Gmbh | Antimikrobiell ausgerüstete Gipsbauplatten |
| WO2010010700A1 (ja) * | 2008-07-23 | 2010-01-28 | 花王株式会社 | 抗菌剤含有液の製造方法 |
| CN102060673A (zh) * | 2010-12-24 | 2011-05-18 | 淄博德丰化工有限公司 | 邻苯基苯酚钠盐的制备工艺 |
| KR102450300B1 (ko) * | 2022-06-23 | 2022-10-05 | 디케이화인케미칼 주식회사 | 건축용 향균성 셀룰로오스 제조방법 및 그에 의하여 제조되는 건축용 항균성 셀룰로오스 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993700A (en) * | 1973-02-20 | 1976-11-23 | The Dow Chemical Company | Purification of p-phenylphenol |
| NL7406965A (nl) * | 1974-05-24 | 1975-11-26 | Stamicarbon | Werkwijze voor de winning van ortho-fenylfenol. |
| DE3204079A1 (de) * | 1982-02-06 | 1983-08-18 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von hydroxydiphenylen |
| DE3303220A1 (de) * | 1983-02-01 | 1984-08-02 | Bayer Ag, 5090 Leverkusen | Verfahren zur gleichzeitigen gewinnung von 4-hydroxydiphenyl und 4,4'-dihydroxydiphenyl |
| US5629350A (en) * | 1996-03-20 | 1997-05-13 | The Dow Chemical Company | Suspension formulations of ortho-phenylphenol |
| DE19859136A1 (de) * | 1998-12-21 | 2000-06-29 | Pluss Stauffer Ag | Phenol und/oder Phenolderivate enthaltende Formulierung mit tiefem Gefrierpunkt |
| US6362152B1 (en) * | 2000-04-07 | 2002-03-26 | The Dow Chemical Company | Low color and low haze formulations of sodium o-phenylphenate |
| RU2298543C2 (ru) * | 2000-05-12 | 2007-05-10 | Омиа Аг | Водный жидкий состав с низкой температурой замерзания, содержащий феноляты, способ его приготовления, водная суспензия или дисперсия, включающая состав |
-
2000
- 2000-08-17 DE DE10040165A patent/DE10040165A1/de not_active Withdrawn
-
2001
- 2001-07-27 AR ARP010103591A patent/AR030004A1/es unknown
- 2001-08-06 AT AT01118722T patent/ATE305217T1/de not_active IP Right Cessation
- 2001-08-06 DK DK01118722T patent/DK1180326T3/da active
- 2001-08-06 EP EP01118722A patent/EP1180326B1/de not_active Expired - Lifetime
- 2001-08-06 DE DE50107552T patent/DE50107552D1/de not_active Expired - Fee Related
- 2001-08-06 ES ES01118722T patent/ES2246969T3/es not_active Expired - Lifetime
- 2001-08-10 JP JP2001243925A patent/JP2002060303A/ja not_active Withdrawn
- 2001-08-14 CA CA002355031A patent/CA2355031C/en not_active Expired - Fee Related
- 2001-08-14 BR BR0103352-2A patent/BR0103352A/pt not_active IP Right Cessation
- 2001-08-15 NZ NZ513554A patent/NZ513554A/xx unknown
- 2001-08-15 TW TW090119958A patent/TWI241885B/zh not_active IP Right Cessation
- 2001-08-15 AU AU59894/01A patent/AU782681B2/en not_active Ceased
- 2001-08-15 MY MYPI20013837A patent/MY129761A/en unknown
- 2001-08-15 MX MXPA01008240A patent/MXPA01008240A/es active IP Right Grant
- 2001-08-16 CN CNB011339616A patent/CN1234272C/zh not_active Expired - Fee Related
- 2001-08-16 KR KR1020010049218A patent/KR100733104B1/ko not_active IP Right Cessation
- 2001-08-16 CO CO01067085A patent/CO5251481A1/es not_active Application Discontinuation
- 2001-08-16 US US09/931,664 patent/US6544441B2/en not_active Expired - Fee Related
- 2001-08-16 NO NO20013985A patent/NO20013985L/no not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US6544441B2 (en) | 2003-04-08 |
| EP1180326B1 (de) | 2005-09-28 |
| JP2002060303A (ja) | 2002-02-26 |
| AU5989401A (en) | 2002-02-21 |
| ES2246969T3 (es) | 2006-03-01 |
| AR030004A1 (es) | 2003-07-23 |
| NO20013985L (no) | 2002-02-18 |
| CA2355031A1 (en) | 2002-02-17 |
| US20020040977A1 (en) | 2002-04-11 |
| CN1339253A (zh) | 2002-03-13 |
| MY129761A (en) | 2007-04-30 |
| DE10040165A1 (de) | 2002-02-28 |
| TWI241885B (en) | 2005-10-21 |
| NO20013985D0 (no) | 2001-08-16 |
| AU782681B2 (en) | 2005-08-18 |
| DE50107552D1 (de) | 2005-11-03 |
| MXPA01008240A (es) | 2004-11-10 |
| CA2355031C (en) | 2009-10-06 |
| KR100733104B1 (ko) | 2007-06-27 |
| KR20020014729A (ko) | 2002-02-25 |
| DK1180326T3 (da) | 2005-11-28 |
| BR0103352A (pt) | 2002-03-26 |
| CO5251481A1 (es) | 2003-02-28 |
| NZ513554A (en) | 2003-01-31 |
| ATE305217T1 (de) | 2005-10-15 |
| EP1180326A1 (de) | 2002-02-20 |
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