CN102578107B - 低温稳定性溶液 - Google Patents

低温稳定性溶液 Download PDF

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CN102578107B
CN102578107B CN201110461821.1A CN201110461821A CN102578107B CN 102578107 B CN102578107 B CN 102578107B CN 201110461821 A CN201110461821 A CN 201110461821A CN 102578107 B CN102578107 B CN 102578107B
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isothiazolinone
weight
liquid concentrate
dcoit
concentrate
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CN102578107A (zh
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R·G·哈梅尔
R·莱维
T·科勒
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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

本发明涉及4，5-二氯-2-(正辛基-4-异噻唑啉-3-酮)(“DCOIT”)的液体浓缩物，该浓缩物在低于结冻温度的温度下保持稳定不会发生结晶或结冻。

Description

低温稳定性溶液
技术领域
本发明涉及4，5-二氯-2-(正辛基-4-异噻唑啉-3-酮)(“DCOIT”)的液体浓缩物，该浓缩物在低于结冻温度(sub-freezing)的温度下保持稳定不会发生结晶或结冻。
背景技术
众所周知可以将生物杀灭剂加入热塑性树脂组合物(即塑料)、嵌缝胶、密封剂和其它的制品中，以保护这些制品使其免于发生微生物降解。由于工艺的原因，人们已知可以以浓缩物的形式提供生物杀灭剂，例如为液体浓缩物的形式。虽然人们提出了大量的生物杀灭剂，但是异噻唑啉酮，特别是DCOIT，能够可靠地用于这些应用，特别是包括制品的户外风化的那些应用。但是，在室温下，包括DCOIT在内的许多的异噻唑啉酮是固体形式的，因此很难进行处理。这些异噻唑啉酮在溶解于液体载剂的情况下更易于进行处理，特别是溶于增塑剂，该增塑剂在最终应用的组合物中发挥其常规的增塑功能。但是，虽然异噻唑啉酮，特别是DCOIT的增塑剂溶液在室温下(即20-25℃)是稳定的，但是当溶液的温度变冷的时候会发生结冻，在冬季进行运输和储存的时候可能会发生此种问题。这种情况是人们非常不愿意看到的，因为收到结冻的浓缩物的制造商不仅需要对浓缩物进行结冻，而且还需要采取一些步骤保证异噻唑啉酮能够完全重新溶解，浓缩物保持均一。
欧洲专利第0910953号对该结冻问题进行了讨论，公开了以下的内容：包含4-25重量％的异噻唑啉酮化合物、25-88重量％的一种或多种可以将异噻唑啉酮化合物溶于其中的增塑剂、以及8-50重量％的苄醇的溶液浓缩物能够在低于结冻温度的条件下保持稳定，不发生结晶和/或结冻。较佳的是，所述浓缩物包含至少10重量％的DCOIT以及至少15重量％的苄醇，在某些情况下，优选包含至少15重量％的DCOIT以及至少40重量％的苄醇。DCOIT是优选的化合物，因为其相对于其它的异噻唑啉酮化合物，特别是在户外条件下，DCOIT具有改进的稳定性(即耐候性)。美国专利第5,554,635号公开了异噻唑啉酮与增塑剂的浓缩物，通过加入至少4重量％的生物杀灭助剂三氯生(2，4，4’-三氯-2’-羟基二苯基醚)，该浓缩物在低于零度的温度下保持稳定，不会发生结晶化或者结冻。
我们已经发现在与某些限定种类的增塑剂结合使用的情况下，异噻唑啉酮，优选DCOIT，不需要使用助溶剂苄醇或三氯生以获得稳定性。因此本发明涉及一种液体浓缩物，该浓缩物包括4-40重量％的异噻唑啉酮以及60-96重量％的苯甲酸酯增塑剂(一种或多种苯甲酸酯)，所述浓缩物基本不含助溶剂。
出于本发明的目的，助溶剂表示能够溶解和/或可溶于异噻唑啉酮以及苯甲酸酯增塑剂的有机溶剂，包括但不限于苄醇和单烷基酚。术语“基本不含”表示含量小于4重量％，优选小于3重量％，优选小于2重量％，优选小于1重量％，优选0重量％。术语“在等于或低于结冻温度的温度下保持稳定，不会发生结冻或结晶”表示在等于或低于0℃的温度下，该组合物保持澄清，或者如果该组合物在等于或低于0℃的温度下变混浊，则在加热至室温的时候变澄清。
可用于本发明的异噻唑啉酮包括但不限于2-甲基-4-异噻唑啉-3-酮，4-甲基-1，2-苯并异噻唑啉-3-酮，4-丁基-1，2-苯并异噻唑啉-3-酮，正辛基-4-异噻唑啉-3-酮，以及DCOIT和它们的混合物。优选的异噻唑啉酮是正辛基-4-异噻唑啉-3-酮和DCOIT，更优选是DCOIT。所述组合物优选包含等于或小于30重量％的异噻唑啉酮，更优选等于或小于20重量％的异噻唑啉酮，更优选等于或小于15重量％的异噻唑啉酮，优选等于或小于12重量％的异噻唑啉酮。所述组合物优选包含等于或大于5重量％的异噻唑啉酮，更优选等于或大于8重量％的异噻唑啉酮。
本发明的液体浓缩物基本不含助溶剂。
本发明的液体浓缩物基本不含苄醇。
本发明的液体浓缩物基本不含三氯生。
优选的苯甲酸酯是苯甲酸(C4-C22)烷基酯，二醇苯甲酸酯，以及它们的混合物。最优选的是二醇苯甲酸酯及其混合物。许多所述苯甲酸酯可以购自伊斯特曼化学品公司(Eastman Chemical Company)，商品名为“BenzoflexTM”。
实施例
表1列出了用于实施例的苯甲酸酯增塑剂的组成。在各个测试中，在烧杯中将12.5克DCOIT加入112.5克苯甲酸酯增塑剂中，加热至54℃，在全部的DCOIT看起来均已溶解之后，保持1-2分钟。在加热过程中对该组合物充分混合。将各种组合物转移到透明玻璃小管中，在-10℃和60℃进行30天的溶液稳定性测试。表2列出了溶液储存30天之后的观察结果。
表1
表2
DCOIT在苯甲酸酯中10％的溶液在30天之后的观察结果
  -10℃   60℃
  Benzoflex 2088   澄清   稳定
  Benzofiex 2-45   结冻，解冻后澄清   稳定
  Benzoflex 9-88SG   澄清   稳定
  Benzoflex 131   澄清   稳定
  Benzoflex 284   澄清   稳定
  Benzoflex P-200   澄清   稳定
  Benzoflex-354   澄清   稳定
  Benzoflex 9-88   澄清   稳定
实施例2
二苯甲酸酯购自希格玛-艾尔德里奇公司(Sigma Aldrich)，购得的该二苯甲酸酯包含与相应的BenzoflexTM材料相同的二苯甲酸酯。在锥形瓶中，在搅拌和室温条件下将固体DCOIT加入苯甲酸酯中并升温至50℃，制得DCOIT在苯甲酸酯中的10％的溶液。将制得的淡黄色溶液转移到具有保护帽盖的烧瓶中，在特定温度下储存。根据测试方法DIN ISO 935测量低温环境下的晶体形成(浊点)。还评价了该溶液在升高的温度下的稳定性(55℃)表3列出了测得的溶液的稳定性观察结果。
表3

Claims (8)

1.一种液体浓缩物，其包含以下组分a和b的均匀溶液:
a.大于8重量％至40重量％的异噻唑啉酮；以及
b.60-96重量％的苯甲酸酯增塑剂；
所述浓缩物不含有助溶剂且不含有三氯生。
2.如权利要求1所述的液体浓缩物，其特征在于，所述异噻唑啉酮是4,5-二氯-2-(正辛基-4-异噻唑啉-3-酮)或者正辛基-4-异噻唑啉-3-酮。
3.如权利要求1所述的液体浓缩物，其特征在于，所述异噻唑啉酮是DCOIT。
4.如权利要求1所述的液体浓缩物，包含等于或小于30重量％的异噻唑啉酮。
5.如权利要求1所述的液体浓缩物，包含等于或小于15重量％的异噻唑啉酮。
6.如权利要求1所述的液体浓缩物，其特征在于，所述苯甲酸酯增塑剂是苯甲酸(C4–C22)烷基酯,二醇苯甲酸酯,或者它们的混合物。
7.如权利要求1所述的液体浓缩物，其特征在于，所述苯甲酸酯增塑剂是二醇苯甲酸酯的混合物。
8.如权利要求1所述的液体浓缩物，其特征在于，所述异噻唑啉酮是异噻唑啉酮的混合物。
CN201110461821.1A 2010-12-29 2011-12-27 低温稳定性溶液 Active CN102578107B (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5498344A (en) * 1995-02-02 1996-03-12 Morton International, Inc. Low-temperature-stabilized isothiazolinone concentrates
US5554635A (en) * 1995-02-07 1996-09-10 Morton International, Inc. Liquid isothiazolinone concentrates having improved low temperature-stability and improved anti-bacterial properties
EP0910953A1 (en) * 1997-09-08 1999-04-28 Morton International, Inc. Low temperature-stabilized isothiazolinone concentrates

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4683080A (en) * 1984-06-11 1987-07-28 Morton Thiokol, Inc. Microbiocidal compositions comprising an aryl alkanol and a microbiocidal compound dissolved therein
US5585033A (en) * 1995-07-21 1996-12-17 Huls America Inc. Liquid formulations of 1,2-benzisothiazolin-3-one
US5990214A (en) * 1997-07-31 1999-11-23 Velsicol Chemical Corporation Liquid glycol benzoate compositions
JP4567955B2 (ja) * 2002-08-05 2010-10-27 日本エンバイロケミカルズ株式会社 工業用抗菌組成物
JP5094328B2 (ja) * 2007-10-19 2012-12-12 住化エンビロサイエンス株式会社 工業用抗菌組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5498344A (en) * 1995-02-02 1996-03-12 Morton International, Inc. Low-temperature-stabilized isothiazolinone concentrates
US5554635A (en) * 1995-02-07 1996-09-10 Morton International, Inc. Liquid isothiazolinone concentrates having improved low temperature-stability and improved anti-bacterial properties
EP0910953A1 (en) * 1997-09-08 1999-04-28 Morton International, Inc. Low temperature-stabilized isothiazolinone concentrates

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JP5466221B2 (ja) 2014-04-09
BRPI1106908A2 (pt) 2013-06-11
US20120172403A1 (en) 2012-07-05
BRPI1106908A8 (pt) 2017-10-10
JP2012140409A (ja) 2012-07-26
CN102578107A (zh) 2012-07-18
EP2471367A1 (en) 2012-07-04

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