CN108329228A - A kind of Perfluoropolyether amide quaternary ammonium salts and preparation method containing hydroxyalkyl - Google Patents
A kind of Perfluoropolyether amide quaternary ammonium salts and preparation method containing hydroxyalkyl Download PDFInfo
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- CN108329228A CN108329228A CN201810271384.9A CN201810271384A CN108329228A CN 108329228 A CN108329228 A CN 108329228A CN 201810271384 A CN201810271384 A CN 201810271384A CN 108329228 A CN108329228 A CN 108329228A
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- perfluoropolyether
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract
A kind of Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl, it is characterised in that molecular formula is as follows：Wherein n is 1-20；R is-(CH2)mCH2OH, m are 1-5；X is Cl or Br.Product of the present invention is nontoxic, product good water solubility, high surface activity.
Description
Technical field
Present invention relates particularly to a kind of Perfluoropolyether amide quaternary ammonium salts and preparation method thereof containing hydroxyalkyl.
Background technology
Technical background
Fluorinated surfactant is a kind of important special surfactant, and surface is lived in current all surface activating agent
Property highest, therefore also someone is referred to as " super surfactant ", with the incomparable particularity of other surfaces activating agent
Energy.Therefore, fluorinated surfactant can enhance product in addition to using the active occasion of general surface using fluorinated surfactant
Performance, such as outside ink, coating, washing, oil recovery field, be also applied to fluoroprotein foam extinguishing agent, plating inhibitor, knit
Object finishing agent etc..But traditional fluorinated surfactant with full-fluorine octyl sulfuryl fluoride, perfluorooctane sulfonate and its salt and
Various related derivatives (being referred to as PFOS) can be in food since such surfactant is not easy to be degraded in nature
Bioaccumulation in chain, and can have toxicity to humans and animals, and it is attributed to persistence organic pollutant (POPs),
And on August 30th, 2013, the Standing Committee of the National People's Congress examines and approves《Stockholm about persistence organic pollutant is public
About》Further limit the use of traditional fluorinated surfactant.
Perfluoropolyether surfactants are a kind of novel fluorinated surfactants, have good water solubility, surfactant
The features such as high, wetability is strong and degradable environment friendly, referred to as substitutes having for traditional fluorinated surfactant in some fields
Imitate substitute.The product of the censored perfluoropolyether salt for having accepted certain external company of U.S.EPA, and such product is also
The certification that U.S. FDA and German BFR are contacted about food is passed through.Synthesis is prepared by four-step reaction in Zhou Jiehua
Perfluoropolyether is spread out sulfonate type perfluorinated surfactant, lowest surface tension value and cmc values be respectively 20.03mN/m and
(Zhou Jiehua, Meng Weidong, yellow flame root perfluoropolyether derive the synthesis of sulfonate type fluorocarbon surfactant to 1.34 × 10-4g/L
And performance printing and dyeing assistants 2014,1 (31):9-12).The perfluoropolyether surfactants preparation process, which is crossed, needs four steps, yield
It is low, it is unfavorable for industrialized production.
Invention content
The object of the present invention is to provide a kind of yield high Perfluoropolyether amide quaternary ammonium salts and preparation containing hydroxyalkyl
Method.
Perfluoropolyether amide propyl two is made by amidation process under conditions of triethylamine is acid binding agent in the present invention
Methyl tertiary amine；Perfluoropolyether amide propyl-dimethyl tertiary amine and halohydrin in a solvent quaternized obtained product containing hydroxyalkyl
Perfluoropolyether amide quaternary ammonium salts.The preparation method is simply total to three-step reaction, and product purity is high, and product is with good
Wetability, high surfactant and relatively traditional fluorinated surfactant water have preferably water-soluble.
A kind of Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl of the present invention, molecular formula are as follows：
Wherein n is 1-20；R is-(CH2)mCH2OH, m are 1-5；X is Cl or Br.
A kind of novel Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl, boundary's micellar concentration is 10-4-10-5mol/L；With high surface, lowest surface tension 20-16mN/m；And have good wetability, survey its
Contact angle on parafilm reaches 0 °, can completely be sprawled on parafilm.
A kind of preparation method of Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl of the present invention, includes the following steps：
The first step, first by triethylamine and N, N- dimethyl -1,3- propane diamine is added in solvent, in 0- in 1-2 hours
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under the conditions of 5 DEG C to stir, then replys room temperature, be heated to 40-50 DEG C
Under conditions of react 3-4 hours；Revolving removes solvent and unreacted reactant, and water washing 3-5 times three times is used in combination, and perfluoropolyether is made
Amido propyl dimethyl tertiary amine；
Second step, Perfluoropolyether amide propyl-dimethyl tertiary amine and halohydrin pass through under conditions of solvent and heating
Quaternization reaction obtains crude product Perfluoropolyether amide quaternary ammonium salts；
The crude product made in step 2 is removed solvent and unreacted halohydrin by suction filtration, is dried to obtain wax by third
Shape target product.
In first step reaction process, it is 10-20 times of reactant that solvent, which is ether, ethyl acetate or isopropanol its additive amount,
Volume, the molar ratio of perfluoropolyether acyl fluorides, N, N- dimethyl -1,3- propane diamine and triethylamine are 1：1：1-5, initial reaction
Temperature is 0-5 DEG C, and the reaction time is 1-2 hours, is reacted again under conditions of being then heated to 40-50 DEG C 3-4 hours.
The structural formula of perfluoropolyether acyl fluorides is in first step building-up process：
Wherein n is the integer of 1-20；
In second step reaction process, it is Perfluoropolyether amide propyl-dimethyl that solvent, which selects isopropanol or ethyl alcohol, dosage,
The molar ratio of 10-20 times of tertiary amine and halohydrin total volume, Perfluoropolyether amide propyl-dimethyl tertiary amine and halohydrin is 1:
1.1-2, reaction temperature are 50-70 DEG C, reaction time 5-10 hour.
The structural formula of the intermediate Perfluoropolyether amide propyl-dimethyl tertiary amine generated in second step building-up process is：
Wherein n is the integer of 1-20；
The structural formula of halohydrin is in second step reaction process：
Wherein m is the integer of 1-5, X Cl, Br.
The Perfluoropolyether amide quaternary ammonium salts product containing hydroxyalkyl of the present invention is yellow gummy solid.
Above-mentioned perfluorinated surfactant can be used for the wetting agent of ink and pesticide；It can be used for protein foam extinguishing agent.
The present invention has the following technical effect that：
First, the synthesis yield for the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl that the present invention synthesizes is in 88%-
96%, and Zhou Jiehua perfluoropolyether derives the yield of sulfonate type fluorocarbon surfactant in 50%-65%.
Second, the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl that the present invention synthesizes have in hydrophobic group and hydrophilic group
Oxygen atom, so with water-soluble well, overcome tradition with perfluoro caprylic acid spread out based on fluorinated surfactant poorly water-soluble
The shortcomings that, carbon fluorine chain when identical the solubility of product of the present invention be 3-10 times of traditional perfluoroalkyl surfactants；
Third, quaternizing agent halohydrin of the present invention is than traditional cation perfluoroalkyl surfactants high surface
The quaternizing agent iodomethane of agent is more environmentally-friendly.
4th, both there is the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl that the present invention synthesizes traditional fluorine surface to live
Property agent high surfactant, and have bactericidal properties, to staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-
8099) killing rate of effect 10min is respectively 95.0-99.6% and 95.3-99.0%.
5th, the relatively traditional fluorine surface-active of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl that the present invention synthesizes
Agent is degradable, and the primary degradation rate of product will not be accumulated with food chain in vivo up to 88.2%-99.4%, can be
Industrial circle substitutes the application of parts of traditional fluorinated surfactant.
Description of the drawings：
Fig. 1 is the infared spectrum of the Perfluoropolyether amide quaternary ammonium salts of the invention containing hydroxyalkyl.It can from Fig. 1
Go out 1050cm-1And 1240cm-1The peak of left and right is-CF2Asymmetric stretching vibration peak；In 1884cm in raw material-1The peak at place is in
It is displaced to 1710cm in mesosome and product-1, show acyl fluorides key in original (- COF) be broken, formed new amido bond (-
CONH -), and 3000-3200cm in intermediate and product-1The peak at place is the-vibrational spectrum of NH；3650cm in product-1
To 3350cm-1Range shows-CH2The presence of OH illustrates to synthesize successfully.
Fig. 2 is the surface tension collection of illustrative plates of the Perfluoropolyether amide quaternary ammonium salts of the invention containing hydroxyalkyl.It can from Fig. 2
To find out that the surface tension of water can be dropped to 18mN/L by the surfactant from 72mN/m, and its aqueous solution exists
Just reach its critical micelle concentration when 0.024mmol/L, illustrate this product no matter from reduce surface tension ability or effect
All show high surface-active.
Specific implementation mode
Embodiment 1：
(1) raw materials and consumption
Oligomeric perfluoropolyether acyl fluorides (n=1) compound 9.96g, N, N- dimethyl -1,3- propane diamine 2.24g, triethylamine
2.22g, chlorethanol 1.61g, anhydrous ether and isopropanol are respectively 30ml and 40ml；
(2) specific preparation method
First by above-mentioned triethylamine and N, N- dimethyl -1,3- propane diamine is proportionally added in anhydrous ether, 0
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under the conditions of DEG C to stir, be dripped off after 1 hour, be returned to room temperature, reheats
To 40 DEG C, react 3 hours；Revolving removes solvent and unreacted reactant, and water washing 3 times three times are used in combination, and intermediate is made；It will be intermediate
Body and chlorethanol, which are put by above-mentioned mass ratio in isopropanol, is heated to 50 DEG C, reacts 5 hours, revolving is removed and removes solvent
With unreacted quaternizing agent, it is product Perfluoropolyether amide quaternary ammonium salts to obtain yellow gummy solid, and yield is
96%.
The product that K12 surface tension instruments are surveyed can make the surface tension of water drop to 17.7mN/m from 72mN/m, and should
Contact angle of the water on parafilm can also be dropped to 0 ° from 105 ° by product, complete wetting hydrophobic surface.The primary biology drop of product
Xie Du is 90.0%, acts on staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-8099) killing of 10min
Rate is respectively 98.0% and 99.0%.
Embodiment 2：
(1) raw materials and consumption
A kind of oligomeric 1.84 g of perfluoropolyether acyl fluorides (n=8) compound 30.54g, N, N- dimethyl -1,3- ethylenediamine, three
Ethamine 2.22g, chlorethanol 1.61g, ethyl acetate and absolute ethyl alcohol are respectively 50ml and 60ml；
(2) specific preparation method
First by above-mentioned triethylamine and N, N- dimethyl -1,3- ethylenediamines are proportionally added in ethyl acetate, 3
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under the conditions of DEG C to stir, dripped off after 1.5 hours, then revert to room temperature,
50 DEG C are heated to, is reacted 4 hours；Revolving removes solvent and unreacted reactant, and water washing 5 times three times are used in combination, and intermediate is made；
Intermediate and chlorethanol are put by above-mentioned mass ratio in absolute ethyl alcohol and are heated to 60 DEG C, is reacted 8 hours, revolving removes
Low-boiling-point substance impurity, it is product Perfluoropolyether amide quaternary ammonium salts, yield 92% to obtain yellow gummy solid.
The product that K12 surface tension instruments are surveyed can make the surface tension of water drop to 17.1mN/m from 72mN/m, and should
Contact angle of the water on parafilm can also be dropped to 0 ° from 105 ° by product, complete wetting hydrophobic surface.The primary biology drop of product
Xie Du is 89.7%, acts on staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-8099) killing of 10min
Rate is respectively 98.7% and 98.5%
Embodiment 3：
(1) raw materials and consumption
A kind of oligomeric perfluoropolyether acyl fluorides (n=15) compound 51.12g, N, N- dimethyl -1,3- propane diamine 2.24g,
The bromo- 1- amylalcohols 3.34g of triethylamine 2.22g, 5-, anhydrous ether and isopropanol are respectively 60ml and 60ml；
(2) specific preparation method
First by above-mentioned triethylamine and N, N- dimethyl -1,3- propane diamine is proportionally added in anhydrous ether, -0
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under the conditions of DEG C to stir, be dripped off after 1 hour, replys room temperature, be heated to
It 45 DEG C, reacts 4 hours；Revolving removes solvent and unreacted reactant, and water washing 4 times three times are used in combination, and intermediate is made；By intermediate
It is put into absolute ethyl alcohol by above-mentioned mass ratio with the bromo- 1- amylalcohols of 5- and is heated to 65 DEG C, reacted 7 hours, revolving removes low boiling
Object impurity, it is product Perfluoropolyether amide quaternary ammonium salts, yield 95% to obtain yellow gummy solid.
The product that K12 surface tension instruments are surveyed can make the surface tension of water drop to 17.6mN/m from 72mN/m, and should
Contact angle of the water on parafilm can also be dropped to 13 ° from 105 ° by product, wettable hydrophobic surface.The primary biology drop of product
Xie Du is 90.1%, acts on staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-8099) killing of 10min
Rate is respectively 98.5% and 98.1%.
Embodiment 4：
(1) raw materials and consumption
A kind of oligomeric perfluoropolyether acyl fluorides (n=20) compound 65.82g, N, N- dimethyl -1,3- propane diamine 2.24g, three
Ethamine 4.24g, chlorethanol 1.61g, ethyl acetate and isopropanol are respectively 40ml and 50ml；
(2) specific preparation method
First by above-mentioned triethylamine and N, N- dimethyl -1,3- propane diamine is proportionally added in ethyl acetate, 5
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under the conditions of DEG C to stir.It is dripped off after 2 hours, replys room temperature, be heated to
It 50 DEG C, reacts 4 hours；Revolving removes solvent and unreacted reactant, and water washing 4 times three times are used in combination, and intermediate is made；By intermediate
It is put into absolute ethyl alcohol by above-mentioned mass ratio with chloropropyl alcohol and is heated to 70 DEG C, reacted 10 hours, it is miscellaneous that revolving removes low-boiling-point substance
Matter, it is product Perfluoropolyether amide quaternary ammonium salts, yield 88% to obtain yellow gummy solid.
The product that K12 surface tension instruments are surveyed can make the surface tension of water drop to 16.5mN/m from 72mN/m, and should
Contact angle of the water on parafilm can also be dropped to 20 ° from 105 ° by product, wettable hydrophobic surface.The primary biology drop of product
Xie Du is 88.9%, acts on staphylococcus aureus (ATCC-6538) and Escherichia coli (ATCC-8099) killing of 10min
Rate is respectively 99.1% and 97.5%.
Claims (10)
1. a kind of Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl, it is characterised in that molecular formula is as follows：
Wherein n is 1-20；R is-(CH2)mCH2OH, m are 1-5；X is Cl or Br.
2. a kind of Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as described in claim 1, it is characterised in that described
Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl, boundary's micellar concentration is 10-4-10-5mol/L；Lowest surface tension is
20-16mN/m, the contact angle on parafilm reach 0 °.
3. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 1 or 2, special
Sign is to include the following steps：
The first step, first by triethylamine and N, N- dimethyl -1,3- propane diamine is added in solvent, in 0-5 DEG C of item in 1-2 hours
Make perfluoropolyether acyl fluorides slowly instill in above-mentioned mixed liquor under part to stir, then reply room temperature, is heated to 40-50 DEG C of condition
Lower reaction 3-4 hours；Revolving removes solvent and unreacted reactant, and water washing 3-5 times three times is used in combination, and Perfluoropolyether amide propyl is made
Dimethyl tertiary amine；
Second step, Perfluoropolyether amide propyl-dimethyl tertiary amine and halohydrin, under conditions of solvent and heating, by quaternized
Reaction, obtains crude product Perfluoropolyether amide quaternary ammonium salts；
The crude product made in step 2 is removed solvent and unreacted halohydrin by suction filtration, is dried to obtain wax-like mesh by third
Mark product.
4. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is in first step reaction process, solvent is ether, ethyl acetate or isopropanol, and additive amount is the body of 10-20 times of reactant
Product.
5. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is perfluoropolyether acyl fluorides in first step reaction process：N, N- dimethyl -1,3- propane diamine：The molar ratio of triethylamine is 1：1：1-
5。
6. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is that the structural formula of perfluoropolyether acyl fluorides in first step building-up process is：
Wherein n is the integer of 1-20.
7. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
Be in second step reaction process, solvent be isopropanol or ethyl alcohol, dosage be Perfluoropolyether amide propyl-dimethyl tertiary amine and
10-20 times of halohydrin total volume.
8. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is in second step reaction process that the molar ratio of Perfluoropolyether amide propyl-dimethyl tertiary amine and halohydrin is 1:1.1-2.
9. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is in second step reaction process that reaction temperature is 50-70 DEG C, reaction time 5-10 hour.
10. a kind of preparation method of the Perfluoropolyether amide quaternary ammonium salts containing hydroxyalkyl as claimed in claim 3, feature
It is that the structural formula of halohydrin in second step building-up process is：
Wherein m is the integer of 1-5, X Cl, Br.
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| CN201810271384.9A CN108329228B (en) | 2018-03-29 | 2018-03-29 | Perfluoro polyether amide propyl quaternary ammonium salt containing hydroxyalkyl and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109106608A (en) * | 2018-09-18 | 2019-01-01 | 中国日用化学研究院有限公司 | A kind of cleaning skin solid particle and the facial cleanser and preparation method thereof for preventing skin deposits solid particle |
| CN116103021A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Foaming agent for oil-based drilling fluid and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433813A (en) * | 2008-11-28 | 2009-05-20 | 上海瀛正科技有限公司 | Hexafluoropropylene-based quaternary ammonium salt cationic surfactant, synthesizing method and use |
| CN102389745A (en) * | 2011-08-15 | 2012-03-28 | 华中师范大学 | Preparation method of fluorine-containing double-type cationic surfactant and use thereof |
| RU2500705C1 (en) * | 2012-08-15 | 2013-12-10 | Борис Николаевич Максимов | Method of making ski wax |
| CN106146294A (en) * | 2015-04-08 | 2016-11-23 | 中化近代环保化工(西安)有限公司 | A kind of perfluoro methyl vinyl ether and the production method of intermediate thereof |
-
2018
- 2018-03-29 CN CN201810271384.9A patent/CN108329228B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101433813A (en) * | 2008-11-28 | 2009-05-20 | 上海瀛正科技有限公司 | Hexafluoropropylene-based quaternary ammonium salt cationic surfactant, synthesizing method and use |
| CN102389745A (en) * | 2011-08-15 | 2012-03-28 | 华中师范大学 | Preparation method of fluorine-containing double-type cationic surfactant and use thereof |
| RU2500705C1 (en) * | 2012-08-15 | 2013-12-10 | Борис Николаевич Максимов | Method of making ski wax |
| CN106146294A (en) * | 2015-04-08 | 2016-11-23 | 中化近代环保化工(西安)有限公司 | A kind of perfluoro methyl vinyl ether and the production method of intermediate thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109106608A (en) * | 2018-09-18 | 2019-01-01 | 中国日用化学研究院有限公司 | A kind of cleaning skin solid particle and the facial cleanser and preparation method thereof for preventing skin deposits solid particle |
| CN116103021A (en) * | 2021-11-10 | 2023-05-12 | 中石化石油工程技术服务有限公司 | Foaming agent for oil-based drilling fluid and preparation method and application thereof |
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Inventor after: Bai Yanyun Inventor after: Wang Wanxu Inventor after: Shen Jixian Inventor after: Wang Guoyong Inventor after: Ma Xiaoyuan Inventor after: Dan Shumei Inventor after: Liu Xiaoying Inventor before: Wang Wanxu Inventor before: Shen Jixian Inventor before: Wang Guoyong Inventor before: Bai Yanyun Inventor before: Ma Xiaoyuan Inventor before: Dan Shumei Inventor before: Liu Xiaoying |
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