CN102336898A - Copolyester, its production method and application - Google Patents
Copolyester, its production method and application Download PDFInfo
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- CN102336898A CN102336898A CN2010102364930A CN201010236493A CN102336898A CN 102336898 A CN102336898 A CN 102336898A CN 2010102364930 A CN2010102364930 A CN 2010102364930A CN 201010236493 A CN201010236493 A CN 201010236493A CN 102336898 A CN102336898 A CN 102336898A
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Abstract
The invention discloses a copolyester, a production method and application thereof. The copolyester is produced by carrying out copolymerization on dihydric alcohol, diacid or esterified derivatives of diacid, silicon containing compound or/and fluorine compound, wherein, the content of the silicon containing compound or/and fluorine compound accounts for 0.2-30.0 wt% of the total amount of the copolyester. The invention has obvious advantages. According to the invention, the produced copolyester is hydrophobic, and has high performance and low cost, and can be produced into hydrophobic fabrics through spinning and deep processing.
Description
Technical field
The present invention relates to a kind of copolyesters and working method thereof and purposes.
Background technology
Polyester is having a wide range of applications aspect fiber, film, the plastics owing to its excellent performance.But because the restriction of polyester construction, in the occasion that polyester uses as fiber, the shortcoming of its water absorbability and water-repellancy has just manifested to come out, then this just greatly limitations the Application Areas of trevira.Like every plum rain season, people will feel that mood is not well, the waist heavy discomfort that also can become.This unhappy and discomfort are not only from airborne moisture, and it also is enough tedious being soaked with rain.Really, people can be kept off the rain with umbrella or raincoat, but can produce a contrary effect sometimes.If rain very heavily, will seep water in the raincoat, damp from head to foot, and airtight, the people is more felt bad.
In sporting world also is the same, and the water vapour permeability of sweat shirt is good more, and dress is just comfortable more, and this is self-evident.That is to say,, just require dress material to have water vapour permeability and water-repellancy, and the support water-repellancy is exactly a kind of character of a kind of being referred to as " hydrophobicity " for comfortable and easy to wear.Umbrella is waterproof, and this watertightness is hydrophobicity just.Is the hydrophobicity of why saying dress material a key issue? Clearly; When water attached to dress material on the time; If this dress material does not possess hydrophobicity, water droplet will not drop attached to the dress material surface always so, and party early is seeped into the dress material the inside; Also because water forms moisture film on dress material surface, for guaranteeing that the gap between the fiber that water vapour permeability keeps all stops up.If dress material has hydrophobicity, water just stays on the surface incessantly, also just can not cause the undesirable state of affairs.People once spent many time up and down in the water-repellancy and the water vapour permeability of dress material very early; But in order to process the more superior dress material of water vapour permeability; Not merely be that the requirement dress material is waterproof, and require to be bonded at the water droplet on surface, can keep minimal size and landing to get off as much as possible; That is to say, require it to have excellent hydrophobic property.
Find through patent retrieval, like number of patent application CN200810205055.0, inscribe one's name the preparation method into polymer hydrophobic surface, this article is mainly through prepared polymer dispersion liquid and hydrophobic silica dispersion liquid; Process hydrophobic coating after two kinds of dispersion liquids are mixed, finally be sprayed on the surface of various materials.Made finished product has higher hydrophobic performance in this method, but weak point its to use a large amount of organic solvents.
In addition, find in literature search, the article " Prepared by Sol Gel Method biomimetic super hydrophobic film " that Feng Zhou etc. delivered on " chemical journal " (2006 64 8 phases of volume), this article has the super-hydrophobicity film through sol-gel method with independently adorning to have prepared.Its weak point is that step is too in loaded down with trivial details.Therefore hydrophobicity problem how to improve polyester material has been carried.
Summary of the invention
The object of the present invention is to provide a kind of have good hydrophobic performance and the low copolyesters of cost.
Technical solution of the present invention is:
A kind of copolyesters, mainly by the esterified derivative of divalent alcohol, diprotic acid or diprotic acid, the silicon-containing compound shown in the formula 1 or/and the fluorochemicals copolymerization shown in the formula 2 form;
Formula 1:
Wherein n is 1～20 integer, and greater than 20, then the viscosity of organic silanol is too big, influences the manufacturing and the product performance of copolyesters as if n; M is 1 or 2, R
1～R
7For carbonatoms is 1～18 alkyl or aromatic base group (like methyl, phenyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-or the like), R ' is ester group, carboxamido-group or inferior carboxamido-group;
Formula 2:
Wherein x is 0～12 integer, and y is 3～20 integer, and z is 1 or 2, R " be ester group, carboxamido-group or inferior carboxamido-group.
The copolymerization units of formula 1 silicon-containing compound is or/and the copolymerization units weight of formula 2 fluorochemicalss accounts for 0.2～30wt% of copolyesters gross weight.The copolymerization units of formula 1 silicon-containing compound be or/and the weight of the copolymerization units of formula 2 fluorochemicalss when 0.2wt% is following, can not reach the invention effect of anticipation, measures when too much, then can influence the final performance of product.
Said silicon-containing compound is the compound that obtains by after monohydroxy ZGK 5 or monoamine based polysiloxane and ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride.
Said fluorochemicals is the compound that obtains by after monohydroxy fluorine alcohol or monoamine base fluorine amine and ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride.
Silicon-containing compound of the present invention is preferably by the product of monohydroxy ZGK 5 and ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride; Fluorochemicals is preferably by the product of monohydroxy fluorine alcohol with ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride.
Monohydroxy ZGK 5 wherein can be: monohydroxy silicone oil etc.; Monohydroxy fluorine alcohol can be: perfluoro octyl ethanol, perfluor heptyl ethanol, perfluor nonyl ethanol etc.; Three or four-functional group carboxylic acid and carboxylic acid anhydride thereof can have for example: pyromellitic acid anhydride, trimellitic anhydride, Pyromellitic Acid, trimesic acid etc.
The reaction product of preferred monohydroxy silicone oil of the present invention and pyromellitic acid anhydride; The reaction product of monohydroxy fluorine alcohol and pyromellitic acid anhydride.
The working method of copolyesters according to the invention comprises the following steps:
(1) reacts by monohydroxy ZGK 5 or monoamine based polysiloxane and ternary or quaternary carboxylic acid or its carboxylic acid anhydride, generate as shown in the formula 1 represented silicon-containing compound;
Formula 1:
Wherein n is 1～20 integer, and m is 1 or 2, R
1～R
7For carbonatoms is 1～18 alkyl or aromatic base group, R ' is ester group, carboxamido-group or inferior carboxamido-group;
(2) react by monohydroxy fluorine alcohol or monoamine base fluorine amine and ternary or quaternary carboxylic acid or its carboxylic acid anhydride, generate as shown in the formula the fluorochemicals shown in 2;
Formula 2:
Wherein x is 0～12 integer, and y is 3～20 integer, and z is 1 or 2, R " be ester group, carboxamido-group or inferior carboxamido-group.
(3) di-carboxylic acid or derivatives thereof and divalent alcohol are carried out precondensation as main raw material and obtain the small molecules polymkeric substance; Again the small molecules polymkeric substance is carried out polycondensation; Add silicon-containing compound that step (1) obtains or/and the fluorochemicals that step (2) obtains in prepolymerization reaction stage or polycondensation stage, thereby obtain copolyesters.
Raw material divalent alcohol in the copolyesters of the present invention can be aliphatic diol or aromatic diol, one or more in the terepthaloyl moietie of aliphatic, Ucar 35, the butyleneglycol.
Raw material di-carboxylic acid in the copolyesters of the present invention can be aliphatic dibasic acid or aromatic acid; Aliphatic dibasic acid can be that carbonatoms is 3 to 20 representative examples of saturated aliphatic diprotic acid, one or more of preferred propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid etc.; Aromatic acid can be terephthalic acid, m-phthalic acid, naphthalene diacid etc., and is at least a in preferred terephthalic acid and the m-phthalic acid.
The verivate of the raw material di-carboxylic acid among the present invention in the copolyesters can be the methyl esters, ethyl ester, propyl ester etc. of above-mentioned di-carboxylic acid, the methyl esters of preferred di-carboxylic acid.
Under the prerequisite that does not influence effect of the present invention, can also add polyfunctional copolymer compositions such as benzene tricarboxylic acid, benzene tetracarboxylic acid, USP Kosher, tetramethylolmethane.
Copolyesters of the present invention can use the common polymerization method of industry to produce, and promptly at first carries out direct esterification or transesterification reaction, obtain low-molecular-weight petchem after, further carry out polycondensation under the high temperature high vacuum and obtain polymkeric substance.Can add catalyzer in the transesterify stage, can be: contain the compound of sodium, lithium, magnesium, calcium, manganese, titanium, zinc, cobalt, tin etc., be preferably the acetate of these metallic compounds.
In high vacuum pyritous polycondensation phase, the metallic compound that can use titaniferous, antimony, germanium, cobalt, tin etc. is as catalyzer.
Among the present invention,, can also add various heat-resistant agents in order to improve the thermotolerance of polyester, phosphorus compound for example, the phosphorus compound that the present invention uses has no particular limits, and can be phosphoric acid, phosphorous acid, phosphonic acids or their lower alkyl esters and phenolic aldehyde ester.Specifically can be phosphoric acid, tricresyl phosphate methyl, tricresyl phosphate ethyl, tricresyl phosphate phenolic aldehyde, phosphorous acid, tricresyl phosphite methyl, methyl-phosphorous acid, phenolic aldehyde phosphonic acids, phenylbenzene phosphonic acids, methyl methylphosphonic acid, phenolic aldehyde phosphinic acid ethyl ester, phenylbenzene phosphonic acids phenolic aldehyde ester or phosphoryl ETHYLE ACETATE etc.
Silicon-containing compound according to the invention also can join in the reaction system in the step of reaction of polycondensation of polyester or/and fluorochemicals can join in the stage of direct esterification or transesterify in the reaction system of polyester.
Its intrinsicviscosity of the copolyesters that the present invention obtains is that 0.5dl/g is above for well, and it is interior for well to the scope of 1.2dl/g that the preferable range of copolyesters intrinsicviscosity is 0.6dl/g.
Do not influencing under the prerequisite scope of effect of the present invention; Can be in the polymkeric substance manufacturing or/and the spinning stage add various additives, for example: hindered phenol anti-oxidants, uvioresistant photo etching, the anti-photostabilizer of hindered amines, matting agent, inorganic particulate, nucleation reagent, skimmer, incombustible agent etc.
Promptly add silicon-containing compound or/and fluorochemicals can obtain the low hydrophobicity polyester of performance height and cost through technology disclosed by the invention.The present invention can make fiber and then form fabric through known method in addition, and the finished product that makes has the good hydrophobic performance.
Weigh the hydrophobicity of fabric among the present invention through the size of surface contact angle.Specific as follows: contact angle express liquid between 0 ° to 30 ° has good wetting property to solid surface, better drawout; Contact angle express liquid between 30 °～90 ° has certain wettability to solid surface, but is not fine, and when contact angle during greater than 90 °, liquid has not presented wettability to solid surface, promptly so-called hydrophobicity.
Embodiment
In order to further specify the advantage more than the present invention, will carry out detailed explanation from listed examples and comparative example below.Yet the present invention has more than and is limited to following embodiment.The measuring method of each item index in the embodiment of the invention is described below.
Surface contact angle:
(Thermo Co., USA), (surface tension of zero(ppm) water is 72.6 * 10-3N/m for the polyester piece good before and after the test processes and the contact angle of zero(ppm) water to use surface tension instrument (DCA322).)
Embodiment 1:
44 parts of (weight) addings of monohydroxy silicone oil are had in the reactor drum of stirring; In the nitrogen scope, be warmed up to gradually under 100 ℃～120 ℃ the condition, add the pyromellitic acid dianhydride of 5.5 parts (weight) gradually; Reaction under the nitrogen atmosphere agitation condition; After solution becomes clarification, keep reaction after 1 hour, cooling is placed subsequent use.Promptly generate the silicon-containing compound that is shown below, wherein n is 10, and m is 2, and R1～R7 is a methyl, and R ' is an ester group.
In having the device that stirs with rectifying tower, dropping into 130 kilograms of terephthalic acids carries out direct esterification with 56 kilograms terepthaloyl moietie and reacts; When the esterification rate is 95% when above; Finish esterification; Then reaction solution being divided a word with a hyphen at the end of a line to has in the reaction kettle of high-vacuum apparatus, and ready 1.0wt% silicon-containing compound (with respect to copolyesters weight) joins in the reaction system before, and the content of titanium elements is 5ppm with respect to the weight of polyester.Under atmospheric pressure be decompressed to about 300Pa through one hour then, temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, temperature in the kettle was 290 ℃, and resulting pressure is about 200Pa, reach the polymer viscosity of regulation after, the polymkeric substance that spues, pelletizing.The intrinsicviscosity of section is 0.67dl/g.
The section that obtains is according to the spinning technique of routine, and spinning is carried out in dry back under 280 ℃ of conditions, through obtaining the fiber of 48dtex/24f after extending, should extend the processing of silk high order, makes plain weave fabric.Surface contact angle test shows, this surface contact angle are 95 °.
Embodiment 2～embodiment 3:
The preparation method sees attached list 1 in detail with embodiment 1.
Embodiment 4:
44 parts of (weight) addings of perfluoro octyl ethanol are had in the reactor drum of stirring; In the nitrogen scope, be warmed up to gradually under 100 ℃～120 ℃ the condition, add the pyromellitic acid dianhydride of 10.3 parts (weight) gradually; Reaction under the nitrogen atmosphere agitation condition; After solution becomes clarification, keep reaction after 1 hour, cooling is placed subsequent use.Promptly generate the silicon-containing compound that is shown below, wherein y is 7, and x is 2, and z is 2, R " be ester group.
In having the device that stirs with rectifying tower, dropping into 130 kilograms of terephthalic acids carries out direct esterification with 56 kilograms terepthaloyl moietie and reacts; When the esterification rate is 95% when above; Finish esterification; Then reaction solution being divided a word with a hyphen at the end of a line to has in the reaction kettle of high-vacuum apparatus, and ready 1.0wt% fluorochemicals (with respect to copolyesters weight) joins in the reaction system before, and the content of titanium elements is 5ppm with respect to the weight of polyester.Under atmospheric pressure be decompressed to about 300Pa through one hour then, temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, temperature in the kettle was 290 ℃, and resulting pressure is about 200Pa, reach the polymer viscosity of regulation after, the polymkeric substance that spues, pelletizing.The intrinsicviscosity of section is 0.67dl/g.
The section that obtains is according to the spinning technique of routine, and spinning is carried out in dry back under 280 ℃ of conditions, through obtaining the fiber of 48dtex/24f after extending, should extend the processing of silk high order, makes plain weave fabric.Surface contact angle test shows, this surface contact angle are 101 °.
Embodiment 5～embodiment 6:
The preparation method sees attached list 1 in detail with embodiment 1.
Embodiment 7:
44 parts of (weight) addings of perfluor nonyl ethanol are had in the reactor drum of stirring; In the nitrogen scope, be warmed up to gradually under 100 ℃～120 ℃ the condition, add the pyromellitic acid dianhydride of 9.3 parts (weight) gradually; Reaction under the nitrogen atmosphere agitation condition; After solution becomes clarification, keep reaction after 1 hour, cooling is placed subsequent use.Promptly generate the silicon-containing compound that is shown below, wherein y is 8, and x is 2, and z is 2, R " be ester group.
In having the device that stirs with rectifying tower, dropping into 130 kilograms of terephthalic acids carries out direct esterification with 56 kilograms terepthaloyl moietie and reacts; When the esterification rate is 95% when above; Finish esterification; Then reaction solution being divided a word with a hyphen at the end of a line to has in the reaction kettle of high-vacuum apparatus, and ready 5.0wt% fluorochemicals (with respect to copolyesters weight) joins in the reaction system before, and the content of titanium elements is 5ppm with respect to the weight of polyester.Under atmospheric pressure be decompressed to about 300Pa through one hour then, temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, temperature in the kettle was 290 ℃, and resulting pressure is about 200Pa, reach the polymer viscosity of regulation after, the polymkeric substance that spues, pelletizing.The intrinsicviscosity of section is 0.67dl/g.
The section that obtains is according to the spinning technique of routine, and spinning is carried out in dry back under 280 ℃ of conditions, through obtaining the fiber of 48dtex/24f after extending, should extend the processing of silk high order, makes plain weave fabric.Surface contact angle test shows, this surface contact angle are 130 °.
Embodiment 8～embodiment 9:
Silicon-containing compound is with embodiment 1, and fluorochemicals is with embodiment 4, and other sees attached list 1 in detail with implementing 1.
Comparative example 1:
The ordinary polyester fabric is tested through surface contact angle, and this surface contact angle is 63 °.
Subordinate list 1:
Claims (6)
1. copolyesters is characterized in that: this copolyesters mainly by the esterified derivative of divalent alcohol, diprotic acid or diprotic acid, the silicon-containing compound shown in the formula 1 or/and the fluorochemicals copolymerization shown in the formula 2 form;
Formula 1:
Wherein n is 1～20 integer, and m is 1 or 2, R
1～R
7For carbonatoms is 1～18 alkyl or aromatic base, R ' is ester group, carboxamido-group or inferior carboxamido-group;
Formula 2:
Wherein x is 0～12 integer, and y is 3～20 integer, and z is 1 or 2, R " be ester group, carboxamido-group or inferior carboxamido-group.
2. copolyesters according to claim 1 is characterized in that: the copolymerization units of silicon-containing compound in this copolyesters is or/and the copolymerization units weight of fluorochemicals accounts for 0.2～30.0wt% of copolyesters gross weight.
3. copolyesters according to claim 1 and 2 is characterized in that: said silicon-containing compound is the compound that obtains by after monohydroxy ZGK 5 or monoamine based polysiloxane and ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride.
4. copolyesters according to claim 1 and 2 is characterized in that: said fluorochemicals is the compound that obtains by after monohydroxy fluorine alcohol or monoamine base fluorine amine and ternary or quaternary carboxylic acid or the reaction of its carboxylic acid anhydride.
5. the working method of the said copolyesters of claim 1 is characterized in that: comprise the following steps:
(1) reacts by monohydroxy ZGK 5 or monoamine based polysiloxane and ternary or quaternary carboxylic acid or its carboxylic acid anhydride, generate as shown in the formula 1 represented silicon-containing compound;
Formula 1:
Wherein n is 1～20 integer, and m is 1 or 2, R
1～R
7For carbonatoms is 1～18 alkyl or aromatic base, R ' is ester group, carboxamido-group or inferior carboxamido-group;
(2) react by monohydroxy fluorine alcohol or monoamine base fluorine amine and ternary or quaternary carboxylic acid or its carboxylic acid anhydride, generate as shown in the formula the fluorochemicals shown in 2;
Formula 2:
Wherein x is 0～12 integer, and y is 3～20 integer, and z is 1 or 2, R " be ester group, carboxamido-group or inferior carboxamido-group.
(3) di-carboxylic acid or derivatives thereof and divalent alcohol are carried out precondensation as main raw material and obtain the small molecules polymkeric substance; Again the small molecules polymkeric substance is carried out polycondensation; Add silicon-containing compound that step (1) obtains or/and the fluorochemicals that step (2) obtains in prepolymerization reaction stage or polycondensation stage, thereby obtain copolyesters.
6. the application of the said copolyesters of claim 1 in the preparation hydrophobic fibre.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010236493.0A CN102336898B (en) | 2010-07-16 | 2010-07-16 | Copolyester, its production method and application |
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| CN201010236493.0A CN102336898B (en) | 2010-07-16 | 2010-07-16 | Copolyester, its production method and application |
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| CN102336898A true CN102336898A (en) | 2012-02-01 |
| CN102336898B CN102336898B (en) | 2015-03-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526324A (en) * | 2013-10-14 | 2014-01-22 | 江苏恒力化纤股份有限公司 | High-strength low-elongation creep-resistant polyester industrial yarn and preparation method |
| CN105814111A (en) * | 2013-12-17 | 2016-07-27 | 威士伯采购公司 | Silicone-modified polyester coating |
| WO2019062428A1 (en) * | 2017-09-27 | 2019-04-04 | 南通星辰合成材料有限公司 | Polyester segmented copolymer and preparation method therefor and application thereof |
| CN111041591A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Modified polyester for labor protection fabric |
| CN113529281A (en) * | 2021-08-10 | 2021-10-22 | 山东大学 | Graphene/polysiloxane spinning fiber membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0510631A1 (en) * | 1991-04-24 | 1992-10-28 | Dow Corning Toray Silicone Company, Limited | Siloxane modified polyester for fibre treatment |
| CN101139434A (en) * | 2007-09-30 | 2008-03-12 | 大连理工大学 | Fluorinated polyesters with low surface energy and preparation method thereof |
| JP2009007685A (en) * | 2007-06-26 | 2009-01-15 | Teijin Fibers Ltd | Water-repellent polyester fiber and textile comprising the same |
-
2010
- 2010-07-16 CN CN201010236493.0A patent/CN102336898B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0510631A1 (en) * | 1991-04-24 | 1992-10-28 | Dow Corning Toray Silicone Company, Limited | Siloxane modified polyester for fibre treatment |
| JP2009007685A (en) * | 2007-06-26 | 2009-01-15 | Teijin Fibers Ltd | Water-repellent polyester fiber and textile comprising the same |
| CN101139434A (en) * | 2007-09-30 | 2008-03-12 | 大连理工大学 | Fluorinated polyesters with low surface energy and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526324A (en) * | 2013-10-14 | 2014-01-22 | 江苏恒力化纤股份有限公司 | High-strength low-elongation creep-resistant polyester industrial yarn and preparation method |
| CN103526324B (en) * | 2013-10-14 | 2015-06-17 | 江苏恒力化纤股份有限公司 | High-strength low-elongation creep-resistant polyester industrial yarn and preparation method |
| CN105814111A (en) * | 2013-12-17 | 2016-07-27 | 威士伯采购公司 | Silicone-modified polyester coating |
| US11104762B2 (en) | 2013-12-17 | 2021-08-31 | Valspar Sourcing, Inc. | Silicone-modified polyester coating |
| WO2019062428A1 (en) * | 2017-09-27 | 2019-04-04 | 南通星辰合成材料有限公司 | Polyester segmented copolymer and preparation method therefor and application thereof |
| CN111041591A (en) * | 2019-12-27 | 2020-04-21 | 刘大刚 | Modified polyester for labor protection fabric |
| CN113529281A (en) * | 2021-08-10 | 2021-10-22 | 山东大学 | Graphene/polysiloxane spinning fiber membrane and preparation method thereof |
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| CN102336898B (en) | 2015-03-25 |
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