CN102660872B - Size mixture for sizing filament, and preparation method and application of size mixture - Google Patents
Size mixture for sizing filament, and preparation method and application of size mixture Download PDFInfo
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- CN102660872B CN102660872B CN201210135678.1A CN201210135678A CN102660872B CN 102660872 B CN102660872 B CN 102660872B CN 201210135678 A CN201210135678 A CN 201210135678A CN 102660872 B CN102660872 B CN 102660872B
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Abstract
The invention discloses a size mixture for sizing filament. The size mixture is characterized by comprising the following components in percentage by weight: 5 to 25 percent of water soluble polyester, and 75 to 95 percent of acrylic size, wherein the viscosity of the water soluble polyester is 0.35 to 0.6. The composite can be adhered to terylene well; the adhesion and the tensile property of the size are greatly improved; the permeability of the acrylic size can be improved, and the viscosity is reduced; and by matching the water soluble polyester and the acrylic size, the performance of the size can be improved. The sizing percentage is reduced, and cost is saved.
Description
Technical field
The invention belongs to textile sizing technical field, be specifically related to a kind of slurry mix for long filament starching, preparation method and application.
Background technology
Slurry divides two natural with synthetic classes.The former has starch, modified starch, algin etc.The latter uses carboxymethyl cellulose (CMC), polyvinyl alcohol, polyacrylate etc.Both also can be made into mixed slurry mutually.The slurry of current domestic long filament starching is mainly acrylic size, but general acrylic size film-strength is inadequate, is prone to lax.And aspect polyester filament starching, its adhesiveness, ABRASION RESISTANCE all have much room for improvement, consumption is excessive in addition easily causes sizing moisture absorption and sticks.The present invention therefore.
Summary of the invention
The object of the invention is to provide a kind of slurry mix for long filament starching, has solved in prior art aspect polyester filament starching slurry adhesiveness, ABRASION RESISTANCE is inadequate, needs consumption large, easily causes sizing moisture absorption and the problem such as glutinous.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
For a slurry mix for long filament starching, it is characterized in that described slurry mix counts with the percentage by weight of its component:
Water-soluble polyester 5～25%;
Acrylic size 75～95%.
Preferably, the binary acid that described water-soluble polyester is is 1.2～1.7 by molar ratio of alcohol to acid and dihydroxylic alcohols are controlled at and between 220-255 ℃, carry out esterification and ester exchange reaction accounting under the catalyst existence condition of all reactant quality 0.03% temperature, after reaction finishes, then be warmed up between 250-280 ℃, under reduced pressure, polycondensation prepares; Wherein in reactant, acid accounts for all sour molar percentages with its component and counts:
Terephthalic acid (TPA) or ester 60-80%;
M-phthalic acid or ester 10-25%;
Sodium Dimethyl Isophthalate-5-sulfonate 10-40%;
Other binary acid 0-5%;
Wherein in reactant, alcohol accounts for all sour molar percentages with its component and counts:
Ethylene glycol 80-90%;
Other dihydroxylic alcohols 10-20%.
Preferably, described other binary acid is selected from: malonic acid, adipic acid, azelaic acid, decanedioic acid, phthalic anhydride, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, maleic acid, Isosorbide-5-Nitrae-naphthalene diacid one or more any combination wherein.
Preferably, described other dihydroxylic alcohols is selected from: diethylene glycol (DEG), triethylene glycol, BDO, neopentyl glycol, 1,4-CHDM, hexylene glycol one or more any combination wherein.
Preferably, described catalyst is selected from: Zn, Mn, Mg, Ca, Co acetate, butyl titanate, isopropyl titanate, Triaethanolamine titanium, Dibutyltin oxide, antimonous oxide,, one or more any combination of antimony glycol.
Preferably, described acrylic size is to obtain by emulsion copolymerization with acrylic acid, methyl acrylate, acrylonitrile, acrylamide and methacrylic acid.
Preferably, the mass ratio of described acrylic acid, methyl acrylate, acrylonitrile, acrylic acid amides, methacrylic acid is 15:16:10:24:19; Described acrylic acid, methyl acrylate, acrylonitrile, acrylic acid amides, methacrylic acid prepare acrylic size by emulsion polymerization.
Preferably, wherein the viscosity of water-soluble polyester between 0.35～0.6.
The preparation method who another object of the present invention is to provide a kind of described slurry mix for long filament starching, is characterized in that said method comprising the steps of:
(1) binary acid that is 1.2～1.7 by molar ratio of alcohol to acid and dihydroxylic alcohols are controlled at and between 220-255 ℃, carry out esterification and ester exchange reaction accounting under the catalyst existence condition of all reactant quality 0.03% temperature, after reaction finishes, then be warmed up between 250-280 ℃, under reduced pressure, polycondensation prepares water-soluble polyester; Wherein in reactant, binary acid accounts for all sour molar percentages with its component and counts:
Terephthalic acid (TPA) or ester 60-80%;
M-phthalic acid or ester 10-25%;
Sodium Dimethyl Isophthalate-5-sulfonate 10-40%;
Other binary acid 0-5%;
Wherein in reactant, dihydroxylic alcohols accounts for all sour molar percentages with its component and counts:
Ethylene glycol 80-90%;
Other dihydroxylic alcohols 10-20%;
(2) water-soluble polyester and acrylic size are mixed and obtain the slurry mix for long filament starching by predetermined ratio.
Another object of the present invention is to provide the application of a kind of described slurry mix for long filament starching aspect polyester filament starching.
The structure of the water-soluble polyester that the present invention obtains is similar to polyster fibre thereby terylene is had to good adhesiveness, and viscosity and the surface tension of its aqueous solution are all very little, makes it in starching process, be easy to infiltration and makes long filament form boundling.After drying room is dried, polyester serous coat has moderate flexibility and lower hydroscopicity, the performances such as adhesive force, tensile force of serous coat are very significantly improved, and polyester destarch is easy.
This patent relates to a kind of slurry mix for polyester filament weaving.By using the collocation of water-soluble polyester and acrylic size to make for improving the result of use of slurry.
A slurry mix for long filament weaving, is comprised of water-soluble polyester and acrylic size, and wherein the weight content 5～25% of water-soluble polyester is, the weight content of acrylic size is 75～95%.Wherein water-soluble polyester is made by following methods:
1) will account for the M-phthalic acid of the 60-80% terephthalic acid (TPA) of all sour molar weights or ester, 10-25% or the acid of ester, the Sodium Dimethyl Isophthalate-5-sulfonate of 10-40% and other binary acid of 0-5% and account for the ethylene glycol of all alcohol molar weight 80-90%, other dihydroxylic alcohols of 10-20% and account for all catalyst that feed intake quality 0.03% and put in reactor and mix, wherein acid-alcohol ratio be 1.2～1.7;
2) temperature is raised between 220-255 ℃ and carries out esterification and ester exchange reaction, after reaction finishes, be then warmed up between 250-280 ℃, under reduced pressure, polycondensation is prepared and obtains.
Other binary acid of synthesizing water-solubility polyester is selected from: wherein one or more of malonic acid, adipic acid, azelaic acid, decanedioic acid, phthalic anhydride, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, maleic acid, Isosorbide-5-Nitrae-naphthalene diacid.Other dihydroxylic alcohols of synthesizing water-solubility polyester is selected from: wherein one or more of diethylene glycol (DEG), triethylene glycol, BDO, neopentyl glycol, 1,4-CHDM, hexylene glycol.Used catalyst is selected from: Zn, Mn, M g, Ca, Co acetate, butyl titanate, isopropyl titanate, Triaethanolamine titanium, Dibutyltin oxide, antimonous oxide,, antimony glycol one or more.The synthetic water-soluble polyester viscosity obtaining is between 0.35～0.6.
Described acrylic acid, methyl acrylate, acrylonitrile, acrylamide and methacrylic acid for acrylic size obtain by emulsion copolymerization; Concrete, acrylic size by take acrylic acid, methyl acrylate, acrylonitrile, acrylic acid amides, methacrylic acid in mass ratio example as: 15:16:10:24:19 is prepared and is obtained by the method for emulsion polymerisation.
The present invention obtains a kind of slurry mix for polyester filament weaving, by using the collocation of water-soluble polyester and acrylic size to make for improving the result of use of slurry.The present invention is for the slurry mix of long filament weaving, by water-soluble polyester and acrylic size, formed, wherein the weight content 5～25% of water-soluble polyester is, the weight content of acrylic size is 75～95%, can provide strong making up for the performance of acrylic size in polyester filament starching, improved the serviceability of slurry and can make reduced viscosity, the rate of sizing declines, cost-saving.
With respect to scheme of the prior art, advantage of the present invention is:
By the slurry that adopts said method to obtain, its advantage is: because water-soluble polyester grout structure is close with polyester filament, terylene is had to good adhesiveness, adhesive force and the tensile property of slurry are all greatly improved, can improve the permeability of acrylic size simultaneously, reduce viscosity, by the collocation of water-soluble polyester and acrylic size, use, can improve the performance of slurry.And the rate of sizing is declined, cost-saving.
The specific embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1
1, the preparation of water-soluble polyester:
By 95.8kg terephthalic acid (TPA), 12kg M-phthalic acid, 15.6kg Sodium Dimethyl Isophthalate-5-sulfonate, 8kg 1,4-cyclohexane cyclohexanedimethanodibasic, 40.1kg ethylene glycol, 16.6kg neopentyl glycol, 50g isopropyl titanate are put in reactor, with nitrogen replacement, discharge air, stir and heat up, reaction between 220-255 ℃.When accessory substance reaches after theoretical value, decompression polycondensation, reaction temperature is at 250-280 ℃, stops reaction after reaching terminal, is filled with nitrogen and eliminates vacuum, extruding and discharging.
2, acrylic size is synthetic:
Following monomer is mixed:
First emulsifier sodium lauryl sulfate (accounting for the 2-4% of monomer total amount) and water (monomer total amount 3.2 times) are joined in the reactor that reflux condenser is housed, stir.Then by the monomer mixing in advance and initator (initator is potassium peroxydisulfate, account for monomer total amount 0.06%) be added drop-wise in reactor, stir and maintain the temperature at reaction between 75～80 ℃, reaction 4h, more obtain acrylic size with ammonia neutralization;
3, the synthetic water-soluble polyester of the 1st step water-soluble polyester is joined in acrylic size, mix to mixed slurry, wherein the ratio of water-soluble polyester is 15%, acrylic size ratio is 85%.
Embodiment 2
1, the preparation of water-soluble polyester:
By 105kg terephthalic acid (TPA), 23kg M-phthalic acid, 13.2kg Sodium Dimethyl Isophthalate-5-sulfonate, 5kg adipic acid, 53kg ethylene glycol, 23.4kg1,4-butanediol, 46g Dibutyltin oxide and zinc acetate are put in reactor, with nitrogen replacement, discharge air, stir and heat up, reaction between 220-255 ℃.When accessory substance reaches after theoretical value, decompression polycondensation, reaction temperature is at 250-280 ℃, stops reaction after reaching terminal, is filled with nitrogen and eliminates vacuum, extruding and discharging.
2, acrylic size is synthetic:
Following monomer is mixed:
First emulsifier sodium lauryl sulfate (accounting for the 2-4% of monomer total amount) and water (monomer total amount 3.2 times) are joined in the reactor that reflux condenser is housed, stir.Then by the monomer mixing in advance and initator (potassium peroxydisulfate, account for monomer total amount 0.06%) be added drop-wise in reactor, stir and maintain the temperature at reaction between 75～80 ℃, reaction 4h, more obtain acrylic size with ammonia neutralization.
3, the synthetic water-soluble polyester of the 1st step water-soluble polyester is joined in acrylic size, mix to mixed slurry, wherein the ratio of water-soluble polyester is 20%, acrylic size ratio is 80%.
Embodiment 3
1, the preparation of water-soluble polyester:
By 95.8kg terephthalic acid (TPA), 12kg M-phthalic acid, 15.6kg Sodium Dimethyl Isophthalate-5-sulfonate, 8kg 1,4-cyclohexane cyclohexanedimethanodibasic, 40.1kg ethylene glycol, 16.6kg neopentyl glycol, 50g isopropyl titanate are put in reactor, with nitrogen replacement, discharge air, stir and heat up, reaction between 220-255 ℃.When accessory substance reaches after theoretical value, decompression polycondensation, reaction temperature is at 250-280 ℃, stops reaction after reaching terminal, is filled with nitrogen and eliminates vacuum, extruding and discharging.
2, acrylic size is synthetic:
Following monomer is mixed:
First emulsifier sodium lauryl sulfate (accounting for the 2-4% of monomer total amount) and water (monomer total amount 3.2 times) are joined in the reactor that reflux condenser is housed, stir.Then by the monomer mixing in advance and initator (potassium peroxydisulfate, account for monomer total amount 0.06%) be added drop-wise in reactor, stir and maintain the temperature at reaction between 75～80 ℃, reaction 4h, cooling, more obtain acrylic size with ammonia neutralization.
3, the synthetic water-soluble polyester of the 1st step water-soluble polyester is joined in acrylic size, mix to mixed slurry, wherein the ratio of water-soluble polyester is 25%, acrylic size ratio is 75%.
The performance comparison of embodiment 4 and domestic commercially available acrylic size
The present embodiment has been bought domestic commercially available acrylic size, and by invention slurry and domestic commercially available acrylic size by testing on polyester filament starching machine, detect its performance and contrast.It is below its slurry nature examination result.
The different slurry character contrasts of table 1
By table 1 data, show, slurry of the present invention is not changing under sizing technique condition, can obviously reduce the rate of sizing, under the prerequisite of guaranteed performance, can also reduce solid content, cost-saving.
2, sizing performance contrast:
Data by table 2 show, slurry of the present invention can largely improve the cohesive force of sizing, increase interaction force between yarn, improve ABRASION RESISTANCE, can also improve slashing strength, improve adhesive force, extensibility aspect also improves a lot simultaneously, and can keep a proper hydroscopicity, thereby size performance is improved greatly.
The performance test table of the different sizing of table 2
Above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that Spirit Essence is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (8)
1. for a slurry mix for long filament starching, it is characterized in that described slurry mix counts with the percentage by weight of its component:
Water-soluble polyester 5～25%;
Acrylic size 75～95%;
The binary acid that described water-soluble polyester is is 1.2～1.7 by molar ratio of alcohol to acid and dihydroxylic alcohols are controlled at and between 220-255 ℃, carry out esterification and ester exchange reaction accounting under the catalyst existence condition of all reactant quality 0.03% temperature, after reaction finishes, then be warmed up between 250-280 ℃, under reduced pressure, polycondensation prepares; Wherein in reactant, acid accounts for all sour molar percentages with its component and counts:
Wherein in reactant, alcohol accounts for all alcohol molar percentages with its component and counts:
Ethylene glycol 80-90%;
Other dihydroxylic alcohols 10-20%;
Described acrylic size is to obtain by emulsion copolymerization with acrylic acid, methyl acrylate, acrylonitrile, acrylamide and methacrylic acid.
2. the slurry mix for long filament starching according to claim 1, it is characterized in that described other binary acid is selected from: malonic acid, adipic acid, azelaic acid, decanedioic acid, phthalic anhydride, 1,4-cyclohexane cyclohexanedimethanodibasic, maleic acid, Isosorbide-5-Nitrae-naphthalene diacid one or more any combination wherein.
3. the slurry mix for long filament starching according to claim 1, it is characterized in that described other dihydroxylic alcohols is selected from: diethylene glycol (DEG), triethylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-CHDM, hexylene glycol one or more any combination wherein.
4. the slurry mix for long filament starching according to claim 1, is characterized in that described catalyst is selected from: any combination of one or more of Zn, Mn, Mg, Ca, Co acetate, butyl titanate, isopropyl titanate, Triaethanolamine titanium, Dibutyltin oxide, antimonous oxide, antimony glycol.
5. the slurry mix for long filament starching according to claim 1, the mass ratio that it is characterized in that described acrylic acid, methyl acrylate, acrylonitrile, acrylamide, methacrylic acid is 15:16:10:24:19; Described acrylic acid, methyl acrylate, acrylonitrile, acrylamide, methacrylic acid prepare acrylic size by emulsion polymerization.
6. the slurry mix for long filament starching according to claim 1, is characterized in that the viscosity of described water-soluble polyester is between 0.35～0.6.
7. a preparation method for the slurry mix for long filament starching described in claim 1～6 any one, is characterized in that said method comprising the steps of:
(1) binary acid that is 1.2～1.7 by molar ratio of alcohol to acid and dihydroxylic alcohols are controlled at and between 220-255 ℃, carry out esterification and ester exchange reaction accounting under the catalyst existence condition of all reactant quality 0.03% temperature, after reaction finishes, then be warmed up between 250-280 ℃, under reduced pressure, polycondensation prepares water-soluble polyester; Wherein in reactant, binary acid accounts for all sour molar percentages with its component and counts:
Wherein in reactant, dihydroxylic alcohols accounts for all alcohol molar percentages with its component and counts:
Ethylene glycol 80-90%;
Other dihydroxylic alcohols 10-20%;
(2) water-soluble polyester and acrylic size are mixed and obtain the slurry mix for long filament starching by predetermined ratio.
8. the application of the slurry mix for long filament starching described in claim 1～6 any one aspect polyester filament starching.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210135678.1A CN102660872B (en) | 2012-05-04 | 2012-05-04 | Size mixture for sizing filament, and preparation method and application of size mixture |
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| CN201210135678.1A CN102660872B (en) | 2012-05-04 | 2012-05-04 | Size mixture for sizing filament, and preparation method and application of size mixture |
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| CN102660872A CN102660872A (en) | 2012-09-12 |
| CN102660872B true CN102660872B (en) | 2014-04-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028582A (en) * | 1983-07-25 | 1985-02-13 | 互応化学工業株式会社 | Size composition |
| FR2722804B1 (en) * | 1994-07-22 | 1996-09-13 | Rhone Poulenc Chimie | LATEX COMPOSITION FOR SIZING THREADS OR TEXTILE FIBERS AND SIZING METHOD |
| CN101967225A (en) * | 2010-10-11 | 2011-02-09 | 苏州瀚海化学有限公司 | Method for preparing water-soluble sulfo-copolyester |
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