CN102731754A - Polyester polymerizing black stock solution dying method - Google Patents
Polyester polymerizing black stock solution dying method Download PDFInfo
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- CN102731754A CN102731754A CN201210227606XA CN201210227606A CN102731754A CN 102731754 A CN102731754 A CN 102731754A CN 201210227606X A CN201210227606X A CN 201210227606XA CN 201210227606 A CN201210227606 A CN 201210227606A CN 102731754 A CN102731754 A CN 102731754A
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- Prior art keywords
- polyester
- slurry
- carbon black
- kettle
- black
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- 229920000728 polyester Polymers 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000000379 polymerizing effect Effects 0.000 title abstract 3
- 239000011550 stock solution Substances 0.000 title abstract 2
- 239000006229 carbon black Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 238000004040 coloring Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 150000007942 carboxylates Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000011045 prefiltration Methods 0.000 claims description 6
- 238000005360 mashing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000010469 Glycine max Nutrition 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a polyester polymerizing black stock solution dying method. The method comprises the following steps: mixing purified terephthalic acid with glycol, and then feeding the mixture into an esterification kettle to carry out esterification; and adding carbon black slurry on a pipeline in front of a prepolymerization kettle, mixing the materials uniformly with a slurry disperser, filtering the product with a filter after prepolymerizing the materials in the prepolymerization kettle, and finally obtaining the black polyester after finally polymerizing the product in a final polymerization kettle, wherein the polyester product contains 1.5-2.0wt% of carbon black and 0.15-0.20wt% of dispersing agent. The method has the advantages of low production cost, good product quality, high blackness and good slurry mixing in the polyester polymerization process, and has good application prospects.
Description
Technical field
The invention belongs to the original liquid coloring field, particularly a kind of polyester black original liquid coloring method.
Background technology
Up to ten thousand tons/year of 60-70, polyester is deceived silk mainly from two kinds of technology to the consumption of the black silk of polyester at present in China, and the one, spinning solution painted (that is: Masterbatch method), ten thousand tons/year of 40-50; The 2nd, cone dyeing, ten thousand tons/year of 20-30.The former is owing to the carbon black particle difficulties in dispersion, and spinning property is poor, and the carbon black add-on is restricted, causes blackness not enough; The latter is then with high costs, and produces large amount of sewage.Polyester black original liquid coloring technology ties up in the production process of polyester and adds carbon black, i.e. adding carbon black under the state of " small molecules, LV ", and it all has much advantage on carbon black dispersion, carbon black add-on and production cost in theory.Polyester black original liquid coloring technology is through grinding, surface treatment, adding stablizer, joins a series of engineerings such as slurry, and carbon black and terepthaloyl moietie are made into the slurry of certain proportioning, injects polymerization reaction system then.Adopt carbon black to add technology, on the economic benefit, on the product performance and aspect each side such as environmental protection incomparable advantage is all arranged.
Carbon black pellet has very strong surfactivity, very easily reunite, and blackness is high more, and particle is more little, and it is more difficult to disperse.Because the single fiber cross section of fiber is all very little; What have only has tens microns; Therefore the original liquid coloring of carbon black on fiber is the most difficult field of the painted application of carbon black, also do not have sophisticated polyester black original liquid coloring technology so far in the world, more do not have the production line of mass-producing, serialization.At present whole world polyester output is up to 5,000 ten thousand tons/year, and wherein the consumption of black silk grows with each passing day, the successful development of polyester original liquid coloring technology, no matter on quality, on the cost, or environmental protection on all have meaning.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polyester black original liquid coloring method, and this method production cost is low, good product quality, blackness height, and the slurry good mixing has a good application prospect in the polyester process.
A kind of polyester black original liquid coloring method of the present invention comprises:
This paradigmatic system is three still technical process: pure terephthalic acid PTA and terepthaloyl moietie MEG are dropped into slurry tank, after stirring, send into esterifying kettle continuously through mashing pump and carry out esterification, the carboxylate of generation gets into prepolymerization kettle through the carboxylate pipeline; On the carboxylate pipeline, inject dispersion agent and carbon black slurry simultaneously, and behind slurry decollator thorough mixing, get into prepolymerization kettle with carboxylate, the carboxylate pipeline keeps 230-240 ℃, pressure 3.5-4.0Kg, and the carbon black concentration in the carbon black slurry is 10wt%; The prepolymer that prepolymerization kettle is come out filters through prefilter; Deliver to terminal polymerization kettle, further polymerization promptly obtains black polyester; Wherein, the sooty weight percent content in the polyester product is 1.5-2.0%, and the weight percent content of dispersion agent is 1.5-2.0 ‰.
Said slurry decollator comprises spreader plate, a 4-6 mixing section, paddle, baffle plate and rotating shaft; Separated by spreader plate between the mixing section, rotating shaft runs through through mixing section, is positioned in the inner rotating shaft of mixing section to be welded with paddle; Be provided with baffle plate around the paddle, spreader plate is provided with micropore.(as shown in Figure 2)
Crossing the filter core hole during said prefilter filters is 30 microns.
The cycle of said prefilter is 15-20 days.
Beneficial effect
Production cost of the present invention is low, good product quality, blackness height, and the slurry good mixing has a good application prospect in the polyester process.
Description of drawings
Fig. 1 is a technical matters schema of the present invention; Wherein, 1 is MEG, and 2 is PTA, and 3 for reclaiming terepthaloyl moietie, and 4 is the PTA slurry tank, and 5 is esterifying kettle, and 6 is water, and 7 is catalyzer, and 8 is the carbon black slurry, and 9 is prepolymerization kettle, and 10 is water, and 11 is terminal polymerization kettle, and 12 is strainer, and 13 is water, and 14 is polyester fondant, and 15 is the slurry decollator;
Fig. 2 is the synoptic diagram of slurry decollator; Wherein, 1 is material, and 2 is spreader plate, and 3 is mixing section, and 4 is paddle, and 5 is baffle plate, and 6 are rotating shaft.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Carbon black slurry the key technical indexes:
1. carbon content 10-20%
2. contain and disperse dosage 1-2%
3.D50 less than 0.5 micron, D99 is less than 3.0 microns
4. more than the vacuum filtration transmitance 1300-1500ml
5. leave standstill three months not stratified, do not precipitate
6. day output is 60 tons
Pure terephthalic acid and terepthaloyl moietie mixing back entering esterifying kettle are carried out esterification; Add dispersion agent and carbon black slurry (carbon black concentration 10wt%) on the carboxylate pipeline before prepolymerization kettle and in the slurry decollator, mix well; System pressure 3.5Kg, 230 ℃ of system temperatures get into the prepolymerization kettle pre-polymerization after strainer filters; Cycle is 20 days, in terminal polymerization kettle, gathers eventually at last to obtain polyester; Wherein, the carbon black weight percent content in the polyester product is 1.5%, and the weight percent content of dispersion agent is 1.5 ‰.
The slurry decollator comprises spreader plate, 6 mixing sections, paddle, baffle plate and rotating shafts; Separated by spreader plate between the mixing section, rotating shaft runs through through mixing section, is positioned in the inner rotating shaft of mixing section to be welded with paddle; Be provided with baffle plate around the paddle, spreader plate is provided with micropore.
Pure terephthalic acid and terepthaloyl moietie mixing back entering esterifying kettle are carried out esterification, add dispersion agent and carbon black slurry (carbon black concentration 10wt%) on the pipeline before prepolymerization kettle and in the slurry decollator, mix well system pressure 4.0Kg; 240 ℃ of system temperatures; Get into the prepolymerization kettle pre-polymerization after strainer filters, the cycle is 15 days, in terminal polymerization kettle, gathers eventually at last to obtain polyester wherein; Carbon black weight percent content in the polyester product is 2.0%, and the weight percent content of dispersion agent is 2.0 ‰.
The slurry decollator comprises spreader plate, 4 mixing sections, paddle, baffle plate and rotating shafts; Separated by spreader plate between the mixing section, rotating shaft runs through through mixing section, is positioned in the inner rotating shaft of mixing section to be welded with paddle; Be provided with baffle plate around the paddle, spreader plate is provided with micropore.
The comparison of the present invention and common half delustring production of polyester:
1. that common half delustring polyester adds is TiO
2-terepthaloyl moietie slurry, the TiO that adds in the polyester product
2Content is about 0.3%.And the present invention adds is carbon black-terepthaloyl moietie slurry, and the content of carbon black that adds in the polyester product is about 1.5-2.0%.
Because carbon black compares TiO
2Disperse difficulty to want big many, and content of carbon black is also than TiO
2Big several times of content, so the production difficulty improves greatly.
2. the present invention has increased custom-designed diverting device, to replace traditional static mixer, lets carbon black on micro-meter scale, distribute more evenly.
3. the kinematic viscosity owing to system's material behind the adding carbon black increases, and has added excessive terepthaloyl moietie, so processing condition of the present invention are also different, are mainly:
1. after adding from the carbon black slurry, the original high 1-2KG of the pressure ratio of system.
2. the temperature of prepolymerization kettle, terminal polymerization kettle and pipeline thereof improves 3-5 ℃.
3. the strainer cycle shortened to 15-20 days from original 30-40 days.
4. owing to added excessive terepthaloyl moietie, make that reclaiming terepthaloyl moietie increases, the virgin ethylene glycol add-on reduces, even is 0.
4. owing to added dispersion agent in the carbon black slurry, its content in polyester is 1-2 ‰, and the result shows that its post-treatment performance impact to polyester production process and polyester is little.
The comparison of the present invention and Masterbatch method:
1. the present invention ties up to and adds the carbon black slurry in the polyester process, promptly under the state of " low molecule, LV ", add slurry, and the Masterbatch method adds the Masterbatch melt at polyester fondant, and promptly the state in " polymer, HV " adds the Masterbatch melt down.Obviously, the former mixing homogeneity is necessarily good than the latter, like be soya-bean milk mix with soya-bean milk be bound to than glue mix with glue come evenly.
2. the present invention adopts custom-designed diverting device, have the function of micropore multi-stage diffluence mixing, and the Masterbatch rule is to mix through the spinning screw extrusion machine.
3. polyester carbon content of the present invention is 1.5%-2.0%, and the polyester carbon content of Masterbatch method is generally 0.9%, is up to 1.2%.Therefore the polyester product blackness of present technique is than high many of Masterbatch method.
4. can find out from the data of following table no matter the present invention all is superior to the Masterbatch method from production cost, quality product and supplies consumption each side.
Table 1 POY of the present invention and the Masterbatch method POY condition of production are relatively
| POY of the present invention | |
|
| 1. full-rolling rate | 94—96% | 88—92% |
| 2. waste silk rate | 0.8—1.0% | 1.2—1.5% |
| 3. |
15—20 | 10—15 |
The main quality index of table 2 POY of the present invention and Masterbatch method POY relatively
| POY of the present invention | |
|
| 1. breaking tenacity CN/dtex | 2.10—2.20 | 2.00—2.10 |
| 2. blackness | Contain charcoal 1.5-2.0% | Contain charcoal 0.9-1.2% |
Table 3 POY of the present invention and Masterbatch method POY and common half light POY production cost are relatively
Claims (4)
1. polyester black original liquid coloring method comprises:
Pure terephthalic acid and terepthaloyl moietie are dropped into slurry tank, after stirring, send into esterifying kettle continuously through mashing pump and carry out esterification, the carboxylate of generation gets into prepolymerization kettle through the carboxylate pipeline; On the carboxylate pipeline, inject dispersion agent and carbon black slurry simultaneously, and behind slurry decollator thorough mixing, get into prepolymerization kettle with carboxylate, the carboxylate pipeline keeps 230-240 ℃, pressure 3.5-4.0Kg, and the carbon black concentration in the carbon black slurry is 10wt%; The prepolymer that prepolymerization kettle is come out filters through prefilter; Deliver to terminal polymerization kettle, further polymerization promptly obtains black polyester; Wherein, the sooty weight percent content in the polyester product is 1.5-2.0%, and the weight percent content of dispersion agent is 1.5-2.0 ‰.
2. a kind of polyester black original liquid coloring method according to claim 1; It is characterized in that: said slurry decollator comprises spreader plate, a 4-6 mixing section, paddle, baffle plate and rotating shaft; Separated by spreader plate between the mixing section, rotating shaft runs through through mixing section, is positioned in the inner rotating shaft of mixing section to be welded with paddle; Be provided with baffle plate around the paddle, spreader plate is provided with micropore.
3. a kind of polyester black original liquid coloring method according to claim 1 is characterized in that: crossing the filter core hole during said prefilter filters is 30 microns.
4. a kind of polyester black original liquid coloring method according to claim 1, it is characterized in that: the cycle of said prefilter is 15-20 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227606XA CN102731754A (en) | 2012-06-29 | 2012-06-29 | Polyester polymerizing black stock solution dying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210227606XA CN102731754A (en) | 2012-06-29 | 2012-06-29 | Polyester polymerizing black stock solution dying method |
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| Publication Number | Publication Date |
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| CN102731754A true CN102731754A (en) | 2012-10-17 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031755A (en) * | 2012-12-28 | 2013-04-10 | 苏州世名科技股份有限公司 | Glycol-based pigment dispersoid for dacron stock solution coloring and preparation method of dispersoid |
| CN104499079A (en) * | 2014-11-27 | 2015-04-08 | 上海聚友化工有限公司 | Method for preparing black polyester fiber by dope dyeing |
| CN106008939A (en) * | 2016-07-28 | 2016-10-12 | 中国纺织科学研究院 | Black PET as well as preparation method and device thereof and black PET fiber as well as preparation method, device and application thereof |
| CN108867105A (en) * | 2018-06-13 | 2018-11-23 | 广东溢达纺织有限公司 | Special dark color terylene and its colouring method |
| CN111286804A (en) * | 2019-11-29 | 2020-06-16 | 浙江华欣新材料股份有限公司 | Preparation method of dope-dyed melt direct-spinning super-black polyester fiber |
| WO2023192067A1 (en) | 2022-03-28 | 2023-10-05 | Cabot Corporation | Dispersions of carbon black in alkylene glycol and in situ polymerization of polyester therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237656A (en) * | 1999-06-08 | 1999-12-08 | 张锡明 | Blending polyester profiled tangling yarn and its production method |
| CN2465790Y (en) * | 2001-01-16 | 2001-12-19 | 齐英翔 | Dynamic mixer |
| CN101735430A (en) * | 2009-12-29 | 2010-06-16 | 上海聚友化工有限公司 | Method for continuously preparing modified polyester |
-
2012
- 2012-06-29 CN CN201210227606XA patent/CN102731754A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237656A (en) * | 1999-06-08 | 1999-12-08 | 张锡明 | Blending polyester profiled tangling yarn and its production method |
| CN2465790Y (en) * | 2001-01-16 | 2001-12-19 | 齐英翔 | Dynamic mixer |
| CN101735430A (en) * | 2009-12-29 | 2010-06-16 | 上海聚友化工有限公司 | Method for continuously preparing modified polyester |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031755A (en) * | 2012-12-28 | 2013-04-10 | 苏州世名科技股份有限公司 | Glycol-based pigment dispersoid for dacron stock solution coloring and preparation method of dispersoid |
| CN103031755B (en) * | 2012-12-28 | 2014-12-03 | 苏州世名科技股份有限公司 | Glycol-based pigment dispersoid for dacron stock solution coloring and preparation method of dispersoid |
| CN104499079A (en) * | 2014-11-27 | 2015-04-08 | 上海聚友化工有限公司 | Method for preparing black polyester fiber by dope dyeing |
| CN104499079B (en) * | 2014-11-27 | 2016-05-25 | 上海聚友化工有限公司 | A kind of original liquid coloring is prepared the method for black polyester fiber |
| CN106008939A (en) * | 2016-07-28 | 2016-10-12 | 中国纺织科学研究院 | Black PET as well as preparation method and device thereof and black PET fiber as well as preparation method, device and application thereof |
| CN108867105A (en) * | 2018-06-13 | 2018-11-23 | 广东溢达纺织有限公司 | Special dark color terylene and its colouring method |
| CN111286804A (en) * | 2019-11-29 | 2020-06-16 | 浙江华欣新材料股份有限公司 | Preparation method of dope-dyed melt direct-spinning super-black polyester fiber |
| WO2023192067A1 (en) | 2022-03-28 | 2023-10-05 | Cabot Corporation | Dispersions of carbon black in alkylene glycol and in situ polymerization of polyester therewith |
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Application publication date: 20121017 |