CN1880357A - Normal atmosphere cation-dyeable flame-proof copolyester slice and its production method - Google Patents
Normal atmosphere cation-dyeable flame-proof copolyester slice and its production method Download PDFInfo
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- CN1880357A CN1880357A CN 200510043752 CN200510043752A CN1880357A CN 1880357 A CN1880357 A CN 1880357A CN 200510043752 CN200510043752 CN 200510043752 CN 200510043752 A CN200510043752 A CN 200510043752A CN 1880357 A CN1880357 A CN 1880357A
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Abstract
This invention discloses a flame-proof copolyester slicer that can be colored by a normal pressure positive ion dye and method for making same, comprising: terephthalic acid and ethandiol as basic raw material, semi-continuous direct esterification is applied for production; add in reactive m-phthalic acid and composite stabilizer of phosphonium flame retardant and sulphonic acid metal salt at esterification or condensation stage, and produce the modified copolyester by random and block copolymerization. The finished product of this invention is characterized of long and superior fire-retardancy performance, high thermal stability, and good weaving property. The fabric produced by this product can be boiling dyed using positive ion at normal pressure, with high dying fastness, bright color, and full color spectrum.
Description
Technical field
The invention belongs to the terylene chemical technology field, particularly relate to a kind of flame-proof copolyester slice and manufacture method of normal atmosphere cation-dyeable.
Background technology
Along with the raising of people's fire-fighting consciousness, become increasingly active to the research and the application and development of flame retardant polyester and fiber in countries in the world, and various flame retardant polyesters and fiber product constantly come out.The method for modifying flame of polyester has two kinds of blend and copolymerization, copolymerization method is to add the compound contain two or more active function groups and to contain certain ignition-proof element to do the method for fire-retardant monomer by the synthetic flame-retardant modified polyester of copolymerization in polyester production process, compare with blending method, stable owing to its product flame retardant properties, lasting and good spinnability becomes present polyester flame-retardant main methods of modification and means.
The fire retardant that is used for the polyester flame-retardant modification mainly is halogen-containing and the phosphorated fire retardant, because halogen belongs to the gas phase fire retardant mechanism, have and be fuming greatly and easily produce halogen gas and the shortcoming of corrosion processing equipment, substantially all adopt phosphonium flame retardant at present, but existing phosphor-containing flame-retardant copolyester generally all exists thermal characteristics or poor mechanical property, deficiencies such as spinning crystallization difficulty, therefore further the high performance flame retardant polyester of research and development is very important.
In addition, the fire-retardant polyester fibre fabric is used for the bunting of automobile, curtain etc. mostly, to its color style, colour fastness (especially light fastness) require high, but because the polyester molecule chain structure is tight, polarity is less, can only adopt dispersed dye to dye, fugitive color, thus limited the application of flame-retardant modified polyester.
Adopt ester-interchange method to produce the existing report of method of fire-retardant-cationic polyester staple fibre, but this method unit consumption is big, cost is high, and the transesterification reaction by-product carbinol is bigger to human body harm, to fire-fighting and safety requirements height.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of flame-proof copolyester slice and manufacture method of normal atmosphere cation-dyeable are provided, make that this copolyester section not only has lastingly, good flame retardant property, and thermostability height, good spinnability, fabric by its manufacturing can be used the cationic dyestuff boiling dyeing at normal pressure, the dyefastness height, bright in luster, chromatogram is complete.
The technical solution adopted for the present invention to solve the technical problems is: a kind of flame-proof copolyester slice of normal atmosphere cation-dyeable comprises following component and weight part:
Terephthalic acid 30～100
Ethylene glycol 30～100
The m-phthalic acid composition 2.0～10.5 that contains the metal organic sulfonate base
Response type phosphonium flame retardant 3.5～20
One package stabilizer 0.1～1.0
Catalyzer 0.001～0.05.
Described copolyester section, its limiting viscosity are 0.55～0.65, and fusing point is 230～250 ℃.
Described response type phosphonium flame retardant is the compound with following formula:
HOOPR1-R2COOH
R1 is alkyl or C6 and above aryl or benzyl thereof, and R2 is open chain or the cyclic alkyl of C1～C15.
Above-mentioned fire retardant need be mixed with the ethylene glycol modulating liquid of fire retardant earlier, and its flame retardant agent content is 20-60% (weight ratio, down together).
Described one package stabilizer is at least two kinds a compound ligand in Triphenyl phosphate, organic quaternary ammonium salt, antioxidant and the sodium-acetate, and not only form and aspect are good to adopt the copolyesters that this stablizer produces, and the thermostability height, good spinnability.
Compound 5-metal organic sulfonate base-dimethyl isophthalate (hereinafter referred to as SIPE) that the m-phthalic acid composition that contains the metal organic sulfonate base that uses in the present invention adopts ethylene glycol and SIPM to carry out transesterify, metal among the SIPE, can use sodium, potassium, lithium etc., but sodium most preferably.
After introducing contains the m-phthalic acid composition of metal organic sulfonate base in the dye accessible flame-proof copolyester of above-mentioned atmospheric cation of the present invention, metal ion wherein easily and the positively charged ion in the cationic dyestuff exchange, dyestuff just is fixed on the polyester molecule with ionic linkage, thereby has improved the dyestuff dye uptake and the colour fastness of trevira.
A kind of manufacture method of flame-proof copolyester slice of normal atmosphere cation-dyeable, it is to be basic raw material with terephthalic acid, ethylene glycol, adopt semicontinuous direct esterification method to produce, add the response type phosphonium flame retardant in esterification or polycondensation phase, contain the m-phthalic acid composition and the one package stabilizer of metal organic sulfonate base, the modified copolyester of making through random and block copolymerization.
A kind of manufacture method of flame-proof copolyester slice of normal atmosphere cation-dyeable, it comprises the steps:
A. terephthalic acid, ethylene glycol, compound stablizer are mixed with slurry uniformly by above-mentioned recipe ratio;
B. above-mentioned slurry is continuously added esterifying kettle with certain flow, 240～260 ℃ of esterification temperatures, esterification 2～4 hours;
C. before esterification end or polycondensation, add phosphonium flame retardant respectively, contain the m-phthalic acid composition and the catalyzer of metal organic sulfonate base;
D. polycondensation 30min under normal pressure;
E. polycondensation 0.5～3 hour under rough vacuum, 250～270 ℃ of temperature;
F. carry out the condition of high vacuum degree polycondensation again, the vacuum tightness absolute pressure is controlled at below the 100pa in the still, and temperature is controlled at 270～285 ℃, and the time is 1～3 hour, after copolyesters viscosity reaches requirement, and the beginning discharging.
The manufacture method of the dye accessible flame-proof copolyester slice of above-mentioned atmospheric cation is to adopt the method for making polyester of semicontinuous direct esterification, described semicontinuous direct esterification working system, be with terephthalic acid, ethylene glycol is the method for making polyester of basic raw material, when a collection of esterification finished to move material before characteristics were, in esterifying kettle, stay the esterifying liquid of part heat, continuously add in esterifying kettle with certain flow terephthalic acid and the ethylene glycol slurry for preparing then, reaction is carried out under higher esterification yield always, compare with periodical operation, because the solubleness of terephthalic acid in esterifying liquid is much larger than the solubleness in ethylene glycol, speed of response is accelerated greatly, has improved quality product.
The dye accessible flame-proof copolyester slice of above-mentioned atmospheric cation of the present invention is pressed GB 5454 tests, and its limiting oxygen index(LOI) LOI value is 27.5%; This copolyester section is made fiber and the grey cloth of 150D/48f under certain spinning condition, detect by GB/T 5455-1997 vertical combustion method through national cotton textile quality supervision and test center, the result is 0 for warp-wise and broadwise after flame time, the time of glowing is 0, char length is respectively 126mm and 144mm, has reached the B1 level requirement that fire-retardant woven fabrics is used as furnishing fabric.
The invention has the beneficial effects as follows, owing to adopted terephthalic acid, ethylene glycol, the m-phthalic acid composition that contains the metal organic sulfonate base, the response type phosphonium flame retardant, one package stabilizer, catalyzer constitutes the dye accessible flame-proof copolyester slice of atmospheric cation, with terephthalic acid, ethylene glycol is basic raw material, adopt semicontinuous direct esterification method to produce, add the response type phosphonium flame retardant in esterification or polycondensation phase, the m-phthalic acid composition and the one package stabilizer that contain the metal organic sulfonate base, through random and block copolymerization and make modified copolyester, after the copolyester section that makes is thus made trevira, has good cationic dye capable of dyeing, its dyeing temperature is at 98 ℃, normal pressure can boil and dye dark color, and it is bright-colored, chromatogram is complete, and the rerum natura and the light fastness of gained fiber are good.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail; But the flame-proof copolyester slice and the manufacture method of a kind of normal atmosphere cation-dyeable of the present invention are not limited to embodiment.Any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done following examples all still belong in the scope of technical solution of the present invention.
Embodiment one, the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable of the present invention and manufacture method, be in the making beating still, 1.10 to be made into slurry after the metering of terephthalic acid and ethylene glycol with being in molar ratio, add 0.1% weight (relative terephthalic acid, one package stabilizer down together) stirs, make slurry continuous then, add equably in the esterifying kettle that leaves preceding a collection of half amount esterifying liquid and carry out esterification, keep 240～260 ℃ of esterification temperatures, (calculation formula: in the time of the esterification water yield (kg)=terephthalic acid inlet amount (kg) * 0.217), esterification is finished to treat to reach calculated value by esterification water quantity of distillate.
The carboxylate of half is moved in the preshrunk still, phosphonium flame retardant and 3% the SIPE (metal wherein is a sodium) and the antimonous oxide that is dissolved in ethylene glycol that accounts for polymer weight 0.03% of adding 12%, be warming up to 250～270 ℃ gradually behind the normal pressure polycondensation 30min, and progressively decompression, in 0.5～3 hour, absolute pressure is reduced to 1Kpa, polymkeric substance moved into continue to be decompressed to below the absolute pressure 100pa in the final minification still, and be warming up to 270～285 ℃ gradually, when final minification still beater motor power reaches in-line viscometer numerical value on 5A and the self-circulation pipeline and reaches 3.5, reaction is reached home, the beginning discharging obtains the copolyester section that table 1 is put down in writing.
Embodiment two, and the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable of the present invention and manufacture method add 8% phosphonium flame retardant and 5% SIPE, carry out the polyreaction identical with embodiment one, obtain the copolyester section of table 1 record.
Embodiment three, and the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable of the present invention and manufacture method add 4% phosphonium flame retardant and 10% SIPE, carry out the polyreaction identical with embodiment one, obtain the copolyester section of table 1 record.
Embodiment four, the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable of the present invention and manufacture method, finish the phosphonium flame retardant of back in esterification from esterifying kettle adding 8%, further esterification 30min, esterification temperature is controlled at 230～255 ℃, enters the preshrunk still afterwards, adds 5% SIPE, carry out the polyreaction identical, obtain the copolyester section of table 1 record with embodiment one.
Following table has provided every performance index of four groups of embodiment copolyester sections that carry out under the different condition; Wherein the fire retardant of embodiment two adds from the preshrunk still, and the fire retardant of embodiment four adds from esterifying kettle.
Four groups of embodiment copolyester section performance index of carrying out under table 1 different condition
| Embodiment | 1 | 2 | 3 | 4 |
| The phosphonium flame retardant consumption, % | 12 | 8 | 4 | 8 |
| The SIPE consumption, % | 3 | 5 | 10 | 5 |
| Limiting viscosity (dl/g) | 0.601 | 0.585 | 0.582 | 0.597 |
| Glycol ether content (w.t%) | 3.3 | 3.2 | 3.5 | 3.8 |
| Content of carboxyl end group (mol/t) | 27.6 | 29.1 | 25.3 | 28.4 |
| Fusing point (℃) | 240.75 | 238.18 | 235.71 | 237.54 |
| Colourity b value | 9.8 | 7.25 | 8.5 | 7.74 |
| Colourity L value | 66.2 | 64.8 | 65.4 | 65.7 |
| Thermal weight loss (%) | 1.92 | 2.24 | 2.32 | 2.30 |
| Spinning operation | Good | Well | Generally | Well |
| LOI, % (section ester bar) | 28.9 | 27.5 | 27.0 | 28.1 |
| Fiber light fastness (8 grades of systems) | 5 | 6 | 6 | 6 |
Claims (6)
1. the flame-proof copolyester slice of a normal atmosphere cation-dyeable, it is characterized in that: it comprises following component and weight part:
Terephthalic acid 30～100
Ethylene glycol 30～100
The m-phthalic acid composition 2.0～10.5 that contains the metal organic sulfonate base
Response type phosphonium flame retardant 3.5～20
One package stabilizer 0.1～1.0
Catalyzer 0.001～0.05.
2. the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable according to claim 1, it is characterized in that: described copolyester section, its limiting viscosity are 0.55～0.65, fusing point is 230～250 ℃.
3. the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable according to claim 1, it is characterized in that: described response type phosphonium flame retardant is the compound with following formula:
HOOPR1-R2COOH
R1 is alkyl or C6 and above aryl or benzyl thereof, and R2 is open chain or the cyclic alkyl of C1～C15.
4. the flame-proof copolyester slice of a kind of normal atmosphere cation-dyeable according to claim 1 is characterized in that: described one package stabilizer is at least two kinds a compound ligand in Triphenyl phosphate, organic quaternary ammonium salt, antioxidant and the sodium-acetate.
5. the manufacture method of the flame-proof copolyester slice of a normal atmosphere cation-dyeable, it is characterized in that: it is to be basic raw material with terephthalic acid, ethylene glycol, adopt semicontinuous direct esterification method to produce, add the response type phosphonium flame retardant in esterification or polycondensation phase, contain the m-phthalic acid composition and the one package stabilizer of metal organic sulfonate base, make modified copolyester through random and block copolymerization.
6. the manufacture method of the flame-proof copolyester slice of a normal atmosphere cation-dyeable, it is characterized in that: it comprises the steps:
A. terephthalic acid, ethylene glycol, compound stablizer are mixed with slurry uniformly by above-mentioned recipe ratio;
B. above-mentioned slurry is continuously added esterifying kettle with certain flow, 240～260 ℃ of esterification temperatures, esterification 2～4 hours;
C. before esterification end or polycondensation, add phosphonium flame retardant respectively, contain the m-phthalic acid composition and the catalyzer of metal organic sulfonate base;
D. polycondensation 30min under normal pressure;
E. polycondensation 0.5～3 hour under rough vacuum, 250～270 ℃ of temperature;
F. carry out the condition of high vacuum degree polycondensation again, the vacuum tightness absolute pressure is controlled at below the 100pa in the still, and temperature is controlled at 270～285 ℃, and the time is 1～3 hour, after copolyesters viscosity reaches requirement, and the beginning discharging.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100437527A CN100556932C (en) | 2005-06-16 | 2005-06-16 | A kind of flame-proof copolyester slice of normal atmosphere cation-dyeable and manufacture method |
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| CNB2005100437527A CN100556932C (en) | 2005-06-16 | 2005-06-16 | A kind of flame-proof copolyester slice of normal atmosphere cation-dyeable and manufacture method |
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| CN1880357A true CN1880357A (en) | 2006-12-20 |
| CN100556932C CN100556932C (en) | 2009-11-04 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008085852A1 (en) * | 2007-01-10 | 2008-07-17 | Eastman Chemical Company | Use of copolymerizable sulfonate salts to promote char formation in polyesters and copolyesters |
| CN102352027A (en) * | 2011-08-08 | 2012-02-15 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN102677298A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Spinning cloth |
| CN108166094A (en) * | 2017-12-28 | 2018-06-15 | 宁波三同编织有限公司 | A kind of easily dye, flame retardant cationic polyester fiber fabric and preparation method thereof |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN108624010A (en) * | 2018-06-07 | 2018-10-09 | 广东轻工职业技术学院 | A kind of electrostatically dissipative high grade of transparency polyester and preparation method thereof |
| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye dyeable polyester fiber based on autocatalysis |
-
2005
- 2005-06-16 CN CNB2005100437527A patent/CN100556932C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008085852A1 (en) * | 2007-01-10 | 2008-07-17 | Eastman Chemical Company | Use of copolymerizable sulfonate salts to promote char formation in polyesters and copolyesters |
| CN102352027A (en) * | 2011-08-08 | 2012-02-15 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN102352027B (en) * | 2011-08-08 | 2013-02-06 | 张大省 | Cationic dye dyeable polyester and superfine fibers thereof |
| CN102677298A (en) * | 2012-05-29 | 2012-09-19 | 蔡紫林 | Spinning cloth |
| CN108166094A (en) * | 2017-12-28 | 2018-06-15 | 宁波三同编织有限公司 | A kind of easily dye, flame retardant cationic polyester fiber fabric and preparation method thereof |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN108624010A (en) * | 2018-06-07 | 2018-10-09 | 广东轻工职业技术学院 | A kind of electrostatically dissipative high grade of transparency polyester and preparation method thereof |
| CN115821418A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye dyeable polyester fiber based on autocatalysis |
| CN115821418B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for preparing high-sulfonate-content antibacterial flame-retardant cationic dye-dyeable polyester fiber based on autocatalysis |
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| CN100556932C (en) | 2009-11-04 |
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Effective date of registration: 20090626 Address after: Fujian Haicang investment zone of Xiamen City, Ma Qing Road, No. 1268 post encoding: 361026 Applicant after: Xiamen Xiang Lu chemical fiber Limited by Share Ltd Co-applicant after: Dragon Special Resin (Xiamen) Co., Ltd. Address before: Fujian Haicang investment zone of Xiamen City, Ma Qing Road, No. 1268 post encoding: 361026 Applicant before: Xianglu Chemical Fibre Co., Ltd., Xiamen City |
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Assignee: Dragon Special Resin (Xiamen) Co., Ltd. Assignor: Xianglu Chemical Fibre Co., Ltd., Xiamen City|Dragon Special Resin (Xiamen) Co., Ltd. Contract fulfillment period: 2009.9.25 to 2014.9.25 contract change Contract record no.: 2009351000074 Denomination of invention: Normal atmosphere cation-dyeable flame-proof copolyester slice and its production method Granted publication date: 20091104 License type: Exclusive license Record date: 2009.11.2 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.25 TO 2014.9.25; CHANGE OF CONTRACT Name of requester: TENGLONG SPECIAL RESIN (XIAMEN) CO., LTD. Effective date: 20091102 |