CN1359962A - Process for preparing flame-retarding phosphorus copolymerized terylene chips - Google Patents
Process for preparing flame-retarding phosphorus copolymerized terylene chips Download PDFInfo
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- CN1359962A CN1359962A CN 02109909 CN02109909A CN1359962A CN 1359962 A CN1359962 A CN 1359962A CN 02109909 CN02109909 CN 02109909 CN 02109909 A CN02109909 A CN 02109909A CN 1359962 A CN1359962 A CN 1359962A
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Abstract
A flame-retarding copolymerized terylene chip is prepared on the basis of ordinary preparing process of terylene chip and is characterized by that after the esterifying step in the process to prepare polyester is finished, the flame-retarding agent, which is prepared from 2-carboxyethyl phenylphosphoric acid through dissolving it in ethylene glycol (EG), is added. Its advantages are high and durable flame-retarding effect, no toxicity and high spinnability.
Description
(1) technical field
The present invention relates to the preparation method of a kind of manufacture method of flame-resistant terylene, particularly a kind of flame-retarding phosphorus copolymerized terylene chips, belong to the terylene chemical technology field.
(2) background technology
Terylene flame-retardant modified has blending and modifying, two kinds of methods of modification by copolymerization.Blending and modifying is to add to add fire retardant system flame retardant polyester fiber in blending fire retardant agent system blending fire retardant terylene chips or the spinning process in the terylene manufacturing processed, blending method is because of fire retardant bad dispersibility in product, be difficult to and melt body mix, easily dissociate out during spinning, cause difficulty in spinning, influence the physicals of the flame retardant effect and the fiber of product; Modification by copolymerization is to add the compound contain two or more active function groups and to contain certain ignition-proof element to do fire-retardant monomer by copolymerization process production copolymerization flame-resistant terylene in the terylene manufacturing processed, the dacron product good spinnability that this method is produced, flame retardant effect is evenly lasting.Terylene flame-retardant modified with regard to the ignition-proof element that adopts, the original adoption halogen is as ignition-proof element, because halogen belongs to the gas phase fire retardant mechanism, has and is fuming greatly and easily produces halogen gas and the shortcoming of corrosion processing equipment, the basic at present phosphorus flame retardant that adopts.Phosphorous flame-retardant copolymerization terylene good stability, Halogen, nontoxic, flame retardant properties is stable lasting, is that bromine system, blend retardant polyester are incomparable.
The method of taking directly to add fire retardant can prepare flame-retarding phosphorus copolymerized terylene chips, adopt 2-propyloic benzenephosphonic acid to do the copolymerization fire retardant and produce the existing report of flame retardant polyester by direct esterification method route, its operational path is that fire retardant directly joins in the system, there is following shortcoming in this operational path: (1) fire retardant production technique causes fire retardant to contain chlorion inevitably, therefore corrode the section production unit, iron level height in the section, spinning property descends.(2) this production technique has higher requirements to fire retardant purity, otherwise can influence esterification speed.(3) fire retardant participates in esterification, because the fire retardant decomposition temperature is low, the restriction esterification temperature can not be high, otherwise can cause that fire retardant decomposes, and influences flame retardant effect.(4) remaining reducing substance in the fire retardant is reduced to antimony with The catalytic antimony trioxide, causes the hue difference of cutting into slices, even burnt hair.(5) simultaneously because fire retardant has been realized production domesticization, but because the practical situation of manufacturer, the fire retardant undried of buying, contain a large amount of moisture,, bring disadvantageous effect to actual production about 20%, how to use moisture fire retardant to produce high-quality fire-retardant slice and become new problem, solve the not problem that can use of drying of fire retardant simultaneously, also can reduce the fire retardant drying process, thereby reduce the fire retardant production cost.At above problem, the present invention adopts a kind of brand-new production technique, fire retardant 2-propyloic benzenephosphonic acid is at first carried out esterification with ethylene glycol (EG), distillation is purified, be mixed with ethylene glycol (EG) solution of fire retardant, finishing the back in the esterification of polyester manufacture process adds, prepare the flame-resistant terylene section by copolymerization process, effectively remove the chlorion in the reaction system, chipping qualities obviously improves, the section fusing point improves 10 ℃ to more than 250 ℃, iron ion content is reduced to 2ppm by 9ppm, and the section form and aspect improve, and the L value raises, the b value descends, and the section spinning property improves greatly.Simultaneously the fire retardant purity requirement is descended, can save the drying step that fire retardant is produced, the fire retardant cost is descended.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of new flame-retarding phosphorus copolymerized terylene chips is provided.
Method of the present invention comprises uses pure terephthalic acid, ethylene glycol, catalyzer, auxiliary agent to carry out flame-retarding phosphorus copolymerized dose of esterification, copolymerization employing, before the esterification post polymerization, join in the system, prepare the flame-resistant terylene section by copolymerization process, the content of control fire retardant add-on in section is 2～6wt%.Concrete grammar is as follows:
The fire retardant that the present invention adopts is a flame-retarding phosphorus copolymerized dose of 2-propyloic benzenephosphonic acid, and its molecular formula is:
Above-mentioned fire retardant can moisture 2～30wt%.
Above-mentioned fire retardant is made into ethylene glycol (EG) modulating liquid of fire retardant earlier, and its flame retardant agent content is 20～60wt% (weight percent, back is together).
The preparation of fire retardant modulating liquid: the ratio in flame retardant agent content 20～60wt% adds fire retardant 2-propyloic benzenephosphonic acid and ethylene glycol (EG), stirs, and is warming up to 140～160 ℃, and modulating liquid homogeneous phase after-filtration is standby.
Then, carry out esterification, polymerization.Concrete operations are as follows: with ethylene glycol (EG), pure terephthalic acid (PTA) is that 1.2～1.3 ratio joins the making beating of making beating still in molar ratio, catalyzer, auxiliary agent add by conventional production process of the prior art, enter esterifying kettle continuously after the making beating evenly, esterification under 250～260 ℃ of temperature, judge by the prior art aquifer yield and the end of esterification promptly to reach more than 95% of theoretical aquifer yield.
Carboxylate is pressed into polymeric kettle, is ethylene glycol (EG) solution that the ratio of 2～6wt% adds the fire retardant get ready in the content of fire retardant in section, stirs, and polymerization technique polymerization routinely, polymerization finish the back discharging, pelletizing gets the flame retardant polyester section.
The fire retardant 2-propyloic benzenephosphonic acid characteristic that the present invention adopts is as follows:
Appearance white or micro-yellow powder
Phosphorus content 14.5 ± 0.5%
Acid number 522.0 ± 4.0mgKOH/g
Fusing point 〉=152 ℃
Stability thermolysis initial temperature is 258 ℃
The present invention compared with prior art has following characteristics:
(1) used fire retardant is flame-retarding phosphorus copolymerized dose, good stability, Halogen, nontoxic, spinning process smoke-free and tasteless, clean environment.
(2) product is the copolymerization fire-retardant slice, and flame-retardant composition is combined on the polyester macromolecule chain with chemical bonded refractory, compares with the blend fire-retardant slice, and flame retardant effect is even and lasting.
(3) ethylene glycol (EG) solution of fire retardant through being modulated to fire retardant in advance adds before esterification finishes post polymerization, section fusing point height, and form and aspect are good, and reactor is not had corrosion.
(4) can be directly used in spinning phosphorus be permanent fire-retardant fibre to this flame retardant polyester, and good spinnability is fit to spin short silk, long filament, high-speed spinning.
(5) production equipment and other processing parameters are identical with conventional PET, easily produce and promote.
(4) embodiment
Embodiment 1: get 100kg EG and add the modulation jar, under agitation add 100kg fire retardant 2-propyloic benzenephosphonic acid, be warming up to 160 ℃ of ethylene glycol (EG) modulating liquids that get the 50wt% fire retardant.
Get 2000kg pure terephthalic acid (PTA), the making beating of 950kg ethylene glycol (EG) adding making beating still, enter esterifying kettle continuously after the making beating evenly, normal pressure esterification under 255 ℃ of temperature, esterification 440kg finishes, move into polymeric kettle, add the above-mentioned fire retardant modulating liquid of 190kg, in rough vacuum, 240～270 ℃ of following precondensation of temperature get terylene chips in high vacuum (90Pa), 283 ℃ of polymerizations of temperature.The section index sees Table one.
Comparative Examples 1: get 2000kg pure terephthalic acid (PTA), 950kg ethylene glycol, 95kg fire retardant 2-propyloic benzenephosphonic acid and directly add the making beating of making beating still, enter esterifying kettle continuously after the making beating evenly, normal pressure esterification under 255 ℃ of temperature, esterification water outlet 450kg finishes, move into polymeric kettle, in rough vacuum, 240～270 ℃ of following precondensation of temperature, at high vacuum (95Pa), 282 ℃ of polymerizations of temperature get terylene chips.The section index sees Table one.
Comparative Examples 2: get 125kg fire retardant 2-propyloic benzenephosphonic acid (moisture 20%), prepare fire-retardant slice according to the method for embodiment 1.The section index sees Table one.
Comparative Examples 3: get 119kg fire retardant 2-propyloic benzenephosphonic acid (moisture 20%), prepare fire-retardant slice according to the method for Comparative Examples 1.The section index sees Table one.
Table one, flame-resistant terylene microtomy index:
| Project | Unit | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| The section index | |||||
| Limiting viscosity [η] | dl/g | ?0.692 | ?0.694 | ?0.692 | ?0.690 |
| Fusing point Tm | ℃ | ?250-252 | ?242-244 | ?248-250 | ?239-241 |
| The end carboxyl contains | mol/t | ?32.8 | ?33.6 | ?33.0 | ?33.1 |
| Colourity b value | ?6.5 | ?8.1 | ?6.8 | ?8.0 | |
| DEG content | ％ | ?2.9 | ?3.5 | ?3.0 | ?3.7 |
| Aggregated particle | Individual/mg | ?0 | ?0 | ?0 | ?0 |
| Iron ion content | mg/mg | ?3 | ?8.5 | ?3 | ?9.0 |
| Limited oxygen index LOI | ％ | ?28.5 | ?28.5 | ?28.5 | ?28.0 |
By above embodiment and Comparative Examples as can be seen, the section fusing point height of method preparation of the present invention, form and aspect are good, and reactor is not had corrosion, can use moisture fire retardant.
Embodiment 2: get 100kg EG and add the modulation jar, under agitation add 133kg fire retardant 2-propyloic benzenephosphonic acid (moisture 25%), be warming up to 160 ℃ of ethylene glycol (EG) modulating liquids that get the 50wt% fire retardant.
Get 2000kg pure terephthalic acid (PTA), the making beating of 950kg ethylene glycol (EG) adding making beating still, enter esterifying kettle continuously after the making beating evenly, normal pressure esterification under 255 ℃ of temperature, esterification water outlet 440kg finishes, move into polymeric kettle, add the above-mentioned fire retardant modulating liquid of 190kg, in rough vacuum, 240～270 ℃ of following precondensation of temperature are at high vacuum (90Pa), 284 ℃ of polymeric terylene chips of temperature.
Embodiment 3: get 100kg EG and add the modulation jar, under agitation add 83kg fire retardant 2-propyloic benzenephosphonic acid (moisture 25%), be warming up to 160 ℃ of ethylene glycol (EG) modulating liquids that get the 40wt% fire retardant.
Get 2000kg pure terephthalic acid (PTA), the making beating of 950kg ethylene glycol (EG) adding making beating still, enter esterifying kettle continuously after the making beating evenly, normal pressure esterification under 260 ℃ of temperature, esterification water outlet 440kg finishes, move into polymeric kettle, add the above-mentioned fire retardant modulating liquid of 210kg, in rough vacuum, 240～270 ℃ of following precondensation of temperature get terylene chips in high vacuum (85Pa), 285 ℃ of polymerizations of temperature.
Claims (5)
1. the preparation method of a flame-retarding phosphorus copolymerized terylene chips, comprise and use pure terephthalic acid, ethylene glycol, catalyzer, auxiliary agent to carry out esterification, copolymerization, the invention is characterized in, adding phosphorus before esterification finishes post polymerization is reactive flame retardant 2-propyloic benzenephosphonic acid, and the content of fire retardant add-on in section is 2～6wt% weight percent.
2. the preparation method of flame-retarding phosphorus copolymerized terylene chips as claimed in claim 1 is characterized in that described fire retardant is modulated into the ethylene glycol solution of fire retardant earlier before adding the pet reaction system, and wherein flame retardant agent content is 20～60wt% weight percent.
3. the preparation method of flame-retarding phosphorus copolymerized terylene chips as claimed in claim 1 is characterized in that the moisture 2～30wt% weight percent of described fire retardant.
4. the preparation method of flame-retarding phosphorus copolymerized terylene chips as claimed in claim 1 or 2, it is characterized in that the preparation of described fire retardant modulating liquid: in flame retardant agent content 20～-ratio of 60wt% adds fire retardant 2-propyloic benzenephosphonic acid and ethylene glycol, stir, be warming up to 140～160 ℃, modulating liquid homogeneous phase after-filtration.
5. the preparation method of flame-retarding phosphorus copolymerized terylene chips as claimed in claim 1 or 2, it is characterized in that described esterification, the concrete operations of copolymerization are: with ethylene glycol, the pure terephthalic acid is that 1.2～1.3 ratio joins the making beating of making beating still in molar ratio, add conventional catalyst and auxiliary agent, enter esterifying kettle continuously after the making beating evenly, esterification under 250～260 ℃ of temperature, carboxylate is pressed into polymeric kettle, in the content of fire retardant in section is the ethylene glycol solution of the ratio adding fire retardant of 2～6wt%, stir, polymerization, polymerization finishes the back discharging, pelletizing gets the flame retardant polyester section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB02109909XA CN1167726C (en) | 2002-01-09 | 2002-01-09 | Process for preparing flame-retarding phosphorus copolymerized terylene chips |
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| CNB02109909XA CN1167726C (en) | 2002-01-09 | 2002-01-09 | Process for preparing flame-retarding phosphorus copolymerized terylene chips |
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| CN1359962A true CN1359962A (en) | 2002-07-24 |
| CN1167726C CN1167726C (en) | 2004-09-22 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101020744B (en) * | 2007-03-19 | 2010-04-14 | 四川大学 | Nanometer composite polyester material and its double in-situ preparation process |
| CN101148498B (en) * | 2007-10-18 | 2010-08-18 | 四川大学 | Degradable anti-flaming copolyester, preparation method thereof and mixing material prepared from the same and aliphatic polyester |
| CN101153422B (en) * | 2006-09-29 | 2010-12-08 | 东丽纤维研究所（中国）有限公司 | Flame-proof polyester superfine fibre pile fabric |
| CN101362821B (en) * | 2008-09-26 | 2011-04-20 | 江苏中鲈科技发展股份有限公司 | PTT polyester chip and method for preparing antistatic PTT polyester fibres |
| CN101200535B (en) * | 2006-12-13 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Flame retardant cationic dyeable polyesters and preparation method |
| CN101333287B (en) * | 2007-06-29 | 2011-11-30 | 厦门翔鹭化纤股份有限公司 | Method for preparing fire retardant co-polymerization modified polyester |
| CN101568673B (en) * | 2006-12-21 | 2012-05-09 | 可隆株式会社 | Method of preparing flame-retardant polyester fiber and flame-retardant polyester fiber |
| CN102605499A (en) * | 2011-12-21 | 2012-07-25 | 浙江四通化纤有限公司 | Environmentally friendly flame-retardant polyester bulk deformation yarn and preparation method thereof |
| CN113122955A (en) * | 2019-12-31 | 2021-07-16 | 太仓市泽记新材料有限公司 | Polyester yarn with flame retardant property and preparation process thereof |
| WO2023124145A1 (en) | 2021-12-31 | 2023-07-06 | 江苏新视界先进功能纤维创新中心有限公司 | Method for preparing cationic dyeable flame-retardant high-strength polyester fiber |
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2002
- 2002-01-09 CN CNB02109909XA patent/CN1167726C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153422B (en) * | 2006-09-29 | 2010-12-08 | 东丽纤维研究所（中国）有限公司 | Flame-proof polyester superfine fibre pile fabric |
| CN101200535B (en) * | 2006-12-13 | 2011-11-23 | 东丽纤维研究所（中国）有限公司 | Flame retardant cationic dyeable polyesters and preparation method |
| US8388879B2 (en) | 2006-12-21 | 2013-03-05 | Kolon Industries, Inc. | Method of preparing flame-retardant polyester fiber and flame-retardant polyester fiber |
| CN101568673B (en) * | 2006-12-21 | 2012-05-09 | 可隆株式会社 | Method of preparing flame-retardant polyester fiber and flame-retardant polyester fiber |
| US9150689B2 (en) | 2006-12-21 | 2015-10-06 | Kolon Industries, Inc. | Method of preparing flame-retardant polyester fiber and flame-retardant polyester fiber |
| CN101020744B (en) * | 2007-03-19 | 2010-04-14 | 四川大学 | Nanometer composite polyester material and its double in-situ preparation process |
| CN101333287B (en) * | 2007-06-29 | 2011-11-30 | 厦门翔鹭化纤股份有限公司 | Method for preparing fire retardant co-polymerization modified polyester |
| CN101148498B (en) * | 2007-10-18 | 2010-08-18 | 四川大学 | Degradable anti-flaming copolyester, preparation method thereof and mixing material prepared from the same and aliphatic polyester |
| CN101362821B (en) * | 2008-09-26 | 2011-04-20 | 江苏中鲈科技发展股份有限公司 | PTT polyester chip and method for preparing antistatic PTT polyester fibres |
| CN102605499B (en) * | 2011-12-21 | 2015-07-08 | 浙江四通化纤有限公司 | Environmentally friendly flame-retardant polyester bulk deformation yarn and preparation method thereof |
| CN102605499A (en) * | 2011-12-21 | 2012-07-25 | 浙江四通化纤有限公司 | Environmentally friendly flame-retardant polyester bulk deformation yarn and preparation method thereof |
| CN113122955A (en) * | 2019-12-31 | 2021-07-16 | 太仓市泽记新材料有限公司 | Polyester yarn with flame retardant property and preparation process thereof |
| WO2023124145A1 (en) | 2021-12-31 | 2023-07-06 | 江苏新视界先进功能纤维创新中心有限公司 | Method for preparing cationic dyeable flame-retardant high-strength polyester fiber |
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