CN102690410A - Method for producing modified polyester and fiber thereof - Google Patents
Method for producing modified polyester and fiber thereof Download PDFInfo
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- CN102690410A CN102690410A CN201210144113XA CN201210144113A CN102690410A CN 102690410 A CN102690410 A CN 102690410A CN 201210144113X A CN201210144113X A CN 201210144113XA CN 201210144113 A CN201210144113 A CN 201210144113A CN 102690410 A CN102690410 A CN 102690410A
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- poly ester
- modified poly
- tetramethylolmethane
- esterification
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Abstract
The invention relates to the technical field of polyester fibers. In order to solve the problem that the polyester fiber lacks a dyeing property and hydrophilicity because a hydrophilic group is absent in a polyester molecular chain, the invention discloses a method for producing a modified polyester and a fiber thereof. The method comprises adding pure terephthalic acid and ethylene glycol into a reactor, uniformly mixing and esterifying, adding a fiber modifier when esterification degree reaches 80-90% and stirring, and acquiring the modified polyester through condensation polymerization when the esterification is completed. The modified polyester fiber is acquired by spinning the modified polyester according to a conventional spinning method. The modified polyester fiber of the invention improves the hydrophilicity and the dyeing property of the polyester fiber, improves softness and has nice feel.
Description
Technical field
The present invention relates to the trevira technical field, relate in particular to the working method of a kind of modified poly ester and fiber thereof.
Background technology
Trevira is the most important components of synthon, because of its good physical and chemical performance is widely used in textile garment, and fields such as industrial silk.Trevira is to obtain polyethylene terephthalate by terephthalic acid and terepthaloyl moietie polymerization, passes through the fiber that melt-spinning and aftertreatment obtain then.Trevira has character such as HS, snappiness, heat-resisting, wear-resisting, fast light, smooth surface.Thereby but cause its dyeing behavior and hydrophilic deficiency owing to lack hydrophilic radical in the polyester molecule chain.
The hydrophilically modified method of traditional trevira mainly is that trevira and fabric are carried out surface treatment, and this method washing fastness and weathering resistance are all relatively poor, and its hydrophilic effect reduces gradually behind the life-time service.The tensio-active agent that when surface treatment, uses causes a large amount of pollutions to environment, and operation is many, and cost is high.So in the trevira production process, add the hydrophilic modifying material, can fundamentally improve its wetting ability and dyeability, not only reduced cost, again environmental protection more.
The Chinese patent publication number is the working method that CN1247240A discloses a kind of copolyester fiber, in its described copolyesters, contains to gather (C2-4 aklylene glycol) unit the tetramethylolmethane unit and the ethyloic phosphonic acids unit of trace.Its main purpose provide a kind of can with dispersed dye relatively easy carry out painted copolyester fiber, coloured fibre has quite high dyestuff ability to accept, in this method, tetramethylolmethane plays the effect of a branching agent.In the carboxylic esterification degree is 50%～95% o'clock adding tetramethylolmethane, to guarantee to generate long-chain branch.People such as Yu Muhuo adopt the solid state polymerization means with tetramethylolmethane as branching agent, prepared PET-PENTA copolyesters, improve its branched structure, obtained the unexistent characteristic of linear polymeric.But in above-described method, the hydroxyl of tetramethylolmethane fails to obtain to keep, and the wetting ability of trevira is not improved, and reason is that four hydroxyls of tetramethylolmethane all can be participated in reaction in the polyethylene terephthalate building-up process.And the introducing of tetramethylolmethane can only increase the degree of branching of polymkeric substance, and the increase of degree of branching makes the spinning property variation of fiber.
The Chinese patent publication number is that CN1803884A discloses a kind of annular aliphatic carbonate and its synthetic method of polymers; In its method, mention and earlier tetramethylolmethane and phenyl aldehyde being reacted; Two hydroxyl protections of tetramethylolmethane are got up, only keep two other hydroxyl.But this reaction needed concentrated hydrochloric acid and catalyzer, the separated product process is more complicated also.
Summary of the invention
Thereby cause its dyeing behavior and hydrophilic insufficient problem owing to lack hydrophilic radical in the polyester molecule chain in order to solve trevira; The present invention proposes the working method of a kind of modified poly ester and fiber thereof; Trevira after the modification has improved the wetting ability and the dyeability of trevira; And improved pliability, good hand touch.
The objective of the invention is to realize through following technical scheme: the working method of a kind of modified poly ester and fiber thereof is following steps:
(1) pure terephthalic acid and terepthaloyl moietie being added in the reaction kettle, after mixing, is 220～290 ℃ in temperature; Esterification takes place down in pressure 60～550kPa; Reaction 2～7h, wherein, the mol ratio of pure terephthalic acid and terepthaloyl moietie is 100:110～160;
(2) in the esterification of step (1), when Zhi Huadu is 80～90%, add stir behind the fibre modifier, after esterification accomplishes, polycondensation obtains modified poly ester, polycondensation high vacuum (20～100Pa), carry out under 270～290 ℃ of conditions of temperature.Wherein, the pure terephthalic acid's in fibre modifier and the step (1) mass ratio is 0.001～0.02:1; As preferably, fibre modifier and pure terephthalic acid's mass ratio is 0.005 ~ 0.02:1.Through a large amount of laboratories and production line experiment the adding opportunity and the add-on of fibre modifier have been carried out careful research; Finally find to be 80～90% at Zhi Huadu; When fibre modifier that adds and pure terephthalic acid's mass ratio were 0.01～0.02:1, resulting product performance were ideal.
(3) modified poly ester that step (2) is obtained obtains modified polyester fiber by conventional spinning processes spinning.As preferably, modified poly ester carries out melt-spinning under 290 ~ 300 ℃ of temperature, prepare corresponding modified polyester fiber.
As preferably, the present invention adopts five still production technique, comprises that two esterifying kettles, two prepolymerization reaction stills and a final minification gather reaction kettle.
Fibre modifier described in the step (2) has as follows the structural formula shown in (I):
The preparation method of fibre modifier is following steps: tetramethylolmethane is added in the diethylamine solvent stir, the mol ratio of tetramethylolmethane and diethylamine is 1:2, obtains fibre modifier behind reaction 1～2h down for 90～100 ℃ in temperature.Between diethylamine and tetramethylolmethane, generated hydrogen bond in the reaction; Key of the present invention is that four hydroxyls of tetramethylolmethane have and have only two and diethylamine formation hydrogen bond, because the space structure of tetramethylolmethane is an orthopyramid shape, four hydroxyls are distributed in four angles of orthopyramid respectively; So chemical reaction characteristic is identical; And after any two hydroxyls and diethylamine form hydrogen bond, produces sterically hindered, make two other hydroxyl extremely difficult with diethylamine formation hydrogen bond.
Reaction equation is following:
The present invention is in the production process of normal polyester and fiber thereof, through in esterification process, adding a spot of tetramethylolmethane properties-correcting agent raw material, according to the differentiation trevira of conventional melt-spun process preparation.The preparation process comprises that adding is that a kind of properties-correcting agent of feedstock production carries out copolyreaction with the tetramethylolmethane; This properties-correcting agent is to form hydrogen bond properties-correcting agent by tetramethylolmethane and diethylamine through certain reaction; Half oh group on the tetramethylolmethane is fallen in sealing, in the esterification process of polyester, adds this properties-correcting agent then, prepares modified poly ester by common process; According to conventional melt-spun process, feasible again and tetramethylolmethane hydroxyl bonded diethylamine removes the modified polyester fiber of preparation then.
Owing to add tetramethylolmethane properties-correcting agent, in final polymerisate, introduced hydroxyl, thereby improved the wetting ability and the dyeability of trevira, and improved pliability, good hand touch; Existing trevira production technology of adding tetramethylolmethane because four hydroxyl reaction activity of tetramethylolmethane are identical, very easily produces the branching phenomenon, makes the spinning property variation.Final polymerisate does not have hydroxyl, does not reach the effect of improving wetting ability and dyeability, compares with existing production technology, and the present invention can not produce the branching phenomenon, and the spinning property of trevira, wetting ability and dyeability etc. all are improved.The invention belongs to the micro-modification to trevira, production process is simple, utilizes synthetic and spinning production unit of existing polyester and technology to produce.
Compared with prior art, the invention has the beneficial effects as follows:
(1) modified polyester fiber of the present invention has improved pliability, good hand touch;
(2) differential fiber of the present invention can not produce the branching phenomenon, and the spinning property of modified polyester fiber, wetting ability and dyeability etc. all are improved;
(3) production process of the present invention is simple, utilizes the production unit and the technology of existing polyester to produce.
Embodiment
Below in conjunction with embodiment the present invention is done further explain, raw materials used all commercially available among the embodiment.
Embodiment 1
(1) preparation of differential fiber agent: the adding of 136g (1mol) tetramethylolmethane is equipped with in the reaction kettle of 146g (2mol) diethylamine solvent, stirs, react 1h down for 90 ℃, between diethylamine and tetramethylolmethane, generated hydrogen bond, obtain fibre modifier in temperature;
(2) 1660g (10mol) pure terephthalic acid and 868g (14mol) terepthaloyl moietie being added in the esterifying kettle, after mixing, is 230 ℃ in temperature; Esterification takes place down in pressure 300kPa; Reaction 2.5h in esterification, adds the fibre modifier of 1.7g step (1) preparation when Zhi Huadu is 80%; After esterification is accomplished under 40Pa, 280 ℃ of conditions of temperature polycondensation 3h obtain modified poly ester, product property viscosity 0.671.
(3) modified poly ester is carried out melt-spinning under 292 ℃ of temperature and obtain modified polyester fiber.
Modified polyester fiber carried out dyeing at normal pressure 1 hour with the grand carbuncle RD-GFL200 dyestuff of the good fortune of 2% weight ratio concentration under 90 ℃, K/S is 1.02 as a result, dye uptake 7.7%, and as a comparison, unmodified normal polyester fiber K/S value and dye uptake are about 0.
Embodiment 2
(1) preparation of differential fiber agent: the adding of 136g (1mol) tetramethylolmethane is equipped with in the reaction kettle of 146g (2mol) diethylamine solvent, stirs, react 1h down for 95 ℃, between diethylamine and tetramethylolmethane, generated hydrogen bond, obtain fibre modifier in temperature;
(2) 1660g (10mol) pure terephthalic acid and 744g (12mol) terepthaloyl moietie being added in the esterifying kettle, after mixing, is 230 ℃ in temperature; Esterification takes place down in pressure 300kPa; Reaction 2.5h in esterification, adds the fibre modifier of 1.7g step (1) preparation when Zhi Huadu is 85%; After esterification is accomplished under 60Pa, 283 ℃ of conditions of temperature polycondensation 3h obtain modified poly ester, product property viscosity 0.668.
(3) modified poly ester is carried out melt-spinning under 292 ℃ of temperature, obtain modified polyester fiber.
Differential fiber carried out dyeing at normal pressure 1 hour with the grand carbuncle RD-GFL200 dyestuff of the good fortune of 2% weight ratio concentration under 90 ℃, K/S is 1.07 as a result, dye uptake 7.8%, and as a comparison, unmodified normal polyester fiber K/S value and dye uptake are about 0.
Embodiment 3
(1) preparation of differential fiber agent: the adding of 136g (1mol) tetramethylolmethane is equipped with in the reaction kettle of 146g (2mol) diethylamine solvent, stirs, react 2h down for 100 ℃, between diethylamine and tetramethylolmethane, generated hydrogen bond, obtain fibre modifier in temperature;
(2) 1660g (10mol) pure terephthalic acid and 992g (16mol) terepthaloyl moietie being added in the esterifying kettle, after mixing, is 230 ℃ in temperature; Esterification takes place down in pressure 300kPa; Reaction 2.5h in esterification, adds the fibre modifier of 33g step (1) preparation when Zhi Huadu is 90%; After esterification is accomplished under 80Pa, 285 ℃ of conditions of temperature polycondensation 3.5h obtain modified poly ester, product property viscosity 0.639.
(3) modified poly ester is carried out melt-spinning under 292 ℃ of temperature, obtain modified polyester fiber.
Differential fiber carried out dyeing at normal pressure 1 hour with the grand carbuncle RD-GFL200 dyestuff of the good fortune of 2% weight ratio concentration under 90 ℃, K/S is 2.43 as a result, dye uptake 16.7%, and as a comparison, unmodified normal polyester fiber K/S value and dye uptake are about 0.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (3)
1. the working method of modified poly ester and fiber thereof is characterized in that the working method of modified poly ester and fiber thereof is following steps:
(1) pure terephthalic acid and terepthaloyl moietie being added in the reaction kettle, after mixing, is 220～290 ℃ in temperature; Esterification takes place down in pressure 60～550kPa; Reaction 2～7h, wherein, the mol ratio of pure terephthalic acid and terepthaloyl moietie is 100:110～160;
(2) in the esterification of step (1); Stirring behind the adding fibre modifier, esterification are accomplished aftercondensated and are obtained modified poly ester when Zhi Huadu is 80～90%; Wherein, the pure terephthalic acid's in fibre modifier and the step (1) mass ratio is 0.001～0.02:1;
(3) modified poly ester that step (2) is obtained obtains modified polyester fiber by conventional spinning processes spinning.
2. the working method of a kind of modified poly ester according to claim 1 and fiber thereof is characterized in that, the fibre modifier described in the step (2) has as follows the structural formula shown in (I):
3. the working method of a kind of modified poly ester according to claim 1 and 2 and fiber thereof; It is characterized in that; The preparation method of fibre modifier is following steps: tetramethylolmethane is added in the diethylamine solvent stir; The mol ratio of tetramethylolmethane and diethylamine is 1:2, obtains fibre modifier behind reaction 1～2h down for 90～100 ℃ in temperature.
Priority Applications (1)
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| CN 201210144113 CN102690410B (en) | 2012-05-11 | 2012-05-11 | Method for producing modified polyester and fiber thereof |
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| CN 201210144113 CN102690410B (en) | 2012-05-11 | 2012-05-11 | Method for producing modified polyester and fiber thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334174A (en) * | 2013-06-26 | 2013-10-02 | 浙江恒逸高新材料有限公司 | Preparation method and application of modified polyester stretch yarn with special-shaped section |
| CN106519202A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Micro-crystalline cellulose modified polyester preparation method |
| CN108048946A (en) * | 2018-01-28 | 2018-05-18 | 尚福平 | A kind of hydrophilic fire-retardant polyester fibre material and preparation method thereof |
| CN111484608A (en) * | 2020-03-16 | 2020-08-04 | 东华大学 | Preparation method capable of producing PBT resin stably for long period |
| CN113774661A (en) * | 2021-09-28 | 2021-12-10 | 浙江弘尚智能科技股份有限公司 | Polyamide fiber-imitated polyester fiber pantyhose |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247240A (en) * | 1998-09-10 | 2000-03-15 | 卢吉齐默尔股份公司 | Copolymer fiber |
| JP2005273059A (en) * | 2004-03-24 | 2005-10-06 | Toray Ind Inc | Hygroscopic polyester fiber and method for producing the same |
| JP2009084357A (en) * | 2007-09-28 | 2009-04-23 | Toray Ind Inc | Manufacturing method of modified polyester |
-
2012
- 2012-05-11 CN CN 201210144113 patent/CN102690410B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247240A (en) * | 1998-09-10 | 2000-03-15 | 卢吉齐默尔股份公司 | Copolymer fiber |
| JP2005273059A (en) * | 2004-03-24 | 2005-10-06 | Toray Ind Inc | Hygroscopic polyester fiber and method for producing the same |
| JP2009084357A (en) * | 2007-09-28 | 2009-04-23 | Toray Ind Inc | Manufacturing method of modified polyester |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334174A (en) * | 2013-06-26 | 2013-10-02 | 浙江恒逸高新材料有限公司 | Preparation method and application of modified polyester stretch yarn with special-shaped section |
| CN103334174B (en) * | 2013-06-26 | 2015-05-13 | 浙江恒逸高新材料有限公司 | Preparation method and application of modified polyester stretch yarn with special-shaped section |
| CN106519202A (en) * | 2016-10-27 | 2017-03-22 | 浙江恒逸高新材料有限公司 | Micro-crystalline cellulose modified polyester preparation method |
| CN106519202B (en) * | 2016-10-27 | 2018-07-17 | 浙江恒逸高新材料有限公司 | A kind of preparation method of microcrystalline cellulose modified poly ester |
| CN108048946A (en) * | 2018-01-28 | 2018-05-18 | 尚福平 | A kind of hydrophilic fire-retardant polyester fibre material and preparation method thereof |
| CN111484608A (en) * | 2020-03-16 | 2020-08-04 | 东华大学 | Preparation method capable of producing PBT resin stably for long period |
| CN111484608B (en) * | 2020-03-16 | 2021-08-06 | 东华大学 | Preparation method capable of producing PBT resin stably for long period |
| CN113774661A (en) * | 2021-09-28 | 2021-12-10 | 浙江弘尚智能科技股份有限公司 | Polyamide fiber-imitated polyester fiber pantyhose |
| CN113774661B (en) * | 2021-09-28 | 2023-04-25 | 浙江弘尚智能科技股份有限公司 | Polyester fiber panty hose of imitative polyamide fibre |
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| CN102690410B (en) | 2013-10-09 |
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