CN103421169B - A kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre - Google Patents
A kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre, comprising: 1) with terephthalic acid, ethylene glycol, and other dibasic alcohol acrylic monomer are reaction raw materials, carry out esterification; 2) under polycondensation catalyst existence condition, further esterification and precondensation, finally under high negative pressure vacuum condition, carry out polycondensation, obtained low-molecular-weight polyester.The polyester product molecular weight that the present invention obtains is lower, and aggregated particle content is little, and the melt uniformity of polyester is high, the spinning property had, obtained conjugated fibre rigidity is low, loft high, and can be used for multicomponent fibre conjugate spinning, row yielding and performance also significantly improve.
Description
Technical field
The invention belongs to the preparation field of low-molecular-weight polyester, particularly a kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre.
Background technology
Polyester material can spinning filament or short silk as taking, and can carry out spinning by single-component, also can with high-viscosity polyester, the new polyester such as functional polyester and PTT, PBT carries out polycomponent spinning, obtainedly comprises two component or three component composite fibers.The multicomponent fibre having realized suitability for industrialized production is at present higher with bicomponent composite fibre output.Bicomponent composite fibre makes the performance of conjugated fibre be adjusted in a big way because of the different molecular structure of each component and physicals, thus has adapted to many-sided performance requriements.As the conjugated fibre of different shrinking percentage gained, because different superpolymer has certain contraction poor, this fibrid is made to have stable three-dimensional conjugate, its volume height is fluffy, elasticity number, and feel is soft, interfibrous coherent number during spinning, covering power is strong, and gloss makes moderate progress, and has certain woolly aspect; The core-skin fibre obtained with the plastic resin spinning of different melting points can be used for Low Temperature Thermal binder fibre; If a kind of in two kinds of polymkeric substance is the thermoplastic polymer of aromatic polyester or other rub resistances, then can improve the mechanical property of fiber; If two components have one for hydroaropic substance, then can improve the water-absorbent of fiber; If add various function reality in the cortex of core-skin conjugated fibre or sandwich layer, as UV resistance agent, temperature sensing color changing agent, conducting material etc., just various functional fibre can be obtained.
According to different components distribution situation in the fibre, parallel composite fiber can be divided into, core-sheath fiber and decentralized conjugated fibre (be referred to as again fabric of island-in-sea type or islands-in-sea bicomponent fibre, wherein a kind of component is dispersed in another component matrix with microfilament shape).Conjugated fibre can be used for manufacturing wool fabrics, silk type fabric, artificial suede, waterproof moisture permeating fabric, cleanness clothing and extraordinary filtering material etc.
According to the development of New-type composite fibre, current PTT(gathers terephthalic acid 1,3 propylene glycol esters) polyester dacron of and PET(Polyethylene Terephthalates-namely present) two-pack compound shin-gosen has very strong development potentiality.PTT and PET bicomponent composite fibre has the comfortable feel of polyamide fibre, the bulkiness of acrylic fibers, the rebound resilience of spandex, the high-strength of terylene and dimensional stability concurrently.The fabric of this fiber is well-pressed, good stability of the dimension, soft, rebound resilience good, anti-chlorine, anti-aging, have the special performances such as ptt fiber stain resistance is strong and dry and comfortable concurrently, deeply by consumers.Be suitable for through many downstream equipment processing such as compiling, spray water, be jet.Ptt fiber has the characteristic of terylene, polyamide fibre, acrylic fibers concurrently, except antifouling property well except, be easy to dyeing, soft, high resilience in addition, extensibility is equally good with spandex fibre, be easier to process compared with spandex fiber spandex, PTT also has the features such as dry and comfortable, well-pressed in addition, is very applicable to textile garment fabric; PTT be applicable to pure spin or with cellulosic fibre and natural fiber, synthon compound, produce carpet, plain clothes, fashionable dress, underwear, sweat shirt, swimsuit and socks etc., in the near future, ptt fiber probably becomes the trend of 21 century large fiber type by progressively substituting terylene and polyamide fibre.Current pure ptt fiber price is high, development need process.PTT and PET bicomponent composite fibre effectively reduces fabric cost, and fabric property haves both at the same time, and therefore, PTT and PET bicomponent composite fibre has larger development potentiality.Current PTT and PET bicomponent composite fibre proportional range is generally: PET accounts for 55%-60%, and PTT accounts for 40%-45%.Low-molecular-weight polyester PET and high molecular PTT is adopted to be that raw materials melt spinning obtains, obtained Bicomponent side-by-side type conjugated fibre.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre, the polyester product molecular weight that the method obtains is lower, aggregated particle content is little, the melt uniformity of polyester is high, the spinning property had, obtained conjugated fibre rigidity is low, loft high, and can be used for multicomponent fibre conjugate spinning, row yielding and performance also significantly improve.
The preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre of the present invention, comprising:
1) with following three kinds of components for reaction raw materials,
A: terephthalic acid;
B: ethylene glycol;
C: the monomer with two carboxyl reaction functional group except terephthalic acid, the monomer with two hydroxyl reaction functional group except ethylene glycol are reaction raw materials or the mixture both it;
Above-mentioned reaction raw materials is carried out esterification at 220 ~ 250 DEG C of temperature, esterification pressures 20 ~ 50kPa, react and be not less than 92% to esterification yield, reaction process removes the water of generation;
2) by the esterification products of above-mentioned reaction raw materials, under polycondensation catalyst existence condition, under the condition of-2 ~-10kpa, temperature of reaction is 250 ~ 260 DEG C and carries out further esterification and precondensation, 1.5 ~ 2.5 hours reaction times; Then under-0.1 ~-2KPa condition, polycondensation temperature is 260 ~ 290 DEG C, 2 ~ 3 hours reaction times, obtained low-molecular-weight polyester.
In described step 1), reaction raw materials molar ratio is (monomer of the two carboxyl reaction functional group of terephthalic acid+have): (monomer of the two hydroxyl reaction functional group of ethylene glycol+have)=1: 1.1 ~ 1.8.
The monomer with two carboxyl reaction functional group in described step 1) is selected from the mixture of one or more in m-phthalic acid, 1,6-hexanodioic acid, 1, 4-succinic acid etc.; The described monomer with two hydroxyl reaction functional group is selected from the mixture of one or more in 1,6-hexylene glycol, BDO, 1,3-PD, Isosorbide-5-Nitrae-cyclohexanediol, glycol ether, polyoxyethylene glycol (relative molecular weight 500-5000) etc.
In described step 1), the mol ratio of each reaction raw materials is terephthalic acid: monomer=1 with two carboxyl reaction functional group: 0 ~ 0.1; Ethylene glycol: the monomer with two hydroxyl reaction functional group is reaction raw materials=1: 0 ~ 0.1, the monomer with two carboxyl reaction functional group can not be 0 with the consumption of the monomer with two hydroxyl reaction functional group simultaneously.
Described step 2) in polycondensation catalyst be selected from one in antimony glycol, antimony acetate or antimonous oxide, the theoretical yield weight that the consumption of polycondensation catalyst obtains polyester based on polycondensation is benchmark, counts 180 ~ 300ppm/kg with antimony ion.
The number-average molecular weight Mn of described low-molecular-weight polyester is 16000-25000, weight-average molecular weight Mw be 31000-45000, molecular weight distribution PD is 1.85-1.95, and agglutination particle (>=10 μm) quantity is for being not more than 0.4/mg.
Key of the present invention is to add other dibasic alcohol acrylic monomer, and control esterification and polycondensation process, obtained low-molecular-weight polyester, the number-average molecular weight Mn of this low-molecular-weight polyester controls at 16000-25000, weight-average molecular weight Mw controls at 31000-45000, molecular weight distribution PD controls at 1.85-1.95, agglutination particle (>=10 μm) quantity controls be not more than 0.4/mg, its molecular weight is significantly reduced compared with normal polyester, control the content of aggregated particle, molecular weight distribution is suitable, is conducive to the spinning property of low-molecular-weight polyester.
This low-molecular-weight polyester can carry out polycomponent spinning with high-viscosity polyester, functional polyester and other other new polyesters such as such as PTT, PBT etc., the multicomponent fibre of obtained excellent performance.As spinning material, the various additives as other in above-mentioned polyester, can also being added as required, as matting agent, producing the stablizer of thermal destruction, the toning agent etc. of adjustment form and aspect for preventing polyester.
beneficial effect
Compared with prior art, the invention has the advantages that obtained polyester product molecular weight is lower, aggregated particle content is little, the melt uniformity of polyester is high, there is good spinning property, obtained conjugated fibre rigidity is low, loft high, and can be used for multicomponent fibre conjugate spinning, row yielding and performance also significantly improve; Meanwhile, preparation technology of the present invention is simple, and cost is low, can complete in general-purpose equipment, has good industrial applications prospect.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1 ~ 9
1) with terephthalic acid, ethylene glycol, the monomer with two carboxyl reaction functional group except terephthalic acid, and the monomer with two hydroxyl reaction functional group except ethylene glycol is reaction raw materials (proportioning raw materials is in table 1), esterification is carried out at 250 DEG C of temperature, esterification pressures 30kPa, reaction process removes the water of generation, when reacting esterification yield and reaching 95%, esterification completes;
2) esterification products intermediate is under polycondensation catalyst existence condition, and under the condition of-2KPa, temperature of reaction is 260 DEG C of polyester oligomers carrying out that further esterification and prepolymerization reaction obtain certain polymerization degree, and the reaction times is 2 hours; Then under-0.1KPa vacuum condition, polycondensation temperature is 280 DEG C, 2 hours reaction times, obtained low-molecular-weight polyester.
Comparative example 1 ~ 3
1. the reaction raw materials proportioning of comparative example 1 is in table 1, and other reaction process conditions are identical with embodiment 1 ~ 9.
2. the reaction raw materials proportioning of comparative example 2 is in table 1, polycondensating process: temperature of reaction 280 DEG C, and reaction pressure-0.1KPa, reaction times 2.5hr, other reaction process conditions are identical with embodiment 1 ~ 9.
3. the conventional bright PET chips that oil of SPC is produced taken from by the polyester of comparative example 3.
Table 1
* only adopt terephthalic acid, ethylene glycol in comparative example 1 ~ 2, do not add other dibasic alcohol acrylic monomer; Comparative example 3 directly takes from commercially available conventional bright PET chips.
Measure the molecular weight and molecualr weight distribution of embodiment and comparative example low-molecular-weight polyester, and other primary quality measure, data are in table 2.
Table 2
Although preferred embodiment discloses as above by the present invention; so itself and be not used to limit content of the present invention; anyly be familiar with this those skilled in the art; not departing from main spirits of the present invention and context; when doing various change and retouching, the protection domain therefore invented should be as the criterion with the basic right claimed range applied for a patent.
Claims (6)
1., for the manufacture of a preparation method for the low-molecular-weight polyester of multicomponent fibre, comprising:
1) with following three kinds of components for reaction raw materials,
A: terephthalic acid
B: ethylene glycol
C: the monomer with two carboxyl reaction functional group except terephthalic acid, the monomer with two hydroxyl reaction functional group except ethylene glycol are reaction raw materials or the mixture both it;
Above-mentioned reaction raw materials is carried out esterification at 220 ~ 250 DEG C of temperature, esterification pressures 20 ~ 50kPa, react and be not less than 92% to esterification yield, reaction process removes the water of generation;
2) by the esterification products of above-mentioned reaction raw materials, under polycondensation catalyst existence condition, under the condition of negative pressure 2 ~ 10kpa, temperature of reaction is 250 ~ 260 DEG C and carries out further esterification and precondensation, 1.5 ~ 2.5 hours reaction times; Then under-0.1 ~-2KPa condition, polycondensation temperature is 260 ~ 290 DEG C, 2 ~ 3 hours reaction times, obtained low-molecular-weight polyester; Wherein: the number-average molecular weight Mn of described low-molecular-weight polyester is 16000-25000, weight-average molecular weight Mw be 31000-45000, molecular weight distribution PD is 1.85-1.95, the agglutination particle quantity of particle diameter >=10 μm is for being not more than 0.4/mg.
2. the preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre according to claim 1, it is characterized in that: described step 1) in, reaction raw materials molar ratio is the monomer with two carboxyl reaction functional group: monomer=1 with two hydroxyl reaction functional group: 1.1 ~ 1.8.
3. the preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre according to claim 1, it is characterized in that: described step 1) in the monomer with two carboxyl reaction functional group except terephthalic acid be selected from m-phthalic acid, 1, the mixture of one or more in 6-hexanodioic acid, 1, 4-succinic acid.
4. the preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre according to claim 1, it is characterized in that: the described monomer with two hydroxyl reaction functional group except ethylene glycol is selected from 1,6-hexylene glycol, 1,4-butyleneglycol, 1, the mixture of one or more in ammediol, Isosorbide-5-Nitrae-cyclohexanediol, glycol ether, polyoxyethylene glycol.
5. the preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre according to claim 1, is characterized in that: described step 1) in the mol ratio of each reaction raw materials be terephthalic acid: monomer=1 with two carboxyl reaction functional group except terephthalic acid: 0 ~ 0.1; Ethylene glycol: the monomer with two hydroxyl reaction functional group except ethylene glycol is reaction raw materials=1: 0 ~ 0.1, the monomer with two carboxyl reaction functional group except terephthalic acid can not be 0 with the consumption with the monomer of two hydroxyl reaction functional group except ethylene glycol simultaneously.
6. the preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre according to claim 1, it is characterized in that: described step 2) in polycondensation catalyst be selected from one in antimony glycol, antimony acetate or antimonous oxide, the theoretical yield weight that the consumption of polycondensation catalyst obtains polyester based on polycondensation is benchmark, counts 180 ~ 300ppm/kg with antimony ion.
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| CN105566616B (en) * | 2014-10-15 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of application of copolyesters preparation method and gained copolyesters in 3D printing |
| CN106397746A (en) * | 2016-09-09 | 2017-02-15 | 珠海万通化工有限公司 | PBAT resin and preparation method thereof |
| CN109137137B (en) * | 2018-08-28 | 2019-10-18 | 上海海凯生物材料有限公司 | A kind of elastic composite fiber and its manufacturing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3427287A (en) * | 1961-08-30 | 1969-02-11 | Goodyear Tire & Rubber | Method for preparing polyester resins |
| KR20010061648A (en) * | 1999-12-28 | 2001-07-07 | 이구택 | Polyester copolymer having propylene in the main chain and preparing method thereof |
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| JPS601887B2 (en) * | 1979-07-12 | 1985-01-18 | 東洋紡績株式会社 | Manufacturing method of polyester low polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3427287A (en) * | 1961-08-30 | 1969-02-11 | Goodyear Tire & Rubber | Method for preparing polyester resins |
| KR20010061648A (en) * | 1999-12-28 | 2001-07-07 | 이구택 | Polyester copolymer having propylene in the main chain and preparing method thereof |
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