CN103421169A - Preparation method for low molecular weight polyester used for manufacturing multi-component fiber - Google Patents
Preparation method for low molecular weight polyester used for manufacturing multi-component fiber Download PDFInfo
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- CN103421169A CN103421169A CN2013102943689A CN201310294368A CN103421169A CN 103421169 A CN103421169 A CN 103421169A CN 2013102943689 A CN2013102943689 A CN 2013102943689A CN 201310294368 A CN201310294368 A CN 201310294368A CN 103421169 A CN103421169 A CN 103421169A
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Abstract
The invention relates to a preparation method for low molecular weight polyester used for manufacturing multi-component fiber, which comprises the following steps: 1) conducting esterification reaction with reaction raw materials of terephthalic acid, ethylene-glycol and monomers of other dihydric alcohol acids; 2) further esterizing and pre-polycondensation under the condition that polycondensation catalyst is existed, and finally conducting polycondensation reaction under the condition of high negative pressure and vacuum to manufacture low molecular weight polyester. A polyester product manufactured by the invention has lower molecular weight, small content of condensation particles, and high uniformity in melt of polyester, has the characteristics of good spinnability, low rigidity in the manufactured composition fiber, high filling power, and the like, and can be used for composite spinning of the multi-component fiber; and as a result, the finished product rate and the performance are obviously improved.
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
But polyester material, as taking spinning filament or short silk, can carry out spinning by single-component, also can with high-viscosity polyester, the new polyesters such as functional polyester and PTT, PBT carry out the polycomponent spinning, make and comprise two components or three component composite fibers.At present realized that the multicomponent fibre of suitability for industrialized production is 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, thereby has adapted to many-sided performance requriements.Conjugated fibre as different shrinking percentage gained, because different superpolymer have certain contraction poor, make this fibrid there is 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 the 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, can improve the mechanical property of fiber; If two components have one for hydroaropic substance, can improve the water-absorbent of fiber; If add various function reality in the cortex of core-skin conjugated fibre or sandwich layer, as anti-ultraviolet agent, temperature sensing color changing agent, conducting material etc., just can make various functional fibres.
Distribution situation according to different components in fiber, can be divided into parallel composite fiber, 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 the 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 poly-terephthalic acid 1,3 propylene glycol ester of PTT() and the PET(Polyethylene Terephthalates-be present polyester dacron) the compound shin-gosen of two-pack has very strong development potentiality.PTT and PET bicomponent composite fibre have the comfortable feel of polyamide fibre, the bulkiness of acrylic fibers, the rebound resilience of spandex, the high-strength and dimensional stability of terylene 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 the ptt fiber stain resistance is strong and dry and comfortable concurrently, favored by the human consumer.Be suitable for through volume, water spray, many downstream equipment processing such as jet.Ptt fiber has the characteristic of terylene, polyamide fibre, acrylic fibers concurrently, except antifouling property well, be easy in addition dyeing, soft, high resilience, extensibility is equally good with spandex fibre, compare with the spandex fiber spandex and be easier to processing, PTT also has the characteristics such as dry and comfortable, well-pressed in addition, is applicable to very much textile garment fabric; PTT is applicable to pure spin or compound with cellulosic fibre and natural fiber, synthon, produce carpet, plain clothes, fashionable dress, underwear, sweat shirt, swimsuit and socks etc., in the near future, ptt fiber probably will progressively substitute terylene and polyamide fibre and become the trend of large fiber type of 21 century.Current pure ptt fiber price is high, process of development need.PTT and PET bicomponent composite fibre effectively reduce fabric cost, and fabric property haves both at the same time, and therefore, PTT and PET bicomponent composite fibre have larger development potentiality.PTT and PET bicomponent composite fibre proportional range are generally at present: PET accounts for 55%-60%, and PTT accounts for 40%-45%.Adopting low-molecular-weight polyester PET and high molecular PTT is that the raw materials melt spinning makes, and makes the two-pack parallel composite fiber.
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 makes is lower, aggregated particle content is little, the melt uniformity of polyester is high, the spinning property had, the conjugated fibre rigidity made is low, the loft high, can be used for the multicomponent fibre conjugate spinning, and row yielding and performance also obviously improve.
The preparation method of a kind of low-molecular-weight polyester for the manufacture of multicomponent fibre of the present invention comprises:
1) take following three kinds of components is 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 its both mixture;
Above-mentioned reaction raw materials is carried out to esterification at 220～250 ℃ of temperature, and esterification pressure 20～50kPa, react to esterification yield and be not less than 92%, and reaction process is removed the water of generation;
2) by the esterification products of above-mentioned reaction raw materials, under the polycondensation catalyst existence condition, in-2～-condition of 10kpa under, temperature of reaction is 250～260 ℃ and carries out further esterification and precondensation, 1.5～2.5 hours reaction times; Then-0.1～-the 2KPa condition under, the polycondensation temperature is 260～290 ℃, in 2～3 hours reaction times, makes low-molecular-weight polyester.
In described step 1), the reaction raw materials molar ratio is (monomer of the two carboxyl reaction of terephthalic acid+have functional group): (monomer of the two hydroxyl reaction of ethylene glycol+have functional group)=1: 1.1～1.8.
The monomer with two carboxyl reaction functional group in described step 1) is selected from m-phthalic acid, 1, the mixture of one or more in 6-hexanodioic acid, 1, 4-succinic acid etc.; The described monomer with two hydroxyl reaction functional group is selected from one or more the mixture 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: have the monomer of two carboxyl reaction functional group=1: 0～0.1; Ethylene glycol: the monomer with two hydroxyl reaction functional group is reaction raw materials=1: 0～0.1, and 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) polycondensation catalyst in is selected from a kind of in antimony glycol, antimony acetate or antimonous oxide, and the theoretical yield weight that the consumption of polycondensation catalyst obtains polyester based on polycondensation is benchmark, with antimony ion, counts 180～300ppm/kg.
The number-average molecular weight Mn of described low-molecular-weight polyester is 16000-25000, and weight-average molecular weight Mw is 31000-45000, and molecular weight distribution PD is 1.85-1.95, and agglutination particle (>=10 μ m) quantity is for being not more than 0.4/mg.
Key of the present invention is to add other dibasic alcohol acids monomers, and control esterification and polycondensation process, make low-molecular-weight polyester, the number-average molecular weight Mn of this low-molecular-weight polyester is controlled at 16000-25000, weight-average molecular weight Mw is controlled at 31000-45000, molecular weight distribution PD is controlled at 1.85-1.95, agglutination particle (>=10 μ m) quantity is controlled at and is not more than 0.4/mg, compare with normal polyester and effectively reduced its molecular weight, controlled 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 the polycomponent spinning with high-viscosity polyester, functional polyester and other other new polyesters such as PTT, PBT, makes the multicomponent fibre of excellent performance.As spinning material, can also add as required the various additives as other in above-mentioned polyester, as matting agent, for preventing polyester, produce the stablizer of thermal destruction, adjust the toning agent of form and aspect etc.
Beneficial effect
Compared with prior art, the invention has the advantages that the polyester product molecular weight made is lower, aggregated particle content is little, the melt uniformity of polyester is high, there is good spinning property, the conjugated fibre rigidity made is low, the loft high, can be used for the multicomponent fibre conjugate spinning, and row yielding and performance also obviously improve; Simultaneously, preparation technology of the present invention is simple, and cost is low, can in general-purpose equipment, complete, and has good industrial applications prospect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications 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 limited range equally.
Embodiment 1～9
1) with terephthalic acid, ethylene glycol, the monomer with two carboxyl reaction functional group except terephthalic acid, and the monomer of the two hydroxyl reaction of having except ethylene glycol functional group is reaction raw materials (proportioning raw materials is in Table 1), carry out esterification at 250 ℃ of temperature, esterification pressure 30kPa, reaction process is removed the water of generation, when the reaction esterification yield reaches 95%, esterification completes;
2) the esterification products intermediate is under the polycondensation catalyst existence condition, and under the condition of-2KPa, temperature of reaction is 260 ℃ and carries out the polyester oligomer that further esterification and prepolymerization reaction obtain certain polymerization degree, and the reaction times is 2 hours; Then under-0.1KPa vacuum condition, the polycondensation temperature is 280 ℃, in 2 hours reaction times, makes 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: 280 ℃ of temperature of reaction, and reaction pressure-0.1KPa, reaction times 2.5hr, other reaction process conditions are identical with embodiment 1～9.
3. the polyester of comparative example 3 is taken from the conventional bright PET chips that oil of SPC is produced.
Table 1
* only adopt terephthalic acid, ethylene glycol in comparative example 1～2, do not add other dibasic alcohol acids monomers; Comparative example 3 is directly taken 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 main quality index, data are in Table 2.
Table 2
Although the present invention discloses preferred embodiment as above; so it is not in order to limit content of the present invention; anyly be familiar with this skill person; within not breaking away from main spirits of the present invention and context; when doing various changes and retouching, therefore the protection domain of invention should be as the criterion with the basic right claimed range of applying for a patent.
Claims (7)
1. the preparation method for the manufacture of the low-molecular-weight polyester of multicomponent fibre comprises:
1) take following three kinds of components is reaction raw materials,
A: terephthalic acid
B: ethylene glycol
The monomer of the two carboxyl reaction of C having except terephthalic acid functional group, the monomer with two hydroxyl reaction functional group except ethylene glycol are reaction raw materials or its both mixture;
Above-mentioned reaction raw materials is carried out to esterification at 220～250 ℃ of temperature, and esterification pressure 20～50kPa, react to esterification yield and be not less than 92%, and reaction process is removed the water of generation;
2) by the esterification products of above-mentioned reaction raw materials, under the polycondensation catalyst existence condition, under the condition of negative pressure 2～10kpa, temperature of reaction is 250～260 ℃ and carries out further esterification and precondensation, 1.5～2.5 hours reaction times; Then-0.1～-the 2KPa condition under, the polycondensation temperature is 260～290 ℃, in 2～3 hours reaction times, makes low-molecular-weight polyester.
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: in described step 1), the reaction raw materials molar ratio is (monomer of the two carboxyl reaction of terephthalic acid+have functional group): (monomer of the two hydroxyl reaction of ethylene glycol+have functional group)=1: 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: the monomer with two carboxyl reaction functional group in described step 1) is 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 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, it is characterized in that: in described step 1), the mol ratio of each reaction raw materials is terephthalic acid: have the monomer of two carboxyl reaction functional group=1: 0～0.1; Ethylene glycol: the monomer with two hydroxyl reaction functional group is reaction raw materials=1: 0～0.1, and 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.
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: the polycondensation catalyst described step 2) is selected from a kind of 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, with antimony ion, counts 180～300ppm/kg.
7. 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 number-average molecular weight Mn of described low-molecular-weight polyester is 16000-25000, weight-average molecular weight Mw is 31000-45000, molecular weight distribution PD is 1.85-1.95, and agglutination particle (>=10 μ m) quantity is for being not more than 0.4/mg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310294368.9A CN103421169B (en) | 2013-07-12 | 2013-07-12 | A kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre |
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| CN201310294368.9A CN103421169B (en) | 2013-07-12 | 2013-07-12 | A kind of preparation method of the low-molecular-weight polyester for the manufacture of multicomponent fibre |
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| CN103421169A true CN103421169A (en) | 2013-12-04 |
| CN103421169B CN103421169B (en) | 2015-08-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566616A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Copolyester preparation method and application of copolyester prepared thereby in 3 D printing |
| WO2018045931A1 (en) * | 2016-09-09 | 2018-03-15 | 珠海万通化工有限公司 | Pbat resin and preparation method therefor |
| CN109137137A (en) * | 2018-08-28 | 2019-01-04 | 上海海凯生物材料有限公司 | A kind of elastic composite fiber and its manufacturing method |
Citations (3)
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|---|---|---|---|---|
| US3427287A (en) * | 1961-08-30 | 1969-02-11 | Goodyear Tire & Rubber | Method for preparing polyester resins |
| JPS5614524A (en) * | 1979-07-12 | 1981-02-12 | Toyobo Co Ltd | Production of polyester low polymer |
| 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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2013
- 2013-07-12 CN CN201310294368.9A patent/CN103421169B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3427287A (en) * | 1961-08-30 | 1969-02-11 | Goodyear Tire & Rubber | Method for preparing polyester resins |
| JPS5614524A (en) * | 1979-07-12 | 1981-02-12 | Toyobo Co Ltd | Production of polyester low polymer |
| KR20010061648A (en) * | 1999-12-28 | 2001-07-07 | 이구택 | Polyester copolymer having propylene in the main chain and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李旦等: ""PTT/PET并列型复合纺丝工艺研究"", 《合成纤维》 * |
| 马文宁: ""间苯二甲酸与二甘醇对PET共聚改性的研究"", 《合成纤维工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566616A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Copolyester preparation method and application of copolyester prepared thereby in 3 D printing |
| 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 |
| WO2018045931A1 (en) * | 2016-09-09 | 2018-03-15 | 珠海万通化工有限公司 | Pbat resin and preparation method therefor |
| CN109137137A (en) * | 2018-08-28 | 2019-01-04 | 上海海凯生物材料有限公司 | A kind of elastic composite fiber and its manufacturing method |
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| CN103421169B (en) | 2015-08-19 |
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