CN102534856B - Preparation method of spandex spinning stock solution by PCL dry method - Google Patents
Preparation method of spandex spinning stock solution by PCL dry method Download PDFInfo
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Abstract
The invention discloses a preparation method of a spandex spinning stock solution by a PCL dry method, which adopts a mixed diol formed by mixing PCL with polytetramethylene glycol as a reaction raw material, wherein the molar ratio of the PCL and polytetramethylene glycol in the mixed diol is 1:1-5, and the mixed diol is added with acid additives. The invention partially substitutes polyether diol by PCL (polycaprolactone diol), and thus the prepared prepolymer and polymer with a same molecular weight have low viscosity; the concentration of the spinning stock solution is increased correspondingly; the spinning speed is increased; the consumption of solvents and energy is reduced; the raw material cost is reduced; and finally the spandex production cost is greatly reduced. Meanwhile, the problem of poor spinning performance of spandex spinning stock solutions prepared by PPG is solved.
Description
Technical field
The present invention relates to a kind of urethane elastic fiber production technology, especially relate to a kind of PCL of utilization (polycaprolactone dihydroxylic alcohols) dry method and spin the preparation method of spandex fiber stoste.
Background technology
Tradition solution dry method spins that urethane elastic fiber production technology Shi Yi U.S. English Weida, Korea S's star dawn and Japanese Japan spins as representative, the condensate of its spinning solution is with PTMEG PTMEG (polytetramethylene ether diol) and MDI (diphenyl methane-4,4 ' vulcabond) performed polymer reacting with mol ratio 1: 1.5～2 ratios, with Diamines chain extender and prepolymer reaction, reach certain molecular weight again, and regulate concentration with DMF or DMAc, make the condensate of required viscosity.Chinese patent discloses another kind of fire-resistant high-resiliency spandex fabric and preparation method thereof (publication number: CN 101113534A), this spandex fibre comprises polyether Glycols, vulcabond, n-butanol, mixed amine, antioxidant, the easypro agent of lubricated solution, ultra-violet absorber, anti-yellowing agent and dimethylacetylamide, wherein the mol ratio of polyether Glycols and vulcabond is 1: 1.55～1.8, the weight ratio of polyether Glycols and n-butanol is 100: 0.05～0.15, above component forms pre-polymerization intermediate jointly, the weight ratio of pre-polymerization intermediate and mixed amine is 100: 1.5～2.0, the two and dimethylacetylamide form high molecular polymer, high molecular polymer and the antioxidant that is 0.5～1.5% with respect to pre-polymerization intermediate weight ratio, 0.02～0.1% the easypro agent of lubricated solution, 0.02～0.1% ultra-violet absorber, 0.5～2% anti-yellowing agent and dimethylacetylamide form spinning solution, mixed amine is ethylenediamine and end terminator monoamine, and the two ratio that is 1: 0.1～0.3 according to mol ratio mixes, and adds that it is 1～3% mixed amine solution that solvent dimethylacetylamide allotment becomes concentration, end terminator is dimethylamine, or diethylamine, or 21 n-butylamines, or cyclohexylamine, or n-amylamine, or monoethanolamine or its mixture.The preparation method of this spandex fibre comprises polymerization and two operations of spinning, wherein polymerization process is: in the first reactor, by polyether Glycols and vulcabond, pressed, n-butanol obtains pre-polymerization intermediate by prepolymerization: add solvent dimethylacetylamide to dissolve pre-polymerization intermediate, cooling, pre-polymerization midbody solution is transferred to the second reactor: pre-polymerization midbody solution cools in the second reactor, stir, be transferred in chain extension storage tank: the pre-polymerization midbody solution in chain extension storage tank and mixed amine rapid mixing in high-speed stirring mixer is even, cooling, through the continuous chain extending reaction polymer that secures satisfactory grades, transfer hold-up vessel: by antioxidant, the easypro agent of lubricated solution, ultra-violet absorber, anti-yellowing agent and solvent dimethylacetylamide are added in emulsion dispersion groove in advance, obtain emulsion, add high molecular polymer, obtain additive seasoning liquid: the high molecular polymer in hold-up vessel is mixed with additive seasoning liquid, obtain fire-resistant high-resiliency spandex fabric spinning solution: spinning solution after filtration, maturation process, spinning solution after completing can be used for spinning and produces.But this kind of most of condensate of method is PTMEG, and due to reasons such as the supply of material, raw materials, PTMEG price has reached 30000 yuan/ton at present, and also has up-trend, causes spandex thread production cost high.Chinese patent also disclose a kind of PPG of utilization dry method spin the former liquid and preparation method thereof of spandex fiber (publication number: CN101575406A), the spandex fibre poor performance that this legal system is standby.
Summary of the invention
Technical problem solved by the invention is to provide a kind of PCL of utilization (polycaprolactone dihydroxylic alcohols) dry method and spins the preparation method of spandex fiber stoste, it is mainly to solve in the existing spandex preparation method of prior art to adopt a large amount of PTMEGs, and the prices of raw and semifnished materials of PTMEG are higher, cause the technical problems such as spandex thread production cost is larger.
Above-mentioned technical problem of the present invention is solved by the following technical programs:
A kind of PCL of utilization dry method is spun the preparation method of spandex fiber stoste, the mixing glycol forming after it adopts PCL to mix with polytetramethylene ether diol is as reaction raw materials, in described mixing glycol, the mol ratio of PCL and polytetramethylene ether diol is 1: 1～5, in described mixing glycol, is also added with acids additive.The present invention adopts PCL (polycaprolactone dihydroxylic alcohols) part to replace polytetramethylene ether diol, adopt indium addition acids additive to increase both mixabilities, solved well the higher Cost Problems of the prices of raw and semifnished materials of PTMEG, the spandex fiber stoste preparing thus also has good performance simultaneously.Use PCL (polycaprolactone dihydroxylic alcohols) as raw material, performed polymer and the condensate viscosity of the same molecular amount making are low, can also improve spinning speed, thereby reduce solvent and energy resource consumption.Described acids additive is for improving the acids of the reactivity of PCL (polycaprolactone dihydroxylic alcohols) and polytetramethylene ether diol.Preferred benzoic acid, sulfuric acid or phosphoric acid.
Preparation method of the present invention, the molecular weight of wherein said PCL is 1500～3000, degree of unsaturation < 0.05mmol/g, PCL (polycaprolactone dihydroxylic alcohols) is low-unsaturation-degree; The molecular weight of described polytetramethylene ether diol is 1500～3000.The addition of described acids additive is for can evenly mix PCL and polytetramethylene ether diol.Preferred concentration is 72～98%, and addition is for mixing 3～50ppm of glycol gross weight.
Preparation method of the present invention comprises that any one take dry method that above-mentioned mixing glycol is raw material and spin the preparation method of spandex fiber stoste, a kind of preferred embodiment of the present invention of take is example, and the preparation method that the PCL of utilization dry method of the present invention is spun spandex fiber stoste specifically comprises the following steps:
(1) PCL is mixed with polytetramethylene ether diol, the mol ratio of PCL and polytetramethylene ether diol is 1: 1～5, then in mixture, is added into acids additive and evenly mixes, and forms and mixes glycol;
(2) in above-mentioned mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1: 1.5～2;
(3) above-mentioned performed polymer and DMAc are mixed to form to prepolymer solution, homogeneous solution, until prepolymer solution concentration is 35～50%, is then cooled to 5～10 ℃; Wherein the concentration of prepolymer solution refers to the ratio of its interior solid and solution gross mass;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 2～6%, and the solute in two amine aqueous solutions is propane diamine and ethylenediamine, the mol ratio of propane diamine and ethylenediamine is 1: 1～5;
(5) chain extension solution reaches after target viscosities, is added end-capping reagent simple function group amine cessation reaction, with DMAc solvent, is in harmonious proportion to 30%～40% concentration, after the placement sufficient time, forms spandex fiber stoste.
Above-mentioned preparation method, the target viscosities that in wherein said step (5), chain extension solution reaches is 3000～8000poise.
Above-mentioned preparation method, after being added into DMAc and being in harmonious proportion, then is added into antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter in wherein said step (5), then after the standing sufficient time, forms spandex fiber stoste.Antioxidant can improve the stability of stoste and spandex thread, and ultra-violet absorber can improve the ultraviolet-resistent property of spandex thread, and anti-yellow agent can improve the weatherability of spandex thread, and dyeing promoter can improve the dyeability of spandex thread.
Above-mentioned preparation method, wherein said antioxidant is preferably Hinered phenols antioxidant, and ultra-violet absorber is preferably benzotriazole, and anti-yellow agent is preferably hindered amines, and dyeing promoter is preferably polyurethanes.
Above-mentioned preparation method, the time of placing in wherein said step (5) is 48～72 hours.
The present invention is by using PCL (polycaprolactone dihydroxylic alcohols) part to replace PTMEG, make performed polymer and the condensate viscosity of the same molecular amount that makes low, can corresponding raising spinning solution concentration, and can improve spinning speed, thereby reduce solvent and energy resource consumption, and can reduce cost of material, finally can be so that spandex production cost significantly reduces.Also solved the poor problem of spandex fiber stoste spinning properties of utilizing PPG to prepare simultaneously.
The specific embodiment
For further illustrating the present invention, illustrate with the following Examples:
Embodiment 1
A kind of PCL of utilization of this example (polycaprolactone dihydroxylic alcohols) dry method is spun the former liquid and preparation method thereof of spandex fiber, the steps include:
(1) PCL (polycaprolactone dihydroxylic alcohols) is mixed with polytetramethylene ether diol, the molecular weight of PCL (polycaprolactone dihydroxylic alcohols) is 2200, the molecular weight of polytetramethylene ether diol is 1800, PCL (polycaprolactone dihydroxylic alcohols) is 1: 4 with the mol ratio of polytetramethylene ether diol, in mixture, being added into acids additive evenly mixes again, form and mix glycol, wherein acids additive is sulfuric acid, the concentration of acids additive is 95%, and the addition of acids additive is the 10ppm of PCL (polycaprolactone dihydroxylic alcohols) and PTMEG gross weight;
(2) in mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1: 1.8;
(3) performed polymer and DMAc are mixed to form to prepolymer solution, solution concentration is 44%, is cooled to 5 ℃;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 2.5%, and the solute in two amine aqueous solutions is propane diamine, ethylenediamine and pentanediamine, and mol ratio is 1: 3: 1;
(5) chain extension solution reaches after target viscosities 5000poise, added end-capping reagent diethylamine cessation reaction, being added into DMAc solvent is in harmonious proportion to 34% concentration again, be added into antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter, place and form spandex fiber stoste after 48 hours.
Embodiment 2
A kind of PCL of utilization of this example (polycaprolactone dihydroxylic alcohols) dry method is spun the former liquid and preparation method thereof of spandex fiber, the steps include:
(1) PCL (polycaprolactone dihydroxylic alcohols) is mixed with polytetramethylene ether diol, the molecular weight of PCL (polycaprolactone dihydroxylic alcohols) is 2500, the molecular weight of polytetramethylene ether diol is 2000, PCL (polycaprolactone dihydroxylic alcohols) is 1: 2.5 with the mol ratio of polytetramethylene ether diol, in mixture, being added into acids additive evenly mixes again, form and mix glycol, wherein acids additive is sulfuric acid, the concentration of acids additive is 95%, and acids additive is the 20ppm of PCL (polycaprolactone dihydroxylic alcohols) and PTMEG gross weight;
(2) in mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1: 1.8;
(3) performed polymer and DMAc are mixed to form to prepolymer solution, solution concentration is 40%, is cooled to 5 ℃;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 5%, and the solute in two amine aqueous solutions is propane diamine and ethylenediamine, the mol ratio of propane diamine and ethylenediamine is 1: 5;
(5) chain extension solution reaches after target viscosities 6000poise, added end-capping reagent DEA cessation reaction, be added into again DMAc solvent and be in harmonious proportion to 34% concentration, be added into antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter, place and form spandex fiber stoste after 72 hours.
Embodiment 3
A kind of PCL of utilization of this example (polycaprolactone dihydroxylic alcohols) dry method is spun the former liquid and preparation method thereof of spandex fiber, the steps include:
(1) PCL (polycaprolactone dihydroxylic alcohols) is mixed with polytetramethylene ether diol, the molecular weight of PCL (polycaprolactone dihydroxylic alcohols) is 3000, the molecular weight of polytetramethylene ether diol is 2200, PCL (polycaprolactone dihydroxylic alcohols) is 1: 1 with the mol ratio of polytetramethylene ether diol, in mixture, being added into acids additive evenly mixes again, form and mix glycol, wherein acids additive is benzoic acid, the concentration of acids additive is 72%, and acids additive is the 50ppm of PCL (polycaprolactone dihydroxylic alcohols) and PTMEG gross weight;
(2) in mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1: 2;
(3) performed polymer and DMAc are mixed to form to prepolymer solution, solution concentration is 40%, is cooled to 5 ℃;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 5%, and the solute in two amine aqueous solutions is propane diamine and ethylenediamine, the mol ratio of propane diamine and ethylenediamine is 1: 5;
(5) chain extension solution reaches after target viscosities 7000poise, added end-capping reagent DEA cessation reaction, be added into again DMAc solvent and be in harmonious proportion to 34% concentration, be added into antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter, place and form spandex fiber stoste after 72 hours.
Embodiment 4
A kind of PCL of utilization of this example (polycaprolactone dihydroxylic alcohols) dry method is spun the former liquid and preparation method thereof of spandex fiber, the steps include:
(1) PCL (polycaprolactone dihydroxylic alcohols) is mixed with polytetramethylene ether diol, the molecular weight of PCL (polycaprolactone dihydroxylic alcohols) is 2500, the molecular weight of polytetramethylene ether diol is 3000, PCL (polycaprolactone dihydroxylic alcohols) is 1: 5 with the mol ratio of polytetramethylene ether diol, in mixture, being added into acids additive evenly mixes again, form and mix glycol, wherein acids additive is phosphoric acid, the concentration of acids additive is 95%, and acids additive is the 3ppm of PCL (polycaprolactone dihydroxylic alcohols) and PTMEG gross weight;
(2) in mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1: 1.5;
(3) performed polymer and DMAc are mixed to form to prepolymer solution, solution concentration is 40%, is cooled to 5 ℃;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 5%, and the solute in two amine aqueous solutions is propane diamine and ethylenediamine, the mol ratio of propane diamine and ethylenediamine is 1: 5;
(5) chain extension solution reaches after target viscosities 8000poise, added end-capping reagent DEA cessation reaction, be added into again DMAc solvent and be in harmonious proportion to 34% concentration, be added into antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter, place and form spandex fiber stoste after 72 hours.
The spandex fiber stoste obtaining in above-described embodiment is made to elastic spandex fiber after deaeration, adopt static stretch method to measure its performance, result is as follows:
Take 20D spandex fibre as example: more than fracture strength 25CN;
Extension at break 600～650%;
Stress 3.0～6.5CN during 300% elongation;
300% elasticity of elongation response rate >=96%;
Boiling water shrinkage≤15%.
Above-described embodiment is described the preferred embodiment of the present invention; not scope of the present invention is limited; design under the prerequisite of spirit not departing from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention, all should fall in the definite protection domain of claims of the present invention.
Claims (7)
1. a preparation method who utilizes PCL dry method to spin spandex fiber stoste, it is characterized in that: the mixing glycol forming after adopting PCL to mix with polytetramethylene ether diol is as reaction raw materials, in described mixing glycol, the mol ratio of PCL and polytetramethylene ether diol is 1:1～5, in described mixing glycol, is also added with acids additive; Described acids additive is benzoic acid, sulfuric acid or phosphoric acid; The molecular weight of described PCL is 1500～3000, degree of unsaturation <0.05mmol/g; The molecular weight of described polytetramethylene ether diol is 1500～3000.
2. preparation method according to claim 1, is characterized in that: the concentration of described acids additive is 72～98%, and the addition of acids additive is for mixing 3～50ppm of glycol gross weight.
3. preparation method according to claim 1 and 2, is characterized in that: comprise the following steps:
(1) PCL is mixed with polytetramethylene ether diol, the mol ratio of PCL and polytetramethylene ether diol is 1:1～5, then in mixture, is added into acids additive and evenly mixes, and forms and mixes glycol;
(2) in above-mentioned mixing glycol, be added into diphenyl methane-4,4 ' vulcabond, forms performed polymer, wherein mixes glycol and diphenyl methane-4, and the mol ratio of 4 ' vulcabond is 1:1.5～2;
(3) above-mentioned performed polymer and DMAc are mixed to form to prepolymer solution, homogeneous solution, until prepolymer solution concentration is 35～50%, is then cooled to 5～10 ℃;
(4) cooled prepolymer solution is carried out to chain extension by two amine aqueous solutions, form chain extension solution, two amine aqueous solutions are made solvent with DMAc, and its concentration is 2～6%, and the solute in two amine aqueous solutions is propane diamine and ethylenediamine, the mol ratio of propane diamine and ethylenediamine is 1:1～5;
(5) chain extension solution reaches after target viscosities, is added end-capping reagent simple function group amine cessation reaction, with DMAc solvent, is in harmonious proportion to 30%～40% concentration, after the placement sufficient time, forms spandex fiber stoste.
4. preparation method according to claim 3, is characterized in that: the target viscosities that in described step (5), chain extension solution reaches is 3000～8000poise.
5. preparation method according to claim 3, it is characterized in that: after being added into DMAc in described step (5) and being in harmonious proportion, be added into again antioxidant, ultra-violet absorber, anti-yellow agent, dyeing promoter, then after the standing sufficient time, form spandex fiber stoste.
6. preparation method according to claim 5, is characterized in that: described antioxidant is Hinered phenols antioxidant, and ultra-violet absorber is benzotriazole, and anti-yellow agent is hindered amines, and dyeing promoter is polyurethanes.
7. preparation method according to claim 3, is characterized in that: the time of placing in described step (5) is 48～72 hours.
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| CN103194814A (en) * | 2013-04-07 | 2013-07-10 | 浙江四海氨纶纤维有限公司 | Polymer for increasing speed for spinning fine-denier filaments in Nisshinbo dry process |
| CN111388939B (en) * | 2020-05-21 | 2022-07-12 | 乐山师范学院 | Wear-resistant dustproof dance pad and preparation method thereof |
| KR20230063914A (en) * | 2021-10-29 | 2023-05-10 | 효성티앤씨 주식회사 | Biodegradable spandex and method for preparing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1396320A (en) * | 2001-03-14 | 2003-02-12 | 杜邦-东丽株式会社 | Polyurethane spandex and its manufacturing method, cottons and silks and swimwear |
| CN101096778A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing polyether type comfortable spandex fibre |
| CN101148494A (en) * | 2007-10-26 | 2008-03-26 | 张勇 | Method for producing urethane elastomer and application |
| CN101260181A (en) * | 2008-04-09 | 2008-09-10 | 南通华盛高聚物科技发展有限公司 | Melt spinning spandex interlinkage agent and producing method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396320A (en) * | 2001-03-14 | 2003-02-12 | 杜邦-东丽株式会社 | Polyurethane spandex and its manufacturing method, cottons and silks and swimwear |
| CN101096778A (en) * | 2007-07-06 | 2008-01-02 | 烟台氨纶股份有限公司 | Process for producing polyether type comfortable spandex fibre |
| CN101148494A (en) * | 2007-10-26 | 2008-03-26 | 张勇 | Method for producing urethane elastomer and application |
| CN101260181A (en) * | 2008-04-09 | 2008-09-10 | 南通华盛高聚物科技发展有限公司 | Melt spinning spandex interlinkage agent and producing method thereof |
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