CN103145958B - Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester - Google Patents
Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester Download PDFInfo
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- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
- D04H1/5412—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres sheath-core
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/542—Adhesive fibres
- D04H1/55—Polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The present invention relates to a kind of preparation method of core-skin type polyester low melting point recycled polyester, described low melting point recycled polyester is for following raw material is by degraded and polycondensation and obtaining: a. regenerative raw materials; B. methyl alcohol; C. one or more in base tin laurate of zinc acetate, Potassium ethanoate, manganese acetate, magnesium acetate, plumbic acetate, cobalt chloride, tetrabutyl titanate, titanium isopropylate and fourth two; D. m-phthalic acid, one or more in hexanodioic acid and sebacic acid; E. neopentyl glycol, hexylene glycol, one or more in butyleneglycol and polyoxyethylene glycol; F. the catalytic antimony trioxide and Cobaltous diacetate; G. stablizer trimethyl phosphite 99; Low melting point recycled polyester of the present invention can be used for preparing core-skin type polyester staple fiber, improves the added value that polyester waste material prepares regenerative polyester staple fiber, and the core-skin type regenerative polyester staple fiber of preparation has steady quality, colory feature.Can be used for producing in the industries such as non-woven, flocking, matrix material.
Description
Technical field
The present invention relates to and belong to experimental branch line technical field, particularly relate to a kind of preparation method of core-skin type polyester low melting point recycled polyester.
Background technology
Low melting point core-skin type complex polyester staple fibre refers to that the polymkeric substance with low-melting point polyester is different with normal polyester these two kinds is distributed in the fiber made among same fiber with skin-core structure.Cortex is low-melting point polyester, it preserves the part of properties of normal polyester, has the feature of good consistency with normal polyester.Low melting point core-skin composite fiber is mainly used in heat-bondable fibre, and in non-woven is produced, Main Function is low-melting fiber cortex polymer fusing at a certain temperature, thus plays in fibrous reticulum and cohere effect.Because low-melting point polyester staple fiber has, intensity is high, bulkiness good, elastic restoration ratio is high, and the non-woven produced has soft, elasticity high, is widely used in the fields such as the sanitary material such as surgical mask, bandage and house decorative material at present.
Production method at present for low-melting point polyester staple fiber has more research report.As patent of invention " a kind of copolyester with low melting point and preparation method thereof " (application number: the method for design 200810063395.4) disclosing copolyester with low melting point, melting point polyester can be down to 110 DEG C, and this copolyester with low melting point crystal property is good, limiting viscosity is high, particle not easily adhesion, have good spinning property etc.Patent of invention " a kind of production method of low-melting point polyester staple fiber " (application number: 200410072878.2) adopt 120 DEG C ~ 130 DEG C low melting point polyester chips after low-temperature vacuum drying, low melting point staple fibre can be obtained through melt-spinning.Patent of invention " a kind of low melting point short fiber of parallel type compound " (application number: be that water-soluble polyester component and polytrimethylene terephthalate component are composited low melting point short fiber side by side 200810123792.6), this fiber has good percent thermal shrinkage stability.Research about low melting point core-sheath trevira also has some to report.As patent of invention " a kind of production method of sheath-core type low-melting point polyester staple fiber ", (application number: 200810163542.5) it is characterized in that cortex is the low-melting point polyester melt obtained by fused mass directly spinning, sandwich layer is the conventional PET polyester fondant obtained by conventional PET section spinning process.But utilize reworked material to prepare polyester staple fiber not report so far as the sandwich layer of core-sheath compound fibre.
Along with polyester material developing rapidly and using in each field, the quantity discharged of polyester waste material grows with each passing day, its refractory organics now causes great pollution to environment, and due to the shortage of current industrial raw material, has become needed for sustainable development society the recycling of polyester waste material.Staple fibre major part prepared by current polyester waste material is for low additional fields such as weighting materials.Study modified tune adhering process, solve the technical barrier that polyester waste material source is wide, complicated component, quality fluctuation are large, utilize polyester waste material to prepare and there are the key subjects that high value-added product becomes regeneration industry transition and upgrade.In addition, this technology substitutes the spinning of eutectic polyester slice with fused mass directly spinning, and preferably resolve that low-melting point polyester drying cost is large, poor stability, fiber spinnability difference etc. is a series of asks questions, production cost declines to a great extent.
Summary of the invention
In order to solve the technical problem utilizing reworked material to prepare the existence of polyester sheath core type conjugated fibre, first object of the present invention is to provide a kind of methanol degradation to produce the method for core-skin type polyester low melting point recycled polyester, low melting point recycled polyester prepared by the method can be used for preparing core-skin type polyester staple fiber, improve the added value that polyester waste material prepares regenerative polyester staple fiber, the core-skin type regenerative polyester staple fiber of preparation has steady quality, colory feature.Second object of the present invention is to provide the low melting point recycled polyester adopting above-mentioned method to prepare.3rd object of the present invention is to provide the application of the low melting point recycled polyester adopting above-mentioned method to prepare.
In order to realize first above-mentioned object, present invention employs following technical scheme:
Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester, and described low melting point recycled polyester is obtained by degraded and polycondensation for following raw material:
A. regenerative raw materials;
B. methyl alcohol;
C. one or more in base tin laurate of zinc acetate, Potassium ethanoate, manganese acetate, magnesium acetate, plumbic acetate, cobalt chloride, tetrabutyl titanate, titanium isopropylate and fourth two;
D. m-phthalic acid, one or more in hexanodioic acid and sebacic acid;
E. neopentyl glycol, hexylene glycol, one or more in butyleneglycol and polyoxyethylene glycol;
F. the catalytic antimony trioxide and Cobaltous diacetate;
G. stablizer trimethyl phosphite 99;
Concrete grammar is as follows:
1) mix after a, b and c being fed intake, the mass ratio that feeds intake of a and b is 1:4 ~ 14, and the mass ratio of a and c is 100:0.5 ~ 1; Degradation temperature is 170 ~ 250 DEG C, pressure is 1.5 ~ 4.0Mpa, reaction times is 2.5 ~ 5h, equipressure reacts when getting back to normal atmosphere and terminates, filtered by reactant, the liquid in rotation evaporation obtained, boils off methyl alcohol and ethylene glycol respectively, the solids obtained is dissolved in hot ethanol and filters, and gained liquid boils off ethanol and obtains dimethyl terephthalate (DMT);
2) esterification of dimethyl terephthalate (DMT) and ethylene glycol is carried out under nitrogen pressurization, and the molar ratio of dimethyl terephthalate (DMT) and d is 2 ~ 5:1; The molar ratio of dimethyl terephthalate (DMT) and e is 3 ~ 19:1; The mol ratio of dimethyl terephthalate (DMT) and ethylene glycol is: 20:80 ~ 80:20; The molar ratio of alkyd is 1.4 ~ 1.6:1; F and g feeds intake as 200 ~ 600ppm of sour total amount, and described alcohol is the summation of ethylene glycol and e; The temperature of esterification is 180 ~ 250 DEG C, and pressure is 0.05MPa ~ 0.4MPa, reaction times 1.5 ~ 3h; Polycondensation temperature is 250 ~ 285 DEG C, and vacuum tightness is 30 ~ 200Pa, reaction times 2.5 ~ 5h.
As preferably, the fusing point of described low melting point recycled polyester is 70 ~ 160 DEG C, content of carboxyl end group≤35mmol/kg, and limiting viscosity is 0.5dL/g ~ 1.OdL/g.
As preferred again, the limiting viscosity of described low melting point recycled polyester is 0.55dL/g ~ 0.75dL/g.
As preferably, described regenerative raw materials comprise in regenerative piece of polyester bottle and Waste Polyester textiles one or more.
In order to realize second above-mentioned object, present invention also offers above-mentioned preparation method and preparing low melting point recycled polyester.
In order to realize second above-mentioned object, present invention also offers a kind of core-skin type regenerative polyester staple fiber, the cortex of this core-skin type regenerative polyester staple fiber adopts above-mentioned low melting point recycled polyester.
Low melting point recycled polyester of the present invention can be used for preparing core-skin type polyester staple fiber, improves the added value that polyester waste material prepares regenerative polyester staple fiber, and the core-skin type regenerative polyester staple fiber of preparation has steady quality, colory feature.Can be used for producing in the industries such as non-woven, flocking, matrix material.
Embodiment
embodiment 1
1, the preparation of low-melting point polyester is regenerated: the mass ratio that feeds intake of regenerative raw materials and methyl alcohol is 1:6; The mass ratio of regenerative raw materials and zinc acetate is 100:0.5; Above raw material is by Methanolysis post polymerization preparation regeneration low-melting point polyester: degradation temperature is 190 DEG C, pressure is 2.5Mpa, reaction times is 3h, equipressure reacts when getting back to normal atmosphere and terminates, filtered by reactant, the liquid in rotation evaporation obtained, boils off methyl alcohol and ethylene glycol respectively, the solids obtained is dissolved in hot ethanol and filters, and gained liquid boils off ethanol and obtains dimethyl terephthalate (DMT) (DMT).Dimethyl terephthalate (DMT) (DMT) is 3:1 with the molar ratio of m-phthalic acid (IPA); Dimethyl terephthalate (DMT) (DMT) is 7:1 with the molar ratio of neopentyl glycol (NPG); Dimethyl terephthalate (DMT) (DMT) is 1:2 with the mol ratio of ethylene glycol; The molar ratio of alcohol (summation of ethylene glycol and neopentyl glycol (NPG)) acid is 1.5:1; The 300ppm that the catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) they are total amount sour in reaction system, then add the stablizer trimethyl phosphite 99 (TMP) that weight is 0.01% (relatively sour composition).Esterification is carried out under nitrogen pressurization, and temperature is 220 DEG C, and pressure is 0.15MPa, reaction times 2.2h; Polycondensation temperature is 275 DEG C, and vacuum tightness is 90Pa, reaction times 3.5h.The fusing point of the low-melting point polyester obtained is 110 DEG C, and content of carboxyl end group is 25mmol/kg, and limiting viscosity is 0.69dL/g.
2, the preparation of recycled polyester: adopt bottle chips through the technical process of cleaning, drum dried, cascade filtration, liquid-phase tackifying.Wherein, drum dried temperature is 130 DEG C, and time of drying is 8h.The step of liquid-phase tackifying is as follows: the melt that the temperature 1) after screw rod melting is 0.55dl/g 270 DEG C of limiting viscosities is pumped to vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 DEG C, and after stopping 30min under condition, limiting viscosity can reach 0.68dl/g; 2) after, melt enters the modified tune of secondary and glues device, the melt temperature that the modified tune of secondary glues in device is identical with vacuum separation tower with vacuum tightness, under the effect of rotatable propeller, melt constantly advances, melt viscosity constantly increases, angle of rake speed of rotation is 5r/min, residence time 20min, final melt characteristic viscosity is at 0.79dl/g.The fusing point of recycled polyester is 264 DEG C, and content of carboxyl end group is 16 mmol/kg, and limiting viscosity is 0.79dl/g.
3, core-skin type regenerative polyester staple fiber: above-mentioned low-melting point polyester and recycled polyester are entered composite spinneret pack with the accurate measurement of 4:6 core-skin weight respectively, the melt sprayed from the spinning jet of composite component, through cooling, winding, boundling, drawing-off, sizing, cut-out and packing, core-skin type regenerative polyester staple fiber can be obtained.The drying temperature of recycled polyester is 150 DEG C, and time of drying is 7h, extruder temperature 280 DEG C; Low-melting point polyester spinning pipeline holding temperature is 230 DEG C, and recycled polyester spinning pipeline holding temperature is 275 DEG C, and spinning body temperature is 280 DEG C; Ring quenching wind-warm syndrome is 15 DEG C, and wind speed is 2.0m/s; Spinning speed is 1100m/min; Ratio of drawing is 2.0, drawing temperature 60 DEG C, and drawing speed is 110m/min.The core-skin type regenerative polyester staple fiber quality index obtained through above-mentioned production technique is:
Linear density: 4.21dtex
Breaking tenacity: 3.14cN/dtex
Elongation at break: 40%
Cutting length: 51.2mm.
embodiment 2
1, the preparation of low-melting point polyester is regenerated: the mass ratio that feeds intake of regenerative raw materials and water is 1:4; The mass ratio of regenerative raw materials and Potassium ethanoate is 100:0.5; Above raw material is by hydrolysis post polymerization preparation regeneration low-melting point polyester: hydrolysis temperature is 220 DEG C, pressure is 4.5Mpa, reaction times is 2.8h, when reaction end equipressure gets back to normal atmosphere, reactant is filtered, the evaporation of gained liquid in rotation obtains ethylene glycol, then is dissolved in DMF by filtering solids thing and filters, and gained liquid recrystallization obtains terephthalic acid (TPA).Terephthalic acid (TPA) is 3.5:1 with the molar ratio of hexanodioic acid (AA); Terephthalic acid (TPA) is 6:1 with the molar ratio of hexylene glycol (HG); Terephthalic acid (TPA) is 1.5:1 with the mol ratio of ethylene glycol; The molar ratio of alkyd is 1.5:1; The 300ppm that the catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) they are total amount sour in reaction system, then add the stablizer trimethyl phosphite 99 (TMP) that weight is 0.01% (relatively sour composition).Esterification is carried out under nitrogen pressurization, and temperature is 220 DEG C, and pressure is 0.3MPa, reaction times 2.5h; Polycondensation temperature is 275 DEG C, and vacuum tightness is 80Pa, reaction times 3h, and the fusing point of the low-melting point polyester obtained is 105 DEG C, and content of carboxyl end group is 28mmol/kg, and limiting viscosity is 0.67dL/g.
2, the preparation of recycled polyester: adopt bottle chips through the technical process of cleaning, drum dried, cascade filtration, liquid-phase tackifying.Wherein, drum dried temperature is 110 DEG C, and time of drying is 7h.The step of liquid-phase tackifying is as follows: the melt that the temperature 1) after screw rod melting is 0.55dl/g 270 DEG C of limiting viscosities is pumped to vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 DEG C, and after stopping 30min under condition, limiting viscosity can reach 0.68dl/g; 2) after, melt enters the modified tune of secondary and glues device, the melt temperature that the modified tune of secondary glues in device is identical with vacuum separation tower with vacuum tightness, under the effect of rotatable propeller, melt constantly advances, melt viscosity constantly increases, angle of rake speed of rotation is 5r/min, residence time 15min, final melt characteristic viscosity is at 0.78dl/g.The fusing point of recycled polyester is 269 DEG C, and content of carboxyl end group is 14 mmol/kg, and limiting viscosity is 0.78dl/g.
3, core-skin type regenerative polyester staple fiber: above-mentioned low-melting point polyester and recycled polyester are entered composite spinneret pack with the accurate measurement of 5:5 core-skin weight respectively, the melt sprayed from the spinning jet of composite component, through cooling, winding, boundling, drawing-off, sizing, cut-out and packing, core-skin type regenerative polyester staple fiber can be obtained.The drying temperature of recycled polyester raw material is 140 DEG C, and time of drying is 7.5h, extruder temperature 270 DEG C; Low-melting point polyester spinning pipeline holding temperature is 220 DEG C, and recycled polyester spinning pipeline holding temperature is 275 DEG C, and spinning body temperature is 280 DEG C; Ring quenching wind-warm syndrome is 20 DEG C, and wind speed is 3.0m/s; Spinning speed is 1000m/min; Ratio of drawing is 3.0, drawing temperature 56 DEG C, and drawing speed is 120m/min.The core-skin type regenerative polyester staple fiber quality index obtained through above-mentioned production technique is:
Linear density: 4.05dtex
Breaking tenacity: 3.22cN/dtex
Elongation at break: 42%
Cutting length: 51.6mm.
embodiment 3
1, the preparation of low-melting point polyester is regenerated: the mass ratio that feeds intake of regenerative raw materials and ethylene glycol is 1:3.5; The mass ratio of regenerative raw materials and fourth two base tin laurate is 100:0.5; Alcoholysis reaction temperature is 196 DEG C, and pressure is 0.15MPa, and the reaction times is 2h, and the limiting viscosity of reaction solution reaches 0.29dl/g.After reaction terminates, reaction solution Rapid Thermal is filtered, underpressure distillation is carried out to filtrate and reclaims ethylene glycol, liquid (being solid under normal temperature) after underpressure distillation is dissolved in hot alcohol, ester, chlorinated hydrocarbon, ketone equal solvent, heat filtering goes out insolubles, and filtrate naturally cooling obtains ethylene glycol terephthalate (BHET) and oligopolymer thereof.M-phthalic acid (IPA), neopentyl glycol (NPG), the catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) and stablizer trimethyl phosphite 99 (TMP) is added in ethylene glycol terephthalate (BHET) and oligopolymer thereof, carry out polycondensation, the polycondensation temperature of ethylene glycol terephthalate (BHET) and oligopolymer thereof is 275 DEG C, vacuum tightness is 95Pa, reaction times 3.5h.The fusing point of the low-melting point polyester obtained is 115 DEG C, and content of carboxyl end group is 30mmol/kg, and limiting viscosity is 0.68dL/g.The molar weight that feeds intake of m-phthalic acid (IPA) is quality/450 of regenerative raw materials; The molar weight that feeds intake of neopentyl glycol (NPG) is regenerative raw materials quality/960; The molar ratio of alkyd is 1.4; The 400ppm that the catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) they are total amount sour in reaction system, then add the stablizer trimethyl phosphite 99 (TMP) that weight is 0.01% (relatively sour composition).
2, the preparation of recycled polyester: adopt bottle chips through the technical process of cleaning, drum dried, cascade filtration, liquid-phase tackifying.Wherein, drum dried temperature is 100 DEG C, and time of drying is 7h.The step of liquid-phase tackifying is as follows: the melt that the temperature 1) after screw rod melting is 0.55dl/g 270 DEG C of limiting viscosities is pumped to vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 DEG C, and after stopping 30min under condition, limiting viscosity can reach 0.68dl/g; 2) after, melt enters the modified tune of secondary and glues device, the melt temperature that the modified tune of secondary glues in device is identical with vacuum separation tower with vacuum tightness, under the effect of rotatable propeller, melt constantly advances, melt viscosity constantly increases, angle of rake speed of rotation is 5r/min, residence time 15min, final melt characteristic viscosity is at 0.78dl/g.The fusing point of recycled polyester is 267 DEG C, and content of carboxyl end group is 16 mmol/kg, and limiting viscosity is 0.78dl/g.
3, core-skin type regenerative polyester staple fiber: above-mentioned low-melting point polyester and recycled polyester are entered composite spinneret pack with the accurate measurement of 6:4 core-skin weight respectively, the melt sprayed from the spinning jet of composite component, through cooling, winding, boundling, drawing-off, sizing, cut-out and packing, core-skin type regenerative polyester staple fiber can be obtained.The drying temperature of recycled polyester raw material is 140 DEG C, and time of drying is 7h, extruder temperature 280 DEG C; Low-melting point polyester spinning pipeline holding temperature is 230 DEG C, and recycled polyester spinning pipeline holding temperature is 270 DEG C, and spinning body temperature is 285 DEG C; Ring quenching wind-warm syndrome is 22 DEG C, and wind speed is 2.5m/s; Spinning speed is 900m/min; Ratio of drawing is 2.5, drawing temperature 55 DEG C, and drawing speed is 110m/min.The core-skin type regenerative polyester staple fiber quality index obtained through above-mentioned production technique is:
Linear density: 4.24 dtex
Breaking tenacity: 2.67 cN/dtex
Elongation at break: 47%
Cutting length: 50.8mm.
Claims (3)
1. methanol degradation produces the method for core-skin type polyester low melting point recycled polyester, it is characterized in that low melting point recycled polyester is obtained by degraded and polycondensation for following raw material:
1) mass ratio that feeds intake of regenerative raw materials and methyl alcohol is 1:6; The mass ratio of regenerative raw materials and zinc acetate is 100:0.5; Above raw material is by Methanolysis post polymerization preparation regeneration low-melting point polyester: degradation temperature is 190 DEG C, pressure is 2.5Mpa, reaction times is 3h, equipressure reacts when getting back to normal atmosphere and terminates, filtered by reactant, the liquid in rotation evaporation obtained, boils off methyl alcohol and ethylene glycol respectively, the solids obtained is dissolved in hot ethanol and filters, and gained liquid boils off ethanol and obtains dimethyl terephthalate (DMT);
2) molar ratio of dimethyl terephthalate (DMT) and m-phthalic acid is 3:1; The molar ratio of dimethyl terephthalate (DMT) and neopentyl glycol is 7:1; The mol ratio of dimethyl terephthalate (DMT) and ethylene glycol is 1:2; The summation of ethylene glycol and neopentyl glycol is 1.5:1 with the molar ratio of acid; The catalytic antimony trioxide and Cobaltous diacetate are the 300ppm of sour total amount in reaction system, then add the stablizer trimethyl phosphite 99 that weight is relatively sour composition 0.01%; Esterification is carried out under nitrogen pressurization, and temperature is 220 DEG C, and pressure is 0.15MPa, reaction times 2.2h; Polycondensation temperature is 275 DEG C, and vacuum tightness is 90Pa, reaction times 3.5h; The fusing point of the low-melting point polyester obtained is 110 DEG C, and content of carboxyl end group is 25mmol/kg, and limiting viscosity is 0.69dL/g.
2. preparation method according to claim 1 prepares low melting point recycled polyester.
3. a core-skin type regenerative polyester staple fiber, is characterized in that: the cortex of this core-skin type regenerative polyester staple fiber adopts low melting point recycled polyester according to claim 2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310091294.9A CN103145958B (en) | 2013-03-21 | 2013-03-21 | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester |
| PCT/CN2014/073750 WO2014146587A1 (en) | 2013-03-21 | 2014-03-20 | Method for producing low-melting-point recycled polyester used for sheath-core polyester by methanol degradation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310091294.9A CN103145958B (en) | 2013-03-21 | 2013-03-21 | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103145958A CN103145958A (en) | 2013-06-12 |
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| CN103147163B (en) * | 2013-03-21 | 2015-03-18 | 宁波大发化纤有限公司 | Skin-core type recycled polyester staple fiber and preparation method thereof |
| CN103145957B (en) * | 2013-03-21 | 2015-08-26 | 宁波大发化纤有限公司 | Degradation of ethylene glycol produces the method for core-skin type polyester low melting point recycled polyester |
| CN103145958B (en) * | 2013-03-21 | 2015-08-26 | 宁波大发化纤有限公司 | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester |
| EP3466388B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a nonwoven material with antimony-free polyethylene terephthalate |
| EP3466385B1 (en) * | 2017-10-06 | 2020-05-27 | The Procter & Gamble Company | Absorbent article or wipe comprising a nonwoven material with bicomponent fibers comprising antimony-free polyethylene terephthalate |
| CN109666180A (en) * | 2018-12-21 | 2019-04-23 | 江苏中信世纪新材料有限公司 | A method of using organotin catalysts solution degradation unsaturated polyester material |
| DE112020002068T5 (en) * | 2019-07-15 | 2022-01-05 | Primaloft, Inc. | Recycled polyester binding fiber |
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| CN1275995A (en) * | 1997-10-17 | 2000-12-06 | 伊斯曼化学公司 | Depolymerization process for recycling polyesters |
| CN101445972A (en) * | 2008-12-29 | 2009-06-03 | 浙江理工大学 | Method for producing sheath-core type low-melting point polyester staple fiber |
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| US5712410A (en) * | 1997-03-03 | 1998-01-27 | Eastman Kodak Company | Gas phase crystallization of dimethyl terephthalate |
| CN103145958B (en) * | 2013-03-21 | 2015-08-26 | 宁波大发化纤有限公司 | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester |
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| CN1275995A (en) * | 1997-10-17 | 2000-12-06 | 伊斯曼化学公司 | Depolymerization process for recycling polyesters |
| CN101445972A (en) * | 2008-12-29 | 2009-06-03 | 浙江理工大学 | Method for producing sheath-core type low-melting point polyester staple fiber |
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