CN103145958A - Method for producing low-melting-point renewable polyester for sheath-core polyester through methanol degradation - Google Patents
Method for producing low-melting-point renewable polyester for sheath-core polyester through methanol degradation Download PDFInfo
- Publication number
- CN103145958A CN103145958A CN2013100912949A CN201310091294A CN103145958A CN 103145958 A CN103145958 A CN 103145958A CN 2013100912949 A CN2013100912949 A CN 2013100912949A CN 201310091294 A CN201310091294 A CN 201310091294A CN 103145958 A CN103145958 A CN 103145958A
- Authority
- CN
- China
- Prior art keywords
- polyester
- melting point
- core
- low melting
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention relates to a method for producing low-melting-point renewable polyester for sheath-core polyester. The low-melting-point renewable polyester is prepared from the following raw materials through degradation and polycondensation: (a) renewable raw materials; (b) methanol; (c) one or more of zinc acetate, potassium acetate, manganese acetate, magnesium acetate, lead acetate, cobalt chloride, tetrabutyl titanate, tetraisopropyl titanate and dibutyltin dilaurate; (d) one or more of m-phthalic acid, adipic acid and sebacic acid; (e) one or more of neopentyl glycol, hexanediol, butanediol and polyethylene glycol; (f) catalysts, namely antimony trioxide and cobalt acetate; and (g) a stabilizer, namely trimethyl phosphate. The low-melting-point renewable polyester produced by the method can be applied to the preparation of sheath-core polyester staple fibers, so that the added value of polyester wastes in preparation of renewable polyester staple fibers is increased, and the prepared sheath-core renewable polyester staple fibers have the characteristics of stable quality and excellent quality. The method can be applied to the production of industries, such as non-woven fabrics, flocking and composite materials.
Description
Technical field
The present invention relates to belong to the chemical fibre production technical field, relate in particular to the preparation method that a kind of core-skin type polyester is used the low melting point recycled polyester.
Background technology
Low melting point core-skin type complex polyester staple fibre refers to be distributed in low-melting point polyester and these two kinds of different polymkeric substance of normal polyester the fiber of making among same fiber with skin-core structure.Cortex is low-melting point polyester, and it has kept the part of properties of normal polyester, has the characteristics of good consistency with normal polyester.The low melting point core-skin composite fiber is mainly used in heat-bondable fibre, and Main Function is low-melting fiber cortex polymer fusing at a certain temperature in non-woven production, coheres effect thereby play in fibrous reticulum.Intensity is high, bulkiness good, elastic restoration ratio is high because low-melting point polyester staple fiber has, and the non-woven of producing has soft, elasticity high is widely used in the fields such as the sanitary materials such as surgical mask, bandage and house decorative material at present.
Production method for low-melting point polyester staple fiber has more research report at present.As patent of invention " a kind of copolyester with low melting point and preparation method thereof " (application number: the method for design that 200810063395.4) discloses copolyester with low melting point, melting point polyester can be down to 110 ℃, and this copolyester with low melting point crystal property is good, limiting viscosity is high, particle is difficult for 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 ℃～130 ℃ low melting point polyester chips through after low-temperature vacuum drying, can get the low melting point staple fibre through melt-spinning.(application number: 200810123792.6) disclosed is water-soluble polyester component and the polytrimethylene terephthalate component low melting point short fiber that is composited side by side to patent of invention " the low melting point short fiber that a kind of parallel type is compound ", and this fiber has good percent thermal shrinkage stability.Research about low melting point core-sheath trevira also has some reports.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 that obtains by fused mass directly spinning, the conventional PET polyester fondant of sandwich layer for obtaining by conventional PET section spinning process.But utilizing reworked material to prepare polyester staple fiber does 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 has now caused great pollution to environment, and due to the present shortage of industrial raw material, and the recycling of polyester waste material has been become the required of sustainable development society.Most of for low additional fields such as weighting materials with the staple fibre of polyester waste material preparation at present.Study modified accent adhering process, solve that the polyester waste material source is wide, complicated component, technical barrier that quality fluctuation is large, utilize the polyester waste material preparation to have the key subjects that high value-added product becomes upgrading transition of regeneration industry.In addition, this technology substitutes the spinning of eutectic polyester slice with fused mass directly spinning, a series of the asking questions such as preferably resolve that the low-melting point polyester drying cost is large, poor stability, fiber spinnability are poor, and production cost declines to a great extent.
Summary of the invention
Utilize reworked material to prepare the technical problem that polyester sheath core type conjugated fibre exists in order to solve, first purpose of the present invention is to provide a kind of methyl alcohol degraded to produce the method that the core-skin type polyester is used the low melting point recycled polyester, the low melting point recycled polyester of the method preparation can be used for preparing the core-skin type polyester staple fiber, improved 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 characteristics.Second purpose of the present invention is to provide the low melting point recycled polyester that adopts above-mentioned method preparation.The 3rd purpose of the present invention is to provide the application of the low melting point recycled polyester that adopts above-mentioned method preparation.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
The method that the core-skin type polyester is used the low melting point recycled polyester is produced in the methyl alcohol degraded, and described low melting point recycled polyester makes by degraded and polycondensation for following raw material:
A. regenerative raw materials;
B. methyl alcohol;
C. one or more in zinc acetate, Potassium ethanoate, manganese acetate, magnesium acetate, plumbic acetate, cobalt chloride, tetrabutyl titanate, titanium isopropylate and the basic tin laurate of 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) with a, b with mix after c feeds intake, the mass ratio that feeds intake of a and b is 1:4～14, the mass ratio of a and c is 100:0.5～1; Degradation temperature is 170～250 ℃, pressure is 1.5～4.0Mpa, reaction times is 2.5～5h, when equipressure is got back to normal atmosphere, reaction finishes, reactant is filtered, and the liquid in rotation evaporation that obtains boils off respectively methyl alcohol and ethylene glycol, the solids that obtains 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 adds to depress at nitrogen and carries out, 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; Feeding intake of f and g is 200～600ppm of sour total amount, and described alcohol is the summation of ethylene glycol and e; The temperature of esterification is 180～250 ℃, and pressure is 0.05MPa～0.4MPa, reaction times 1.5～3h; The polycondensation temperature is 250～285 ℃, 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 ℃, 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 comprises one or more in regenerative piece of polyester bottle and useless polyester-containing textiles.
In order to realize second above-mentioned purpose, the present invention also provides above-mentioned preparation method to prepare the low melting point recycled polyester.
In order to realize second above-mentioned purpose, the present invention also provides a kind of core-skin type regenerative polyester staple fiber, and 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 the core-skin type polyester staple fiber, has improved 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 characteristics.Can be used for producing in the industries such as non-woven, flocking, matrix material.
Embodiment
Embodiment 1
1, the preparation of regeneration low-melting point polyester: 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 prepares the regeneration low-melting point polyester by methyl alcohol alcoholysis post polymerization: degradation temperature is 190 ℃, pressure is 2.5Mpa, reaction times is 3h, when equipressure is got back to normal atmosphere, reaction finishes, reactant is filtered, and the liquid in rotation evaporation that obtains boils off respectively methyl alcohol and ethylene glycol, the solids that obtains 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 catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) are the 300ppm of sour total amount in reaction system, then to add weight be the stablizer trimethyl phosphite 99 (TMP) of 0.01% (relatively sour composition).Esterification adds to depress at nitrogen carries out, and temperature is 220 ℃, and pressure is 0.15MPa, reaction times 2.2h; The polycondensation temperature is 275 ℃, and vacuum tightness is 90Pa, reaction times 3.5h.The fusing point of the low-melting point polyester that obtains is 110 ℃, 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, the drum dried temperature is 130 ℃, and be 8h time of drying.The step of liquid-phase tackifying is as follows: 1) temperature after the screw rod melting is 0.55dl/g 270 ℃ of limiting viscosities melt is pumped to the vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 ℃, stop 30min under condition after limiting viscosity can reach 0.68dl/g; 2) melt enters the sticking device of the modified accent of secondary afterwards, melt temperature in the sticking device of the modified accent of secondary is identical with the vacuum separation tower with vacuum tightness, melt constantly advances under the effect of rotatable propeller, 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 ℃, 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 that sprays from the spinning jet of composite component, through cooling, coiling, boundling, drawing-off, typing, cut-out and packing, can get the core-skin type regenerative polyester staple fiber.The drying temperature of recycled polyester is 150 ℃, and be 7h time of drying, 280 ℃ of extruder temperatures; Low-melting point polyester spinning pipeline holding temperature is 230 ℃, and recycled polyester spinning pipeline holding temperature is 275 ℃, and spinning body temperature is 280 ℃; Ring quenching wind-warm syndrome is 15 ℃, and wind speed is 2.0m/s; Spinning speed is 1100m/min; Ratio of drawing is 2.0, and 60 ℃ of drawing temperatures, drawing speed are 110m/min.The core-skin type regenerative polyester staple fiber quality index that obtains 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 regeneration low-melting point polyester: 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 prepares the regeneration low-melting point polyester by the hydrolysis post polymerization: hydrolysis temperature is 220 ℃, pressure is 4.5Mpa, reaction times is 2.8h, when reaction end equipressure is got back to normal atmosphere, reactant is filtered, gained liquid in rotation evaporation obtains ethylene glycol, then will filter solids and be dissolved in DMF and filtering, 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 catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) are the 300ppm of sour total amount in reaction system, then to add weight be the stablizer trimethyl phosphite 99 (TMP) of 0.01% (relatively sour composition).Esterification adds to depress at nitrogen carries out, and temperature is 220 ℃, and pressure is 0.3MPa, reaction times 2.5h; The polycondensation temperature is 275 ℃, and vacuum tightness is 80Pa, and reaction times 3h, the fusing point of the low-melting point polyester that obtains are 105 ℃, 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, the drum dried temperature is 110 ℃, and be 7h time of drying.The step of liquid-phase tackifying is as follows: 1) temperature after the screw rod melting is 0.55dl/g 270 ℃ of limiting viscosities melt is pumped to the vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 ℃, stop 30min under condition after limiting viscosity can reach 0.68dl/g; 2) melt enters the sticking device of the modified accent of secondary afterwards, melt temperature in the sticking device of the modified accent of secondary is identical with the vacuum separation tower with vacuum tightness, melt constantly advances under the effect of rotatable propeller, 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 ℃, 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 that sprays from the spinning jet of composite component, through cooling, coiling, boundling, drawing-off, typing, cut-out and packing, can get the core-skin type regenerative polyester staple fiber.The drying temperature of recycled polyester raw material is 140 ℃, and be 7.5h time of drying, 270 ℃ of extruder temperatures; Low-melting point polyester spinning pipeline holding temperature is 220 ℃, and recycled polyester spinning pipeline holding temperature is 275 ℃, and spinning body temperature is 280 ℃; Ring quenching wind-warm syndrome is 20 ℃, and wind speed is 3.0m/s; Spinning speed is 1000m/min; Ratio of drawing is 3.0, and 56 ℃ of drawing temperatures, drawing speed are 120m/min.The core-skin type regenerative polyester staple fiber quality index that obtains 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 regeneration low-melting point polyester: 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 basic tin laurates is 100:0.5; The alcoholysis reaction temperature is 196 ℃, and pressure is 0.15MPa, and the reaction times is 2h, and the limiting viscosity of reaction solution reaches 0.29dl/g.After reaction finishes, the reaction solution Rapid Thermal is filtered, filtrate is carried out underpressure distillation reclaim ethylene glycol, liquid after underpressure distillation (being solid under normal temperature) is dissolved in heat alcohol, ester, chlorinated hydrocarbon, ketone equal solvent, heat filtering is gone out insolubles, and the filtrate naturally cooling obtains ethylene glycol terephthalate (BHET) and oligopolymer thereof.Add m-phthalic acid (IPA), neopentyl glycol (NPG), the catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) and stablizer trimethyl phosphite 99 (TMP) in ethylene glycol terephthalate (BHET) and oligopolymer thereof, carry out polycondensation, the polycondensation temperature of ethylene glycol terephthalate (BHET) and oligopolymer thereof is 275 ℃, vacuum tightness is 95Pa, reaction times 3.5h.The fusing point of the low-melting point polyester that obtains is 115 ℃, 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 the 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 catalytic antimony trioxide (Sb203) and Cobaltous diacetate (Co (Ac) 2) are the 400ppm of sour total amount in reaction system, then to add weight be the stablizer trimethyl phosphite 99 (TMP) of 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, the drum dried temperature is 100 ℃, and be 7h time of drying.The step of liquid-phase tackifying is as follows: 1) temperature after the screw rod melting is 0.55dl/g 270 ℃ of limiting viscosities melt is pumped to the vacuum separation tower through melt Conveying, melt is 100pa in vacuum tightness, temperature is 280 ℃, stop 30min under condition after limiting viscosity can reach 0.68dl/g; 2) melt enters the sticking device of the modified accent of secondary afterwards, melt temperature in the sticking device of the modified accent of secondary is identical with the vacuum separation tower with vacuum tightness, melt constantly advances under the effect of rotatable propeller, 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 ℃, 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 that sprays from the spinning jet of composite component, through cooling, coiling, boundling, drawing-off, typing, cut-out and packing, can get the core-skin type regenerative polyester staple fiber.The drying temperature of recycled polyester raw material is 140 ℃, and be 7h time of drying, 280 ℃ of extruder temperatures; Low-melting point polyester spinning pipeline holding temperature is 230 ℃, and recycled polyester spinning pipeline holding temperature is 270 ℃, and spinning body temperature is 285 ℃; Ring quenching wind-warm syndrome is 22 ℃, and wind speed is 2.5m/s; Spinning speed is 900m/min; Ratio of drawing is 2.5, and 55 ℃ of drawing temperatures, drawing speed are 110m/min.The core-skin type regenerative polyester staple fiber quality index that obtains 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 (6)
1. the method that the core-skin type polyester is used the low melting point recycled polyester is produced in the methyl alcohol degraded, and it is characterized in that: the low melting point recycled polyester makes by degraded and polycondensation for following raw material:
A. regenerative raw materials;
B. methyl alcohol;
C. one or more in zinc acetate, Potassium ethanoate, manganese acetate, magnesium acetate, plumbic acetate, cobalt chloride, tetrabutyl titanate, titanium isopropylate and the basic tin laurate of 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) with a, b with mix after c feeds intake, the mass ratio that feeds intake of a and b is 1:4～14, the mass ratio of a and c is 100:0.5～1; Degradation temperature is 170～250 ℃, pressure is 1.5～4.0Mpa, reaction times is 2.5～5h, when equipressure is got back to normal atmosphere, reaction finishes, reactant is filtered, and the liquid in rotation evaporation that obtains boils off respectively methyl alcohol and ethylene glycol, the solids that obtains 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 adds to depress at nitrogen and carries out, 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; Feeding intake of f and g is 200～600ppm of sour total amount, and described alcohol is the summation of ethylene glycol and e; The temperature of esterification is 180～250 ℃, and pressure is 0.05MPa～0.4MPa, reaction times 1.5～3h; The polycondensation temperature is 250～285 ℃, and vacuum tightness is 30～200Pa, reaction times 2.5～5h.
2. the method that the core-skin type polyester is used the low melting point recycled polyester is produced in methyl alcohol degraded according to claim 1, and it is characterized in that: the fusing point of low melting point recycled polyester is 70～160 ℃, content of carboxyl end group≤35mmol/kg, and limiting viscosity is 0.5dL/g ~ 1.OdL/g.
3. the method that the core-skin type polyester is used the low melting point recycled polyester is produced in methyl alcohol degraded according to claim 2, and it is characterized in that: the limiting viscosity of low melting point recycled polyester is 0.55dL/g ~ 0.75dL/g.
4. the method that the core-skin type polyester is used the low melting point recycled polyester is produced in methyl alcohol degraded according to claim 1, and it is characterized in that: regenerative raw materials comprises one or more in regenerative piece of polyester bottle and useless polyester-containing textiles.
5. according to claim 1 ~ 4 described preparation methods of any one claim prepare the low melting point recycled polyester.
6. a core-skin type regenerative polyester staple fiber, is characterized in that: the cortex employing low melting point recycled polyester claimed in claim 5 of this core-skin type regenerative polyester staple fiber.
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 true CN103145958A (en) | 2013-06-12 |
| CN103145958B CN103145958B (en) | 2015-08-26 |
Family
ID=48544310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310091294.9A Active CN103145958B (en) | 2013-03-21 | 2013-03-21 | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103145958B (en) |
| WO (1) | WO2014146587A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014146587A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Method for producing low-melting-point recycled polyester used for sheath-core polyester by methanol degradation |
| WO2014146582A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Skin-core type recycled polyester staple fiber and preparation method thereof |
| WO2014146591A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Skin-core type recycled polyester staple fiber and preparation method thereof |
| 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 |
| US20220178051A1 (en) * | 2019-07-15 | 2022-06-09 | Primaloft, Inc. | Recycled polyester binder fiber |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| EP3466388B1 (en) | 2017-10-06 | 2020-05-20 | The Procter & Gamble Company | Absorbent article comprising a nonwoven material with antimony-free polyethylene terephthalate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-03-21 CN CN201310091294.9A patent/CN103145958B/en active Active
-
2014
- 2014-03-20 WO PCT/CN2014/073750 patent/WO2014146587A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014146587A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Method for producing low-melting-point recycled polyester used for sheath-core polyester by methanol degradation |
| WO2014146582A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Skin-core type recycled polyester staple fiber and preparation method thereof |
| WO2014146591A1 (en) * | 2013-03-21 | 2014-09-25 | 宁波大发化纤有限公司 | Skin-core type recycled polyester staple fiber and preparation method thereof |
| 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 |
| US20220178051A1 (en) * | 2019-07-15 | 2022-06-09 | Primaloft, Inc. | Recycled polyester binder fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014146587A1 (en) | 2014-09-25 |
| CN103145958B (en) | 2015-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145957B (en) | Degradation of ethylene glycol produces the method for core-skin type polyester low melting point recycled polyester | |
| CN103147163B (en) | Skin-core type recycled polyester staple fiber and preparation method thereof | |
| CN103145958B (en) | Methanol degradation produces the method for core-skin type polyester low melting point recycled polyester | |
| CN103147162A (en) | Sheath-core type polyester short fiber with core layer made of recycled polyester and preparation method thereof | |
| CN103145959B (en) | Hydrolytic deterioration produces the method for core-skin type polyester low melting point recycled polyester | |
| CN103146020A (en) | High-melting-point renewable polyester for core layers of sheath-core polyester staple fibers and preparation method and application thereof | |
| CN102146598B (en) | PHBV-containing biobased chemical fiber and preparation method thereof | |
| CN102392318B (en) | Biobased biodegradable fiber and preparation method thereof | |
| CN101434691A (en) | Different-shrinkage copolyester and preparation method thereof | |
| JP6639661B2 (en) | High elastic modulus / low shrinkage polyester industrial yarn and method for producing the same | |
| CN114262952B (en) | Composite material and preparation method and application thereof | |
| JP4617872B2 (en) | Polylactic acid fiber | |
| CN113005563A (en) | Preparation method of low-melting-point PTT sheath-core composite copolyester fiber | |
| CN103173889A (en) | Wool-like polyester staple fiber and preparation method thereof | |
| CN115896976A (en) | Regenerated low-melting-point polyester composite fiber with flame retardant function and preparation method thereof | |
| CN115726057A (en) | Regenerated low-melting-point polyester composite fiber with ultraviolet shielding function and preparation method thereof | |
| KR102115821B1 (en) | Low melting polyester resin and polyester composite fiber with excellent thermal fusing property using the same | |
| Hsiao et al. | Analysis of physical properties of PET/CD‐PET polyblend hollow fiber and its kinetics of alkaline hydrolysis | |
| CN109722741B (en) | Sheath-core flame-retardant filament and preparation method thereof | |
| JP2023011638A (en) | Recycled polyester resin and method for producing recycled polyester resin | |
| KR101250351B1 (en) | Antibacterial fire retardancy recycled polyester filament for interior and method thereof | |
| Lommerts | High-performance fibers based on flexible polar polymer molecules | |
| US4025491A (en) | Poly(tetramethylene dibromoterephthalate) yarns | |
| KR101240340B1 (en) | Fire retardancy recycled polyester filament for interior and method thereof | |
| JPH10212652A (en) | Polyester filament based non woven fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201126 Address after: No.8 Xingyao Road, Binhai New Town, Yuyao Economic Development Zone, Ningbo City, Zhejiang Province Patentee after: Yuyao Dafa Chemical Fiber Co.,Ltd. Address before: 315336 No. two, No. 266 Binhai Road, Hangzhou Bay Development Zone, Zhejiang, Ningbo Patentee before: NINGBO DAFA CHEMICAL FIBER Co.,Ltd. |