WO2014146587A1 - 甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法 - Google Patents

甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法 Download PDF

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WO2014146587A1
WO2014146587A1 PCT/CN2014/073750 CN2014073750W WO2014146587A1 WO 2014146587 A1 WO2014146587 A1 WO 2014146587A1 CN 2014073750 W CN2014073750 W CN 2014073750W WO 2014146587 A1 WO2014146587 A1 WO 2014146587A1
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Prior art keywords
polyester
low
sheath
melting
acetate
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PCT/CN2014/073750
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English (en)
French (fr)
Inventor
钱军
王方河
唐世君
邢喜全
秦丹
马哲峰
杜芳
王秀华
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宁波大发化纤有限公司
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Publication of WO2014146587A1 publication Critical patent/WO2014146587A1/zh

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    • 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

Definitions

  • the invention relates to the technical field of chemical fiber production, in particular to a preparation method of a low melting point recycled polyester for a sheath-core type polyester.
  • the low-melting-point sheath-core composite polyester staple fiber refers to a fiber obtained by distributing a core-core structure of the two different polymers of a low-melting-point polyester and a conventional polyester in the same fiber.
  • the skin layer is a low melting point polyester which retains some of the characteristics of conventional polyesters and has good compatibility with conventional polyesters.
  • the low melting point sheath-core composite fiber is mainly used for the heat bonding fiber, and the main function in the production of the nonwoven fabric is that the low melting point fiber skin layer polymer melts at a certain temperature, thereby exerting a bonding effect in the fiber web.
  • the produced non-woven fabric has the characteristics of soft handfeel and high elasticity, and is widely used in sanitary masks, bandages and other sanitary materials and interior decoration materials. field.
  • the invention patent "a low melting point copolyester and a preparation method thereof" discloses a design method of a low melting point copolyester, the melting point of the polyester can be lowered to 110 ° C, and the low melting point copolyester crystallizes Good performance, high intrinsic viscosity, difficult adhesion of particles, good spinnability, etc.
  • Invention patent "manufacturing method of low melting point polyester staple fiber” (application number: 200410072878.2 The low melting point short fiber is obtained by melt spinning after low temperature vacuum drying of the polyester chip having a low melting point of 120 ° C to 130 ° C.
  • Invention patent "a side-by-side composite low-melting staple fiber” (application number: 200810123792.6) discloses that a water-soluble polyester component and a polytrimethylene terephthalate component are juxtaposed into a low-melting staple fiber, and the fiber has good heat shrinkage stability. There have been some reports on the research of low melting core-sheath composite polyester fibers.
  • the invention patent "manufacturing method of sheath-core type low-melting polyester staple fiber" (application No.: 200810163542.5) is characterized in that the skin layer is a low-melting polyester melt obtained by direct spinning of a melt, and the core layer is passed through conventional PET.
  • a conventional PET polyester melt obtained by a slicing process obtained by a slicing process.
  • the use of recycled materials for the preparation of polyester staple fibers as the core layer of sheath-core composite fibers has not been reported so far.
  • polyester waste Recycling has become a necessity for a sustainable society.
  • Most of the short fibers currently prepared from polyester waste are used in low-addition fields such as fillers. Studying the quenching and tempering process to solve the technical problems of wide sources of polyester waste, complex composition and high quality fluctuations.
  • the use of polyester waste to prepare products with high added value has become a major issue in the transformation and upgrading of the recycling industry.
  • the technology replaces low-melting polyester chip spinning with melt direct spinning, which better solves a series of problems such as high drying cost, poor stability and poor fiber spinnability of Russian low-melting polyester, and the production cost is greatly reduced.
  • the first object of the present invention is to provide a method for producing a low-melting point regenerated polyester for a sheath-core type polyester by methanol degradation, which is prepared by the method
  • the low-melting-recycled polyester can be used for preparing the sheath-core type polyester staple fiber, and the added value of the polyester waste to prepare the recycled polyester staple fiber is improved, and the prepared sheath-core type recycled polyester staple fiber has the characteristics of stable quality and excellent quality.
  • a second object of the present invention is to provide a low melting point regenerated polyester prepared by the above process.
  • a third object of the present invention is to provide an application of the low melting point regenerated polyester prepared by the above method.
  • Methanol degradation produces a low-melting-recycled polyester for sheath-core polyester, which is obtained by degradation and polycondensation of the following raw materials:
  • neopentyl glycol e. one or more of neopentyl glycol, hexanediol, butylene glycol and polyethylene glycol;
  • the mass ratio of a and b is 1:4 to 14
  • the mass ratio of a to c is 100:0.5 to 1
  • the degradation temperature is 170 to 250 ° C
  • the pressure is 1.5.
  • the reaction time is 2.5 ⁇ 5h
  • the reaction is completed when the pressure returns to atmospheric pressure
  • the reaction is filtered, the obtained liquid is rotary evaporated, methanol and ethylene glycol are separately evaporated, and the obtained solid is dissolved in hot ethanol.
  • the obtained liquid is evaporated to ethanol to obtain dimethyl terephthalate;
  • the esterification reaction of dimethyl terephthalate with ethylene glycol is carried out under nitrogen pressure, and the molar ratio of dimethyl terephthalate to d is 2 to 5:1;
  • the molar ratio of ester to e is 3 to 19:1;
  • the molar ratio of dimethyl terephthalate to ethylene glycol is 20:80 to 80:20;
  • the molar ratio of alkyd is 1.4 to 1.6:1;
  • the feed of f and g is 200-600 ppm of the total amount of the acid, the alcohol is the sum of ethylene glycol and e;
  • the temperature of the esterification reaction is 180-250 ° C, the pressure is 0.05 MPa-0.4 MPa, and the reaction time is 1.5- 3h;
  • polycondensation reaction temperature is 250 ⁇ 285 ° C, vacuum degree is 30 ⁇ 200Pa, reaction time 2.5 ⁇ 5h.
  • the low-melting-recycled polyester has a melting point of 70 to 160 ° C, a terminal carboxyl group content of ⁇ 35 mmol/kg, and an intrinsic viscosity of 0.5 dL/g to 1.0 OdL/g.
  • the low-melting-recycled polyester has an intrinsic viscosity of 0.55 dL/g to 0.75 dL/g.
  • the recycled raw material comprises one or more of a reconstituted polyester bottle flake and a waste polyester textile.
  • the present invention also provides a low melting point regenerated polyester prepared by the above preparation method.
  • the present invention also provides a sheath-core type regenerated polyester staple fiber, which is made of the above-mentioned low-melting-recycled polyester.
  • the low-melting-recycled polyester of the invention can be used for preparing sheath-core type polyester staple fibers, and the added value of the prepared polyester staple fiber for polyester scrap is improved, and the prepared sheath-core type recycled polyester staple fiber has stable quality and excellent quality. specialty. Can be used in the production of non-woven fabrics, flocking, composite materials and other industries.
  • the mass ratio of recycled raw materials to methanol is 1:6; the mass ratio of recycled raw materials to zinc acetate is 100:0.5; the above raw materials are polymerized by methanol to prepare recycled low-melting polyester.
  • the degradation temperature is 190 ° C, the pressure is 2.5 Mpa, the reaction time is 3 h, the reaction is completed when the pressure returns to atmospheric pressure, the reaction is filtered, the obtained liquid is rotary evaporated, and methanol and ethylene glycol are separately distilled off to obtain a solid matter. It was dissolved in hot ethanol and filtered, and the obtained liquid was evaporated to give dimethyl terephthalate (DMT).
  • DMT dimethyl terephthalate
  • the molar ratio of dimethyl terephthalate (DMT) to isophthalic acid (IPA) is 3:1; the molar ratio of dimethyl terephthalate (DMT) to neopentyl glycol (NPG) is 7:1; the molar ratio of dimethyl terephthalate (DMT) to ethylene glycol is 1:2; the molar ratio of alcohol (sum of ethylene glycol to neopentyl glycol (NPG)) is 1.5:1
  • Catalyst antimony trioxide (Sb203) and cobalt acetate (Co(Ac)2) It is 300 ppm of the total amount of acid in the reaction system, and a stabilizer of trimethyl phosphate is added in an amount of 0.01% by weight (relative to the acid component).
  • the esterification reaction was carried out under a nitrogen pressure at a temperature of 220 ° C, a pressure of 0.15 MPa, a reaction time of 2.2 h, a polycondensation reaction temperature of 275 ° C, a vacuum of 90 Pa, and a reaction time of 3.5 h.
  • the obtained low melting point polyester had a melting point of 110 ° C, a terminal carboxyl group content of 25 mmol/kg, and an intrinsic viscosity of 0.69 dL/g.
  • the preparation of recycled polyester the use of bottle flakes through cleaning, drum drying, multi-stage filtration, liquid phase thickening process.
  • the drum drying temperature was 130 ° C
  • the drying time was 8 h.
  • the steps of liquid phase thickening are as follows: 1) The melt having a temperature of 270 ° C and an intrinsic viscosity of 0.55 dl / g after being melted by the screw is pumped to the vacuum separation tower by melt transfer, and the melt is at a vacuum of 100 Pa, and the temperature is At 280 ° C, the intrinsic viscosity can reach 0.68 dl / g after staying for 30 min; 2) the melt enters the secondary quenching and tempering adjustment device, the melt temperature and vacuum degree in the secondary quenching and tempering device and the vacuum separation tower In the same way, the melt continues to advance under the action of the rotary propeller, the melt viscosity is continuously increased, and the rotation speed of the propeller is 5r/min.
  • the residence time was 20 min and the final melt intrinsic viscosity was 0.79 dl/g.
  • the regenerated polyester had a melting point of 264 ° C, a terminal carboxyl group content of 16 mmol/kg, and an intrinsic viscosity of 0.79 dl/g.
  • sheath-core type recycled polyester staple fiber the above low-melting polyester and recycled polyester are accurately metered into the composite spinneret with a weight of 4:6 core, respectively, and the melt ejected from the spinneret of the composite component
  • the core-type reclaimed polyester staple fiber can be obtained by cooling, winding, bundling, drawing, shaping, cutting and packing.
  • the drying temperature of the recycled polyester is 150 ° C, the drying time is 7 h, the screw temperature is 280 ° C; the low melting point polyester spinning pipe insulation temperature is 230 ° C, the regenerated polyester spinning pipe insulation temperature is 275 ° C, the spinning box temperature It is 280 ° C; the ring air cooling cooling air temperature is 15 ° C, the wind speed is 2.0 m / s; the spinning speed is 1100 m / min; the draft ratio is 2.0, the drawing temperature is 75 ° C, and the drafting speed is 110 m / min.
  • the quality index of the sheath-core type recycled polyester staple fiber obtained by the above production process is:
  • regenerated low-melting polyester the mass ratio of recycled raw materials to water is 1:4; the mass ratio of recycled raw materials to potassium acetate is 100:0.5; the above raw materials are polymerized by hydrolysis to prepare regenerated low-melting polyester: hydrolysis
  • the temperature is 220 ° C, the pressure is 4.5 Mpa, the reaction time is 2.8 h, and when the pressure is returned to the atmospheric pressure, the reaction product is filtered, and the obtained liquid is rotary evaporated to obtain ethylene glycol, and the filtered solid is dissolved in DMF and filtered.
  • the resulting liquid was recrystallized to give terephthalic acid (TPA).
  • the molar ratio of terephthalic acid (TPA) to adipic acid (AA) is 3.5:1; the molar ratio of terephthalic acid (TPA) to hexanediol (HG) is 6:1; terephthalic acid
  • the molar ratio of (TPA) to ethylene glycol is 1.5:1; the molar ratio of alkyd is 1.5:1; catalyst antimony trioxide (Sb203) and cobalt acetate (Co(Ac)2) 300 ppm of the total amount of acid in the reaction system, and a stabilizer of trimethyl phosphate of 0.01% by weight (relative to the acid component) (TMP).
  • the esterification reaction was carried out under nitrogen pressure at a temperature of 220 ° C, a pressure of 0.3 MPa, a reaction time of 2.5 h, a polycondensation reaction temperature of 275 ° C, a vacuum of 80 Pa, and a reaction time of 3 h.
  • the melting point of the obtained low melting point polyester was The terminal carboxyl group content was 28 mmol/kg at 105 ° C, and the intrinsic viscosity was 0.67 dL/g.
  • the preparation of recycled polyester the use of bottle flakes through cleaning, drum drying, multi-stage filtration, liquid phase thickening process.
  • the drum drying temperature was 110 ° C
  • the drying time was 7 h.
  • the steps of liquid phase thickening are as follows: 1) The melt having a temperature of 270 ° C and an intrinsic viscosity of 0.55 dl / g after being melted by the screw is pumped to the vacuum separation tower by melt transfer, and the melt is at a vacuum of 100 Pa, and the temperature is At 280 ° C, the intrinsic viscosity can reach 0.68 dl / g after staying for 30 min; 2) the melt enters the secondary quenching and tempering adjustment device, the melt temperature and vacuum degree in the secondary quenching and tempering device and the vacuum separation tower In the same way, the melt continues to advance under the action of the rotary propeller, the melt viscosity is continuously increased, and the rotation speed of the propeller is 5r/min.
  • the residence time was 15 min and the final melt intrinsic viscosity was 0.78 dl/g.
  • the regenerated polyester had a melting point of 269 ° C, a terminal carboxyl group content of 14 mmol/kg, and an intrinsic viscosity of 0.78 dl/g.
  • sheath-core type recycled polyester staple fiber the above low-melting polyester and recycled polyester are accurately metered into the composite spinneret with a 5:5 core weight, respectively, and the melt ejected from the spinneret of the composite component
  • the core-type reclaimed polyester staple fiber can be obtained by cooling, winding, bundling, drawing, shaping, cutting and packing.
  • the drying temperature of the recycled polyester raw material is 140 ° C, the drying time is 7.5 h, the screw temperature is 270 ° C; the low melting point polyester spinning pipe insulation temperature is 220 ° C, and the regenerated polyester spinning pipe insulation temperature is 275 ° C, the spinning box
  • the body temperature was 280 ° C; the ring blowing cooling air temperature was 20 ° C, the wind speed was 3.0 m / s; the spinning speed was 1000 m / min; the draft ratio was 3.0, the drawing temperature was 70 ° C, and the drafting speed was 120 m / min.
  • the quality index of the sheath-core type recycled polyester staple fiber obtained by the above production process is:
  • ethylene terephthalate ethylene terephthalate
  • IPA isophthalic acid
  • NPG neopentyl glycol
  • SB203 catalyst antimony trioxide
  • Co(Ac) cobalt acetate
  • TMP stabilizer trimethyl phosphate
  • the obtained low melting point polyester had a melting point of 115 ° C, a terminal carboxyl group content of 30 mmol/kg, and an intrinsic viscosity of 0.68 dL/g.
  • the molar amount of isophthalic acid (IPA) is the mass of the recycled raw material / 450; the molar amount of neopentyl glycol (NPG) is the mass of the recycled raw material / 960; the molar ratio of the alkyd is 1.4; the catalyst is antimony trioxide (Sb203) and cobalt acetate (Co(Ac)2)
  • Sb203 antimony trioxide
  • Co(Ac)2 cobalt acetate
  • TMP trimethyl phosphate
  • the preparation of recycled polyester the use of bottle flakes through cleaning, drum drying, multi-stage filtration, liquid phase thickening process.
  • the drum drying temperature was 100 ° C
  • the drying time was 7 h.
  • the steps of liquid phase thickening are as follows: 1) The melt having a temperature of 270 ° C and an intrinsic viscosity of 0.55 dl / g after being melted by the screw is pumped to the vacuum separation tower by melt transfer, and the melt is at a vacuum of 100 Pa, and the temperature is At 280 ° C, the intrinsic viscosity can reach 0.68 dl / g after staying for 30 min; 2) the melt enters the secondary quenching and tempering adjustment device, the melt temperature and vacuum degree in the secondary quenching and tempering device and the vacuum separation tower In the same way, the melt continues to advance under the action of the rotary propeller, the melt viscosity is continuously increased, and the rotation speed of the propeller is 5r/min.
  • the residence time was 15 min and the final melt intrinsic viscosity was 0.78 dl/g.
  • the regenerated polyester had a melting point of 267 ° C, a terminal carboxyl group content of 16 mmol/kg, and an intrinsic viscosity of 0.78 dl/g.
  • sheath-core type recycled polyester staple fiber the above low-melting polyester and recycled polyester are accurately metered into the composite spinneret with a weight of 6:4 core, respectively, and the melt ejected from the spinneret of the composite component
  • the core-type reclaimed polyester staple fiber can be obtained by cooling, winding, bundling, drawing, shaping, cutting and packing.
  • the drying temperature of the recycled polyester raw material is 140 ° C, the drying time is 7 h, the screw temperature is 280 ° C; the low melting point polyester spinning pipe insulation temperature is 230 ° C, the regenerated polyester spinning pipe insulation temperature is 270 ° C, the spinning box The temperature was 285 ° C; the ring air cooling cooling air temperature was 22 ° C, the wind speed was 2.5 m / s; the spinning speed was 900 m / min; the draft ratio was 2.5, the drawing temperature was 60 ° C, and the drafting speed was 110 m / min.
  • the quality index of the sheath-core type recycled polyester staple fiber obtained by the above production process is:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Multicomponent Fibers (AREA)

Abstract

一种皮芯型聚酯用低熔点再生聚酯的制备方法，所述的低熔点再生聚酯为以下原料通过降解和缩聚反应而制得：a.再生原料；b.甲醇；c.醋酸锌、醋酸钾、醋酸锰、醋酸镁、醋酸铅、氯化钴、钛酸四丁酯、钛酸四异丙酯和丁二基月桂酸锡中的一种或多种；d.间苯二甲酸、己二酸和癸二酸中的一种或多种；e.新戊二醇、己二醇、丁二醇和聚乙二醇中的一种或多种；f.催化剂三氧化二锑和醋酸钴；g.稳定剂磷酸三甲酯。所述低熔点再生聚酯可用于制备皮芯型聚酯短纤维，制备的聚酯短纤维可用于生产非织造物、植绒、复合材料等行业中。

Description

甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法 技术领域
本发明涉及属化纤生产技术领域，尤其涉及一种皮芯型聚酯用低熔点再生聚酯的制备方法。
背景技术
低熔点皮芯型复合聚酯短纤维是指用低熔点聚酯和常规聚酯这两种不同的聚合物以皮芯结构分布于同一根纤维之中制成的纤维。皮层是低熔点聚酯，它保留了常规聚酯的部分特性，与常规聚酯具有良好的相容性的特点。低熔点皮芯复合纤维主要用于热粘合纤维，在非织造布生产中主要作用是在一定温度下低熔点纤维皮层聚合物熔化，从而在纤维网中起到黏结效果。由于低熔点涤纶短纤维具有强度高、膨松性好、弹性恢复率高，生产出的非织造布具有手感柔软、弹性高等特点，目前广泛使用在手术口罩、绷带等卫生材料和室内装饰材料等领域。
目前对于低熔点聚酯短纤维的生产方法有较多的研究报道。如发明专利“一种低熔点共聚酯及其制备方法”(申请号:200810063395.4)公开了低熔点共聚酯的设计方法，聚酯熔点可降至110℃，而且该低熔点共聚酯结晶性能好、特性粘度高、粒子不易粘连、具有良好的可纺性等。发明专利“一种低熔点聚酯短纤维的生产方法”(申请号:200410072878.2 )采用120℃～130℃低熔点聚酯切片经过低温真空干燥后，经熔融纺丝可得低熔点短纤维。发明专利“一种并列型复合的低熔点短纤”(申请号: 200810123792.6)公开的是水溶性聚酯组分与聚对苯二甲酸丙二酯组分并列复合而成低熔点短纤，此纤维具有良好的热收缩率稳定性。关于低熔点皮芯复合聚酯纤维的研究也有一些报道。如发明专利“一种皮芯型低熔点聚酯短纤维的生产方法”（申请号：200810163542.5）其特征在于皮层为通过熔体直纺得到的低熔点聚酯熔体，芯层为通过常规PET切片纺工艺得到的常规PET聚酯熔体。但是利用再生料制备聚酯短纤维作为皮芯型复合纤维的芯层至今没有报道。
随着聚酯材料在各领域的迅速发展和使用，聚酯废料的排放量与日俱增，其难降解性现已对环境造成了极大的污染，并且由于目前工业原料的缺乏，对聚酯废料的回收再利用已成为可持续发展社会之所需。目前用聚酯废料制备的短纤维大部分用于填充物等低附加领域。研究调质调粘工艺，解决聚酯废料来源广、成分复杂、质量波动大的技术难题，利用聚酯废料制备具有高附加值的产品成为再生行业转型升级的一个重大课题。另外，该技术以熔体直纺替代低熔聚酯切片纺丝，较好的解决俄低熔点聚酯干燥成本大、稳定性差、纤维可纺性差等一系列问问题，生产成本大幅下降。
 技术问题
为了解决利用再生料制备聚酯皮芯型复合纤维存在的技术问题，本发明的第一个目的在于提供一种甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，该方法制备的低熔点再生聚酯可用于制备皮芯型聚酯短纤维，提高了聚酯废料制备再生聚酯短纤维的附加值，制备的皮芯型再生聚酯短纤维具有质量稳定，品质优良的特点。本发明的第二个目的在于提供采用上述的方法制备的低熔点再生聚酯。本发明的第三个目的在于提供采用上述的方法制备的低熔点再生聚酯的应用。
技术解决方案
为了实现上述的第一个目的，本发明采用了以下的技术方案：
甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，所述的低熔点再生聚酯为以下原料通过降解和缩聚反应而制得：
a.再生原料；
b. 甲醇；
c.醋酸锌、醋酸钾、醋酸锰、醋酸镁、醋酸铅、氯化钴、钛酸四丁酯、钛酸四异丙酯和丁二基月桂酸锡中的一种或多种；
d.间苯二甲酸，己二酸和癸二酸中的一种或多种；
e.新戊二醇，己二醇，丁二醇和聚乙二醇中的一种或多种；
f.催化剂三氧化二锑和醋酸钴；
g.稳定剂磷酸三甲酯；
具体方法如下：
1）将a、b与c投料后混合，a与b的投料质量比为1：4～14，a与c的质量比为100:0.5～1；降解温度为170～250℃，压力为1.5～4.0Mpa，反应时间为2.5～5h，等压力回到大气压时反应结束，将反应物过滤，得到的液体旋转蒸发，分别蒸去甲醇与乙二醇，得到的固体物溶于热乙醇中过滤，所得液体蒸去乙醇得到对苯二甲酸二甲酯；
2）对苯二甲酸二甲酯与乙二醇的酯化反应在氮气加压下进行，对苯二甲酸二甲酯与d的投料摩尔比为2～5:1；对苯二甲酸二甲酯与e的投料摩尔比为3～19:1；对苯二甲酸二甲酯与乙二醇的摩尔比为：20:80～80:20；醇酸的摩尔比例为1.4～1.6:1；f与g的投料为酸总量的200～600ppm，所述的醇为乙二醇与e的总和；酯化反应的温度为180～250℃，压力为0.05MPa～0.4MPa，反应时间1.5～3h；缩聚反应温度为250～285℃，真空度为30～200Pa，反应时间2.5～5h。
作为优选，所述的低熔点再生聚酯的熔点为70～160℃，端羧基含量≤35mmol/kg，特性粘度为0.5dL/g~1.OdL/g。
作为再优选，所述的低熔点再生聚酯的特性粘度为0.55dL/g~0.75dL/g。
作为优选，所述的再生原料包括再生聚酯瓶片和废聚酯纺织品中的一种或多种。
为了实现上述的第二个目的，本发明还提供了上述的制备方法制备得到低熔点再生聚酯。
为了实现上述的第二个目的，本发明还提供了一种皮芯型再生聚酯短纤维，该皮芯型再生聚酯短纤维的皮层采用上述的低熔点再生聚酯。
 有益效果
本发明的低熔点再生聚酯可用于制备皮芯型聚酯短纤维，提高了聚酯废料制备再生聚酯短纤维的附加值，制备的皮芯型再生聚酯短纤维具有质量稳定，品质优良的特点。可用于生产非织造布、植绒、复合材料等行业中。
附图说明
本发明的最佳实施方式
本发明的实施方式
实施例1
1、再生低熔点聚酯的制备：再生原料与甲醇的投料质量比为1：6；再生原料与醋酸锌的质量比为100:0.5；以上原料通过甲醇醇解后聚合制备再生低熔点聚酯：降解温度为190℃，压力为2.5Mpa，反应时间为3h，等压力回到大气压时反应结束，将反应物过滤，得到的液体旋转蒸发，分别蒸去甲醇与乙二醇，得到的固体物溶于热乙醇中过滤，所得液体蒸去乙醇得到对苯二甲酸二甲酯(DMT)。对苯二甲酸二甲酯(DMT)与间苯二甲酸（IPA）的投料摩尔比为3:1；对苯二甲酸二甲酯(DMT)与新戊二醇（NPG）的投料摩尔比为7:1；对苯二甲酸二甲酯(DMT)与乙二醇的摩尔比为1:2；醇（乙二醇与新戊二醇（NPG）的总和）酸的摩尔比例为1.5:1；催化剂三氧化二锑(Sb203)与醋酸钴(Co(Ac)2) 为反应体系中酸总量的300ppm，再加入加入重量为0.01%(相对酸成份)的稳定剂磷酸三甲酯 (TMP)。酯化反应在氮气加压下进行，温度为220℃，压力为0.15MPa，反应时间2.2h；缩聚反应温度为275℃，真空度为90Pa，反应时间3.5h。得到的低熔点聚酯的熔点为110℃，端羧基含量为25mmol/kg，特性粘度为0.69dL/g。
2、再生聚酯的制备：采用瓶片料经过清洗、转鼓干燥、多级过滤、液相增粘的工艺流程。其中，转鼓干燥温度为130℃，干燥时间为8h。液相增粘的步骤如下：1）经螺杆熔融后的温度在270℃特性粘度为0.55dl/g的熔体经熔体输送泵送至真空分离塔，熔体在真空度为100pa，温度为280℃,条件下停留30min之后特性粘度可达到0.68dl/g；2）之后熔体进入二级调质调粘装置，二级调质调粘装置内的熔体温度和真空度与真空分离塔相同，在旋转推进器的作用下熔体不断前进，熔体粘度不断增加，推进器的旋转速度为5r/min ,停留时间20min，最终熔体特性粘度在0.79dl/g。再生聚酯的熔点为264℃，端羧基含量为16 mmol/kg，特性粘度为0.79dl/g。
3、皮芯型再生聚酯短纤维:将上述低熔点聚酯与再生聚酯分别以4:6皮芯重量精确计量进入复合喷丝组件，从复合组件的喷丝板中喷出的熔体，经冷却、卷绕、集束、牵伸、定型、切断和打包，可得皮芯型再生聚酯短纤维。再生聚酯的干燥温度为150℃，干燥时间为7h，螺杆温度280℃；低熔点聚酯纺丝管道保温温度为230℃，再生聚酯纺丝管道保温温度为275℃，纺丝箱体温度为280℃；环吹风冷却风温为15℃，风速为2.0m/s；纺丝速度为1100m/min；牵伸比为2.0，牵伸温度75℃，牵伸速度为110m/min。经上述生产工艺得到的皮芯型再生聚酯短纤维质量指标为:
线密度:4.21dtex
断裂强度:3.14cN/dtex
断裂伸长率:40%
切断长度:51.2mm。
实施例2
1、再生低熔点聚酯的制备：再生原料与水的投料质量比为1：4；再生原料与醋酸钾的质量比为100:0.5；以上原料通过水解后聚合制备再生低熔点聚酯：水解温度为220℃，压力为4.5Mpa，反应时间为2.8h，反应结束等压力回到大气压时，将反应物过滤，所得液体旋转蒸发得到乙二醇，再将过滤固体物溶于DMF中过滤，所得液体重结晶得到对苯二甲酸（TPA）。对苯二甲酸（TPA）与己二酸(AA)的投料摩尔比为3.5:1；对苯二甲酸（TPA）与己二醇（HG）的投料摩尔比为6:1；对苯二甲酸（TPA）与乙二醇的摩尔比为1.5:1；醇酸的摩尔比例为1.5：1；催化剂三氧化二锑(Sb203)与醋酸钴(Co(Ac)2) 为反应体系中酸总量的300ppm，再加入重量为0.01%(相对酸成份)的稳定剂磷酸三甲酯 (TMP)。酯化反应在氮气加压下进行，温度为220℃，压力为0.3MPa，反应时间2.5h；缩聚反应温度为275℃，真空度为80Pa，反应时间3h，得到的低熔点聚酯的熔点为105℃，端羧基含量为28mmol/kg，特性粘度为0.67dL/g。
2、再生聚酯的制备：采用瓶片料经过清洗、转鼓干燥、多级过滤、液相增粘的工艺流程。其中，转鼓干燥温度为110℃，干燥时间为7h。液相增粘的步骤如下：1）经螺杆熔融后的温度在270℃特性粘度为0.55dl/g的熔体经熔体输送泵送至真空分离塔，熔体在真空度为100pa，温度为280℃,条件下停留30min之后特性粘度可达到0.68dl/g；2）之后熔体进入二级调质调粘装置，二级调质调粘装置内的熔体温度和真空度与真空分离塔相同，在旋转推进器的作用下熔体不断前进，熔体粘度不断增加，推进器的旋转速度为5r/min ,停留时间15min，最终熔体特性粘度在0.78dl/g。再生聚酯的熔点为269℃，端羧基含量为14 mmol/kg，特性粘度为0.78dl/g。
3、皮芯型再生聚酯短纤维:将上述低熔点聚酯与再生聚酯分别以5:5皮芯重量精确计量进入复合喷丝组件，从复合组件的喷丝板中喷出的熔体，经冷却、卷绕、集束、牵伸、定型、切断和打包，可得皮芯型再生聚酯短纤维。再生聚酯原料的干燥温度为140℃，干燥时间为7.5h，螺杆温度270℃；低熔点聚酯纺丝管道保温温度为220℃，再生聚酯纺丝管道保温温度为275℃，纺丝箱体温度为280℃；环吹风冷却风温为20℃，风速为3.0m/s；纺丝速度为1000m/min；牵伸比为3.0，牵伸温度70℃，牵伸速度为120m/min。经上述生产工艺得到的皮芯型再生聚酯短纤维质量指标为:
线密度:4.05dtex
断裂强度:3.22cN/dtex
断裂伸长率:42%
切断长度:51.6mm。
实施例3
1、再生低熔点聚酯的制备：再生原料与乙二醇的投料质量比为1：3.5；再生原料与丁二基月桂酸锡的质量比为100:0.5；醇解反应温度为196℃，压力为0.15MPa，反应时间为2h，反应液的特性粘度达到0.29dl/g。反应结束后，将反应液快速热过滤，对滤液进行减压蒸馏回收乙二醇，将减压蒸馏后的液体(常温下为固体)溶于热醇、酯、氯化烃、酮等溶剂中，热过滤出去不溶物，滤液自然冷却得到对苯二甲酸乙二醇酯（BHET）及其低聚物。在对苯二甲酸乙二醇酯（BHET）及其低聚物中加入间苯二甲酸（IPA）、新戊二醇（NPG）、催化剂三氧化二锑(Sb203)与醋酸钴(Co(Ac)2)和稳定剂磷酸三甲酯 (TMP)，进行缩聚反应，对苯二甲酸乙二醇酯（BHET）及其低聚物的缩聚反应温度为275℃，真空度为95Pa，反应时间3.5h。得到的低熔点聚酯的熔点为115℃，端羧基含量为30mmol/kg，特性粘度为0.68dL/g。间苯二甲酸（IPA）的投料摩尔量为再生原料的质量/450；新戊二醇（NPG）的投料摩尔量为再生原料质量/960；醇酸的摩尔比例为1.4；催化剂三氧化二锑(Sb203)与醋酸钴(Co(Ac)2) 为反应体系中酸总量的400ppm，再加入重量为0.01%(相对酸成份)的稳定剂磷酸三甲酯 (TMP)。
2、再生聚酯的制备：采用瓶片料经过清洗、转鼓干燥、多级过滤、液相增粘的工艺流程。其中，转鼓干燥温度为100℃，干燥时间为7h。液相增粘的步骤如下：1）经螺杆熔融后的温度在270℃特性粘度为0.55dl/g的熔体经熔体输送泵送至真空分离塔，熔体在真空度为100pa，温度为280℃,条件下停留30min之后特性粘度可达到0.68dl/g；2）之后熔体进入二级调质调粘装置，二级调质调粘装置内的熔体温度和真空度与真空分离塔相同，在旋转推进器的作用下熔体不断前进，熔体粘度不断增加，推进器的旋转速度为5r/min ,停留时间15min，最终熔体特性粘度在0.78dl/g。再生聚酯的熔点为267℃，端羧基含量为16 mmol/kg，特性粘度为0.78dl/g。
3、皮芯型再生聚酯短纤维:将上述低熔点聚酯与再生聚酯分别以6:4皮芯重量精确计量进入复合喷丝组件，从复合组件的喷丝板中喷出的熔体，经冷却、卷绕、集束、牵伸、定型、切断和打包，可得皮芯型再生聚酯短纤维。再生聚酯原料的干燥温度为140℃，干燥时间为7h，螺杆温度280℃；低熔点聚酯纺丝管道保温温度为230℃，再生聚酯纺丝管道保温温度为270℃，纺丝箱体温度为285℃；环吹风冷却风温为22℃，风速为2.5m/s；纺丝速度为900m/min；牵伸比为2.5，牵伸温度60℃，牵伸速度为110m/min。经上述生产工艺得到的皮芯型再生聚酯短纤维质量指标为:
线密度:4.24 dtex
断裂强度:2.67 cN/dtex
断裂伸长率:47%
切断长度:50.8mm。
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Claims (6)

  1. 甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，其特征在于：低熔点再生聚酯为以下原料通过降解和缩聚反应而制得：
    a.再生原料；
    b.甲醇；
    c.醋酸锌、醋酸钾、醋酸锰、醋酸镁、醋酸铅、氯化钴、钛酸四丁酯、钛酸四异丙酯和丁二基月桂酸锡中的一种或多种；
    d.间苯二甲酸，己二酸和癸二酸中的一种或多种；
    e.新戊二醇，己二醇，丁二醇和聚乙二醇中的一种或多种；
    f.催化剂三氧化二锑和醋酸钴；
    g.稳定剂磷酸三甲酯；
    具体方法如下：
    1）将a、b与c投料后混合，a与b的投料质量比为1：4～14，a与c的质量比为100:0.5～1；降解温度为170～250℃，压力为1.5～4.0Mpa，反应时间为2.5～5h，等压力回到大气压时反应结束，将反应物过滤，得到的液体旋转蒸发，分别蒸去甲醇与乙二醇，得到的固体物溶于热乙醇中过滤，所得液体蒸去乙醇得到对苯二甲酸二甲酯；
    2）对苯二甲酸二甲酯与乙二醇的酯化反应在氮气加压下进行，对苯二甲酸二甲酯与d的投料摩尔比为2～5:1；对苯二甲酸二甲酯与e的投料摩尔比为3～19:1；对苯二甲酸二甲酯与乙二醇的摩尔比为：20:80～80:20；醇酸的摩尔比例为1.4～1.6:1；f与g的投料为酸总量的200～600ppm，所述的醇为乙二醇与e的总和；酯化反应的温度为180～250℃，压力为0.05MPa～0.4MPa，反应时间1.5～3h；缩聚反应温度为250～285℃，真空度为30～200Pa，反应时间2.5～5h。
  2. 根据权利要求1所述的甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，其特征在于：低熔点再生聚酯的熔点为70～160℃，端羧基含量≤35mmol/kg，特性粘度为0.5dL/g~1.0dL/g。
  3. 根据权利要求2所述的甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，其特征在于：低熔点再生聚酯的特性粘度为0.55dL/g~0.75dL/g。
  4. 根据权利要求1所述的甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法，其特征在于：再生原料包括再生聚酯瓶片和废聚酯纺织品中的一种或多种。
  5. 根据权利要求1~4任意一项权利要求所述的制备方法制备得到低熔点再生聚酯。
  6. 一种皮芯型再生聚酯短纤维，其特征在于：该皮芯型再生聚酯短纤维的皮层采用权利要求5所述的低熔点再生聚酯。
PCT/CN2014/073750 2013-03-21 2014-03-20 甲醇降解生产皮芯型聚酯用低熔点再生聚酯的方法 WO2014146587A1 (zh)

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