CN115748003A - High-moisture-absorption regenerated PET (polyethylene terephthalate) fiber and processing technology thereof - Google Patents
High-moisture-absorption regenerated PET (polyethylene terephthalate) fiber and processing technology thereof Download PDFInfo
- Publication number
- CN115748003A CN115748003A CN202211534557.4A CN202211534557A CN115748003A CN 115748003 A CN115748003 A CN 115748003A CN 202211534557 A CN202211534557 A CN 202211534557A CN 115748003 A CN115748003 A CN 115748003A
- Authority
- CN
- China
- Prior art keywords
- parts
- pet fiber
- regenerated
- reacting
- regenerated pet
- 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
-
- 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
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the technical field of PET (polyethylene terephthalate) regenerated fibers, in particular to a high-moisture-absorption regenerated PET fiber and a processing process thereof, wherein the high-moisture-absorption regenerated PET fiber comprises the following preparation processes: (1) Depolymerizing the recovered PET, ethylene glycol and depolymerizing agent to obtain an oligomer; adding polyester polyol, terephthalic acid, trimesic acid and 2-carboxyethyl phenyl hypophosphorous acid, and reacting to obtain regenerated PET; (2) Mixing with a filler and a catalyst, and spinning to obtain a regenerated PET fiber; (3) Dipping in a finishing agent to obtain high-moisture-absorption regenerated PET fibers; the polyester polyol contains a morpholine dione structure. According to the invention, the degradation influence on the main chain caused by 2-carboxyethyl phenyl hypophosphorous acid can be relieved by recovering the copolymerization of oligomer and polyester polyol formed by PET depolymerization and the modification treatment of sodium montmorillonite, and the hydrolysis resistance of the prepared high-moisture-absorption regenerated PET fiber can be improved; and meanwhile, ether bond is introduced into the finishing agent, so that the hydrophilic moisture absorption performance and hydrolysis resistance of the prepared fiber can be further improved.
Description
Technical Field
The invention relates to the technical field of PET (polyethylene terephthalate) regenerated fibers, in particular to a high-moisture-absorption regenerated PET fiber and a processing technology thereof.
Background
In the field of polymer material application, as the most widely applied synthetic fiber at present, polyethylene terephthalate (PET) fiber has the properties of high strength, high modulus, moderate rebound resilience, good wrinkle resistance and the like, the dosage of the PET fiber is increased year by year, and the solid wastes discharged into the nature are also increased rapidly. However, because PET is difficult to degrade in nature, the environment is greatly stressed and damaged in the morning by landfill or incineration, and the waste PET needs to be recycled. In the application of PET, in order to improve the moisture absorption of PET, hydrophilic moisture absorption fibers are prepared in both synthesis and spinning. Conventionally, the fiber surface is coated with certain hygroscopic groups through hydrophilic treatment in dyeing and finishing processes, so that high hygroscopicity is realized, but the washing fastness is poor. Therefore, we propose a high moisture absorption regenerated PET fiber and its processing technology.
Disclosure of Invention
The invention aims to provide a high-moisture-absorption regenerated PET fiber and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a processing technology of high-moisture-absorption regenerated PET fibers comprises the following preparation processes:
(1) Preparation of recycled PET:
mixing the recovered PET, ethylene glycol and a depolymerizing agent, heating to 220-240 ℃, and carrying out depolymerization reaction for 2-4 h under the condition of 0.16-0.20 MPa to obtain an oligomer;
adding polyester polyol and terephthalic acid, and esterifying and dehydrating for 2-3 h at the temperature of 240-260 ℃; adding trimesic acid and 2-carboxyethyl phenyl hypophosphorous acid, and continuing to react for 1-2 h;
carrying out polycondensation reaction for 2-3 h at the temperature of 280-285 ℃ and under the vacuum pressure of 20-100 Pa to obtain regenerated PET;
(2) Preparation of regenerated PET fiber: mixing with a filler and a catalyst, and spinning to obtain a regenerated PET fiber;
(3) Preparing the high-moisture-absorption regenerated PET fiber: and (3) putting the PET fibers into a finishing agent for dipping to obtain the high-moisture-absorption regenerated PET fibers.
Further, the recycled PET comprises the following components in percentage by mass: 60-70 parts of oligomer, 30-40 parts of polyester polyol, 5-8 parts of terephthalic acid, 2-4 parts of trimesic acid and 5-10 parts of 2-carboxyethyl phenyl hypophosphorous acid.
And (3) PET recycling: the intrinsic viscosity is 0.72dl/g, and the product is from Shenghong Yonggang group company Limited;
the depolymerizing agent is T01, the mass ratio of the depolymerizing agent to the recycled PET is 100-150 mg/kg, and the depolymerizing agent is from Shenghong Yonggang group Limited company;
the mass ratio of ethylene glycol to recycled PET was 30g/kg.
Further, the polyester polyol contains a morpholine dione structure and is prepared by the following process:
mixing terephthalic acid, sebacic acid, neopentyl glycol, hexanediol, sodium terephthalate sulfonate and trimellitic anhydride, and reacting for 5-6 hours at the temperature of 150-250 ℃ under the protection of nitrogen atmosphere;
adding tetrabutyl titanate and morpholine diketone derivatives, and reacting for 3-4 h at 230-250 ℃.
Further, the polyester polyol comprises the following components in percentage by mass: 700 to 750 parts of terephthalic acid, 200 to 250 parts of sebacic acid, 725 to 775 parts of neopentyl glycol, 225 to 275 parts of hexanediol, 50 parts of sodium terephthalate, 0.4 to 0.5 part of trimellitic anhydride, 0.4 to 0.5 part of tetrabutyl titanate and 8 to 10 parts of morpholine dione derivatives.
Further, the morpholine dione derivative is prepared by the following process:
step 1, mixing amino diacid and diol, adding concentrated hydrochloric acid, heating to 88-95 ℃, stirring, and reacting for 20-30 min; cooling to room temperature, adding triethylamine, standing for 8-12 h, filtering, washing precipitate, and recrystallizing triethylamine to obtain an esterification product;
step 2, mixing the esterification product and dioxane, adding a sodium hydroxide solution, and stirring for dissolving; slowly adding bromopropionyl bromide at the temperature of 0-5 ℃, finishing the addition within 2h, and reacting for 50-75 min under the protection of nitrogen atmosphere; the room temperature is recovered for continuous reaction for 20 to 30min; adjusting the pH value of the system to 2-3 by using hydrochloric acid, extracting by using ethyl acetate, drying by using anhydrous magnesium sulfate, filtering, spin-drying, precipitating by using ethyl ether, and recrystallizing by using ethyl acetate to obtain a bromopropionyl compound;
step 3, mixing triethylamine and N, N-dimethylformamide, heating to 78-85 ℃, slowly adding a bromopropionyl compound for 10 hours, and reacting for 3-4 hours under the protection of a nitrogen atmosphere; distilling under reduced pressure, dissolving in water, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, and filtering; distilling the precipitate at 45 deg.C under reduced pressure, precipitating with diethyl ether, and recrystallizing with ethyl acetate to obtain morpholine dione derivative.
Further, in step 1, the amino diacid is one or a mixture of two of aminomalonic acid and aspartic acid.
The diol is one or a mixture of neopentyl glycol and hexanediol.
The mol ratio of the amino diacid to the diol is 1: 1.0-1.1;
the proportion of the amino diacid to the concentrated hydrochloric acid is (50-65) g/100mL;
the mass fraction of the concentrated hydrochloric acid is 36-38%.
Further, the ratio of the esterification product to the dioxane in the step 2 is 0.5mmol/mL;
the concentration of the sodium hydroxide solution is 2M;
the molar ratio of the esterification product to the bromopropionyl bromide is 1: 1.10-1.16.
Further, the molar ratio of the bromopropionyl compound to the triethylamine in the step 3 is 1: 1;
the ratio of triethylamine to N, N-dimethylformamide was 1g/100mL.
Since the recycled polyester has a low melting point, a low glass transition temperature, and a high fluidity, it is necessary to recycle the waste PET and depolymerize it for reuse. In the technical scheme, firstly, depolymerizing the recovered PET by adopting an glycolysis method to obtain an oligomer mainly comprising dihydroxy ethyl phthalate; the oligomer is copolymerized with polyester polyol, trimesic acid and 2-carboxyethyl phenyl hypophosphorous acid, so that the chain length of the molecule is increased, the chain structure is changed, and the performance of the prepared regenerated PET is improved. The 2-carboxyethyl phenyl hypophosphorous acid can be used as a flame retardant, so that the flame retardant property of the prepared regenerated PET is effectively improved. However, phosphoric acid and ester bonds are easily subjected to hydrolytic fracture under the action of water, and the hydrolysis reaction is further promoted by acidic products generated by hydrolysis and a high-temperature environment, so that the realization of the lasting moisture absorption performance and the mechanical property of the prepared regenerated PET fiber is not facilitated. Thus, the present application introduces homemade polyester polyols. The polyester polyol contains dibasic acid and dihydric alcohol, sodium terephthalate is added on the basis of alcohol acid reaction esterification, and an ionic group is introduced into the main chain of the polyester polyol, so that the hydrophilicity of the prepared regenerated PET can be improved to a certain extent, the stripping of the filler is facilitated to form a lamellar structure, and the polyester polyol is better combined with the filler. The polyester polyol also contains morpholine dione derivatives, the morpholine dione derivatives are prepared by reacting materials such as amino diacid, diol, bromopropionyl bromide and triethylamine, hydroxyl in a reaction product participates in the preparation of the polyester polyol, and a morpholine dione structure is introduced into a molecular chain of the prepared regenerated PET, so that the affinity of the regenerated PET for water can be improved; has higher rigidity and can improve the thermal stability of the recycled PET. The use of trimesic acid can increase the crosslinking degree of polyester polyol and the recycled PET, and is beneficial to improving the hydrolysis resistance of the recycled PET.
Further, the regenerated PET fiber comprises the following components in percentage by mass: 100 portions of regenerated PET, 0.5 to 2.0 portions of filler and 0.1 to 0.3 portion of catalyst stannous octoate.
Further, the filler is prepared by the following specific processes:
mixing and stirring sodium montmorillonite and deionized water for 1h, heating to 60 ℃, slowly adding the N- (2-chloroethyl) morpholine hydrochloride solution, heating to 80 ℃, and stirring for reaction for 3-4 h.
Further, the mass concentration of the N- (2-chloroethyl) morpholine hydrochloride solution is 15-22%, and the pH value is adjusted to 1-2 by hydrochloric acid;
the proportion of sodium montmorillonite and deionized water is 15g/100mL;
the mass ratio of the sodium-based montmorillonite to the N- (2-chloroethyl) morpholine hydrochloride is 100: 3-14;
sodium-based montmorillonite: from Zhejiang Fenghong New Material Co Ltd;
in the technical scheme, the montmorillonite can be used as a nucleating agent to promote the crystallization of the regenerated PET, is more beneficial to the spinning fiber formation of the prepared regenerated PET, and improves the mechanical property of the regenerated PET. Sodium-based montmorillonite is subjected to modification treatment by N- (2-chloroethyl) morpholine hydrochloride, the N- (2-chloroethyl) morpholine hydrochloride and the N- (2-chloroethyl) morpholine hydrochloride emit cation exchange, the N- (2-chloroethyl) morpholine hydrochloride is introduced into an interlayer structure of the montmorillonite, the interlayer spacing of the montmorillonite is enlarged, molecular chains of polyester are more easily folded and crystallized on the montmorillonite, the regenerated PET has lower crystallization temperature, the crystallization performance of the prepared regenerated PET fiber is further improved, the mechanical property of the regenerated PET fiber is improved, the subsequent dye molecules such as dye can enter the regenerated PET, and the colored PET is favorably dyed and colored. Under the action of a catalyst stannous octoate, part of morpholine dione structures in the regenerated PET and the montmorillonite can undergo ring-opening polymerization, so that the crosslinking degree of the prepared regenerated PET fiber can be increased, the improvement of the hydrolysis resistance of the regenerated PET fiber is facilitated, and the hydrolysis resistance of the prepared high-moisture-absorption regenerated PET fiber is improved.
Further, the step (3) specifically comprises the following steps:
step 1, preparation of finishing agent:
dehydrating polyethylene glycol, heating to 65 ℃, slowly adding isocyano ethyl methacrylate, stirring, refluxing and reacting for 4 hours to obtain unsaturated polyether, and dissolving the unsaturated polyether in 2-butanone to obtain an unsaturated polyether solution;
mixing sodium dodecyl sulfate, dodecyl octyl phenol polyoxyethylene ether and deionized water, and adding methyl methacrylate, acrylic acid, butyl acrylate and glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution to stir at high speed for 25-330 min to be used as pre-emulsion;
taking the other half of the mixed solution, adding 10 percent of pre-emulsion and sodium bicarbonate, stirring, heating to 45-55 ℃, adding half of initiator potassium persulfate, and reacting for 20-40 min; slowly adding the pre-emulsion of the rest components, the other half of the initiator potassium persulfate and the unsaturated polyether solution, finishing the addition within 1h, and reacting for 20-40 min to obtain emulsion; adjusting the solid content of the system to 25-30% to obtain a finishing agent;
step 2, dipping
Putting the regenerated PET fiber into a finishing agent for soaking for 10-15 min, and taking out the mangle; drying at 105-120 deg.c for 100-150 min, and curing at 165-175 deg.c for 50-65 sec to obtain the regenerated PET fiber with high moisture absorption.
Further, the polyethylene glycol dehydration process in the step 1 comprises: vacuum drying at 120 deg.C for 6 hr;
the molar ratio of the polyethylene glycol to the isocyano ethyl methacrylate is 1: 2;
polyethylene glycol: the weight average molecular weight is 400, and the product is from chemical reagents of national drug group;
the mass fraction of the unsaturated polyether in the 2-butanone is 10-30%.
The finishing agent comprises the following components in parts by mass: 2.0-2.2 parts of glycidyl methacrylate, 66-70 parts of methyl methacrylate, 6.5-6.9 parts of acrylic acid, 25-28 parts of butyl acrylate, 2 parts of sodium dodecyl sulfate, 1.5 parts of dodecyl octyl phenol polyoxyethylene ether, 150 parts of deionized water, 0.35 part of sodium bicarbonate, 0.75 part of potassium persulfate and 5-10 parts of unsaturated polyether.
Further, the bath ratio of the regenerated PET fibers in the finishing agent in the step 2 is 1:20; the rolling stock had a rolling stock of 80%.
In the technical scheme, epoxy groups and polyether are introduced into the matrix of the aqueous acrylic emulsion. In the preparation process, an epoxy group introduced by glycidyl methacrylate can react with a carboxyl group in the finishing agent to generate crosslinking curing, so that the intermolecular combination of the finishing agent is enhanced, and the film forming property and hydrolysis resistance of the surface adhesive film of the high-moisture-absorption regenerated PET fiber are improved; crosslinking forms hydroxyl groups and ether bonds, and the hydrophilicity of the resulting fiber is improved. And the hydrophilic polyether chain segment caused by the curing of unsaturated polyether and epoxy extends to the outer side of the fiber, so that the hydrophilic moisture absorption performance and hydrolysis resistance of the prepared fiber can be further improved, and the fiber has better resistance to the acidity generated by the hydrolysis of a 2-carboxyethylphenylphosphinic acid structure.
Compared with the prior art, the invention has the following beneficial effects:
according to the high-moisture-absorption regenerated PET fiber and the processing technology thereof, the low polymer formed by recycling PET depolymerization and the polyester polyol, the copolymerization of trimesic acid and the modification treatment of sodium montmorillonite can relieve the degradation influence of 2-carboxyethyl phenyl hypophosphorous acid on the main chain, and the hydrolysis resistance of the prepared high-moisture-absorption regenerated PET fiber is improved; and meanwhile, ether bond is introduced into the finishing agent, so that the hydrophilic moisture absorption performance and hydrolysis resistance of the prepared fiber can be further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
And (3) PET recycling: the intrinsic viscosity is 0.72dl/g, and the product is from Shenghong Yonggang group, inc.;
the depolymerizing agent is T01 and is from Shenghong Yonggang group Co., ltd;
sodium-based montmorillonite: from Zhejiang Fenghong New materials, inc.;
polyethylene glycol: the weight average molecular weight is 400, and the product is from chemical reagents of national drug group;
example 1
(1) Preparing regenerated PET:
1.1 preparation of morpholinodione derivatives:
s1, mixing 119g of aminomalonic acid and 104g of neopentyl glycol, adding 238mL of 36wt% concentrated hydrochloric acid, heating to 88 ℃, stirring, and reacting for 20min; cooling to room temperature, adding triethylamine, standing for 8h, filtering, washing precipitate, and recrystallizing triethylamine to obtain an esterification product;
s2, mixing 103g of esterification product and 1L of dioxane, adding 2M of sodium hydroxide solution, and stirring for dissolving; slowly adding 119g of bromopropionyl bromide at the temperature of 5 ℃, finishing the addition within 2h, and reacting for 50min under the protection of a nitrogen atmosphere; the room temperature is recovered and the reaction is continued for 20min; adjusting the pH value of the system to 3 by using hydrochloric acid, extracting by using ethyl acetate, drying by using anhydrous magnesium sulfate, filtering, spin-drying, precipitating by using ethyl ether, and recrystallizing by using ethyl acetate to obtain a bromopropionyl compound;
s3, taking 101g of triethylamine, 10LN and N-dimethylformamide, mixing, heating to 78 ℃, slowly adding 340g of bromopropionyl compound, finishing the addition for 10 hours, and reacting for 3 hours under the protection of a nitrogen atmosphere; distilling under reduced pressure, dissolving in water, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, and filtering; distilling the precipitate at 45 deg.C under reduced pressure, precipitating with diethyl ether, and recrystallizing with ethyl acetate to obtain morpholine dione derivative;
1.2 preparation of polyester polyol:
mixing 700g of terephthalic acid, 200g of sebacic acid, 725g of neopentyl glycol, 225g of hexanediol, 50g of sodium terephthalate and 0.4g of trimellitic anhydride, and reacting for 5 hours at the temperature of 150 ℃ under the protection of a nitrogen atmosphere; adding 0.4g of tetrabutyl titanate and 8g of morpholine dione derivatives, and reacting at 230 ℃ for 3h;
1.3. preparation of recycled PET:
mixing 1000g of recovered PET, 30g of ethylene glycol and 100mg of depolymerizing agent, heating to 220 ℃, and carrying out depolymerization reaction for 2h under the condition of 0.16MPa to obtain an oligomer; mixing 60g of oligomer, 30g of polyester polyol and 5g of terephthalic acid, and esterifying and dehydrating for 2 hours at the temperature of 240 ℃; 2g of trimesic acid and 5g of 2-carboxyethyl phenyl hypophosphorous acid are added to continue the reaction for 1 hour; carrying out polycondensation reaction for 2h at the temperature of 280 ℃ and under the vacuum pressure of 20Pa to obtain regenerated PET;
(2) Preparation of regenerated PET fiber:
mixing 150g of sodium-based montmorillonite and 1L of deionized water, stirring for 1h, heating to 60 ℃, slowly adding an N (2-chloroethyl) morpholine hydrochloride solution (5 g of N- (2-chloroethyl) morpholine hydrochloride and 27mL of deionized water, regulating the pH value to 2 by hydrochloric acid), heating to 80 ℃, and stirring for reacting for 3h;
mixing 1000g of regenerated PET, 5g of filler and 1g of catalyst stannous octoate, and spinning to obtain regenerated PET fibers;
(3) Preparing high-moisture-absorption regenerated PET fibers:
s1, preparation of a finishing agent:
taking 400g of polyethylene glycol, drying in vacuum at 120 ℃ for 6h for dehydration, heating to 65 ℃, slowly adding 310g of isocyano ethyl methacrylate, stirring, refluxing and reacting for 4h to obtain unsaturated polyether, and dissolving the unsaturated polyether in 2-butanone to obtain an unsaturated polyether solution, wherein the mass fraction of the unsaturated polyether solution is 10%;
mixing 20g of sodium dodecyl sulfate, 15g of dodecyl octyl phenol polyoxyethylene ether and 1500g of deionized water, and adding 660g of methyl methacrylate, 6.5g of acrylic acid, 250g of butyl acrylate and 20g of glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution, stirring at high speed for 25min to obtain pre-emulsion;
taking the other half of the mixed solution, adding 10% of the pre-emulsion and 3.5g of sodium bicarbonate, stirring, heating to 45 ℃, adding 3.75g of initiator potassium persulfate, and reacting for 20min; slowly adding the pre-emulsion of the rest components, 3.75g of initiator potassium persulfate and 500g of unsaturated polyether solution, finishing the addition within 1 hour, and reacting for 20min to obtain emulsion; adjusting the solid content of the system to 25% to obtain a finishing agent;
s2, dipping
Placing the regenerated PET fibers in a finishing agent for soaking for 10min, wherein the bath ratio is 1:20; taking out the mangle, wherein the mangle residue is 80%; drying at 105 deg.C for 100min, and curing at 165 deg.C for 50s to obtain high moisture absorption regenerated PET fiber.
Example 2
(1) Preparing regenerated PET:
1.1 preparation of morpholinodione derivatives:
s1, mixing 133g of aspartic acid and 124g of hexanediol, adding 230mL of 37wt% concentrated hydrochloric acid, heating to 90 ℃, stirring, and reacting for 25min; cooling to room temperature, adding triethylamine, standing for 102h, filtering, washing precipitate, and recrystallizing triethylamine to obtain an esterification product;
s2, mixing 119.5g of esterification product and 1L of dioxane, adding 2M of sodium hydroxide solution, and stirring for dissolving; slowly adding 121.5g of bromopropionyl bromide at the temperature of 2 ℃, finishing the addition within 2h, and reacting for 60min under the protection of nitrogen atmosphere; the room temperature is recovered and the reaction is continued for 25min; adjusting the pH value of the system to 2.5 by using hydrochloric acid, extracting by using ethyl acetate, drying by using anhydrous magnesium sulfate, filtering, spin-drying, precipitating by using ethyl ether, and recrystallizing by using ethyl acetate to obtain a bromopropionyl compound;
s3, taking 101g of triethylamine, 1LN and N-dimethylformamide, mixing, heating to 80 ℃, slowly adding 373g of bromopropionyl compound, finishing the addition for 10 hours, and reacting for 3.5 hours under the protection of nitrogen atmosphere; distilling under reduced pressure, dissolving in water, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, and filtering; distilling the precipitate at 45 deg.C under reduced pressure, precipitating with diethyl ether, and recrystallizing with ethyl acetate to obtain morpholine dione derivative
1.2 preparation of polyester polyol:
the polyester polyol is prepared by the following process:
mixing 725g of terephthalic acid, 225g of sebacic acid, 750g of neopentyl glycol, 250g of hexanediol, 50g of sodium terephthalate and 0.45g of trimellitic anhydride, and reacting for 5.5 hours at the temperature of 200 ℃ under the protection of a nitrogen atmosphere;
adding 0.45g of tetrabutyl titanate and 9g of morpholine dione derivatives, and reacting at the temperature of 240 ℃ for 3.5h;
1.3. preparation of recycled PET:
mixing 1000g of recovered PET, 30g of ethylene glycol and 125mg of depolymerizing agent, heating to 230 ℃, and performing depolymerization reaction for 3 hours under the condition of 0.18MPa to obtain an oligomer; mixing 65g of oligomer, 35g of polyester polyol and 6g of terephthalic acid, and esterifying and dehydrating for 2.5 hours at the temperature of 250 ℃; adding 3g of trimesic acid and 8g of 2-carboxyethyl phenyl hypophosphorous acid, and continuing to react for 1.5h; performing polycondensation reaction for 2.5h at the temperature of 282 ℃ and under the vacuum pressure of 60Pa to obtain regenerated PET;
(2) Preparing the regenerated PET fiber:
mixing 150g of sodium-based montmorillonite and 1L of deionized water, stirring for 1h, heating to 60 ℃, slowly adding an N- (2-chloroethyl) morpholine hydrochloride solution (8 g of N- (2-chloroethyl) morpholine hydrochloride and 36mL of deionized water, regulating the pH value to 1.5 by hydrochloric acid), heating to 80 ℃, and stirring for reacting for 3.5h;
mixing 1000g of regenerated PET, 12g of filler and 2g of catalyst stannous octoate, and spinning to obtain regenerated PET fibers;
(3) Preparing the high-moisture-absorption regenerated PET fiber:
s1, preparation of a finishing agent:
taking 400g of polyethylene glycol, drying in vacuum at 120 ℃ for 6h for dehydration, heating to 65 ℃, slowly adding 310g of isocyano ethyl methacrylate, stirring, refluxing and reacting for 4h to obtain unsaturated polyether, and dissolving the unsaturated polyether in 2-butanone to obtain an unsaturated polyether solution, wherein the mass fraction of the unsaturated polyether solution is 20%;
mixing 20g of sodium dodecyl sulfate, 15g of dodecyl octyl phenol polyoxyethylene ether and 1500g of deionized water, and adding 68g of methyl methacrylate, 67g of acrylic acid, 260g of butyl acrylate and 21g of glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution, stirring at high speed for 27min to obtain pre-emulsion;
taking the other half of the mixed solution, adding 10% of the pre-emulsion and 3.5g of sodium bicarbonate, stirring, heating to 50 ℃, adding 3.75g of initiator potassium persulfate, and reacting for 30min; slowly adding the pre-emulsion of the rest components, 3.75g of initiator potassium persulfate and 375g of unsaturated polyether solution, finishing the addition within 1 hour, and reacting for 30min to obtain emulsion; adjusting the solid content of the system to 25% to obtain a finishing agent;
s2, dipping
Soaking the regenerated PET fiber in the finishing agent for 12min at a bath ratio of 1:20; taking out the mangle, wherein the mangle residue is 80%; drying at 110 deg.C for 120min, and curing at 170 deg.C for 60s to obtain high moisture absorption regenerated PET fiber.
Example 3
(1) Preparing regenerated PET:
1.1 preparation of morpholinodione derivatives:
s1, mixing 119g of aminomalonic acid and 114g of neopentyl glycol, adding 183mL of 38wt% concentrated hydrochloric acid, heating to 95 ℃, stirring, and reacting for 30min; cooling to room temperature, adding triethylamine, standing for 12h, filtering, washing precipitate, and recrystallizing triethylamine to obtain an esterification product;
s2, mixing 107g of esterification product and 1L of dioxane, adding 2M sodium hydroxide solution, and stirring for dissolving; slowly adding 125g of bromopropionyl bromide at the temperature of 0 ℃, finishing the addition within 2h, and reacting for 75min under the protection of nitrogen atmosphere; the room temperature is recovered and the reaction is continued for 30min; adjusting the pH value of the system to 2 by using hydrochloric acid, extracting by using ethyl acetate, drying by using anhydrous magnesium sulfate, filtering, spin-drying, precipitating by using ethyl ether, and recrystallizing by using ethyl acetate to obtain a bromopropionyl compound;
s3, heating 101g of triethylamine, 10LN and N-bis mixture to 85 ℃, slowly adding 340g of bromopropionyl compound for 10 hours, and reacting for 4 hours under the protection of nitrogen atmosphere; distilling under reduced pressure, dissolving in water, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, and filtering; distilling the precipitate at 45 deg.C under reduced pressure, precipitating with diethyl ether, and recrystallizing with ethyl acetate to obtain morpholine dione derivative
1.2 preparation of polyester polyol:
mixing 750g of terephthalic acid, 250g of sebacic acid, 775g of neopentyl glycol, 275g of hexanediol, 50g of sodium terephthalate and 0.5g of trimellitic anhydride, and reacting for 6 hours at the temperature of 250 ℃ under the protection of a nitrogen atmosphere; adding 0.5g of tetrabutyl titanate and 10g of morpholine dione derivatives, and reacting at the temperature of 250 ℃ for 4 hours;
1.3. preparation of recycled PET:
mixing 1000g of recovered PET, 30g of ethylene glycol and 150mg of depolymerizing agent, heating to 240 ℃, and carrying out depolymerization reaction for 4 hours under the condition of 0.20MPa to obtain an oligomer; mixing 700g of oligomer, 400g of polyester polyol and 80g of terephthalic acid, and esterifying and dehydrating at the temperature of 260 ℃ for 3 hours; adding 40g of trimesic acid and 100g of 2-carboxyethyl phenyl hypophosphorous acid, and continuously reacting for 2 hours; carrying out polycondensation reaction for 3h at the temperature of 285 ℃ and under the vacuum pressure of 100Pa to obtain regenerated PET;
(2) Preparing the regenerated PET fiber:
mixing 150g of sodium-based montmorillonite and 1L of deionized water, stirring for 1h, heating to 60 ℃, slowly adding an N- (2-chloroethyl) morpholine hydrochloride solution (21 g of N- (2-chloroethyl) morpholine hydrochloride and 74mL of deionized water, regulating the pH value to 1 by hydrochloric acid), heating to 80 ℃, and stirring for reacting for 4h; mixing 1000g of regenerated PET, 20g of filler and 3g of catalyst stannous octoate, and spinning to obtain regenerated PET fibers;
(3) Preparing the high-moisture-absorption regenerated PET fiber:
s1, preparation of a finishing agent:
taking 400g of polyethylene glycol, drying in vacuum at 120 ℃ for 6h for dehydration, heating to 65 ℃, slowly adding 310g of isocyano ethyl methacrylate, stirring, refluxing and reacting for 4h to obtain unsaturated polyether, and dissolving the unsaturated polyether in 2-butanone to obtain an unsaturated polyether solution, wherein the mass fraction of the unsaturated polyether solution is 30%;
mixing 20g of sodium dodecyl sulfate, 15g of dodecyl octyl phenol polyoxyethylene ether and 1500g of deionized water, and adding 700g of methyl methacrylate, 69g of acrylic acid, 28g of butyl acrylate and 22g of glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution, stirring at high speed for 30min to obtain pre-emulsion;
taking the other half of the mixed solution, adding 10% of the pre-emulsion and 3.5g of sodium bicarbonate, stirring, heating to 55 ℃, adding 3.75g of initiator potassium persulfate, and reacting for 40min; slowly adding the pre-emulsion of the rest components, 3.75g of initiator potassium persulfate and 303g of unsaturated polyether solution, finishing the addition within 1 hour, and reacting for 40min to obtain emulsion; adjusting the solid content of the system to 25% to obtain a finishing agent;
s2, dipping
Soaking the regenerated PET fiber in the finishing agent for 15min at a bath ratio of 1:20; taking out the mangle, wherein the mangle residual rate is 80%; drying at 120 ℃ for 150min, and curing at 175 ℃ for 65s to obtain the high-moisture-absorption regenerated PET fiber.
Comparative example 1
(1) Preparing regenerated PET:
1.1 preparation of polyester polyol:
mixing 700g of terephthalic acid, 200g of sebacic acid, 725g of neopentyl glycol, 225g of hexanediol, 50g of sodium terephthalate and 0.4g of trimellitic anhydride, and reacting for 5 hours at the temperature of 150 ℃ under the protection of a nitrogen atmosphere; adding 0.4g of tetrabutyl titanate and 8g of hexanediol, and reacting for 3 hours at the temperature of 230 ℃;
1.2. preparation of recycled PET:
mixing 1000g of recovered PET, 30g of ethylene glycol and 100mg of depolymerizing agent, heating to 220 ℃, and carrying out depolymerization reaction for 2h under the condition of 0.16MPa to obtain an oligomer; mixing 60g of oligomer, 30g of polyester polyol and 5g of terephthalic acid, and esterifying and dehydrating for 2 hours at the temperature of 240 ℃; 2g of trimesic acid and 5g of 2-carboxyethyl phenyl hypophosphorous acid are added to continue the reaction for 1 hour; carrying out polycondensation reaction for 2h at the temperature of 280 ℃ and under the vacuum pressure of 20Pa to obtain regenerated PET;
the steps (2, 3) are the same as in example 1, and the high moisture absorption regenerated PET fiber is obtained.
Comparative example 2
(1) Preparing regenerated PET:
mixing 1000g of recovered PET, 30g of ethylene glycol and 100mg of depolymerizing agent, heating to 220 ℃, and carrying out depolymerization reaction for 2h under the condition of 0.16MPa to obtain an oligomer; mixing 60g of oligomer, 30g of linear polyester diol (sourced from Shenzhen Longdi chemical Co., ltd.), and 5g of terephthalic acid, and performing esterification and dehydration at 240 ℃ for 2h; 2g of trimesic acid and 5g of 2-carboxyethyl phenyl hypophosphorous acid are added to continue the reaction for 1 hour; carrying out polycondensation reaction for 2h at the temperature of 280 ℃ and under the vacuum pressure of 20Pa to obtain regenerated PET;
the steps (2, 3) are the same as in example 1, and the high moisture absorption regenerated PET fiber is obtained.
Comparative example 3
(2) Preparation of regenerated PET fiber:
mixing 1000g of regenerated PET, 5g of sodium montmorillonite and 1g of catalyst stannous octoate, and spinning to obtain regenerated PET fibers;
the steps (1, 3) are the same as the comparative example 2, and the high-moisture-absorption regenerated PET fiber is obtained.
Comparative example 4
(3) Preparing high-moisture-absorption regenerated PET fibers:
s1, preparation of a finishing agent:
mixing 20g of sodium dodecyl sulfate, 15g of dodecyl octyl phenol polyoxyethylene ether and 1500g of deionized water, and adding 660g of methyl methacrylate, 6.5g of acrylic acid, 250g of butyl acrylate and 20g of glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution, stirring at high speed for 25min to obtain pre-emulsion;
taking the other half of the mixed solution, adding 10% of pre-emulsion and 3.5g of sodium bicarbonate, stirring, heating to 45 ℃, adding 3.75g of initiator potassium persulfate, and reacting for 20min: slowly adding the pre-emulsion of the rest components and 3.75g of initiator potassium persulfate, finishing the addition within 1h, and reacting for 20min to obtain emulsion; adjusting the solid content of the system to 25% to obtain a finishing agent;
s2, dipping
Soaking the regenerated PET fiber in the finishing agent for 10min at a bath ratio of 1:20; taking out the mangle, wherein the mangle residual rate is 80%; drying at 105 deg.C for 100min, and curing at 165 deg.C for 50s to obtain high moisture absorption regenerated PET fiber.
Steps (1, 2) were the same as in comparative example 3.
Comparative example 5
(3) Preparing high-moisture-absorption regenerated PET fibers:
s1, preparation of a finishing agent:
mixing 20g of sodium dodecyl sulfate, 15g of dodecyl octyl phenol polyoxyethylene ether and 1500g of deionized water, and adding 660g of methyl methacrylate, 6.5g of acrylic acid and 250g of butyl acrylate to obtain a mixed solution; taking half of the mixed solution, stirring at high speed for 25min to obtain pre-emulsion;
taking the other half of the mixed solution, adding 10% of the pre-emulsion and 3.5g of sodium bicarbonate, stirring, heating to 45 ℃, adding 3.75g of initiator potassium persulfate, and reacting for 20min; slowly adding the pre-emulsion of the rest components and 3.75g of initiator potassium persulfate, finishing the addition within 1h, and reacting for 20min to obtain emulsion; adjusting the solid content of the system to 25% to obtain a finishing agent;
s2, dipping
Soaking the regenerated PET fiber in the finishing agent for 10min at a bath ratio of 1:20; taking out the mangle, wherein the mangle residue is 80%; drying at 105 ℃ for 100min to obtain the high-moisture-absorption regenerated PET fiber.
Steps (1, 2) were the same as in comparative example 3.
The regenerated PET fiber is subjected to heat preservation for 2 hours at the temperature of 120 ℃; the model of the spinneret plate is 0.4mm multiplied by 36 holes, the spinning speed is 500m/min, and the drafting multiple is 4 times.
Experiment of
The high moisture absorption recycled PET fibers obtained in example 13 and comparative examples 1 to 5 were used to prepare test pieces, and the properties thereof were measured and the measurement results were recorded:
mechanical properties: testing the tensile property of the sample by using a universal testing machine, wherein the tensile rate is 10mm/min;
hydrophilicity: testing the water contact angle of the sample by using a contact angle tester and a static dropping method; the volume of the experimental water drop is 3 mul;
moisture regain: taking HG/T6503 as a reference standard, and after a test sample (regenerated PET fiber) is dried to constant weight, recording the change rate of the mass as the moisture regain;
hydrolysis resistance: and (3) placing the sample under the conditions of 70 ℃ of temperature and 95% of relative humidity for 5 weeks, testing the tensile property of the sample again, and taking the fracture strength retention rate as a performance index.
| Moisture regain (%) | Contact angle (°) | Breaking strength (cN/dtex) | Retention (%) | |
| Example 1 | 0.73 | 30.52 | 4.66 | 72.6 |
| Example 2 | 0.78 | 29.75 | 4.87 | 73.5 |
| Example 3 | 0.82 | 28.64 | 4.74 | 74.2 |
| Comparative example 1 | 0.56 | 31.28 | 4.42 | 65.8 |
| Comparative example 2 | 0.54 | 32.03 | 3.91 | 62.1 |
| Comparative example 3 | 0.36 | 37.52 | 3.83 | 57.9 |
| Comparative example 4 | / | 43.47 | 3.80 | 57.5 |
| Comparative example 5 | / | 45.26 | 3.69 | 51.4 |
From the data in the table above, it is clear that the following conclusions can be drawn:
the high moisture absorption recycled PET fibers obtained in examples 1 to 3 were compared with the high moisture absorption recycled PET fibers obtained in comparative examples 1 to 5, and the results of the detection were found to be,
compared with comparative examples 1-5, the high moisture absorption regenerated PET fiber obtained in examples 1-3 has higher moisture regain data, the fiber obtained after finishing has lower contact angle, higher breaking strength and retention data,
this fully demonstrates that the present invention achieves an improvement in the moisture absorption and hydrolysis resistance of the highly moisture-absorptive recycled PET fiber.
Compared with example 1, the morpholine dione derivative in the component of comparative example 1 is replaced by hexanediol, and the polyester polyol in comparative example 2 is replaced by linear polyester diol; compared with comparative example 2, the sodium-based montmorillonite in comparative example 3 is not subjected to modification treatment; the moisture regain data of the regenerated PET fibers are obviously reduced, and the breaking strength and retention rate data of the fibers obtained after finishing are slightly reduced; compared with comparative example 3, the finishing agent in comparative example 4 has no component of unsaturated polyether; the finishing agent in the comparative example 5 is not added with unsaturated polyether and glycidyl methacrylate, all performance data are deteriorated, and the tensile property is reduced under the damp and hot conditions, because P-0 bond in 2-carboxyethyl phenyl hypophosphorous acid is hydrolyzed and broken, the molecular weight of polyester is reduced, and the modification treatment of polyester polyol and sodium-based montmorillonite in the invention improves the crosslinking degree of polyester, and is helpful for relieving the reduction of the molecular weight.
The preparation process and the arrangement of the required components can promote the improvement of the moisture absorption and hydrolysis resistance of the high-moisture-absorption regenerated PET fiber.
It should be noted that, in this document, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process item or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process item or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A processing technology of high-moisture-absorption regenerated PET fibers is characterized by comprising the following steps: the preparation method comprises the following preparation processes:
(1) Preparation of recycled PET:
mixing the recovered PET, ethylene glycol and a depolymerizing agent, heating to 220-240 ℃, and carrying out depolymerization reaction for 2-4 h under the condition of 0.16-0.20 MPa to obtain an oligomer;
adding polyester polyol and terephthalic acid, and esterifying and dehydrating for 2-3 h at the temperature of 240-260 ℃; adding trimesic acid and 2-carboxyethyl phenyl hypophosphorous acid, and continuously reacting for 1-2 h;
carrying out polycondensation reaction for 2-3 h at the temperature of 280-285 ℃ and under the vacuum pressure of 20-100 Pa to obtain regenerated PET;
(2) Preparing the regenerated PET fiber: mixing with a filler and a catalyst, and spinning to obtain a regenerated PET fiber;
(3) Preparing high-moisture-absorption regenerated PET fibers: dipping in a finishing agent to obtain the high-moisture-absorption regenerated PET fiber;
the polyester polyol contains a morpholine dione structure.
2. The processing technology of the high moisture absorption recycled PET fiber according to claim 1, characterized in that: the recycled PET comprises the following components in parts by mass: 60-70 parts of oligomer, 30-40 parts of polyester polyol, 5-8 parts of terephthalic acid, 2-4 parts of trimesic acid and 5-10 parts of 2-carboxyethyl phenyl hypophosphorous acid.
3. The processing technology of the high moisture absorption recycled PET fiber according to claim 1, characterized in that: the polyester polyol is prepared by the following process:
mixing terephthalic acid, sebacic acid, neopentyl glycol, hexanediol, sodium terephthalate sulfonate and trimellitic anhydride, and reacting for 5-6 hours at the temperature of 150-250 ℃ under the protection of nitrogen atmosphere;
adding tetrabutyl titanate and morpholine diketone derivatives, and reacting for 3-4 h at 230-250 ℃.
4. The processing technology of the high moisture absorption recycled PET fiber according to claim 3, characterized in that: the polyester polyol comprises the following components in parts by mass: 700 to 750 portions of terephthalic acid, 200 to 250 portions of sebacic acid, 725 to 775 portions of neopentyl glycol, 225 to 275 portions of hexanediol, 50 portions of sodium sulfonate terephthalate, 0.4 to 0.5 portion of trimellitic anhydride, 0.4 to 0.5 portion of tetrabutyl titanate and 8 to 10 portions of morpholine diketone derivatives.
5. The processing technology of the high moisture absorption recycled PET fiber according to claim 3, characterized in that: the morpholine dione derivative is prepared by the following process:
mixing amino diacid and diol, adding concentrated hydrochloric acid, heating to 88-95 ℃, stirring, and reacting for 20-30 min to obtain an esterification product;
mixing the esterification product and dioxane, adding sodium hydroxide solution, and stirring for dissolving; slowly adding bromopropionyl bromide at the temperature of 0-5 ℃, finishing the addition within 2h, and reacting for 50-75 min under the protection of nitrogen atmosphere; recovering the room temperature and continuing the reaction for 20 to 30min to obtain a bromopropionyl compound;
mixing triethylamine and N, N-dimethylformamide, heating to 78-85 ℃, slowly adding a bromopropionyl compound for 10 hours, and reacting for 3-4 hours under the protection of nitrogen atmosphere to obtain the morpholine dione derivative.
6. The processing technology of the high moisture absorption recycled PET fiber according to claim 1, characterized in that: the regenerated PET fiber comprises the following components in parts by mass: 100 portions of regenerated PET, 0.5 to 2.0 portions of filler and 0.1 to 0.3 portion of catalyst stannous octoate.
7. The processing technology of the high moisture absorption recycled PET fiber according to claim 1, characterized in that: the filler is prepared by the following process:
mixing and stirring sodium-based montmorillonite and deionized water for 1h, heating to 60 ℃, slowly adding N- (2-chloroethyl) morpholine hydrochloride solution, heating to 80 ℃, and stirring for reaction for 3-4 h.
8. The processing technology of the high moisture absorption recycled PET fiber according to claim 1, characterized in that: the step (3) specifically comprises the following steps:
step 1, preparation of a finishing agent:
dehydrating polyethylene glycol, heating to 65 ℃, slowly adding isocyanoethyl methacrylate, stirring, refluxing and reacting for 4 hours to obtain unsaturated polyether, and dissolving the unsaturated polyether in 2-butanone to obtain an unsaturated polyether solution;
mixing sodium dodecyl sulfate, dodecyl octyl phenol polyoxyethylene ether and deionized water, and adding methyl methacrylate, acrylic acid, butyl acrylate and glycidyl methacrylate to obtain a mixed solution; taking half of the mixed solution to stir at high speed for 25-330 min to serve as pre-emulsion;
taking the other half of the mixed solution, adding 10 percent of the pre-emulsion and sodium bicarbonate, stirring, heating to 45-55 ℃, adding half of the initiator potassium persulfate, and reacting for 20-40 min; slowly adding the pre-emulsion of the rest components, the other half of initiator potassium persulfate and unsaturated polyether solution, completing the addition within 1h, and reacting for 20-40 min to obtain emulsion; adjusting the solid content of the system to 25-30% to obtain a finishing agent;
step 2, dipping
Putting the regenerated PET fiber into a finishing agent for soaking for 10-15 min, and taking out the mangle; drying at 105-120 deg.c for 100-150 min, and curing at 165-175 deg.c for 50-65 sec to obtain the regenerated PET fiber with high moisture absorption.
9. The processing technology of the high moisture absorption recycled PET fiber according to claim 8, characterized in that: the finishing agent comprises the following components in parts by mass: 2.0-2.2 parts of glycidyl methacrylate, 66-70 parts of methyl methacrylate, 6.5-6.9 parts of acrylic acid, 25-28 parts of butyl acrylate, 2 parts of sodium dodecyl sulfate, 1.5 parts of dodecyl octyl phenol polyoxyethylene ether, 150 parts of deionized water, 0.35 part of sodium bicarbonate, 0.75 part of potassium persulfate and 5-10 parts of unsaturated polyether.
10. A recycled PET fiber with high moisture absorption produced by the process according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211534557.4A CN115748003B (en) | 2022-12-01 | 2022-12-01 | High-hygroscopicity regenerated PET (polyethylene terephthalate) fiber and processing technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211534557.4A CN115748003B (en) | 2022-12-01 | 2022-12-01 | High-hygroscopicity regenerated PET (polyethylene terephthalate) fiber and processing technology thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115748003A true CN115748003A (en) | 2023-03-07 |
| CN115748003B CN115748003B (en) | 2023-10-10 |
Family
ID=85342482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211534557.4A Active CN115748003B (en) | 2022-12-01 | 2022-12-01 | High-hygroscopicity regenerated PET (polyethylene terephthalate) fiber and processing technology thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115748003B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184024A (en) * | 1976-08-23 | 1980-01-15 | Texaco Development Corp. | Polyurethanes prepared from polyols from 2,3-morpholinediones |
| KR20110088307A (en) * | 2010-01-28 | 2011-08-03 | 이동복 | Method for producing polyester polyol for low-temperature adhesive and flame-retardative pandable adhesives from recycled-pet |
| CN107869051A (en) * | 2017-11-30 | 2018-04-03 | 东华大学 | A kind of moisture absorbable and breathable finishing method of the dacron based on click chemistry |
| US20180201728A1 (en) * | 2015-12-29 | 2018-07-19 | Jiangsu Hengli Chemical Fibre Co., Ltd. | A flame-retardant polyester fiber and its preparation method |
| CN109706542A (en) * | 2018-12-27 | 2019-05-03 | 江苏恒力化纤股份有限公司 | A kind of fire-retardant polyester fibre and preparation method thereof |
| CN111334238A (en) * | 2020-03-17 | 2020-06-26 | 北京华腾新材料股份有限公司 | Waterborne polyurethane adhesive with high thermal activation temperature and preparation method thereof |
-
2022
- 2022-12-01 CN CN202211534557.4A patent/CN115748003B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4184024A (en) * | 1976-08-23 | 1980-01-15 | Texaco Development Corp. | Polyurethanes prepared from polyols from 2,3-morpholinediones |
| KR20110088307A (en) * | 2010-01-28 | 2011-08-03 | 이동복 | Method for producing polyester polyol for low-temperature adhesive and flame-retardative pandable adhesives from recycled-pet |
| US20180201728A1 (en) * | 2015-12-29 | 2018-07-19 | Jiangsu Hengli Chemical Fibre Co., Ltd. | A flame-retardant polyester fiber and its preparation method |
| CN107869051A (en) * | 2017-11-30 | 2018-04-03 | 东华大学 | A kind of moisture absorbable and breathable finishing method of the dacron based on click chemistry |
| CN109706542A (en) * | 2018-12-27 | 2019-05-03 | 江苏恒力化纤股份有限公司 | A kind of fire-retardant polyester fibre and preparation method thereof |
| CN111334238A (en) * | 2020-03-17 | 2020-06-26 | 北京华腾新材料股份有限公司 | Waterborne polyurethane adhesive with high thermal activation temperature and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115748003B (en) | 2023-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111286012B (en) | Degradable bio-based 2, 5-furandicarboxylic acid-based copolyester and preparation method and application thereof | |
| US3129133A (en) | Colloidal dispersions of partially cured polyepoxides, their preparation and use for preparing wet strength paper | |
| CN115651165B (en) | Recoverable epoxy resin, preparation method thereof and recovery method thereof | |
| CN114592360B (en) | Polyester fabric solvent dyeing method based on high-molecular printing and dyeing auxiliary | |
| CN115748003A (en) | High-moisture-absorption regenerated PET (polyethylene terephthalate) fiber and processing technology thereof | |
| CN115785626B (en) | Modified plastic particle and preparation method thereof | |
| CN111072938B (en) | Low-melting-point polyester and preparation method thereof | |
| US3936389A (en) | Bis glycol ester of sodium sulfo isophthalic acid from its dimethyl ester | |
| CN103306136B (en) | Crosslinker composition, antigen fibrillation solution spin cellulose fibre and their preparation methods | |
| CN116695272A (en) | Breathable cationic dyeable polyester fiber and preparation method thereof | |
| CN113463222A (en) | High-orientation-degree alginic acid fiber and preparation method thereof | |
| US2314972A (en) | Production of polymeric compounds | |
| CN101130603A (en) | Modified poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same | |
| CN114805771B (en) | Amorphous copolyester with high glass transition temperature and preparation method and application thereof | |
| CN111499853A (en) | Cationic dyeable PET and composite elastic fiber prepared from same | |
| CN116254637A (en) | Waterproof flame-retardant polyester fabric | |
| CN110438583B (en) | Polyester fiber and preparation method thereof | |
| CN114591494A (en) | Biomass-based modified epoxy resin and production process thereof | |
| Zhang et al. | A bio-based N-heterocyclic poly (aryl ether ketone) with a high biomass content and superior properties prepared from two derivatives of guaiacol and 2, 5-furandicarboxylic acid | |
| TWI829988B (en) | Biodegradable polyester and method for preparing the same | |
| CN110724250A (en) | Preparation method and application of aromatic alcohol modified polyester chip | |
| CN115785416B (en) | Poly (ethylene glycol-co-diethylene glycol) oxalate and preparation method thereof | |
| JPS58160316A (en) | Production of high-molecular compound | |
| CN115353597A (en) | High-strength creep-resistant recyclable modified isoprene rubber and preparation method thereof | |
| CN115784877A (en) | Method for recovering dimethyl terephthalate from waste poly (terephthalic acid) -butylene carbonate and repolymerization method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |