CN111101227B - Full-biodegradable copolyester fiber and preparation method thereof - Google Patents

Full-biodegradable copolyester fiber and preparation method thereof Download PDF

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CN111101227B
CN111101227B CN202010005266.0A CN202010005266A CN111101227B CN 111101227 B CN111101227 B CN 111101227B CN 202010005266 A CN202010005266 A CN 202010005266A CN 111101227 B CN111101227 B CN 111101227B
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acid
biodegradable copolyester
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temperature
fully biodegradable
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CN111101227A (en
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乌婧
王华平
林一鸣
陈咏
陈烨
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Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof

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

Abstract

The invention relates to a full-biodegradable copolyester fiber and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, with A1、B1And B2The raw materials are subjected to a first-stage reaction under the action of a first catalyst under the condition of high temperature, and then first-stage products, IXDML and A are taken2And B3The raw materials are subjected to second-stage reaction under the low-temperature condition and under the action of a second catalyst, then polycondensation reaction is carried out to prepare fully biodegradable copolyester, and finally the fully bio-based degradable copolyester fiber is prepared by a melt spinning forming method; the moisture regain of the prepared fiber is more than or equal to 3.3 percent, the surface contact angle is less than or equal to 67 degrees, and the prepared fiber has better thermodynamic property. The invention solves the problems that IXDML is seriously degraded and the molecular weight of a polymerization product is low, thus the spinning requirement can not be met; the prepared fiber has good hygroscopicity, excellent degradation performance and higher mechanical strength, can be applied to the fields of home textiles, clothes, disposable medical and health materials and the like, and has better application prospect.

Description

Full-biodegradable copolyester fiber and preparation method thereof
Technical Field
The invention belongs to the field of fiber preparation, relates to a fully biodegradable copolyester fiber and a preparation method thereof, and particularly relates to a fully biodegradable copolyester fiber based on IXDML and a preparation method thereof.
Background
China is a world-wide textile country, the quantity of waste textiles exceeds 2000 million tons every year, but the recycling rate is less than 10%, and serious resource waste and solid waste pollution are caused. Especially, the polyester fiber (mainly PET-based polyester fiber) accounts for nearly 70 percent of the textile raw material, and the annual output is nearly 4000 ten thousand tons in 2015. Polyethylene terephthalate (PET) used for polyester fiber manufacture has higher glass transition temperature (70-80 ℃), higher crystallinity and higher hydrophobicity due to the high specific gravity of rigid terephthalic acid monomer. The moisture regain of PET in a standard environment is only 0.4%, the contact angle of PET to water is as high as 83 degrees, so that the moisture absorption performance of PET is poor, the static electricity is large when the PET is worn, dust is easy to absorb, the wearing comfort of textiles is affected, and meanwhile, the PET is extremely difficult to biodegrade. It has been demonstrated that fiber manufacturing, fabric processing and laundry processes all produce large amounts of fiber micro-plastics and are widely present in global soils, rivers and oceans, penetrating a wide range of organisms through the food chain. Therefore, the development of biodegradable polymers is one of the important approaches to solve the above problems while the development of the recycling and recycling technology of waste fiber products is vigorously carried out.
Due to the hydrolyzability and the microbial erodibility of ester bonds, the currently known biodegradable polymers are mainly polyester macromolecules, wherein polylactic acid (PLA) and polydiacid diol esters, such as polybutylene succinate (PBS) and copolyester thereof have a high commercial prospect in the development of biodegradable polyester fibers. PLA has better spinning performance and is developed more rapidly. However, the PLA fiber is still high in hydrophobicity, and the moisture regain and the water contact angle of the PLA fiber are respectively 0.65% and 79 degrees, so that the PLA fiber is not obviously improved compared with the polyester fiber. The fabric can cause strong itching when being worn, has general skin-friendly performance, and is limited in the application of direct contact of the skin of underwear and the like with the fabric. Meanwhile, PLA has the characteristics of high glass transition temperature (Tg 57 ℃), low thermal stability, high-temperature easy thermal decomposition and the like, and when the PLA is applied to non-woven fabrics, the problems of high hardness, low softness, poor mechanical property, large brittleness of finished products and the like exist.
For the dibasic acid glycol ester, the moisture regain and the water contact angle of the PBS fiber are respectively 0.6 percent and 86.5 percent, and the hydrophilicity of the PBS fiber is not greatly improved compared with that of the common polyester fiber. Meanwhile, due to the flexibility of the monomer structure of the PBS, the thermal and mechanical properties of the PBS are poor. PBAT modified polyester developed by BASF corporation in Germany, namely poly (butylene terephthalate-co-butylene adipate), compared with PBS, PBAT achieves biodegradability and has more excellent thermal and mechanical properties simultaneously due to the addition of aromatic rigid monomer-terephthalic acid (TPA). however, the addition of TPA reduces the hydrophilicity of polyester, affects the affinity of microorganisms with the polyester surface and inhibits the biodegradation performance, PBAT shows better thermal and mechanical properties when the TPA content is more than 35 mol%, and PBAT is difficult to biodegrade when the TPA content is more than 55 mol%.
In view of the fact that the preparation of the polydiacid dihydric alcohol ester polyester and the processing of the corresponding fiber have higher adaptability with the current mature polyester and terylene fiber, and the variety of the monomers is rich, the development of the biodegradable polyester has high commercial development prospect. However, important consideration in polymer design is how to ensure the biodegradability of polyester and impart more excellent thermal/mechanical properties.
In recent years, the preparation of novel polymers from bio-based monomers has attracted much attention both at home and abroad. Among them, isohexides (isohexides) and their derived monomers are a widely studied class of carbohydrate-based monomers. The chemical structure of the isohexide contains a unique cyclic ether skeleton structure, has high structural rigidity and hydrophilicity, and is expected to improve the thermal or mechanical properties and the biodegradability of the polymer. Since the 80's of the twentieth century, isohexides have been widely used for the synthesis of various polymers such as polyesters, polyamides, polycarbonates, and polyurethanes. At present, one outstanding difficulty in synthesizing polyester by utilizing isohexide is that two hydroxyl groups in the structure are secondary hydroxyl groups, the activity of melt polymerization reaction is low, the synthesized polyester has low viscosity and low molecular weight, the requirements of spinning processing cannot be met, and the subsequent application and development of the synthesized polyester are greatly limited; the thermal degradation of the polymer is aggravated to cause severe yellowing if the reaction time is prolonged or the reaction temperature is increased, so that the chromaticity of the polyester product is poor; the method using solution or interfacial polymerization requires the use of a large amount of solvent or reagent, which is not favorable for large-scale industrial production.
In order to overcome the above problems, a new monomer, isoidide-2,5-dimethanol (IIDML), which is prepared from isohexide as a raw material by hydroxyl-enhanced carbonization has been developed in recent years. According to the difference of the spatial conformation of the methylene hydroxyl functional group at the 2, 5-position, the IIDML has two spatial isomers, namely isomannide-2,5-dimethanol (IMDML) and isosorbose-2, 5-dimethanol (ISOSORBIde-2,5-dimethanol, ISDML), and the three isomers are collectively called IXDML. Compared with the isohexide protomer, the IXDML has higher melt polymerization activity, and meanwhile, as the hydroxyl functional group is still connected with the annular skeleton structure, the IXDML still has higher structural rigidity and can effectively improve the thermal property of the polyester, therefore, when the biodegradable polyester is constructed, the IXDML is used for replacing aromatic monomers (such as terephthalic acid, furan-2, 5-dicarboxylic acid) to be copolymerized with aliphatic diol and aliphatic diacid, and theoretically, the full-fat copolyester with low aromatic monomer content can be prepared. The copolyester not only has higher thermal property than the prior all-aliphatic copolyester (such as PBS, PBAT), but also has high hydrophilicity and excellent biodegradability.
However, in the preparation of the above copolyester by a melt polymerization method, the thermal stability of IXDML is low compared to that of alkane diols (e.g., ethylene glycol, 1, 4-butanediol), and when the polymerization temperature is greater than 200 ℃, side reactions such as branching and crosslinking are likely to occur. The polymerization of aliphatic diol and aliphatic diacid/aromatic diacid usually requires higher reaction temperature (T >200 ℃), and when the monomer is copolymerized with aliphatic diol and aliphatic diacid/aromatic diacid, the problem of difficult realization of multi-component effective copolymerization exists, which causes serious thermal degradation of IXDML and low molecular weight of a polymerization product. The low intrinsic viscosity and molecular weight of the polymer directly cause the prepared fiber to have poor mechanical properties and low practical value.
Therefore, in order to expand the application range of IXDML, especially when the IXDML is used as a comonomer to prepare multi-component copolyester, a method for effectively solving the problems needs to be found, so as to meet the requirements of spinning processing and overcome the problem of processing difficulty, and therefore, the fiber with high moisture regain and small surface contact angle is prepared, and the hydrophilicity and the biodegradability of the fiber are improved.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, when IXDML is used for preparing biodegradable copolyester, multi-component effective copolymerization is difficult to realize, thermal degradation is serious, and the molecular weight of a polymerization product is low, so that the spinning processing requirement cannot be met, and provides full-biodegradable copolyester based on IXDML and a preparation method thereof, so that the full-biodegradable copolyester is prepared into fibers. According to the invention, by regulating and controlling the technological conditions of comonomer esterification or ester exchange reaction, the high-efficiency copolymerization of multiple components is realized, and the problems of serious high-temperature thermal degradation of IXDML and low molecular weight of the product caused by insufficient esterification rate of aliphatic diol and aliphatic dibasic acid or aromatic dicarboxylic acid due to low reaction temperature are effectively solved. The fully biodegradable copolyester fiber provided by the invention has the moisture regain of more than or equal to 3.3%, the surface contact angle of less than or equal to 67 degrees, excellent hydrophilicity, good biodegradability and mechanical strength of more than or equal to 2.5cN/dtex, and can be applied to the fields of home textiles, clothes, disposable medical and health materials and the like.
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of full-biodegradable copolyester fiber comprises synthesizing full-biodegradable copolyester, and melt spinning to obtain full-biodegradable copolyester fiber;
the synthetic process of the full-biodegradable copolyester comprises the following steps: firstly, with A1、B1And B2The raw materials are reacted in the first stage under the action of the first catalyst under the condition of high temperature, and then the first stage product, the rigid monomer and A are used2And B3The raw materials are subjected to a second-stage reaction under the low-temperature condition and the action of a second catalyst, and finally, a polycondensation reaction is carried out to prepare the fully biodegradable copolyester;
the first stage reaction and the second stage reaction are esterification or ester exchange reaction;
A1and A2Is a fatty diol, the two being the same or different, A2Added in an amount of 0 or not, B1And B3Being a fatty dicarboxylic acid and/or an alkyl ester thereof, which may be the same or different, B2Is an aromatic dicarboxylic acid and/or an alkyl ester thereof, added in an amount of 0, or other than 0, and the rigid monomer is IXDML, which contains three isomers, namely: isoidide-2,5-dimethanol (IIDML), isomannide-2,5-dimethanol (IMDML), isosorbose-2, 5-dimethanol (ISOMANNIde-2,5-dimethanol, IMDML), and ISOSORBIde-2,5-dimethanol (ISDML), wherein the second catalyst is more than one of dibutyltin oxide, butylstannic acid, stannous octoate, stannous 2-ethylhexanoate, and tetrabutyl titanate;
the high temperature is 190 ℃ or higher, the low temperature is lower than the temperature of the rigid monomer which just starts to generate thermal degradation side reaction, the thermal degradation side reaction comprises ring opening reaction, crosslinking reaction and the like, when the rigid monomer is IXDML, the temperature of the rigid monomer which just starts to generate thermal degradation side reaction is the temperature of the rigid monomer which just starts to generate thermal degradation reaction with the side with poor stability.
The preparation method of the full-biodegradable copolyester fiber comprises the step of carrying out esterification or ester exchange reaction in two stages mainly because A1、B1And B2The esterification reaction or ester exchange reaction of the components can be carried out more effectively under the condition that the temperature is more than or equal to 190 ℃ (conversion rate)>90%) and in this temperature range, the oxygen heterocycle of the IXDML is subject to ring-opening thermal degradation reaction, which further initiates branching or crosslinking side reactions of the polymer, etc., so that the first stage is carried out at a relatively high temperature in order to achieve A1、B1And B2High esterification/transesterification ratio of the components, while in the second stage the main aim is to ensure the newly added IXDML and A2，B3The esterification or ester exchange reaction can be carried out at a lower temperature, so that the occurrence of thermal degradation side reaction is avoided; if the two-step method is not adopted, when all monomers are added in one step, IXDML is subjected to thermal degradation under the high-temperature condition, the hydroxyl-carboxyl ratio in the system is unbalanced, the gelation phenomenon can occur, or a high polymer cannot be prepared; at relatively low temperatures, the molecular weight is correspondingly low due to the low esterification rate or transesterification rate;
the first catalyst is used for realizing esterification or ester exchange reaction of monomers including certain equivalent of aliphatic dihydric alcohol, aliphatic dicarboxylic acid and/or alkyl ester thereof and aromatic dicarboxylic acid and/or alkyl ester thereof, and accelerating the reaction process; the second catalyst is used for realizing esterification or ester exchange reaction of monomers including IXDML, a certain equivalent of aliphatic diol and a certain equivalent of aliphatic dicarboxylic acid and/or alkyl ester thereof, and accelerating the reaction process.
As a preferable scheme:
one kind as described abovePreparation of fully biodegradable copolyester fibers, A1Or A2Is more than one of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 2, 5-hexanediol and 3, 4-hexanediol;
B1and B3Is more than one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, glutaconic acid, isosorbide-dicarboxylic acid, isomannide-dicarboxylic acid, isoidide-dicarboxylic acid, maleic acid, fumaric acid, callus acid, muconic acid, itaconic acid and a substance C with a chemical molecular formula of HOOC- (CHOH)n-COOH, n is 2,3 or 4;
B2is one or more of phthalic acid, isophthalic acid, 1, 8-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, furan-2, 5-dicarboxylic acid, furan-2, 4-dicarboxylic acid and furan-3, 4-dicarboxylic acid.
The preparation method of the fully biodegradable copolyester fiber comprises the following steps of preparing a first catalyst, a second catalyst, a third catalyst and a fourth catalyst, wherein the first catalyst is a titanium catalyst, an antimony catalyst or a metal acetate; the second catalyst is a mixture of dibutyltin oxide and stannous octoate; research shows that when the first catalyst is tetrabutyl titanate, the molecular weight of the product in the first stage is relatively high; when the second catalyst is a mixture of dibutyltin oxide and stannous octoate, the molecular weight of the product is relatively high, mainly because the dibutyltin oxide and the stannous octoate can generate a certain synergistic effect. In conclusion, the preparation method of the fully biodegradable copolyester has a good effect by adopting a compound system of tetrabutyl titanate, dibutyltin oxide and stannous octoate.
In the preparation method of the fully biodegradable copolyester fiber, the titanium catalyst is tetrabutyl titanate or tetraisopropyl titanate, the antimony catalyst is antimony trioxide, and the metal acetate is more than one of zinc acetate, magnesium acetate, manganese acetate, calcium acetate, sodium acetate and cobalt acetate.
A process for preparing the fully biodegradable copolyester fibers as described above, A1Molar amount of (A) and (B)1And B2The molar weight ratio of the dibasic alcohol is 1.1-1.5: 1 (in the invention, the dibasic alcohol is excessive to realize the complete esterification of the dibasic acid, the excessive dibasic alcohol can be removed by utilizing subsequent high vacuum to realize the hydroxyl-carboxyl ratio balance, if the dibasic alcohol is excessive, the difficulty of vacuum removal is increased, the reaction time is long, the thermal degradation of the copolyester can be caused, if the dibasic acid is excessive, the excessive dibasic acid is difficult to remove due to high boiling point of the dibasic acid, if the dibasic acid and the dibasic alcohol are strictly added according to the ratio of 1:1, a great amount of the dibasic alcohol is volatilized in the high-temperature polymerization process, the hydroxyl-carboxyl ratio imbalance can be caused, and a high-molecular-weight polymer can not be prepared), B2In a molar amount of B1、B2And B30 to 30% of the sum of the molar amounts (B)2It may be added in small or no amount, and the main object of the present invention is to reduce the amount of aromatic monomer used or to add no aromatic monomer), the molar amount of rigid monomer in A1、A2And 0.5 to 99% of the sum of the molar amounts of the rigid monomers, and the molar amount of the rigid monomer is based on A2And 1 to 100% of the sum of the molar amounts of the rigid monomers, B3With the rigid monomer and A2The ratio of the sum of the molar amounts of (a) to (B) is 1:1.01 to 2.01And B2The ratio of the sum of the molar amounts of (A) to (B) is 50 to 2000ppm (too low catalyst usage results in ineffective polymerization, slow reaction time, too high catalyst usage results in waste), a second catalyst and (B)3The molar ratio of (A) to (B) is 50 to 2000 ppm.
In the preparation method of the fully biodegradable copolyester fiber, a heat stabilizer and an antioxidant are also added in the first-stage reaction or the second-stage reaction;
the heat stabilizer is more than one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate;
the antioxidant is more than one of antioxidant 1010, antioxidant 1076 and antioxidant 1425;
in the first stage reaction, the addition amounts of the heat stabilizer and the antioxidant are respectively A1、B1And B20.1-2% and 0.1-2% of the total mass;
in the second stage reaction, the heat stabilizer and the antioxidant are added in the amounts of the rigid monomer and A respectively2、B30.1-2% and 0.1-2% of the total mass;
in the two-stage reaction process, if the addition amounts of the heat stabilizer and the antioxidant are too low, the heat stabilizer and the antioxidant cannot play a role; too high, it is wasteful.
According to the preparation method of the full-biodegradable copolyester fiber, the reaction temperature in the first stage is 190-260 ℃ and the time is 2-5 hours, the reaction temperature and the reaction time are set to realize effective esterification of the three components in the first stage, the high esterification rate cannot be achieved due to too low temperature and too short time, and the thermal degradation is serious due to too high temperature and too long time; the temperature of the second stage reaction is 130-170 ℃, the time is 2-5 hours, the reaction temperature and the reaction time are set mainly for realizing esterification of monomers such as IXDML and the like in the second stage, thermal degradation is avoided, sufficient energy is difficult to provide when the temperature is lower than the temperature or the time is shorter than the temperature, the esterification is incomplete, and the thermal degradation is serious when the temperature is higher than the temperature or the time is longer than the time; the polycondensation reaction is divided into a pre-polycondensation process and a final polycondensation process, the temperature of the pre-polycondensation process is 190-260 ℃, the time is 0.5-2 h, the pressure is 0.05-100 mbar, the temperature of the final polycondensation process is 160-190 ℃, the time is 2-5 h, the pressure is 0.05-10 mbar, the final polycondensation is mainly used for realizing the polymerization of monomers containing IXDML, the thermal degradation is avoided, and the pressure can be gradually reduced to about 0.05-10 mbar from 100mbar when the polycondensation starts.
According to the preparation method of the all-biodegradable copolyester fiber, the first-stage reaction further comprises a prepolymerization reaction after the esterification or ester exchange reaction, the temperature of the prepolymerization reaction is 200-260 ℃, the time is 0.5-2 h, the pressure is 0.05-100 mbar, the prepolymerization process is a pre-polycondensation reaction process between the first esterification or ester exchange reaction and the second esterification or ester exchange reaction, a prepolymer formed by the first esterification or ester exchange reaction can be subjected to primary polycondensation to form a pre-polycondensation polymer, and the melting point of the pre-polycondensation polymer is relatively low, so that the second esterification or ester exchange reaction can be favorably carried out at a low temperature, and the degradation of rigid monomers is reduced.
The preparation method of the fully biodegradable copolyester fiber comprises the following process flows of melt spinning: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching;
the technological parameters of the melt spinning processing are as follows: drying for 10-24 h at a drying temperature of 60-120 ℃, a spinning screw temperature of 160-200 ℃, a spinning speed of 700-1800 m/min, a cooling temperature of 18-26 ℃, a stretching temperature of 60-80 ℃, a pre-stretching ratio of 1.05-1.15, a primary stretching ratio of 2.7-3.2, and a secondary stretching ratio of 1.05-1.15;
the spinning screw is a double screw with a degassing function (air in the melt can be discharged, the spinning efficiency and the uniformity of fibers are improved), and the cooling medium is water.
The invention also provides the fully biodegradable copolyester fiber prepared by the preparation method of the fully biodegradable copolyester fiber, wherein the molecular chain of the fully biodegradable copolyester mainly comprises A1Chain segment, A2Segment, B1Segment, B2Segment, B3The polyester is characterized by comprising chain segments and rigid monomer chain segments, wherein the intrinsic viscosity is 0.35-1.0 dL/g, and the intrinsic viscosity of the polyester is characterized by an Ubbelohde viscometer; the number average molecular weight is 7000-30000 g/mol, and the number average molecular weight of the polyester is characterized by Gel permeation chromatography (Gel permeation chromatography); the molar weight of the rigid monomer in the nuclear magnetic spectrum accounts for A1、A2And the sum of the molar amounts of the rigid monomers in a ratio such that the molar amount of the rigid monomer in the feed is A1、A2And the sum of the molar weight of the rigid monomer is only 0 to 5 percent lower, which indicates that the rigid monomer is effectively grafted into the copolyester molecular chain. Finally, the polyester is prepared into full-biodegradable copolyester fiber with good mechanical property, high quality and excellent degradation property by a melt spinning process, the full-biodegradable copolyester fiber is short fiber, and the titer is 1-3 dtex, 38mm or 51mm in length; the moisture regain of the full-biodegradable copolyester fiber is more than or equal to 3.3 percent, the surface contact angle is less than or equal to 67 degrees, the mechanical strength is more than or equal to 2.5cN/dtex, and the elastic modulus is less than or equal to 65 cN/dtex.
Has the advantages that:
(1) the preparation method of the full-biodegradable copolyester fiber can effectively reduce the thermal degradation, crosslinking and other side reactions of carbohydrate-derived oxygen heterocyclic monomer IXDML in the preparation process of the copolyester, and the prepared copolyester has higher molecular weight and intrinsic viscosity and meets the spinning processing requirements;
(2) the fully biodegradable copolyester prepared by the preparation method of the fully biodegradable copolyester fiber has low content of aromatic monomers and high biodegradability.
(3) The fully biodegradable copolyester fiber prepared by the preparation method of the fully biodegradable copolyester fiber has good mechanical property and excellent hygroscopicity.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of full-biodegradable copolyester fiber comprises the following steps:
(1) the first stage reaction: 1, 4-butanediol, terephthalic acid and adipic acid are taken as raw materials, phosphoric acid and an antioxidant 1010 are added simultaneously, esterification is carried out for 2h under the condition of 190 ℃ and the action of tetrabutyl titanate, and then prepolymerization is carried out for 0.5h under the conditions of 0.05mbar pressure and 200 ℃, wherein the ratio of the molar quantity of the 1, 4-butanediol to the sum of the molar quantities of the terephthalic acid and the adipic acid is 1.1:1, the ratio of the molar quantity of the tetrabutyl titanate to the sum of the molar quantities of the terephthalic acid and the adipic acid is 50ppm, and the addition amounts of the phosphoric acid and the antioxidant 1010 are respectively 0.1 percent and 0.2 percent of the sum of the masses of the 1, 4-butanediol, the terephthalic acid and the adipic acid;
(2) and (3) second-stage reaction: taking the first-stage product, IIDML and adipic acid as raw materials, simultaneously adding phosphoric acid and an antioxidant 1010, and esterifying for 2h under the action of dibutyltin oxide (catalyst) at the temperature of 130 ℃, wherein the molar ratio of the molar amount of the adipic acid to the IIDML is 1:1.01, the molar ratio of the dibutyltin oxide to the adipic acid is 50ppm, and the adding amounts of the phosphoric acid and the antioxidant 1010 are respectively 0.5 percent and 0.3 percent of the sum of the mass of the IIDML and the mass of the adipic acid;
the molar amount of terephthalic acid in the step (1) is 15% of the sum of the molar amounts of terephthalic acid in the step (1), adipic acid in the step (1) and adipic acid in the step (2), and the molar amount of IIDML in the step (2) is 20% of the sum of the molar amounts of 1, 4-butanediol in the step (1) and IIDML in the step (2);
(3) carrying out polycondensation to prepare the full-biodegradable copolyester: precondensation is carried out for 0.5h under the conditions of 0.05mbar pressure and 230 ℃, and then polycondensation is carried out for 2h under the conditions of 0.05mbar pressure and 160 ℃.
The intrinsic viscosity of the prepared fully biodegradable copolyester is 0.78dL/g, the number average molecular weight is 25,700g/mol, and the proportion of the molar weight of the IIDML in a nuclear magnetic spectrum to the sum of the molar weights of the 1, 4-butanediol and the IIDML is 0 percent lower than the proportion of the molar weight of the IIDML to the sum of the molar weights of the 1, 4-butanediol and the IIDML in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 12 hours, the drying temperature is 100 ℃, the spinning screw temperature is 180 ℃, the spinning speed is 1200m/min, the cooling temperature is 24 ℃, the stretching temperature is 70 ℃, the pre-stretching magnification is 1.10, the primary stretching magnification is 2.9, and the secondary stretching magnification is 1.1; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 1.63dtex, the length is 38mm, the moisture regain is 3.8%, the surface contact angle is 63 degrees, the mechanical strength is 3.0cN/dtex, and the modulus is 55 cN/dtex.
Comparative example 1
A preparation method of full biodegradable copolyester fiber, its preparation process is basically the same as example 1, except that the catalyst of the second stage reaction is zinc acetate, the intrinsic viscosity of the finally prepared full biodegradable copolyester is 0.33dL/g, the number average molecular weight is 6,700g/mol, the proportion of the molar weight of IIDML in nuclear magnetic spectrum accounting for the sum of the molar weights of 1, 4-butanediol and IIDML is 4% lower than the proportion of the molar weight of IIDML accounting for the sum of the molar weights of 1, 4-butanediol and IIDML when feeding; the intrinsic viscosity and the number average molecular weight are too low to meet the spinning requirement.
Comparing example 1 with comparative example 1, it can be seen that the intrinsic viscosity of the fully biodegradable copolyester prepared in example 1 is higher, the number average molecular weight is larger, and the proportion of the molar weight of IIDML in the nuclear magnetic spectrum to the sum of the molar weights of 1, 4-butanediol and IIDML is less than that of the molar weight of IIDML in the nuclear magnetic spectrum to the sum of the molar weights of 1, 4-butanediol and IIDML when feeding, because the catalyst for the second-stage reaction in example 1 is dibutyltin oxide and the catalytic activity in a bulk system is better than that of a zinc catalyst, the copolymerization effect is better, the prepared fully biodegradable copolyester has high intrinsic viscosity and large number average molecular weight, and the filament breakage is not easy to occur in a fiber forming process, thereby meeting the spinning requirement.
Comparative example 2
A preparation method of full biodegradable copolyester fiber is basically the same as that in example 1, except that the temperature of the first stage reaction is 170 ℃, the intrinsic viscosity of the finally prepared full biodegradable copolyester is 0.30dL/g, the number average molecular weight is 6,000g/mol, and the proportion of the molar weight of IIDML in a nuclear magnetic spectrum to the sum of the molar weights of 1, 4-butanediol and IIDML is 4% lower than the proportion of the molar weight of IIDML to the sum of the molar weights of 1, 4-butanediol and IIDML in the feeding process; the intrinsic viscosity and the number average molecular weight are too low to meet the spinning requirement.
Comparing example 1 with comparative example 2, it can be seen that the intrinsic viscosity of the fully biodegradable copolyester prepared in example 1 is higher, the number average molecular weight is larger, and the proportion of the molar weight of IIDML in the nuclear magnetic spectrum to the sum of the molar weights of 1, 4-butanediol and IIDML is less than that of the molar weight of IIDML in the nuclear magnetic spectrum to the sum of the molar weights of 1, 4-butanediol and IIDML in the feeding process, because the temperature of the first-stage reaction in example 1 is higher, the esterification degree is more complete, the copolymerization effect is better, the prepared fully biodegradable copolyester has high intrinsic viscosity and large number average molecular weight, and the fiber is not easy to break in the fiber forming process, thereby meeting the spinning requirement.
Comparative example 3
A preparation method of full-biodegradable copolyester fiber is basically the same as that of example 1, except that the temperature of the second stage reaction is 210 ℃, and the final product is gel and is difficult to dissolve in organic solvents (such as hexafluoroisopropanol, trifluoroacetic acid, chloroform, tetrahydrofuran, and the like).
Comparing example 1 with comparative example 3, it can be seen that example 1 can prepare fully biodegradable copolyester with higher intrinsic viscosity and number average molecular weight and no gel formation, because the temperature of the second stage reaction in example 1 is lower than that of the thermal degradation side reaction of IIDML, such as ring opening side reaction, thereby effectively maintaining the hydroxyl-carboxyl ratio and avoiding further crosslinking reaction and gel formation; the gel produced in comparative example 3, which resulted in polyester mostly in amorphous region, did not have significant melting temperature and could not meet the process requirements of melt spinning.
Example 2
A preparation method of full-biodegradable copolyester fiber comprises the following steps:
(1) the first stage reaction: 1, 4-butanediol, terephthalic acid and adipic acid are taken as raw materials, phosphoric acid and an antioxidant 1010 are added simultaneously, esterification is carried out for 2h under the condition of 210 ℃ and the action of tetrabutyl titanate, and then prepolymerization is carried out for 0.5h under the conditions of 0.05mbar pressure and 230 ℃, wherein the ratio of the molar quantity of the 1, 4-butanediol to the sum of the molar quantities of the terephthalic acid and the adipic acid is 1.5:1, the ratio of the molar quantity of the tetrabutyl titanate to the sum of the molar quantities of the terephthalic acid and the adipic acid is 2000ppm, and the addition amounts of the phosphoric acid and the antioxidant 1010 are respectively 0.1 percent and 0.2 percent of the sum of the masses of the 1, 4-butanediol, the terephthalic acid and the adipic acid;
(2) and (3) second-stage reaction: taking the first-stage product, IIDML, 1, 4-butanediol and pimelic acid as raw materials, simultaneously adding phosphoric acid and an antioxidant 1010, and esterifying for 2 hours under the action of dibutyltin oxide at the temperature of 140 ℃, wherein the ratio of the molar weight of pimelic acid to the sum of the molar weight of IIDML and the molar weight of 1, 4-butanediol in the step (2) is 1:2, the molar ratio of dibutyltin oxide to pimelic acid is 68ppm, and the adding amounts of phosphoric acid and antioxidant 1010 are respectively 2% and 0.3% of the sum of the mass of IIDML and pimelic acid;
the molar amount of terephthalic acid in the step (1) is 30% of the sum of the molar amounts of terephthalic acid in the step (1), adipic acid in the step (1) and pimelic acid in the step (2), and the molar amount of IIDML in the step (2) is 0.5% of the sum of the molar amounts of 1, 4-butanediol in the step (1), 1, 4-butanediol in the step (2) and IIDML in the step (2), and is 1% of the sum of the molar amounts of 1, 4-butanediol in the step (2) and IIDML in the step (2);
(3) carrying out polycondensation to prepare the full-biodegradable copolyester: prepolycondensation was carried out for 0.5h under a pressure of 0.05mbar and a temperature of 190 ℃ and final polycondensation was carried out for 2h under a pressure of 0.05mbar and a temperature of 190 ℃.
The intrinsic viscosity of the prepared fully biodegradable copolyester is 0.90dL/g, the number average molecular weight is 26,500g/mol, and the proportion of the molar weight of IIDML in a nuclear magnetic spectrum to the sum of the molar weights of the 1, 4-butanediol in the step (1) and the molar weights of the 1, 4-butanediol and the IIDML in the step (2) is 0 percent lower than the proportion of the molar weight of IIDML to the sum of the molar weights of the 1, 4-butanediol in the step (1) and the molar weights of the 1, 4-butanediol and the IIDML in the step (2) in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 80 ℃, the spinning screw temperature is 170 ℃, the spinning speed is 700m/min, the cooling temperature is 18 ℃, the stretching temperature is 60 ℃, the pre-stretching ratio is 1.05, the primary stretching ratio is 2.7, and the secondary stretching ratio is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 2.05dtex, the length is 38mm, the moisture regain is 3.5%, the surface contact angle is 67 degrees, the mechanical strength is 3.5cN/dtex, and the modulus is 45 cN/dtex.
Example 3
A method for preparing fully biodegradable copolyester fibers, which is substantially the same as that in example 2, is different from the method in that 2, 4-pentanediol is added in step (2) instead of 1, 4-butanediol, and the molar amount of IIDML in step (2) is 50% of the sum of the molar amounts of 2, 4-pentanediol in step (2) and IIDML in step (2).
The intrinsic viscosity of the finally prepared fully biodegradable copolyester is 0.60dL/g, the number average molecular weight is 16,800g/mol, and the proportion of the molar weight of the IIDML in a nuclear magnetic spectrum to the sum of the molar weights of the 1, 4-butanediol in the step (1), the 2, 4-pentanediol in the step (2) and the IIDML is 0 percent lower than the proportion of the molar weight of the IIDML to the sum of the molar weights of the 1, 4-butanediol in the step (1), the 2, 4-pentanediol in the step (2) and the IIDML in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 100 ℃, the spinning screw temperature is 190 ℃, the spinning speed is 900m/min, the cooling temperature is 24 ℃, the stretching temperature is 70 ℃, the pre-stretching ratio is 1.10, the primary stretching ratio is 2.9, and the secondary stretching ratio is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 1.35dtex, the length is 51mm, the moisture regain is 4.0%, the surface contact angle is 59 degrees, the mechanical strength is 2.5cN/dtex, and the modulus is 64 cN/dtex.
Example 4
A process for preparing fully biodegradable copolyester fibers, substantially as described in example 2, except that 1, 4-hexanediol is added in step (2) instead of 1, 4-butanediol, and the molar amount of IIDML in step (2) is 90% of the sum of the molar amounts of 1, 4-hexanediol in step (2) and IIDML in step (2).
The intrinsic viscosity of the finally prepared fully biodegradable copolyester is 0.91dL/g, the number average molecular weight is 21,300g/mol, and the proportion of the molar weight of the IIDML in a nuclear magnetic spectrum to the sum of the molar weights of the 1, 4-butanediol in the step (1), the 1, 4-hexanediol in the step (2) and the IIDML is 0 percent lower than the proportion of the molar weight of the IIDML to the sum of the molar weights of the 1, 4-butanediol in the step (1), the 1, 4-hexanediol in the step (2) and the IIDML in the feeding process;
carrying out melt spinning processing on the prepared fully biodegradable copolyester to prepare fully biodegradable copolyester short fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 110 ℃, the spinning screw temperature is 200 ℃, the spinning speed is 1100m/min, the cooling temperature is 26 ℃, the stretching temperature is 80 ℃, the pre-stretching magnification is 1.15, the primary stretching magnification is 3.1, and the secondary stretching magnification is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 2.08dtex, the length is 38mm, the moisture regain is 4.2%, the surface contact angle is 57 degrees, the mechanical strength is 3.6cN/dtex, and the modulus is 43 cN/dtex.
Example 5
A preparation method of full-biodegradable copolyester fiber comprises the following steps:
(1) the first stage reaction: taking 1, 3-propanediol, dimethyl isophthalate and dimethyl malonate as raw materials, simultaneously adding phosphorous acid and an antioxidant 1076, esterifying for 2.5h under the condition of 215 ℃ and the action of tetraisopropyl titanate, and then pre-polymerizing for 1h under the conditions of 0.7mbar pressure and 220 ℃ wherein the ratio of the molar quantity of the 1, 3-propanediol to the sum of the molar quantities of the dimethyl isophthalate and the dimethyl malonate is 1.2:1, the ratio of the molar quantity of the tetraisopropyl titanate to the sum of the molar quantities of the dimethyl isophthalate and the dimethyl malonate is 250ppm, and the adding amounts of the phosphorous acid and the antioxidant 1076 are respectively 0.3 percent and 0.1 percent of the sum of the masses of the 1, 3-propanediol, the dimethyl isophthalate and the dimethyl malonate;
(2) and (3) second-stage reaction: taking the first-stage product, IIDML and dimethyl malonate as raw materials, simultaneously adding phosphorous acid and an antioxidant 1425, and esterifying for 3h under the action of butylstannoic acid (a catalyst) at the temperature of 148 ℃, wherein the molar ratio of the dimethyl malonate to the IIDML is 1:1.8, the molar ratio of the butylstannoic acid (the catalyst) to the dimethyl malonate is 180ppm, and the addition amounts of the phosphorous acid and the antioxidant 1425 are respectively 0.1 percent and 0.1 percent of the sum of the masses of the DMIIL and the dimethyl malonate;
the molar quantity of the dimethyl isophthalate in the step (1) is 5% of the sum of the molar quantities of the dimethyl isophthalate in the step (1), the dimethyl malonate in the step (1) and the dimethyl malonate in the step (2), and the molar quantity of the IIDML in the step (2) is 18% of the sum of the molar quantities of the 1, 3-propanediol in the step (1) and the IIDML in the step (2);
(3) carrying out polycondensation to prepare the full-biodegradable copolyester: prepolycondensation was carried out for 0.5h at a pressure of 0.1mbar and a temperature of 200 ℃ and final polycondensation was carried out for 5h at a pressure of 0.1mbar and a temperature of 185 ℃.
The final prepared fully biodegradable copolyester has the intrinsic viscosity of 0.93dL/g and the number average molecular weight of 27,200g/mol, and the proportion of the molar weight of the IIDML in a nuclear magnetic spectrum accounting for the sum of the molar weights of the 1, 3-propylene glycol and the IIDML is 0 percent lower than the proportion of the molar weight of the IIDML accounting for the sum of the molar weights of the 1, 3-butylene glycol and the IIDML in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 110 ℃, the spinning screw temperature is 200 ℃, the spinning speed is 1300m/min, the cooling temperature is 24 ℃, the stretching temperature is 80 ℃, the pre-stretching multiplying power is 1.15, the primary stretching multiplying power is 3.1, and the secondary stretching multiplying power is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 2.10dtex, the length is 38mm, the moisture regain is 3.6%, the surface contact angle is 65 degrees, the mechanical strength is 3.8cN/dtex, and the modulus is 40 cN/dtex.
Example 6
A preparation method of full biodegradable copolyester fiber is basically the same as that in example 5, except that no heat stabilizer or antioxidant is added in the first and second reaction stages, the intrinsic viscosity of the finally prepared full biodegradable copolyester is 0.74dL/g, the number average molecular weight is 21,800g/mol, and the proportion of the molar weight of IIDML in a nuclear magnetic spectrum to the sum of the molar weights of 1, 3-propanediol and IIDML is 2 percent lower than that of DMIIL in the process of feeding;
carrying out melt spinning processing on the prepared fully biodegradable copolyester to prepare fully biodegradable copolyester short fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 80 ℃, the spinning screw temperature is 170 ℃, the spinning speed is 900m/min, the cooling temperature is 24 ℃, the stretching temperature is 70 ℃, the pre-stretching ratio is 1.10, the primary stretching ratio is 2.8, and the secondary stretching ratio is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 1.58dtex, the length is 38mm, the moisture regain is 3.3%, the surface contact angle is 66 degrees, the mechanical strength is 3.1cN/dtex, and the modulus is 56 cN/dtex.
Example 7
A process for preparing fully biodegradable copolyester fibers, which is substantially the same as that of example 5, except that the first-stage reaction does not include a prepolymerization process, the finally obtained fully biodegradable copolyester has an intrinsic viscosity of 0.78dL/g and a number average molecular weight of 23,000g/mol, and the ratio of the molar amount of IIDML to the sum of the molar amounts of 1, 3-propanediol and IIDML in a nuclear magnetic spectrum is 1% lower than the ratio of the molar amount of IIDML to the sum of the molar amounts of 1, 3-propanediol and IIDML in the course of feeding.
Comparing example 7 with example 5, it can be seen that the prepolymerization reaction between the first stage esterification reaction and the second stage esterification reaction contributes to the increase of the final molecular weight of the polyester, and the molecular weight and viscosity of the polyester as a whole are higher;
carrying out melt spinning processing on the prepared fully biodegradable copolyester to prepare fully biodegradable copolyester short fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 80 ℃, the spinning screw temperature is 170 ℃, the spinning speed is 900m/min, the cooling temperature is 24 ℃, the stretching temperature is 70 ℃, the pre-stretching ratio is 1.10, the primary stretching ratio is 2.8, and the secondary stretching ratio is 1.15; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 1.60dtex, the length is 38mm, the moisture regain is 3.4%, the surface contact angle is 65 degrees, the mechanical strength is 3.2cN/dtex, and the modulus is 54 cN/dtex.
Example 8
The preparation method of the fully biodegradable copolyester fiber is basically the same as that in example 5, except that the catalyst for the second-stage reaction is a mixture of dibutyltin oxide and stannous octoate in a mass ratio of 1:1, the final fully biodegradable copolyester has an intrinsic viscosity of 0.95dL/g and a number average molecular weight of 28,200g/mol, and the molar weight of IIDML in a nuclear magnetic spectrum accounts for 0% less than the sum of the molar weights of 1, 3-propylene glycol and IIDML when the material is added;
carrying out melt spinning processing on the prepared fully biodegradable copolyester to prepare fully biodegradable copolyester short fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 20 hours, the drying temperature is 110 ℃, the spinning screw temperature is 200 ℃, the spinning speed is 1500m/min, the cooling temperature is 24 ℃, the stretching temperature is 80 ℃, the pre-stretching magnification is 1.15, the primary stretching magnification is 3.1, and the secondary stretching magnification is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 2.25dtex, the length is 38mm, the moisture regain is 3.9%, the surface contact angle is 60 degrees, the mechanical strength is 4.0cN/dtex, and the modulus is 38 cN/dtex.
Example 9
A preparation method of full-biodegradable copolyester fiber comprises the following steps:
(1) the first stage reaction: taking 1, 3-propanediol and succinic acid as raw materials, simultaneously adding hypophosphorous acid and a mixture of an antioxidant 1010 and an antioxidant 1076 with a mass ratio of 1:1, esterifying for 5 hours under the action of antimony trioxide at the temperature of 200 ℃, and then pre-polymerizing for 2 hours under the conditions of 100mbar pressure and 260 ℃, wherein the ratio of the molar weight of the 1, 3-propanediol to the molar weight of the succinic acid is 1.5:1, the ratio of the molar weight of the antimony trioxide to the molar weight of the succinic acid is 1200ppm, the addition amount of the hypophosphorous acid is 2% of the sum of the masses of the 1, 3-propanediol and the succinic acid, and the addition amount of the mixture of the antioxidant 1010 and the antioxidant 1076 with the mass ratio of 1:1 is 2% of the sum of the masses of the 1, 3-propanediol and the succinic acid;
(2) and (3) second-stage reaction: taking a first-stage product, ISDML and succinic acid as raw materials, simultaneously adding a mixture of hypophosphorous acid and an antioxidant 1010, an antioxidant 1076 and an antioxidant 1425 in a mass ratio of 1:1:1, and esterifying for 5 hours at the temperature of 170 ℃ under the action of a mixture of dibutyltin oxide and stannous octoate in a mass ratio of 1:1, wherein the molar ratio of the molar weight of the succinic acid to the molar weight of the ISDML is 1:1.6, the molar ratio of the dibutyltin oxide to the succinic acid is 2000ppm, the addition amount of the hypophosphorous acid is 1.2% of the sum of the masses of the ISDML and the succinic acid, and the addition amount of the mixture of the antioxidant 1010, the antioxidant 1076 and the antioxidant 1425 in a mass ratio of 1:1:1 is 2% of the sum of the masses of the ISDML and the succinic acid;
the molar weight of the ISDML in the step (2) is 99 percent of the sum of the molar weights of the 1, 3-propylene glycol in the step (1) and the ISDML in the step (2);
(3) carrying out polycondensation to prepare the full-biodegradable copolyester: prepolycondensation was carried out for 2h at a pressure of 100mbar and a temperature of 260 ℃ and final polycondensation was carried out for 5h at a pressure of 10mbar and a temperature of 190 ℃.
The intrinsic viscosity of the finally prepared fully biodegradable copolyester is 1.0dL/g, the number average molecular weight is 30,000g/mol, and the proportion of the mol weight of the ISDML in a nuclear magnetic spectrum accounting for the sum of the mol weights of the 1, 3-propylene glycol and the ISDML is 0 percent lower than that of the mol weight of the ISDML accounting for the sum of the mol weights of the 1, 3-propylene glycol and the ISDML in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 24 hours, the drying temperature is 60 ℃, the spinning screw temperature is 200 ℃, the spinning speed is 1800m/min, the cooling temperature is 24 ℃, the stretching temperature is 80 ℃, the pre-stretching magnification is 1.15, the primary stretching magnification is 3.2, and the secondary stretching magnification is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 3.0dtex, the length is 38mm, the moisture regain is 4.8%, the surface contact angle is 52 degrees, the mechanical strength is 4.2cN/dtex, and the modulus is 36 cN/dtex.
Example 10
A preparation method of full-biodegradable copolyester fiber comprises the following steps:
(1) the first stage reaction: taking 1, 2-butanediol, isophthalic acid and glutaric acid as raw materials, simultaneously adding pyrophosphoric acid and an antioxidant 1010, esterifying for 3.5h under the condition of 239 ℃ and the action of zinc acetate (catalyst), and then pre-polymerizing for 1h under the conditions of 30mbar pressure and 230 ℃, wherein the ratio of the molar amount of the 1, 2-butanediol to the sum of the molar amounts of isophthalic acid and glutaric acid is 1.5:1, the ratio of the molar amount of the zinc acetate (catalyst) to the sum of the molar amounts of isophthalic acid and glutaric acid is 1200ppm, and the addition amounts of pyrophosphoric acid and the antioxidant 1010 are respectively 0.4% and 0.6% of the sum of the masses of 1, 2-butanediol, isophthalic acid and glutaric acid;
(2) and (3) second-stage reaction: taking a first-stage product, IMDML and glutaric acid as raw materials, simultaneously adding ammonium phosphate and an antioxidant 1076, and esterifying for 4 hours under the action of stannous 2-ethyl hexanoate (catalyst) at the temperature of 150 ℃, wherein the molar ratio of glutaric acid to IMDML is 1:1.5, the molar ratio of stannous 2-ethyl hexanoate (catalyst) to glutaric acid is 1000ppm, and the addition amounts of the ammonium phosphate and the antioxidant 1076 are respectively 0.6 percent and 0.8 percent of the sum of the masses of IMDML and glutaric acid;
the molar amount of isophthalic acid in the step (1) is 12% of the sum of the molar amounts of isophthalic acid in the step (1), glutaric acid in the step (1) and glutaric acid in the step (2), and the molar amount of IMDML in the step (2) is 48% of the sum of the molar amounts of 1, 2-butanediol in the step (1) and IMDML in the step (2);
(3) carrying out polycondensation to prepare the full-biodegradable copolyester: the polycondensation is carried out for 2h under the conditions of 50mbar pressure and 230 ℃ and the final polycondensation is carried out for 4h under the conditions of 0.5mbar pressure and 175 ℃.
The final prepared fully biodegradable copolyester has the intrinsic viscosity of 0.56dL/g and the number average molecular weight of 12,700g/mol, and the proportion of the molar weight of IMDML in a nuclear magnetic spectrum to the sum of the molar weights of 1, 2-butanediol and IMDML is 5 percent lower than that of the molar weight of IMDML to the sum of the molar weights of 1, 2-butanediol and IMDML in the feeding process;
(4) carrying out melt spinning processing on the fully biodegradable copolyester prepared in the step (3) to prepare fully biodegradable copolyester staple fibers; the melt spinning processing process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching; the technological parameters of the melt spinning processing are as follows: the drying time is 10 hours, the drying temperature is 120 ℃, the spinning screw temperature is 160 ℃, the spinning speed is 700m/min, the cooling temperature is 24 ℃, the stretching temperature is 60 ℃, the pre-stretching ratio is 1.05, the primary stretching ratio is 2.7, and the secondary stretching ratio is 1.05; wherein the spinning screw is a double screw with degassing function, and the medium used for cooling is water;
the titer of the prepared full-biodegradable copolyester staple fiber is 1.0dtex, the length is 51mm, the moisture regain is 3.9%, the surface contact angle is 59 degrees, the mechanical strength is 2.2cN/dtex, and the modulus is 65 cN/dtex.
Examples 11 to 33
A preparation method of fully biodegradable copolyester fibers, which is basically the same as that in example 8, except that the raw materials, the catalyst and the heat stabilizer for the first-stage reaction and the dibasic acid, the catalyst and the heat stabilizer for the second-stage reaction are different in types, specifically and respectively shown in table 1, and the properties of the fully biodegradable copolyester fibers finally prepared are respectively shown in table 2.
TABLE 1
Figure BDA0002355033770000141
Figure BDA0002355033770000151
Figure BDA0002355033770000161
Figure BDA0002355033770000171
TABLE 2
Figure BDA0002355033770000181
Figure BDA0002355033770000191

Claims (9)

1. A preparation method of full-biodegradable copolyester fiber is characterized by comprising the following steps: firstly, synthesizing fully biodegradable copolyester, and then carrying out melt spinning processing on the fully biodegradable copolyester to prepare fully biodegradable copolyester fiber;
the synthetic process of the full-biodegradable copolyester comprises the following steps: firstly, with A1、B1And B2The raw materials are reacted in the first stage under the action of the first catalyst under the condition of high temperature, and then the first stage product, the rigid monomer and A are used2And B3The raw materials are subjected to a second-stage reaction under the low-temperature condition and the action of a second catalyst, and finally, a polycondensation reaction is carried out to prepare the fully biodegradable copolyester;
the first stage reaction and the second stage reaction are esterification or ester exchange reaction; the reaction temperature of the first stage is 190-260 ℃, and the reaction time is 2-5 h; the temperature of the second stage reaction is 130-170 ℃, and the time is 2-5 h; the polycondensation reaction is divided into a pre-polycondensation process and a final polycondensation process, the temperature of the pre-polycondensation process is 190-260 ℃, the time is 0.5-2 h, the pressure is 0.05-100 mbar, the temperature of the final polycondensation process is 160-190 ℃, the time is 2-5 h, and the pressure is 0.05-10 mbar;
A1and A2Is a fatty diol, the two being the same or different, A2Added in an amount of 0 or not, B1And B3Being a fatty dicarboxylic acid and/or an alkyl ester thereof, which may be the same or different, B2The catalyst is aromatic dicarboxylic acid and/or alkyl ester thereof, the addition amount of the aromatic dicarboxylic acid and/or alkyl ester thereof is 0 or not, the rigid monomer is more than one of isoidide-2,5-dimethanol, isomannide-2,5-dimethanol and isosorbide-2,5-dimethanol, and the second catalyst is more than one of dibutyltin oxide, butylstannic acid, stannous octoate, stannous 2-ethylhexanoate and tetrabutyl titanate.
2. The method for preparing fully biodegradable copolyester fiber according to claim 1, wherein A is1Or A2Is selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycolMore than one of 2, 3-butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 4-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 2, 5-hexanediol and 3, 4-hexanediol;
B1and B3Is more than one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, glutaconic acid, isosorbide-dicarboxylic acid, isomannide-dicarboxylic acid, isoidide-dicarboxylic acid, maleic acid, fumaric acid, callus acid, muconic acid, itaconic acid and a substance C with a chemical molecular formula of HOOC- (CHOH)n-COOH, n is 2,3 or 4;
B2is one or more of terephthalic acid, phthalic acid, isophthalic acid, 1, 8-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, furan-2, 5-dicarboxylic acid, furan-2, 4-dicarboxylic acid and furan-3, 4-dicarboxylic acid.
3. The method for preparing fully biodegradable copolyester fiber according to claim 1, wherein the first catalyst is a titanium catalyst, an antimony catalyst or a metal acetate; the second catalyst is a mixture of dibutyltin oxide and stannous octoate.
4. The method for preparing fully biodegradable copolyester fiber according to claim 3, wherein the titanium catalyst is tetrabutyl titanate or tetraisopropyl titanate, the antimony catalyst is antimony trioxide, and the metal acetate is more than one of zinc acetate, magnesium acetate, manganese acetate, calcium acetate, sodium acetate and cobalt acetate.
5. The method for preparing fully biodegradable copolyester fiber according to claim 1, wherein A is1Molar amount of (A) and (B)1And B2The ratio of the sum of the molar amounts of (B) is 1.1 to 1.5:1, B2In a molar amount of B1、B2And B30 to 30% of the sum of the molar amounts, the molar amount of the rigid monomer being based on A1、A2And the molar amount of rigid monomer0.5-99% of the sum, and the molar weight of the rigid monomer accounts for A2And 1 to 100% of the sum of the molar amounts of the rigid monomers, B3With the rigid monomer and A2The ratio of the sum of the molar amounts of (a) to (B) is 1:1.01 to 2.01And B2The ratio of the sum of the molar amounts of (A) and (B) is 50 to 2000ppm, the molar amount of the second catalyst and B3The ratio of the molar weight of (a) is 50 to 2000 ppm.
6. The method for preparing fully biodegradable copolyester fiber according to claim 1, wherein a heat stabilizer and an antioxidant are further added in the first stage reaction or the second stage reaction;
the heat stabilizer is more than one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate;
the antioxidant is more than one of antioxidant 1010, antioxidant 1076 and antioxidant 1425;
in the first stage reaction, the addition amounts of the heat stabilizer and the antioxidant are respectively A1、B1And B20.1-2% and 0.1-2% of the total mass;
in the second stage reaction, the addition amounts of the heat stabilizer and the antioxidant are respectively rigid monomer and A2And B30.1-2% and 0.1-2% of the total mass.
7. The method for preparing fully biodegradable copolyester fiber according to claim 1, wherein the first stage reaction further comprises a prepolymerization reaction after esterification or transesterification, the prepolymerization reaction is carried out at 200-260 ℃ for 0.5-2 h and under 0.05-100 mbar.
8. The preparation method of the fully biodegradable copolyester fiber according to claim 1, wherein the melt spinning process comprises the following steps: drying, melting a spinning screw, extruding, spinning, cooling, winding and stretching;
the technological parameters of the melt spinning processing are as follows: drying for 10-24 h at a drying temperature of 60-120 ℃, a spinning screw temperature of 160-200 ℃, a spinning speed of 700-1800 m/min, a cooling temperature of 18-26 ℃, a stretching temperature of 60-80 ℃, a pre-stretching ratio of 1.05-1.15, a primary stretching ratio of 2.7-3.2, and a secondary stretching ratio of 1.05-1.15;
the spinning screw is a double screw with a degassing function, and the medium used for cooling is water.
9. The fully biodegradable copolyester fiber prepared by the preparation method of the fully biodegradable copolyester fiber according to any one of claims 1 to 8, which is characterized in that: the molecular chain of the full-biodegradable copolyester mainly consists of A1Chain segment, A2Segment, B1Segment, B2Segment, B3The chain segment and the rigid monomer chain segment are combined, the intrinsic viscosity is 0.35-1.0 dL/g, the number average molecular weight is 7000-30000 g/mol, and the molar weight of the rigid monomer in a nuclear magnetic spectrum accounts for A1、A2And the sum of the molar amounts of the rigid monomers in a ratio such that the molar amount of the rigid monomer in the feed is A1、A2The proportion of the sum of the molar weight of the rigid monomer and the molar weight of the rigid monomer is 0-5%;
the fully biodegradable copolyester fiber is short fiber, the titer is 1-3 dtex, and the length is 38mm or 51 mm; the moisture regain of the fully biodegradable copolyester fiber is more than or equal to 3.3 percent, the surface contact angle is less than or equal to 67 degrees, the mechanical strength is more than or equal to 2.5cN/dtex, and the elastic modulus is less than or equal to 65 cN/dtex.
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