CN115897267A - Plant dyeing method of modified degradable polyester - Google Patents
Plant dyeing method of modified degradable polyester Download PDFInfo
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- CN115897267A CN115897267A CN202211407517.3A CN202211407517A CN115897267A CN 115897267 A CN115897267 A CN 115897267A CN 202211407517 A CN202211407517 A CN 202211407517A CN 115897267 A CN115897267 A CN 115897267A
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- degradable
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- 150000001768 cations Chemical class 0.000 claims abstract description 44
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 32
- 229920004933 Terylene® Polymers 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
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- Artificial Filaments (AREA)
Abstract
The application provides a plant dyeing method of modified degradable terylene, which comprises the following steps: s1, carrying out free radical graft polymerization reaction on an ethylene terephthalate oligomer and a cationic high molecular compound, and carrying out belt casting and grain cutting on an obtained reaction product to obtain a cationic modified polyester chip; the cationic polymer compound is a hydrophilic polymer; s2, blending biodegradable master batches into the cation modified polyester chips, and carrying out mixed melt spinning to obtain degradable cation modified polyester fibers; and S3, mixing and adsorbing the degradable cation modified polyester fiber and water-soluble inorganic salt, and then dyeing by adopting plant dye at the temperature lower than 100 ℃ to obtain the dyed fiber. The dyeing method can use the vegetable dye to carry out conventional dyeing on the modified polyester fiber, and simultaneously, the polyester fiber can be degraded under natural conditions, thereby realizing the degradation of the fabric fiber and the vegetable dye.
Description
Technical Field
The invention belongs to the technical field of textile printing and dyeing, and particularly relates to a plant dyeing method of modified degradable terylene.
Background
The polyester fiber has excellent performances of high strength, wear resistance, crease resistance, easy washing, quick drying and the like, and is widely applied to the field of textile and clothing. The polyester fiber is a general name of a fiber which is spun by using polyester generated by polycondensation of various dihydric alcohols and aromatic dicarboxylic acid or ester thereof as a raw material; polyethylene terephthalate fiber is the main variety, commonly called terylene.
The polyester fiber has compact molecular structure, does not have dye-philic groups, is not easy to be directly combined with polyester fiber molecules no matter chemical dyes or plant dyes, so that the polyester fiber is difficult to dye under the conventional conditions, and generally needs to be dyed by disperse dyes under the conditions of high temperature or existence of carriers. The chemical dye usually adopted in common terylene dyeing is disperse dye, and the disperse dye is used for dyeing terylene fibers under the condition of high-temperature melting through affinity and the difference of the internal concentration and the external concentration of dye molecules.
Meanwhile, polyester fiber, which is the first major variety of synthetic fiber, is not directly harmful to the environment, but has a large amount of use, strong resistance to the atmosphere and microorganisms, high crystallinity, and difficult natural decomposition, and its waste has become global environmental pollution. In recent years there has been a considerable increase in the recycling of polyester fibres, but still very low, less than 10%. Therefore, the polyester fiber can be naturally degraded to become a practical and effective solution, and the method conforms to the current low-carbon social development trend.
Disclosure of Invention
The invention aims to provide a plant dyeing method of modified degradable polyester, which can be used for conventionally dyeing modified polyester fibers by using plant dyes, and simultaneously, the polyester fibers can be degraded under natural conditions, so that the degradation of fabric fibers and the plant dyes is realized, and the plant dyeing method is beneficial to environmental protection and the like.
The invention provides a plant dyeing method of modified degradable terylene, which comprises the following steps:
s1, carrying out free radical graft polymerization reaction on an ethylene terephthalate oligomer and a cationic high molecular compound, and carrying out belt casting and grain cutting on an obtained reaction product to obtain a cationic modified polyester chip; the cationic polymer compound is a hydrophilic polymer;
s2, blending biodegradable master batches into the cation modified polyester chips, and carrying out mixed melt spinning to obtain degradable cation modified polyester fibers;
and S3, mixing and adsorbing the degradable cation modified polyester fiber and water-soluble inorganic salt, and then dyeing by adopting plant dye at the temperature lower than 100 ℃ to obtain the dyed fiber.
In the embodiment of the invention, in the step S1, the ethylene terephthalate oligomer is prepared by reacting terephthalic acid and bio-based ethanol to generate ethylene terephthalate, and then performing low vacuum polycondensation.
In the embodiment of the invention, in the step S1, a stabilizer and/or a catalyst is/are added in the low vacuum polycondensation stage for preparing the ethylene terephthalate oligomer, the absolute pressure value of the polycondensation is below 600Pa, the temperature is controlled to be 240-270 ℃, and the reaction is carried out for 50-70 min.
In an embodiment of the present invention, in step S1, the cationic polymer compound is selected from one or more of amido-cationic polyacrylamide, hydroxy-cationic starch, chitosan quaternary ammonium salt and polyepichlorohydrin amide.
In the embodiment of the invention, in the step S1, the absolute value of the pressure of the free radical graft polymerization reaction is below 100Pa, the temperature is controlled between 270 ℃ and 310 ℃, and the reaction time is 80-120 min.
In the embodiment of the invention, in step S2, the main component of the biodegradable masterbatch is one or two of aliphatic polylactic acid and polylactic acid-glycolic acid; the mass ratio of the cation modified polyester chip to the biodegradable master batch is 55-70: 30 to 45 percent.
In the embodiment of the present invention, in step S2, the hybrid melt spinning employs a POY process or an FDY process.
In an embodiment of the present invention, in step S3, the metal cation in the water-soluble inorganic salt is one or more of calcium, potassium, iron and aluminum; the vegetable dye is selected from one or more of polyphenols, porphyrins, anthraquinones and carotenoids.
In the embodiment of the invention, in the step S3, the degradable cation modified polyester fiber and water-soluble inorganic salt are mixed and adsorbed in water, the amount of the water-soluble inorganic salt is within 6% of the weight of the degradable cation modified polyester fiber, and the temperature of the mixed adsorption is 50-90 ℃.
In the embodiment of the invention, in the step S3, the dyeing temperature of the plant dye is 70-90 ℃, and the total heat preservation time is 30-60 min.
Compared with the prior art, the method introduces hydrophilic cationic macromolecules as third monomers for copolymerization and grafting when forming the polyethylene terephthalate polyester chip so as to obtain the cationic modified polyester chip; with the change of the structures, biodegradable materials are added into the modified terylene, and the degradable cation modified terylene fiber is obtained by spinning; finally, the prepared degradable cation modified polyester fiber or product is grafted with metal cations before plant dyeing by mixing water-soluble inorganic salts, the auxiliary agents can be effectively adsorbed on fiber molecules to form corresponding ion coordination bonds, and the combination of the ion bonds or covalent bonds is formed between the plant dye molecules and the fiber under the conventional dyeing condition, so that the plant dye is fixed on the fiber, and the purpose of finally dyeing the fiber is achieved. The plant dyeing process for the degradable modified terylene provided by the invention integrates degradable materials and terylene cation modification, changes the crystallinity and orientation degree of the terylene, increases the gaps among terylene molecules, reduces the strength of the terylene to a certain extent, realizes the dyeing of the terylene fiber by the plant dye through the key processes, can improve the degradation rate of the terylene, simultaneously ensures that the plant dye molecules are degradable biomass, can realize natural biodegradation after the dyed fiber is finally discarded, and realizes the green circulation of people and environment.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The invention provides a plant dyeing method of modified degradable terylene, which comprises the following steps:
s1, carrying out free radical graft polymerization reaction on an ethylene terephthalate oligomer and a cationic high molecular compound, and carrying out belt casting and grain cutting on an obtained reaction product to obtain a cationic modified polyester chip; the cationic polymer compound is a hydrophilic polymer;
s2, fusing biodegradable master batches into the cation modified polyester chips, and carrying out mixing melt spinning to obtain degradable cation modified polyester fibers;
s3, mixing and adsorbing the degradable cation modified polyester fiber and water-soluble inorganic salt, and then dyeing by adopting plant dye at the temperature lower than 100 ℃ to obtain the dyed fiber.
The dyeing method can use the vegetable dye to carry out conventional dyeing on the modified polyester fiber, and simultaneously, the polyester fiber can be degraded under natural conditions, thereby realizing the degradation of the fabric fiber and the vegetable dye, and being beneficial to environmental protection and application.
In the embodiment of the invention, firstly, the ethylene terephthalate oligomer is prepared; preferably, terephthalic acid (PTA) and bio-based Ethylene Glycol (EG) are used as raw monomers, and ethylene terephthalate is produced by esterification or transesterification, and polyethylene terephthalate (PET) is produced by polycondensation.
In some embodiments of the present invention, terephthalic acid and bio-based ethylene glycol are used as raw materials, and the esterification reaction is performed under nitrogen to obtain ethylene terephthalate. The bio-based ethylene glycol is mainly characterized in that the preparation raw materials belong to renewable raw materials, and the sources of the raw materials are as follows: carbohydrates in nature, whether starch-based polysaccharide crops, such as high-yield crops like corn, wheat, potato, sweet potato, beet, etc.; or monosaccharide or polysaccharide crops, such as sweet sorghum, jerusalem artichoke, cassava and the like, can be used as the bio-based ethylene glycol raw material. Specifically, the molar ratio of terephthalic acid to ethylene glycol is 1:1 to 1.5, the reaction temperature is 230 to 270 ℃, the pressure is normal temperature and normal pressure, and the distillation quantity of water reaches more than 90 percent of the theoretical value at the end point of the reaction.
According to the embodiment of the invention, the hydrophilic cationic polymer is introduced when the polyester chip is formed, and is a third monomer, so that the subsequent dyeing combination of the vegetable dye and the polyester fiber is facilitated; specifically, the third hydrophilic polymer monomer is introduced into the oligomer intermediate in the polyester reaction to perform free radical grafting polymerization.
In an embodiment of the invention, the polymerization reaction comprises a polycondensation low vacuum stage and a polycondensation high vacuum stage; in the low vacuum stage, preferably after adding a stabilizer and a catalyst, the intermediate of the esterification reaction starts polycondensation under the condition of negative pressure, the absolute pressure value in the stage is below 600Pa, the temperature is controlled between 240 ℃ and 270 ℃, and the reaction lasts for 50-70 min, so that the ethylene terephthalate oligomer is obtained. And introducing a third monomer hydrophilic cationic polymer after the reaction is finished, continuously vacuumizing, reducing the pressure to be less than 100Pa of an absolute value, controlling the temperature to be 270-310 ℃, and reacting for 80-120 min. And then, cooling, casting a belt, cooling and dicing the obtained reaction product to finally obtain the cation modified polyester chip.
Wherein, the stabilizer is preferably phosphite ester, and the dosage of the phosphite ester is 0.01 to 0.05 percent of the weight of the terephthalic acid. The preferred catalyst is stannous chloride, and the dosage is 0.01-0.05% of the weight of the terephthalic acid. Further, the third monomer is preferably used in an amount of 1 to 10% by weight based on the weight of terephthalic acid.
The third hydrophilic cationic polymer monomer introduced in the embodiment of the invention can be hydrophilic cationic polymer compounds such as amido-cationic polyacrylamide, hydroxyl-cationic starch, chitosan quaternary ammonium salt, polyepichlorohydrin amide and the like, and is copolymerized and grafted to form the cationic modified polyester. The fiber-forming polymer structure of the terylene has higher moisture absorption than that of the common terylene, the molecular weight, the crystallinity and the strength are reduced, and the reduction of the crystallinity can increase the combination capacity of the fiber and a plant dye group, thereby improving the condition that the plant dye can not dye the terylene fiber and increasing the dye-uptake.
The hydrophilic cationic polymer can be a commercial product, the solid content of the hydrophilic cationic polymer is 30-50%, and the PH value is 6-8; molecular weight: 8000-20000 parts. The molecular weight of the modified terylene after copolymerization and grafting can be 7000 to 15000, and the crystallinity is 35 to 50 percent.
In the obtained cation modified polyester chip, the biodegradable master batch is blended in the embodiment of the invention for mixing, melting and spinning to form the degradable cation modified polyester fiber.
The main component of the biodegradable master batch used in the embodiment of the invention is one or the combination of two polymers of aliphatic polylactic acid and polylactic acid-glycolic acid, and the biodegradable master batch and the modified polyester chip are combined together in a melt blending mode, so that the dye can be uniformly combined on the fiber when plant dyeing is carried out subsequently. The biodegradable master batch can be a commercially available degradable material and can also be prepared by self. In some embodiments, in the process of preparing the biodegradable masterbatch, preferably, 5 to 8 parts by mass of a compatibilizer, maleic anhydride, 5 to 10 parts by mass of water, and the balance of one or a combination of more of polylactic acids are added, the mixture is uniformly mixed in a high-speed dispersing device at a temperature of between 80 and 100 ℃, and the mixture is extruded by a double-screw extruder to obtain the biodegradable masterbatch, wherein the molecular weight of the biodegradable masterbatch is less than 60000, and the melt index of the biodegradable masterbatch is between 2 and 5g/min under standard conditions.
The proportion of the amount mixed for spinning is preferably as follows: 60 parts of cationic modified polyester chips and 40 parts of biodegradable master batches. The spinning process is a conventional pre-oriented yarn (POY) production process or a Fully Drawn Yarn (FDY) production process, and the POY production process flow generally comprises the following steps: melt conveying → metering and extruding filament bundle → side air blowing cooling → bundling and oiling → winding and forming → pre-inspection → classification → packaging → warehousing; the FDY production process flow comprises the following steps: melt conveying → spinning → side air blowing cooling → bundling oiling → stretching → network → winding forming → pre-inspecting → grading → packaging → warehousing. Illustratively, the POY spinning speed is 3250m/min; the melt temperature was 290 ℃; wind speed: 0.8m/s; the cross-air humidity is stabilized at about 75%.
After the degradable modified polyester fiber is prepared, the crystallinity of the polyester fiber is reduced, the hygroscopicity is improved, the hand feeling is soft, the bulkiness is high, and the dyeing is easy. The obtained degradable cation modified polyester fiber has the following index requirements:
linear density deviation ratio dpf:2.0% < dpf <3.5%;
coefficient of variation of linear density CV:1.0% < CV <1.7%;
breaking strength: 1.9< -cN/dtex <2.3;
coefficient of variation in breaking strength: 4.5-woven CV-woven fabrics 8;
evenness unevenness: 1.4-woven CV-woven fabrics (2.2);
oil content: <0.4%;
degree of crystallinity: <5%.
After the degradable cation modified polyester fiber is obtained, the embodiment of the invention carries out cation grafting before plant dyeing on the degradable cation modified polyester fiber, and provides dyeing seats for plant dye molecules; the prepared degradable cation modified fiber can also be spun into yarn and fabric products, and then cation grafting is carried out. The specific operation comprises the following steps: the degradable cation modified polyester fiber and the water-soluble inorganic salt are mixed and adsorbed in water, and the temperature can be raised at normal temperature and kept for a certain time to finish the modification of the dyeing pretreatment.
The polyester fiber degraded by cation has certain hydrophilicity, and before dyeing, the embodiment of the invention forms a dyeing seat of the plant dye by grafting the water-soluble inorganic salt and the modified polyester fiber with metal cation. Preferably, the metal cation in the water-soluble inorganic salt is one or more of calcium (Ca), potassium (K), iron (Fe) and aluminum (Al), which may be carbonate, chloride, such as CaCl 2 、K 2 CO 3 、FeCl 3 And the like. The auxiliary agents or the modifying agents can be effectively adsorbed on fiber molecules to form corresponding ion coordination bonds, so that the subsequent combination of the ion bonds or covalent bonds between the plant dye molecules and the fibers is facilitated, the plant dye is fixed on the fibers, and the aim of finally dyeing the polyester fibers is fulfilled.
In the specific embodiment of the invention, the amount of the water-soluble inorganic salt is within 6% of the weight of the degradable cation modified polyester fiber, and preferably, the amount of the modifier is 1-5% of the weight of the fiber. The temperature of the mixed adsorption is preferably 50-90 ℃, the total time of heat preservation is at least 60min, and the mixture is cleaned after the grafting modification treatment is finished and is ready for dyeing.
According to the embodiment of the invention, the plant dye is adopted to carry out conventional dyeing on the polyester degraded fiber after ion grafting, and the dyeing temperature is lower than 100 ℃, so that the dyed fiber is obtained.
In the examples of the present invention, the plant dyes are classified into polyphenols, porphyrins, anthraquinones, carotenoids, etc., and the dye raw materials are typically pomegranate, chlorophyll, madder, gardenia, etc., and commercially available plant dye products can be used. The plant dye molecules with the structures and the modified polyester fiber form ionic bonds or covalent bonds through the dyeing seats and are combined on the fiber, so that the plant dye dyeing of the modified polyester fiber is completed. The plant dye molecules are degradable biomass, and natural biodegradation can be realized after the dyed fiber is finally discarded.
The specific plant dyeing implementation process of the embodiment of the invention comprises the following steps: under the conventional conditions, the temperature is raised at normal temperature, the heating rate is 1-2 ℃/min, the temperature is preferably raised to 70-90 ℃, the overall heat preservation time can be 40-50 min, and the integral dyeing is finished. In the dip dyeing, the bath ratio can be 1.
Through the key processes, the embodiment of the invention realizes that the plant dye dyes the polyester fiber under the conventional conditions, and has more obvious advantages in the aspects of level-dyeing property, fastness index and dyeing depth. And the prepared dyed polyester fiber can realize natural biodegradation after being finally discarded, so that the cyclic utilization of environmental resources is completed, and the polyester fiber is more environment-friendly.
For better understanding of the technical contents of the present invention, the following is mentionedThe present invention will be further described with reference to specific examples. The bio-based ethylene glycol raw material source related to the embodiment of the invention is corn, and the specific parameters are as follows: relative molecular weight: 62.069; melting point: -11.5 ℃; boiling point: 198.0 ℃ and density of 1.1128g/cm 3 (ii) a The chroma (platinum-cobalt) is less than or equal to 10 60; the third monomer of the hydrophilic cationic polymer is amido-cationic polyacrylamide.
The preparation process of the biodegradable master batch comprises the following steps: adding 5 parts of compatilizer maleic anhydride, adding 5 parts of water and the balance of aliphatic polymer, uniformly mixing in high-speed dispersion equipment at the temperature of 80-100 ℃, and extruding the degradable master batch by a double-screw extruder.
The first embodiment is as follows:
terephthalic acid and bio-based ethylene glycol are used as raw materials, and the ethylene terephthalate is prepared by esterification reaction under the condition of nitrogen. The molar ratio of terephthalic acid to ethylene glycol is 1: 1-1.5, the reaction temperature is 230-270 ℃, the pressure is normal temperature and normal pressure, and the distillation amount of water reaches more than 90 percent of the theoretical value at the end point of the reaction.
The stabilizer is: phosphite ester, the dosage is 0.01% -0.05% of the weight of terephthalic acid. The catalyst is as follows: the dosage of the stannous chloride is 0.01 to 0.05 percent of the weight of the terephthalic acid. After phosphite ester and stannous chloride are added, the intermediate of the esterification reaction starts low vacuum polycondensation reaction under the condition of negative pressure, the absolute pressure value of the stage is below 600Pa, the temperature is controlled at 250 ℃, and the reaction is carried out for 70min. After the reaction is finished, introducing a hydrophilic cationic polymer of a third monomer, wherein the dosage of the third monomer is 10 percent of the weight of the terephthalic acid. Continuously vacuumizing, reducing the pressure to be below 100Pa in absolute value, controlling the temperature at 280 ℃ and reacting for 120min. And cooling, casting a belt, cooling and granulating to obtain the cation modified polyester chip.
Slicing basic parameters: viscosity: 0.64 to 0.66; DEG content: <0.13%; water content: <0.4%; melting point: 253 to 256 ℃; b value: <1.0.
According to the proportion of 60 parts of the dosage of the cation modified polyester chip and 40 parts of the dosage of the biodegradable master batch, the biodegradable master batch is blended into the cation modified polyester chip for mixed melt spinning, the spinning process is a conventional POY process, and the spinning speed is 3250m/min; the melt temperature was 290 ℃; wind speed: 0.8m/s; the cross-air humidity is stabilized at about 75 percent, and the degradable cation modified polyester fiber is prepared.
The indexes of the method are as follows: linear density deviation ratio: 2.0% < dpf <3.5%; coefficient of linear density variation: 1.0% < CV <1.7%; breaking strength: 1.9 sNn/dtex <2.3; coefficient of variation in breaking strength: 4.5-woven CV-woven fabrics 8; evenness unevenness: 1.4 Once CV (N) -2.2; oil content: <0.4%; degree of crystallinity: <5%.
The degradable cation modified polyester fiber and water-soluble inorganic salt are mixed and adsorbed in water, and the specific process conditions comprise: the inorganic salt CaCl used 2 The bath ratio is 1:10, the inorganic salt accounts for 5 percent of the weight of the fiber, the temperature is raised at normal temperature, the temperature raising rate is 2 ℃/min, the temperature is raised to 90 ℃, and the total heat preservation time is 60min; and cleaning after finishing.
Plant dyeing is carried out on the pretreated fiber; the adopted vegetable dye is polyphenol dye pomegranate, and the bath ratio is 1:10, the dye is 5 percent of the weight of the fiber, the assistant adopts acetic acid with the dosage of 0.5ml/l, the temperature is raised at normal temperature, the temperature raising rate is 2 ℃/min, the temperature is raised to 70 ℃, the heat preservation time is 40min, and the whole dyeing is finished.
In addition, other vegetable dyes were replaced for dyeing. The following indices are exemplified by passing through CaCl 2 And (5) carrying out ion grafting and then dyeing by using four plant dyes to obtain a test result.
Table 1 dyeing results of example one
Example two:
the preparation was carried out according to the procedure of example one, with the following differences:
the auxiliary agent K adopted 2 CO 3 The bath ratio is 1:10, the dosage of the auxiliary agent is 3 percent of the weight of the fiber, the temperature is raised at normal temperature, the temperature raising rate is 2 ℃/min and is raised to 80 ℃, the overall time of heat preservation is 60min, and the fiber is cleaned after the temperature is raised.
Porphyrin dye chlorophyll, bath ratio 1:10, the dye is 1 percent of the weight of the fiber, the auxiliary agent adopts soda ash with the dosage of 1g/l, the temperature is raised at normal temperature, the temperature rise rate is 1 ℃/min, the temperature is raised to 80 ℃, the heat preservation time is 50min, and the whole dyeing is finished.
The following is an example two 2 CO 3 Dyeing result of four plant dyes by ion grafting
TABLE 2 dyeing results of example two
Example three:
the preparation was carried out according to the procedure of example one, with the following differences:
the adopted auxiliary agent FeCl 3 The bath ratio is 1:10, the dosage of the auxiliary agent is 1 percent of the weight of the fiber, the temperature is raised at normal temperature, the temperature raising rate is 1 ℃/min, the temperature is raised to 50 ℃, the overall time is kept for 60min, and the fiber is cleaned after the temperature is kept.
Anthraquinone dye madder: bath ratio of 1:10, the dye is 3 percent of the weight of the fiber, the auxiliary agent is soda ash with the dosage of 1g/l, the temperature is raised at normal temperature, the temperature is raised to 80 ℃ at the rate of 1 ℃/min, the heat preservation time is 30min, and the whole dyeing is finished.
The following is an example of three-way additive FeCl 3 Dyeing result of four plant dyes by ion grafting
TABLE 3 dyeing results of example III
Example four:
the preparation was carried out according to the procedure of example one, with the following differences:
the adopted auxiliary agent AlCl 3 The bath ratio is1:10, the using amount of the auxiliary agent is 5 percent of the weight of the fiber, the temperature is raised at normal temperature, the temperature raising rate is 2 ℃/min and is raised to 80 ℃, the overall time of heat preservation is 60min, and the fiber is cleaned and dyed after the temperature is up.
A carotenoid dye gardenia, wherein the bath ratio is 1:10, the dye amount is 2 percent of the weight of the fiber, the temperature is raised at normal temperature, the temperature raising rate is 2 ℃/min, the temperature is raised to 90 ℃, the heat preservation time is 30min, and the whole dyeing is finished.
The following are examples of the four-way crossing assistant AlCl 3 Dyeing result of four plant dyes by ion grafting
Table 4 dyeing results of example four
According to the embodiment, the degradable material and the polyester cation modification are integrated, the crystallinity and the orientation degree of the polyester are changed, the gaps among polyester molecules are increased, the strength of the polyester is reduced to a certain degree, the plant dye dyeing of the polyester fiber becomes a reality through the key processes, the degradation rate of the polyester can be improved, meanwhile, the plant dye molecules are degradable biomass, and the natural biodegradation can be realized after the dyed fiber is finally abandoned, so that the green cycle between people and the environment is realized.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A plant dyeing method of modified degradable terylene is characterized by comprising the following steps:
s1, carrying out free radical graft polymerization reaction on an ethylene terephthalate oligomer and a cationic high molecular compound, and carrying out belt casting and grain cutting on an obtained reaction product to obtain a cationic modified polyester chip; the cationic polymer compound is a hydrophilic polymer;
s2, blending biodegradable master batches into the cation modified polyester chips, and carrying out mixed melt spinning to obtain degradable cation modified polyester fibers;
and S3, mixing and adsorbing the degradable cation modified polyester fiber and water-soluble inorganic salt, and then dyeing by adopting plant dye at the temperature lower than 100 ℃ to obtain the dyed fiber.
2. The plant dyeing method for modified degradable terylene according to claim 1, wherein in step S1, the ethylene terephthalate oligomer is prepared by reacting terephthalic acid with bio-based ethanol to generate ethylene terephthalate, and then carrying out low vacuum polycondensation.
3. The plant dyeing method of modified degradable terylene according to claim 2, wherein in step S1, a stabilizer and/or a catalyst is added in the low vacuum polycondensation stage of preparing the ethylene terephthalate oligomer, the absolute pressure value of the polycondensation is below 600Pa, the temperature is controlled at 240-270 ℃, and the reaction is carried out for 50-70 min.
4. The method for vegetable dyeing of modified degradable terylene according to any one of claims 1 to 3, wherein in step S1, the cationic polymer compound is selected from one or more of amido-cationic polyacrylamide, hydroxyl-cationic starch, chitosan quaternary ammonium salt and polyepichlorohydrin amide.
5. The method for plant dyeing of modified degradable terylene according to claim 4, wherein in step S1, the pressure absolute value of the free radical grafting polymerization reaction is below 100Pa, the temperature is controlled between 270 ℃ and 310 ℃, and the reaction time is 80-120 min.
6. The method for dyeing modified degradable polyester fiber with plants as claimed in claim 1, wherein in step S2, the main ingredient of the biodegradable masterbatch is one or two of aliphatic polylactic acid and polylactic-co-glycolic acid; the mass ratio of the cation modified polyester chip to the biodegradable master batch is 55-70: 30 to 45 percent.
7. The plant dyeing method of modified degradable terylene according to claim 6, wherein in step S2, POY process or FDY process is adopted for the mixed melt spinning.
8. The method for plant dyeing of modified degradable terylene according to claim 1, wherein in step S3, the metal cation in the water-soluble inorganic salt is one or more of calcium, potassium, iron and aluminum; the vegetable dye is selected from one or more of polyphenols, porphyrins, anthraquinones and carotenoids.
9. The method for plant dyeing of modified degradable polyester fiber according to claim 8, wherein in step S3, the degradable cation modified polyester fiber is mixed and adsorbed with water-soluble inorganic salt in water, the amount of the water-soluble inorganic salt is within 6% of the weight of the degradable cation modified polyester fiber, and the temperature of the mixed adsorption is 50-90 ℃.
10. The plant dyeing method of the modified degradable terylene according to claim 9, wherein in the step S3, the dyeing temperature of the plant dye is 70-90 ℃, and the total heat preservation time is 30-60 min.
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