CN115874311A - Fragrant polybutylene succinate blending fiber and preparation method thereof - Google Patents
Fragrant polybutylene succinate blending fiber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fragrant poly (butylene succinate) blend fiber and a preparation method thereof, wherein the fragrant poly (butylene succinate) blend fiber consists of poly (butylene succinate) (PBS), copolymerization modified poly (butylene succinate) (co-PBS), an essence/beta-cyclodextrin inclusion compound and a coupling agent; the essence/beta-cyclodextrin inclusion compound is dispersed in the interior and on the surface of the fragrant polybutylene succinate blending fiber, and the coupling agent exists between the essence/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the essence/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate; the preparation method comprises the following steps: (1) preparing copolymerization modified poly (butylene succinate); (2) preparing a fragrance master batch; (3) preparing PBS/flavor master batch; (4) And preparing the dried PBS/flavor master batch into flavor polybutylene succinate blending fiber. The fragrant polybutylene succinate blend fiber prepared by the invention has excellent mechanical property and lasting fragrance release.
Description
Technical Field
The invention belongs to the technical field of functional degradable synthetic polymer fibers, and relates to a fragrant polybutylene succinate blending fiber and a preparation method thereof.
Background
Polybutylene succinate (PBS) is a biodegradable synthetic polymer and has good processability and application performance. The softening point of PBS is 101 ℃, and the higher softening point ensures that PBS meets the heat-resistant requirements of common living products such as tableware, clothes and the like. The melting point of the PBS is 114 ℃, the processing temperature is 140-260 ℃, and the PBS fiber can be prepared by a melt spinning method. The PBS fiber produced by Shaoxing Jiuzhou company has the breaking strength of 2.69cN/dtex and the elongation at break of 29.73 percent, and can be made into disposable products such as disposable dry wet tissues and the like (the structure and the mechanical property of the bio-based PBS fiber [ J ] basic science and bulletin of textile colleges, 2019,32 (1): 6.). With the continuous deepening of the knowledge of the PBS fiber at the production end and the application end, the production and the application of the PBS fiber are continuously expanded.
The fragrant fiber can release fragrance, and has effects of delighting mood, refreshing brain, etc. The preparation method of the fragrant fiber comprises a post finishing and spinning addition method. The subsequent finishing process is simple, is suitable for various fibers such as cotton, wool, chemical fiber and the like, and has the problems of poor washing resistance and influence on hand feeling. The spinning addition is to add the fragrant substance into the fiber in the spinning process, and has the advantages of high content of the fragrant substance and long release time. The fragrant fiber is prepared by a spinning addition method generally by a melt spinning method and a wet spinning method. Aromatic substances are poor in heat resistance and volatile, and a polymer with a low melting point is required to be used as a matrix for preparing aromatic fibers through melt spinning. The lower melting point and processing temperature of PBS are beneficial to blending PBS and low boiling point substances such as essential oil and the like. Patent CN202111520805.5 adopts a bicomponent spinning method, and discloses a preparation method of PBS/plant essential oil fiber with a skin-core structure. Patent CN202110908241.6 also adopts a bicomponent spinning method, and discloses a preparation method of PBS/plant essential oil fiber with a skin-core structure or a sea-island structure. The aromatic fiber with high essential oil content and slow release can be prepared by adopting a bi-component spinning method, but a special bi-component spinning component is required in the bi-component spinning process, and the production process is complex.
Therefore, the production of the fragrant PBS blended fiber with excellent performance by the conventional monofilament spinning equipment is a technical problem waiting for breakthrough.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a fragrant polybutylene succinate (PBS) blend fiber and a preparation method thereof, in particular to a fragrant polybutylene succinate blend fiber which is uniformly dispersed with fragrant substances and is formed by extrusion through conventional monofilament spinning equipment, and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
a fragrant polybutylene succinate blending fiber comprises polybutylene succinate (PBS), copolymerization modified polybutylene succinate (co-PBS), an essence/beta-cyclodextrin inclusion compound and a coupling agent;
the grain size of the essence/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blend fiber is 0.5-2 mu m;
the essence/beta-cyclodextrin inclusion compound is dispersed in the interior and on the surface of the fragrant polybutylene succinate blending fiber, and the coupling agent exists between the essence/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the essence/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the mass ratio of the poly (butylene succinate) to the copolymerization modified poly (butylene succinate) in the fragrant poly (butylene succinate) blend fiber is 80-100; if the dosage of the copolymerized and modified polybutylene succinate is lower than the proportion, the compatibility of the copolymerized and modified polybutylene succinate and the essence/cyclodextrin inclusion compound is not obviously improved, so that the particle size of the essence/cyclodextrin inclusion compound is thicker; if the amount of the copolymerized and modified polybutylene succinate is higher than this ratio, the crystallinity of the fiber is low, resulting in poor mechanical properties.
The specific brand of the poly (butylene succinate) is 1003MD of SHOWA DENTAL ENGINEERING CORPORATION, 1903MD of SHOWA DENTAL ENGINEERING CORPORATION, bioBPS of PTT MCC Corp TM FZ91, PTT MCC BioBPS TM FD92, 803S, a product of blue mountain tun river;
the copolymerization modified polybutylene succinate is a polybutylene succinate copolymer containing six-membered ring structural units.
As a preferable technical scheme:
according to the fragrant polybutylene succinate blending fiber, the contents of all components in the fragrant polybutylene succinate blending fiber are as follows in parts by weight:
80-100 parts of polybutylene succinate;
10-20 parts of copolymerization modified polybutylene succinate;
1-6 parts of an essence/cyclodextrin inclusion compound;
1-5 parts of a coupling agent.
According to the fragrant poly (butylene succinate) blend fiber, the essence/beta-cyclodextrin inclusion compound is a lavender essential oil/beta-cyclodextrin inclusion compound, a lemon essential oil/beta-cyclodextrin inclusion compound, a cinnamon essential oil/beta-cyclodextrin inclusion compound or a grapefruit seed oil/beta-cyclodextrin inclusion compound.
The fragrant polybutylene succinate blend fiber is characterized in that the coupling agent is a silane coupling agent KH550, a silane coupling agent KH560 or a silane coupling agent KH570.
The fragrant polybutylene succinate blend fiber is a monofilament, has the diameter of 0.08-1.06 mm, the breaking strength of 1.5-2.2 cN/dtex, the elongation at break of 35-46% and the initial modulus of 11.1-15.4 cN/dtex.
After the fragrant polybutylene succinate blending fiber is placed at room temperature for 2 weeks, the mass retention rate of essence in the fragrant polybutylene succinate blending fiber is 70-83%;
washing the fragrant polybutylene succinate blend fiber with water according to GB/T8629-2017 standard, wherein the elution rate of the essence after 10 times of washing is 13-28%, and the elution rate of the essence after 30 times of washing is 32-41%.
The invention also provides a preparation method of the fragrant polybutylene succinate blend fiber, which comprises the following steps:
(1) By Ti (OBu) 4 As a catalyst, butanediol, dimethyl succinate and dimer acid (with a trade mark of pripol 1006 or pripol 1009) containing a six-membered ring structural unit are polymerized to prepare copolymerization modified polybutylene succinate;
(2) Uniformly stirring and mixing polybutylene succinate, copolymerization modified polybutylene succinate, an essence/beta-cyclodextrin inclusion compound and a coupling agent, and performing melt extrusion and granulation on the mixture through a double-screw extruder to obtain fragrant master batches;
(3) Mixing polybutylene succinate (PBS) and the flavor master batch by a stirrer to obtain PBS/flavor master batch, and drying the PBS/flavor master batch for 5 hours at the temperature of 80 ℃ by adopting drying equipment;
(4) And (3) preparing the dried PBS/flavor master batch into the flavor polybutylene succinate blended fiber through a melt spinning machine according to the process route of metering → extruding → air blowing cooling → stretching for one time → stretching for two times.
The dimer acid containing a six-membered ester ring structure has a molecular structure as follows:
as a preferred technical scheme:
the preparation method of the fragrant polybutylene succinate blend fiber comprises the following steps of (1): under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid and Ti (OBu) 4 The catalyst is stirred and reacts under the normal pressure condition that the temperature is 180 to 190 ℃ until 90 percent of A is obtainedStopping distilling the alcohol for 80-120 min; the temperature was then increased to 230 ℃ and the pressure was reduced to 0.1mbar, the reaction was ended at constant stirrer torque, the reaction time was 100-120 minutes.
In the method for preparing the fragrant polybutylene succinate blend fiber, the molar ratio of the butanediol, the dimethyl succinate and the dimer acid is 100-140, 5-25, preferably 120 4 The amount of (B) is 150 to 250ppm, preferably 200ppm.
The preparation method of the fragrant polybutylene succinate blend fiber comprises the following process parameters in the step (4): the extrusion temperature is 150-200 ℃, the blowing temperature is 25 ℃, the primary stretching draft ratio is 2-3 times, the secondary stretching ratio is 3-4 times, and the secondary stretching temperature is 60-80 ℃.
The mechanism of the invention is as follows:
beta-cyclodextrin is prepared from starch by the action of microbial enzyme, and is a cyclic compound formed by combining 7 glucose residues with beta-1, 4-glycosidic bonds. The beta-cyclodextrin is a hollow cylinder three-dimensional annular structure, the external hydroxyl has a hydrophilic effect, and the interior of the beta-cyclodextrin is shielded by a C-H bond and has a hydrophobic effect. Beta-cyclodextrin is commonly used as an inclusion compound for flavors and fragrances. Compared with the essence in an uncoated state, the essence/beta-cyclodextrin inclusion compound has good stability and lasting fragrance release.
Applicants blended PBS with the flavor/β -cyclodextrin inclusion compound and prepared a flavored PBS fiber. Experiments show that obvious gaps appear on the cross section of the fiber, and the grain size of the essence/beta-cyclodextrin inclusion compound is 1-4 mu m. The thicker particle size of the inclusion compound indicates that the compatibility of the essence/beta-cyclodextrin inclusion compound and PBS is poor, the inclusion compound is difficult to disperse in PBS fibers, and obvious agglomeration occurs. As a result, the fiber unevenness is high and the mechanical properties are low. To improve the compatibility of the perfume/beta-cyclodextrin inclusion complex with PBS, applicants prepared co-modified PBS (co-PBS). Part of the succinic acid building blocks of co-PBS was replaced by dimer acid. The aliphatic six-membered ring of dimer acid has longer side chains and is also linked to the-COOR group by a polyethylene-like segment. Theoretically, the aliphatic ring structure in co-PBS is similar to the molecular structure of glucose residue in beta-cyclodextrin, which is beneficial to improving the compatibility of the two. Experiments show that the particle size of the internal essence/beta-cyclodextrin inclusion compound of the blended fiber containing copolymerization modified PBS is 0.5-2 mu m, and the cross-sectional structure of the fiber is compact. The reduction in the particle size of the flavor/beta-cyclodextrin inclusion complex indicates an improved uniformity of dispersion of the flavor/beta-cyclodextrin inclusion complex in co-PBS. Compared with PBS, the copolymerization modified PBS has better compatibility with beta-cyclodextrin. The good compatibility of the copolymerization modified PBS and the beta-cyclodextrin is beneficial to the improvement of the performance of the blend fiber, and compared with the blend fiber without the copolymerization modified PBS, the blend fiber containing the copolymerization modified PBS has better mechanical property and fragrance release persistence. In addition, a silane coupling agent is added in the preparation process of the flavor master batch. The silane coupling agent reacts with hydroxyl of the beta-cyclodextrin, so that polar groups on the surface of the essence/beta-cyclodextrin inclusion compound are reduced, and the compatibility of the essence/beta-cyclodextrin inclusion compound with PBS and co-PBS is further improved.
Advantageous effects
(1) According to the fragrant poly (butylene succinate) blend fiber prepared by the invention, PBS and essence are uniformly dispersed, the mechanical property is excellent, and the fragrance is released for a long time;
(2) The components of the fragrant poly (butylene succinate) blend fiber prepared by the invention are degradable synthetic polymers or natural polymers, and the fragrant poly (butylene succinate) blend fiber belongs to environment-friendly materials, and is applied to the fields of mattresses, mosquito-proof and insect-repellent nets and the like which have requirements on essence;
(3) The preparation method prepares the fragrant polybutylene succinate blend fiber by using conventional monofilament spinning equipment, and has the advantages of low requirements on production equipment and simple production process.
Detailed Description
The present invention will be further described with reference to the following 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.
The material information used in the embodiment of the present invention is specifically as follows:
(1) Dimer acid containing six-membered ring structural units: the trade mark is Pripol1009;
(2) Polybutylene succinate: from Showa Denko K.K., under the trade designation 1903MD;
(3) Lavender essential oil/beta-cyclodextrin inclusion compound: preparing a lavender essential oil/beta-cyclodextrin inclusion compound according to literature (study of processes of including lavender essential oil by beta-cyclodextrin [ J ] food science, 2009 (4): 4.) with a wall-to-core ratio of 8;
(4) Lemon essential oil/beta-cyclodextrin inclusion compound: preparing the lemon essential oil/beta-cyclodextrin inclusion compound according to a document (optimization of a lemon essential oil beta-cyclodextrin microcapsule preparation process [ J ]. Proceedings of Weinan college, 2018,33 (4): 6.) and a wall-core ratio of 10;
(5) Cinnamon essential oil/beta-cyclodextrin inclusion compound: cinnamon essential oil/beta-cyclodextrin inclusion compounds are prepared according to literature (cinnamon leaf essential oil/beta-cyclodextrin microcapsule preparation and sustained release characteristics [ J ]. Forest chemical and industry, 2021.) with a wall-core ratio of 4;
(6) Grapefruit seed oil/beta-cyclodextrin inclusion compound: preparing the grapefruit seed oil/beta-cyclodextrin inclusion compound according to the literature (optimization of the grapefruit seed oil-beta-cyclodextrin microcapsule preparation process [ J ]. Chinese oil, 2013,38 (10): 3.) and the wall oil ratio is 4.5.
The test method adopted in the embodiment of the invention is as follows:
(1) Fiber diameter: measuring the fiber diameter by a micrometer, wherein the diameter of the fragrant polybutylene succinate blending fiber is 0.08-1.06 mm;
(2) Breaking strength: testing the breaking strength of the fragrant polybutylene succinate blend fiber by GB/T14344;
(3) Elongation at break: testing the elongation at break of the fragrant polybutylene succinate blend fiber by GB/T14344;
(4) Initial modulus: testing the initial modulus of the fragrant polybutylene succinate blend fiber by GB/T14344;
(5) Quality retention rate of the essence: taking 10g of fragrant poly (butylene succinate) blend fiber, eluting essence in the fiber by adopting an essence solvent, and determining the mass of the essence in the solvent as W1; and taking 10g of fragrant polybutylene succinate blending fiber, placing the fiber for 2 weeks at room temperature, eluting the essence in the fiber placed for 2 weeks by adopting an essence solvent, and determining the mass of the essence in the solvent to be W2. After being placed at room temperature for 2 weeks, the mass retention rate of the essence in the poly (butylene succinate) blend fiber is calculated according to W2/W1 multiplied by 100 percent;
(6) Elution rate of the essence: taking 10g of fragrant poly (butylene succinate) blend fiber, eluting essence in the fiber by adopting an essence solvent, and determining the mass of the essence in the solvent to be M1; taking another 10g of fragrant polybutylene succinate blending fiber, washing the fiber for 10 times, then eluting the essence in the fiber for 10 times by adopting an essence solvent, and determining the mass of the essence in the solvent to be M2; then 10g of fragrant polybutylene succinate blending fiber is taken and washed for 30 times, essence in the fiber is eluted and washed for 30 times by adopting an essence solvent, and the mass of the essence in the solvent is measured to be M3. The elution rate of the essence after washing for 10 times is calculated according to (1-M2/M1) multiplied by 100%, and the elution rate of the essence after washing for 30 times is calculated according to (1-M3/M1) multiplied by 100%.
Example 1
A preparation method of a fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid containing six-membered ring structural units and Ti (OBu) 4 Stirring and reacting for 100 minutes under the normal pressure condition that the temperature is 185 ℃, then increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 110 minutes to prepare copolymerization modified poly (butylene succinate);
wherein the molar ratio of the butanediol, the dimethyl succinate and the dimer acid containing the six-membered ring structural unit is 120 4 The dosage of (A) is 200ppm;
(2) According to the weight parts, uniformly stirring and mixing 90 parts of polybutylene succinate, 15 parts of copolymerization modified polybutylene succinate obtained in the step (1), 3 parts of lavender essential oil/beta-cyclodextrin inclusion compound and 3 parts of silane coupling agent KH550, and melting, extruding and granulating the mixture to obtain fragrant master batch;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (Poly Butylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (4) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of metering → extrusion (the temperature of a spinning nozzle is 175 ℃) → air blowing cooling (the air blowing temperature is 25 ℃) → one-step stretching (the stretching ratio is 2 times, the temperature is 25 ℃) → two-step stretching (the stretching ratio is 4 times, and the temperature is 70 ℃).
The prepared fragrant polybutylene succinate blending fiber consists of polybutylene succinate, copolymerization modified polybutylene succinate, a lavender essential oil/beta-cyclodextrin inclusion compound and a silane coupling agent KH 550; the grain size of the lavender essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blended fiber is 0.7-1.5 mu m; the cross section structure of the fiber is compact and has no holes; the lavender essential oil/beta-cyclodextrin inclusion compound is dispersed in and on the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH550 exists between the lavender essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the lavender essential oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blended fiber is 0.5mm, the breaking strength is 2.0cN/dtex, the elongation at break is 38%, and the initial modulus is 12.4cN/dtex; after being placed at room temperature for 2 weeks, the quality retention rate of the essence in the fragrant polybutylene succinate blend fiber is 83%; and (3) washing the fragrant polybutylene succinate blend fiber according to the GB/T8629-2017 standard, wherein the elution rate of the essence is 13% after washing for 10 times, and the elution rate of the essence is 32% after washing for 30 times.
Comparative example 1
A preparation method of a fragrant polybutylene succinate blended fiber is basically the same as that in example 1, and is different in that step (1) is omitted, and no copolymerization modified polybutylene succinate is added in step (2);
the prepared fragrant poly butylene succinate blending fiber consists of poly butylene succinate and lavender essential oil/beta-cyclodextrin inclusion compound; the grain size of the lavender essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blended fiber is 1-4 mu m; the cross section of the fiber is provided with a large number of holes, and the particle size of the holes is 0.05-0.28 mu m; the lavender essential oil/beta-cyclodextrin inclusion compound is dispersed in and on the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH550 is present between the lavender essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 0.5mm, the breaking strength is 1.3cN/dtex, the elongation at break is 31%, and the initial modulus is 9.8cN/dtex; after being placed at room temperature for 2 weeks, the mass retention rate of the essence in the fragrant polybutylene succinate blend fiber is 65%; washing the fragrant polybutylene succinate blend fiber according to GB/T8629-2017 standard, wherein the elution rate of the essence after 10 times of washing is 37%, and the elution rate of the essence after 30 times of washing is 43%.
Comparing comparative example 1 with example 1, it can be seen that the breaking strength, elongation at break and initial modulus of comparative example 1 are all lower than those of example 1, the mass retention rate of the essence in comparative example 1 is lower than that of example 1, and the elution rate of the essence in comparative example 1 is higher than that of example 1, because no copolymerization modified polybutylene succinate exists in the fiber in comparative example 1, so the particle size of the essence/cyclodextrin inclusion compound in comparative example 1 reaches 1-4 μm, which indicates that the compatibility of PBS and the essence/cyclodextrin inclusion compound is poor, the essence/cyclodextrin inclusion compound is not a structural component for bearing tension of the fiber, and the larger particle size of the essence/cyclodextrin inclusion compound causes a large number of weak points of the structure in the fiber in comparative example 1, resulting in lower mechanical properties of the fiber; in addition, the fiber section of the comparative example 1 has a plurality of holes and a loose fiber structure, and the release of the essence is accelerated, so that the essence in the fiber of the comparative example 1 is released quickly and is easy to elute.
Example 2
A preparation method of a fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, adding butanedioic acidAlcohol, dimethyl succinate, dimer acid containing six-membered ring structural unit and Ti (OBu) 4 Stirring and reacting for 80 minutes under the normal pressure condition that the temperature is 190 ℃, then increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 100 minutes to prepare copolymerization modified poly (butylene succinate);
wherein the molar ratio of the butanediol, the dimethyl succinate and the dimer acid containing the six-membered ring structural unit is 100 4 In an amount of 150ppm;
(2) According to the weight parts, uniformly stirring and mixing 80 parts of polybutylene succinate, 20 parts of copolymerized modified polybutylene succinate obtained in the step (1), 1 part of lemon essential oil/beta-cyclodextrin inclusion compound and 1 part of silane coupling agent KH560, and melting, extruding and granulating the mixture to obtain fragrant master batches;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (polybutylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (3) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of metering → extrusion (spinning nozzle temperature is 150 ℃) → air-blowing cooling (air-blowing temperature is 25 ℃) → one-step stretching (stretching multiple is 2 times, temperature is 25 ℃) → two-step stretching (stretching multiple is 3.5 times, temperature is 80 ℃).
The prepared fragrant poly (butylene succinate) blend fiber consists of poly (butylene succinate), copolymerization modified poly (butylene succinate), lemon essential oil/beta-cyclodextrin inclusion compound and silane coupling agent KH 560; the grain size of the lemon essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blend fiber is 0.5-0.9 mu m; the cross section structure of the fiber is compact and has no holes; the lemon essential oil/beta-cyclodextrin inclusion compound is dispersed in and on the surface of the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH560 is present between the lemon essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the lemon essential oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 0.08mm, the breaking strength is 1.9cN/dtex, the elongation at break is 35%, and the initial modulus is 15.4cN/dtex; after being placed at room temperature for 2 weeks, the quality retention rate of the essence in the fragrant polybutylene succinate blend fiber is 71%; washing the fragrant polybutylene succinate blend fiber according to GB/T8629-2017 standard, wherein the elution rate of the essence after 10 times of washing is 28%, and the elution rate of the essence after 30 times of washing is 41%.
Example 3
A preparation method of fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid containing six-membered ring structural units and Ti (OBu) 4 Stirring and reacting for 120 minutes under the normal pressure condition that the temperature is 185 ℃, then increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 120 minutes to prepare copolymerization modified poly (butylene succinate);
wherein, the molar ratio of butanediol, dimethyl succinate and dimer acid containing six-membered ring structural units is 140 4 In an amount of 250ppm;
(2) According to the weight parts, stirring and uniformly mixing 85 parts of polybutylene succinate, 13 parts of copolymerization modified polybutylene succinate obtained in the step (1), 2 parts of cinnamon essential oil/beta-cyclodextrin inclusion compound and 2 parts of silane coupling agent KH570, and melting, extruding and granulating the mixture to obtain fragrant master batch;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (Poly Butylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (4) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of metering → extrusion (the temperature of a spinning nozzle is 160 ℃) → air blowing cooling (the air blowing temperature is 25 ℃) → one-step stretching (the stretching ratio is 2.5 times, the temperature is 25 ℃) → two-step stretching (the stretching ratio is 3 times, and the temperature is 60 ℃).
The prepared fragrant polybutylene succinate blending fiber consists of polybutylene succinate, copolymerization modified polybutylene succinate, cinnamon essential oil/beta-cyclodextrin inclusion compound and silane coupling agent KH 570; the grain size of the cinnamon essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blending fiber is 0.6-1.2 mu m; the cross section structure of the fiber is compact and has no holes; the cinnamon essential oil/beta-cyclodextrin inclusion compound is dispersed in the interior and on the surface of the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH570 exists between the cinnamon essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the cinnamon essential oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 0.55mm, the breaking strength is 2.2cN/dtex, the elongation at break is 39%, and the initial modulus is 11.1cN/dtex; after being placed at room temperature for 2 weeks, the mass retention rate of the essence in the fragrant polybutylene succinate blend fiber is 78%; and (3) washing the fragrant polybutylene succinate blend fiber according to the GB/T8629-2017 standard, wherein the elution rate of the essence is 25% after washing for 10 times, and the elution rate of the essence is 33% after washing for 30 times.
Example 4
A preparation method of fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid containing six-membered ring structural units and Ti (OBu) 4 Stirring and reacting for 90 minutes under the normal pressure condition with the temperature of 180 ℃, then increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 115 minutes to prepare copolymerization modified poly (butylene succinate);
wherein, the molar ratio of butanediol, dimethyl succinate and dimer acid containing six-membered ring structural units is 130 4 The amount of (A) is 180ppm;
(2) Uniformly stirring and mixing 92 parts of polybutylene succinate, 16 parts of copolymerized modified polybutylene succinate obtained in the step (1), 4 parts of grapefruit seed oil/beta-cyclodextrin inclusion compound and 4 parts of silane coupling agent KH550 in parts by weight, and melting, extruding and granulating the mixture to obtain fragrant master batches;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (polybutylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (3) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of measuring → extruding (the temperature of a spinning nozzle is 180 ℃) → air-blowing cooling (the air-blowing temperature is 25 ℃) → one-step stretching (the stretching multiple is 2.5 times, the temperature is 25 ℃) → two-step stretching (the stretching multiple is 4 times, and the temperature is 65 ℃).
The prepared fragrant poly (butylene succinate) blend fiber consists of poly (butylene succinate), copolymerization modified poly (butylene succinate), a grapefruit seed oil/beta-cyclodextrin inclusion compound and a silane coupling agent KH 550; the particle size of the grapefruit seed oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blend fiber is 0.9-1.4 mu m; the cross section structure of the fiber is compact and has no holes; the pomelo seed oil/beta-cyclodextrin inclusion compound is dispersed in the interior and on the surface of the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH550 exists between the pomelo seed oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the pomelo seed oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 0.71mm, the breaking strength is 2cN/dtex, the elongation at break is 46%, and the initial modulus is 12.8cN/dtex; after being placed at room temperature for 2 weeks, the mass retention rate of the essence in the fragrant polybutylene succinate blending fiber is 79%; and (3) washing the fragrant polybutylene succinate blend fiber according to the GB/T8629-2017 standard, wherein the elution rate of the essence is 19% after washing for 10 times, and the elution rate of the essence is 34% after washing for 30 times.
Example 5
A preparation method of a fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid containing six-membered ring structural units and Ti (OBu) 4 The reaction was stirred at 188 ℃ for 100 minutes under normal pressure, and thenThen increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 110 minutes to prepare copolymerization modified poly (butylene succinate);
wherein, the molar ratio of butanediol, dimethyl succinate and dimer acid containing six-membered ring structural units is 110 4 The dosage of (A) is 220ppm;
(2) According to the weight parts, uniformly stirring and mixing 95 parts of polybutylene succinate, 18 parts of copolymerized modified polybutylene succinate obtained in the step (1), 5 parts of lavender essential oil/beta-cyclodextrin inclusion compound and 5 parts of silane coupling agent KH560, and melting, extruding and granulating the mixture to obtain fragrant master batches;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (Poly Butylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (4) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of metering → extrusion (the temperature of a spinning nozzle is 200 ℃) → air blowing cooling (the air blowing temperature is 25 ℃) → one-way stretching (the stretching ratio is 3 times, the temperature is 25 ℃) → two-way stretching (the stretching ratio is 3.5 times, and the temperature is 75 ℃).
The prepared fragrant poly (butylene succinate) blend fiber consists of poly (butylene succinate), copolymerization modified poly (butylene succinate), lavender essential oil/beta-cyclodextrin inclusion compound and silane coupling agent KH 560; the particle size of the lavender essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blended fiber is 1.1-1.7 mu m; the cross section structure of the fiber is compact and has no holes; the lavender essential oil/beta-cyclodextrin inclusion compound is dispersed in and on the fragrant polybutylene succinate blending fiber, and the silane coupling agent KH560 is present between the lavender essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the lavender essential oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 0.83mm, the breaking strength is 1.8cN/dtex, the elongation at break is 43%, and the initial modulus is 13.4cN/dtex; after being placed at room temperature for 2 weeks, the quality retention rate of the essence in the fragrant polybutylene succinate blending fiber is 81%; and (3) washing the fragrant polybutylene succinate blend fiber according to the GB/T8629-2017 standard, wherein the elution rate of the essence after washing for 10 times is 17%, and the elution rate of the essence after washing for 30 times is 33%.
Example 6
A preparation method of a fragrant polybutylene succinate blend fiber comprises the following specific steps:
(1) Under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid containing six-membered cyclic structure units and Ti (OBu) 4 Stirring and reacting for 110 minutes under the normal pressure condition with the temperature of 185 ℃, then increasing the temperature to 230 ℃, reducing the pressure to 0.1mbar, and continuing to react for 105 minutes to prepare copolymerization modified poly (butylene succinate);
wherein, the molar ratio of butanediol, dimethyl succinate and dimer acid containing six-membered ring structural units is 125 4 In an amount of 165ppm;
(2) According to the weight parts, uniformly stirring and mixing 100 parts of polybutylene succinate, 10 parts of copolymerized modified polybutylene succinate obtained in the step (1), 6 parts of lemon essential oil/beta-cyclodextrin inclusion compound and 5 parts of silane coupling agent KH570, and melting, extruding and granulating the mixture to obtain fragrant master batches;
(3) Mixing polybutylene succinate with the flavor master batch obtained in the step (2) to obtain PBS (Poly Butylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And (4) preparing the dried PBS/flavor master batch obtained in the step (3) into the flavor polybutylene succinate blend fiber according to the process route of metering → extrusion (the temperature of a spinning nozzle is 190 ℃) → air cooling (the air blowing temperature is 25 ℃) → one-step stretching (the stretching ratio is 3 times, the temperature is 25 ℃) → two-step stretching (the stretching ratio is 3 times, and the temperature is 80 ℃).
The prepared fragrant polybutylene succinate blending fiber consists of polybutylene succinate, copolymerization modified polybutylene succinate, lemon essential oil/beta-cyclodextrin inclusion compound and silane coupling agent KH 570; the grain size of the lemon essential oil/beta-cyclodextrin inclusion compound in the fragrant polybutylene succinate blending fiber is 1.1-2.0 mu m; the cross section structure of the fiber is compact and has no holes; the lemon essential oil/beta-cyclodextrin inclusion compound is dispersed in and on the blending fiber of the fragrant polybutylene succinate, and the silane coupling agent KH570 exists between the lemon essential oil/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the lemon essential oil/beta-cyclodextrin inclusion compound and the copolymerized modified polybutylene succinate;
the diameter of the fragrant polybutylene succinate blend fiber is 1.06mm, the breaking strength is 1.5cN/dtex, the elongation at break is 41%, and the initial modulus is 12.5cN/dtex; after being placed at room temperature for 2 weeks, the quality retention rate of the essence in the fragrant polybutylene succinate blending fiber is 78%; washing the fragrant polybutylene succinate blend fiber according to GB/T8629-2017 standard, wherein the elution rate of the essence after 10 times of washing is 23%, and the elution rate of the essence after 30 times of washing is 37%.
Claims (10)
1. A fragrant poly butylene succinate blending fiber is characterized in that: consists of poly (butylene succinate), copolymerization modified poly (butylene succinate), an essence/beta-cyclodextrin inclusion compound and a coupling agent;
the grain size of the essence/beta-cyclodextrin inclusion compound in the fragrant poly butylene succinate blend fiber is 0.5-2 mu m;
the essence/beta-cyclodextrin inclusion compound is dispersed in the interior and on the surface of the fragrant polybutylene succinate blending fiber, and the coupling agent exists between the essence/beta-cyclodextrin inclusion compound and the polybutylene succinate as well as between the essence/beta-cyclodextrin inclusion compound and the copolymerization modified polybutylene succinate;
the mass ratio of the poly (butylene succinate) to the copolymerization modified poly (butylene succinate) in the fragrant poly (butylene succinate) blend fiber is 80-100;
the copolymerization modified polybutylene succinate is a polybutylene succinate copolymer containing six-membered ring structural units.
2. The fragrant polybutylene succinate blend fiber of claim 1, wherein the fragrant polybutylene succinate blend fiber comprises the following components in parts by weight:
80-100 parts of polybutylene succinate;
10-20 parts of copolymerization modified polybutylene succinate;
1-6 parts of essence/cyclodextrin inclusion compound;
1-5 parts of a coupling agent.
3. The fragrant polybutylene succinate blend fiber as claimed in claim 1, wherein the essence/beta-cyclodextrin inclusion compound is lavender essential oil/beta-cyclodextrin inclusion compound, lemon essential oil/beta-cyclodextrin inclusion compound, cinnamon essential oil/beta-cyclodextrin inclusion compound or grapefruit seed oil/beta-cyclodextrin inclusion compound.
4. The fragrant polybutylene succinate blend fiber according to claim 1, wherein the coupling agent is silane coupling agent KH550, silane coupling agent KH560 or silane coupling agent KH570.
5. The fragrant polybutylene succinate blend fiber of claim 1, wherein the fragrant polybutylene succinate blend fiber has a diameter of 0.08-1.06 mm, a breaking strength of 1.5-2.2 cN/dtex, an elongation at break of 35-46%, and an initial modulus of 11.1-15.4 cN/dtex.
6. The fragrant polybutylene succinate blend fiber according to claim 5, wherein after the fragrant polybutylene succinate blend fiber is placed at room temperature for 2 weeks, the mass retention rate of essence in the fragrant polybutylene succinate blend fiber is 70-83%;
washing the fragrant polybutylene succinate blend fiber with water according to GB/T8629-2017 standard, wherein the elution rate of the essence after 10 times of washing is 13-28%, and the elution rate of the essence after 30 times of washing is 32-41%.
7. The method for preparing the fragrant polybutylene succinate blend fiber as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) By Ti (OBu) 4 As a catalyst, polymerizing butanediol, dimethyl succinate and dimer acid containing six-membered ring structural units to prepare copolymerization modified polybutylene succinate;
(2) Uniformly stirring and mixing polybutylene succinate, copolymerization modified polybutylene succinate, an essence/beta-cyclodextrin inclusion compound and a coupling agent, and melting, extruding and granulating the mixture to obtain fragrant master batches;
(3) Mixing polybutylene succinate with the flavor master batch to obtain PBS (Poly Butylene succinate)/flavor master batch, and drying the PBS/flavor master batch at the temperature of 80 ℃ for 5 hours;
(4) And preparing the dried PBS/flavor master batch into the flavor polybutylene succinate blend fiber according to the process route of metering → extruding → air-blowing cooling → one-step stretching → two-step stretching.
8. The preparation method of the fragrant polybutylene succinate blend fiber according to claim 7, wherein the step (1) comprises the following steps: under the protection of nitrogen atmosphere, butanediol, dimethyl succinate, dimer acid and Ti (OBu) 4 Stirring and reacting for 80-120 minutes under the normal pressure condition that the temperature is 180-190 ℃; the temperature was then increased to 230 ℃ and the pressure was reduced to 0.1mbar and the reaction was continued for 100-120 minutes.
9. The preparation method of the aromatic polybutylene succinate blend fiber according to claim 8, wherein the molar ratio of butanediol, dimethyl succinate and dimer acid is (100-140); based on the mass sum of butanediol, dimethyl succinate and dimer acid, ti (OBu) 4 The dosage of the compound is 150-250 ppm.
10. The preparation method of the fragrant polybutylene succinate blend fiber according to claim 7, wherein the process parameters in the step (4) are as follows: the extrusion temperature is 150-200 ℃, the blowing temperature is 25 ℃, the primary stretching multiple is 2-3 times, the secondary stretching multiple is 3-4 times, and the secondary stretching temperature is 60-80 ℃.
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