CN102146598B - PHBV-containing biobased chemical fiber and preparation method thereof - Google Patents

Abstract

The invention relates to a bio-based chemical fiber containing PHBV and a preparation method thereof. There are various deficiencies in the preparation technology of PHBV fibers at present. The bio-based chemical fiber of the present invention is a mixture of PHBV and the second component polymer, and 100 parts by mass of the bio-based chemical fiber contains 1-89 parts of PHBV and 11-99 parts of the second component polymer. Wherein the second component polymer is one or a mixture of P(3HB-co-4HB), PBS, PBAT, PP and PE. The specific preparation method is firstly vacuum-drying the PHBV and the second component macromolecule, then physically mixing in proportion, melt spinning, and finally post-processing. The bio-based chemical fiber disclosed in the present invention has better spinnability at a lower spinning temperature and a higher spinning speed, and has higher mechanical strength and a softer hand feeling that is sustained and stable. Its preparation The method can effectively improve production efficiency and reduce costs.

Description

A kind of bio-based chemical fiber containing PHBV and its preparation method

technical field

The invention belongs to the technical field of polymer materials, and relates to a bio-based chemical fiber containing PHBV and a preparation method thereof.

Background technique

Chemical fiber has become an indispensable and huge amount of chemical products in people's daily life, industrial and agricultural production. Traditional chemical fibers mainly use petroleum-based polymers as raw materials. As petroleum is a non-renewable resource, it is increasingly depleted, which brings a huge crisis to the sustainable development of chemical fibers. To cope with this crisis, people urgently need to develop and utilize renewable resources, especially bio-based chemical fibers.

The raw material of bio-based chemical fiber can be a single bio-based polymer, a mixture of two or more bio-based polymers, or a mixture of bio-based polymers and petroleum-based polymers, and its bio-based carbon content can be in accordance with ASTM D6866, ISO/NP 13833 and other standards are determined by radiocarbon dating techniques. According to the relevant regulations of the United States, Japan, Europe and other developed countries and regions, the use of star or environmental protection labels (such as EcoLogo, OK Biobased, etc.) And then included in the priority procurement plan for biological products. These policies have created opportunities for the promotion and application of bio-based chemical fibers.

In the family of bio-based polymers, polyhydroxybutyrate-valerate (PHBV) has attracted more and more attention due to its good biodegradability, biocompatibility and mechanical properties. PHBV is prepared from starch through microbial fermentation, and can be decomposed into carbon dioxide, water and biomass under soil or compost conditions. The preparation of bio-based chemical fibers from PHBV is conducive to providing a chemical fiber variety that meets the requirements of environmental protection and sustainable development, and at the same time expands its application fields, so it has very important market value.

Fang Zhuangxi et al. (Acta Polymer Sinica, 2004, 4: 500) prepared PHBV ultrafine fibers by electrospinning. Before spinning, PHBV/chloroform solution needs to be prepared, and the average diameter of PHBV fibers is 0.83-1.73 microns.

Qi Zhonghua et al. (Synthesis Technology and Application, 2008, 23: 16) prepared PHBV/Ecoflex ultrafine blended fiber felt by electrospinning method. Before spinning, PHBV/Ecoflex/dichloromethane solution needs to be prepared to obtain PHBV The average diameter of the /Ecoflex blended fiber is 0.09-1.85 microns.

Zhu Shuqi et al. (Synthetic Fibers, 2009, 7: 13) prepared PHBV fibers by dry spinning. Before spinning, PHBV/chloroform solution needs to be prepared, and the as-spun fibers are obtained at a spinning speed of 20 m/min. Stretching 2-5 times at 70 ^o C, and heat setting at 120 ^o C, the breaking strength of PHBV fiber is about 1.8cN/dtex, and the breaking elongation is more than 40%.

Tang Jian et al. (National Polymer Academic Papers Conference, C24, 2003, Hangzhou) prepared PHBV/CO ₂ polymer blend fibers by melt spinning. The mass ratio of PHBV to CO ₂ polymer was 60/40. When When the content of hydroxyvalerate (HV) in PHBV was 7.5%, the fiber forming property of the fiber was better.

Wang Xijian et al. (Synthetic Fiber Industry, 2008, 31: 46) prepared PHBV/PCL blended fibers by melt spinning method, the spinning temperature was 175 ^o C, and the spinning speed was 50-80m/min.

He Jing et al. (Synthetic Fibers, 2008, 1: 10) prepared PHBV/TiO ₂ fibers by melt spinning. TiO ₂ was used as a nucleating agent. A hot water bath was placed under the spinneret to ensure that the fibers had better Excellent spinnability and mechanical properties, the strength of the prepared fiber is 1.052cN/dtex, and the elongation is 157%.

Obviously, people have realized the significance and importance of PHBV as a bio-based chemical fiber material. However, some chemical and physical properties of PHBV, such as easy degradation at higher temperatures, slow crystallization speed, and high brittleness, seriously restrict the development of PHBV fiber preparation technology and the application of PHBV as fiber materials. As mentioned above, the preparation of PHBV fibers by electrospinning and dry spinning can avoid the thermal degradation of PHBV to a certain extent, but it is necessary to prepare PHBV solution before spinning, use volatile and toxic solvents, and spin The speed is low, resulting in lower productivity and higher costs. The preparation of PHBV fibers by melt spinning faces problems such as PHBV thermal degradation, slow crystallization speed, and high brittleness. It can be blended with other polymers (such as CO ₂ polymers, PCL) or added nucleating agents (such as TiO ₂ ) to be improved. However, the CO ₂ polymer is an amorphous polymer, which is not conducive to the improvement of the mechanical strength of the fiber; the melting point of PCL is about 60 ^o C, which is quite different from the melting point of PHBV (150-160 ^o C). The degradation of PCL at 175 ^o C) is also unfavorable for the preparation of high-strength fibers; adding a nucleating agent (TiO ₂ ) can improve the crystallinity of PHBV, but it still needs to place a hot water bath under the spinneret, which limits the spinning process. At the same time, the nucleating agent is also likely to cause blockage of the spinning assembly, which is not conducive to long-term continuous production. Therefore, the mechanical strength of the fiber containing PHBV obtained by the current known methods generally does not exceed 1.8cN/dtex, and it is urgent to develop new bio-based chemical fibers containing PHBV and improve fiber production technology to improve fiber performance and reduce production costs. Meet the use requirements.

Contents of the invention

The first object of the present invention is to provide a bio-based chemical fiber containing polyhydroxybutyrate-valerate (PHBV) in view of the above technical status.

The bio-based chemical fiber of the present invention is a mixture of PHBV and the second component polymer, and the mass parts of each component in the bio-based chemical fiber with 100 parts by mass are:

PHBV 1～89 parts

The second component polymer 11-99 parts.

The preferred solution is:

PHBV 1～9 servings

The second component polymer 91-99 parts.

The PHBV has a weight average molecular weight of 90,000 to 510,000 and a molar content of hydroxyvalerate of 3 to 43%;

The second component macromolecule is 3-hydroxybutyric acid/4-hydroxybutyric acid copolymer [P(3HB-co-4HB)], polybutylene succinate (PBS), polyterephthalate Formic acid-adipate-butylene glycol ester (PBAT), polypropylene (PP), polyethylene (PE) or a mixture of two, the mixing ratio is any ratio.

The weight-average molecular weight of the P(3HB-co-4HB) is 70,000 to 710,000, and the molar content of 4-hydroxybutyric acid is 4 to 20%;

The weight average molecular weight of the PBS is 70,000 to 190,000;

The weight average molecular weight of the PBAT is 20,000 to 80,000;

The melt index of the PP is 3-41g/10min;

The melt index of the PE is 3-41g/10min.

The second object of the present invention is to propose a method for preparing this PHBV-containing bio-based chemical fiber.

The method of the present invention comprises the following steps: (1) vacuum-drying the PHBV and the second component polymer in the bio-based chemical fiber component respectively; (2) drying the dried PHBV and the second component polymer according to the aforementioned (3) inject the mixture into the extrusion equipment with heating device to melt, and then collect the long fibers at the spinning temperature of 174-216 ^o C and the spinning speed of 500-1500m/min, or The non-woven fabric is collected by the melt-blown method at a spinning temperature of 174-216 ^o C; (4) After-treatment of the long fiber or non-woven fabric.

Compared with the prior art, the present invention has the advantages that: compared with ordinary PHBV fibers, the bio-based chemical fiber containing PHBV disclosed by the present invention has a lower spinning temperature (174-216 ^o C) and a higher spinning temperature. It has good spinnability under the silk speed (500-1500m/min), and has high mechanical strength (reaching or exceeding 1.8cN/dtex) and continuous and stable soft hand feeling, so it can meet the requirements of use, and then Expand the field of application. In addition, the melt viscosity of PHBV is low, and when the content is small (1-9 parts), it can "lubricate" the high-molecular components with high content, so that melt spinning can be carried out at a lower spinning temperature (174 ^o C～216 ^o C), so as to effectively avoid or alleviate the thermal degradation of raw materials, further improve the mechanical strength of long melt-spun fibers (reach or exceed 2.0cN/dtex), and reduce the energy consumption of melt-spinning. The present invention also discloses the preparation method of the bio-based chemical fiber containing PHBV, through the melt spinning method at a lower spinning temperature (174-216 ^o C) and a higher spinning speed (500-1500m/min ) to produce long fibers, or use the melt blown method to produce non-woven fabrics at a spinning temperature of 174-216 ^o C, which can effectively improve production efficiency and reduce costs.

Detailed ways

The technical solutions and effects of the present invention will be further described below in conjunction with the embodiments.

Comparative example 1:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 510,000 and a molar content of hydroxyvalerate of 23% for vacuum drying. The drying temperature is 60±5 ^o C, and the drying time is 16 hours. 100 Pa; take 100 kg of dried PHBV, pour it into a single-screw extruder to melt, extrude it into fibers through a metering pump and a spinneret hole, and collect it at a spinning temperature of 172 ^o C and a spinning speed of 500m/min Long fibers, the fibers are severely bonded and frequently broken, it is difficult to obtain continuous long fibers. Comparative Example 1 shows that it is difficult to obtain PHBV long fibers by conventional melt spinning methods.

Comparative example 2:

Take polypropylene (PP) with a melt index of 22g/10min for vacuum drying, the drying temperature is 80±5 ^o C, the drying time is 6 hours, and the vacuum degree is 100Pa; take 100 kg of dried PP, inject it into a single screw extruder Melt in the machine, extrude into fibers through metering pump and spinneret holes, collect continuous long fibers at a spinning temperature of 250 ^o C and a spinning speed of 1000 m/min, draw 1.8 times at 60 ^o C, and then After heat setting at 70 ^o C, the measured tensile strength of the long fiber was 1.7cN/dtex, and the elongation at break was 15%. Comparative Example 2 shows that PP long fibers can be obtained by the usual melt spinning method, but higher spinning temperature is required, and PP fibers are not bio-based chemical fibers.

Comparative example 3:

Take polyhydroxybutyrate-valerate (PHBV) with a weight-average molecular weight of 300,000 and a molar content of 3% hydroxyvalerate for vacuum drying at a drying temperature of 60±5 ^o C and a drying time of 16 hours. 100 Pa; take 100 kg of dried PHBV, pour it into a single-screw extruder to melt, extrude into fibers through a metering pump and a spinneret hole, and collect non-woven fabrics when the spinning temperature is 172 ^o C by melt-blowing method; The non-woven fabric was heat-set at 60 ^° C. The non-woven fabric feels hard and becomes brittle significantly after being placed at room temperature for 1 week. Comparative Example 3 shows that the PHBV non-woven fabric can be obtained by the usual melt-blown method, but the non-woven fabric feels hard and has unstable performance.

Example 1:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 510,000 and a molar content of hydroxyvalerate of 23% and polypropylene (PP) with a melt index of 22g/10min for vacuum drying at 60 ±5 ^o C, the drying time is 16 hours, and the vacuum degree is 100Pa; take 89 kg of dried PHBV and 11 kg of dried PP for physical mixing in a high-speed mixer; inject the mixture into a twin-screw extruder to melt, Extruded into fibers through metering pumps and spinneret holes, and collected to obtain bio-based continuous long fibers, the spinning temperature was 195 ^o C, and the spinning speed was 500 m/min; it was drawn 2.4 times at 61 ^o C, and then stretched at 70 ^{o C} The heat setting was carried out at C, and the tensile strength of the long fiber was measured to be 1.9cN/dtex, the elongation at break was 20%, and the hand feeling was soft, and the hand feeling was still soft after being placed at room temperature for 1 week.

Example 2:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 300,000 and a molar content of hydroxyvalerate of 3% and polyterephthalic acid-adipate-butylene glycol with a weight average molecular weight of 20,000 The ester (PBAT) was vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum degree of 100 Pa; 45 kg of dried PHBV and 55 kg of dried PBAT were physically mixed in a high-speed mixer; The mixture was injected into a single-screw extruder to melt, extruded into fibers through metering pumps and spinneret holes, and collected to obtain bio-based continuous long fibers. The spinning temperature was 174 ^o C and the spinning speed was 1000m/min; at 50 It was stretched 2.3 times at ^o C, and then heat-set at 60 ^o C. The measured tensile strength of the long fiber was 1.8cN/dtex, and the elongation at break was 37%. The back feel is still soft.

Example 3:

Take polyhydroxybutyrate-valerate (PHBV) with a weight-average molecular weight of 510,000 and a molar content of hydroxyvalerate of 23%, polybutylene succinate (PBS) with a weight-average molecular weight of 190,000, and melt Polypropylene (PP) with an index of 3g/10min was vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum of 100Pa; 9 kg of dried PHBV, 45.5 kg of dried PBS and 45.5 kg of dried PP is physically mixed in a high-speed mixer; the mixture is injected into a twin-screw extruder to melt, extruded into fibers through a metering pump and spinneret holes, and collected to obtain bio-based continuous long fibers. The spinning temperature is 216 ^o C, the spinning speed is 1500m/min; stretched 2.0 times at 60 ^o C, and then heat-set at 72 ^o C, the measured tensile strength of the long fiber is 2.5cN/dtex, elongation at break The rate is 31%, and the hand feels soft, and the hand is still soft after being placed at room temperature for 1 week.

Example 4:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 90,000 and a molar content of hydroxyvalerate of 43%, and 3- Hydroxybutyric acid/4-hydroxybutyric acid copolymer [P(3HB-co-4HB)] and polyethylene (PE) with a melt index of 22g/10min were vacuum-dried at 60±5 ^o C for a drying time of 16 hours, the vacuum degree is 100Pa; Take 5 kg of dried PHBV, 85.5 kg of dried P(3HB-co-4HB) and 9.5 kg of dried PE for physical mixing in a high-speed mixer; inject the mixture into the twin-screw Melted in the extruder, extruded into fibers through metering pumps and spinneret holes, and collected to obtain bio-based continuous long fibers, the spinning temperature was 174 ^o C, the spinning speed was 500m ^/ min; times, and then heat-setting at 60 ^o C, the measured tensile strength of the long fiber is 2.2cN/dtex, the elongation at break is 27%, the hand feel is soft, and the hand feel is still soft after being placed at room temperature for 1 week .

Example 5:

Take polyhydroxybutyrate-valerate (PHBV) with a weight-average molecular weight of 250,000 and a molar content of hydroxyvalerate of 5%, polybutylene succinate (PBS) with a weight-average molecular weight of 70,000, and melt Polypropylene (PP) with an index of 41g/10min was vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum degree of 100Pa; 1 kg of dried PHBV, 49.5 kg of dried PBS and 49.5 kg of dried PP was physically mixed in a high-speed mixer; the mixture was injected into a twin-screw extruder to melt, extruded into fibers through metering pumps and spinneret holes, and collected to obtain bio-based continuous long fibers. The spinning temperature was 195 ^o C, the spinning speed is 1000m/min; stretched 2.4 times at 55 ^o C, and then heat-set at 65 ^o C, the measured tensile strength of the long fiber is 2.3cN/dtex, elongation at break The percentage is 32%, and the hand feels soft, and the hand is still soft after being placed at room temperature for 1 week.

Embodiment 6:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 510,000 and a molar content of hydroxyvalerate of 30% and polyethylene (PE) with a melt index of 3g/10min for vacuum drying at a temperature of 60 ±5 ^o C, the drying time is 16 hours, and the vacuum degree is 100Pa; take 89 kg of dried PHBV and 11 kg of dried PE for physical mixing in a high-speed mixer; inject the mixture into a twin-screw extruder to melt, Fibers were extruded through metering pumps and spinneret holes, and bio-based non-woven fabrics were collected at a spinning temperature of 216 ^o C by melt-blown method; the non-woven fabrics were heat-set at 55 ^o C; non-woven fabrics It is soft to the touch, and it is still soft to the touch after being placed at room temperature for 1 week.

Embodiment 7:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 90,000 and a molar content of hydroxyvalerate of 43%, and polyterephthalic acid-adipate-butylene glycol with a weight average molecular weight of 50,000 The ester (PBAT) was vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum degree of 100 Pa; 55 kg of dried PHBV and 45 kg of dried PBAT were physically mixed in a high-speed mixer; The mixture is injected into a single-screw extruder to melt, extruded into fibers through a metering pump and a spinneret hole, and collected by a melt blown method at a spinning temperature of 174 ^o C to obtain a bio-based non-woven fabric; the non-woven fabric Heat setting at 50 ^o C; the non-woven fabric is soft to the touch and remains soft to the touch after 1 week at room temperature.

Embodiment 8:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 150,000 and a molar content of hydroxyvalerate of 3% and 3- Hydroxybutyric acid/4-hydroxybutyric acid copolymer [P(3HB-co-4HB)] was vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum degree of 100 Pa; the dried PHBV 9 kg and 91 kg of dried P(3HB-co-4HB) were physically mixed in a high-speed mixer; the mixture was injected into a single-screw extruder to melt, and extruded into fibers through metering pumps and spinneret holes. The bio-based non-woven fabric was collected by spraying method at a spinning temperature of 174 ^o C; the non-woven fabric was heat-set at 50 ^o C; the non-woven fabric was soft to the touch, and it was still soft after being placed at room temperature for 1 week.

Embodiment 9:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 510,000 and a molar content of hydroxyvalerate of 33%, and 3- Hydroxybutyric acid/4-hydroxybutyric acid copolymer [P(3HB-co-4HB)] and polybutylene succinate (PBS) with a weight average molecular weight of 130,000 were vacuum-dried at a drying temperature of 60±5 ^o C, the drying time is 16 hours, and the vacuum is 100Pa; take 3 kilograms of dried PHBV, 9.5 kilograms of dried P(3HB-co-4HB) and 87.5 kilograms of dried PBS in a high-speed mixer for physical mixing; The mixture is injected into a single-screw extruder to melt, extruded into fibers through a metering pump and a spinneret hole, and the bio-based non-woven fabric is collected at a spinning temperature of 195 ^o C by a melt blown method; the non-woven fabric Heat setting at 50 ^o C; the non-woven fabric is soft to the touch and remains soft to the touch after 1 week at room temperature.

Example 10:

Take polyhydroxybutyrate-valerate (PHBV) with a weight average molecular weight of 450,000 and a molar content of hydroxyvalerate of 6%, and polyterephthalic acid-adipate-butylene glycol with a weight average molecular weight of 80,000 Ester (PBAT) and polyethylene (PE) with a melt index of 41g/10min were vacuum-dried at a drying temperature of 60±5 ^o C, a drying time of 16 hours, and a vacuum of 100Pa; take 1 kg of dried PHBV, dry 49.5 kg of the final PBAT and 49.5 kg of dried PE were physically mixed in a high-speed mixer; the mixture was injected into a twin-screw extruder to melt, extruded into fibers through a metering pump and a spinneret hole, and melt-blown in the spinning process. The bio-based non-woven fabric was collected when the filament temperature was 195 ^o C; the non-woven fabric was heat-set at 50 ^o C; the non-woven fabric was soft to the touch, and it was still soft after being placed at room temperature for 1 week.

Claims (1)

1. A bio-based chemical fiber containing PHBV, characterized in that the bio-based chemical fiber is a mixture of PHBV and the second component macromolecule, and the mass parts are the mass parts of each component in the bio-based chemical fiber of 100 parts The number is: PHBV 1～89 parts The second component polymer 11～99 parts The second component polymer is 3-hydroxybutyric acid/4-hydroxybutyric acid copolymer, polybutylene succinate, polybutylene terephthalate-adipate, polypropylene 1, or a mixture of two types of polyethylene, the mixing ratio is any ratio; The weight average molecular weight of the PHBV is 90,000 to 510,000, and the molar content of hydroxyvalerate is 3 to 43%; The weight-average molecular weight of the 3-hydroxybutyric acid/4-hydroxybutyric acid copolymer is 70,000 to 710,000, and the molar content of 4-hydroxybutyric acid is 4 to 20%; The weight average molecular weight of the polybutylene succinate is 70,000 to 190,000; The weight average molecular weight of the polyterephthalic acid-adipate-butylene glycol ester is 20,000 to 80,000; The melt index of the polypropylene is 3～41g/10min; The melt index of the polyethylene is 3-41g/10min. 2. A method for preparing bio-based chemical fibers containing PHBV, characterized in that the method comprises the following steps: (1) Vacuum drying the PHBV and the second component macromolecule respectively; (2) Drying the dried PHBV and The second component polymers are physically mixed in proportion; (3) The mixture is injected into the extrusion equipment with a heating device to melt, and then the spinning temperature is 174-216 ^o C, and the spinning speed is 500-1500m/min. Collect long fibers at high speed, or collect non-woven fabrics at a spinning temperature of 174-216 ^o C by melt-blown method; (4) Post-treat long fibers or non-woven fabrics; The mass fractions of PHBV and the second component macromolecule in the mixture of 100 mass fractions are: PHBV 1～89 parts The second component polymer 11～99 parts The second component polymer is 3-hydroxybutyric acid/4-hydroxybutyric acid copolymer, polybutylene succinate, polybutylene terephthalate-adipate, polypropylene 1, or a mixture of two types of polyethylene, the mixing ratio is any ratio; The weight average molecular weight of the PHBV is 90,000 to 510,000, and the molar content of hydroxyvalerate is 3 to 43%; The weight-average molecular weight of the 3-hydroxybutyric acid/4-hydroxybutyric acid copolymer is 70,000 to 710,000, and the molar content of 4-hydroxybutyric acid is 4 to 20%; The weight average molecular weight of the polybutylene succinate is 70,000 to 190,000; The weight average molecular weight of the polyterephthalic acid-adipate-butylene glycol ester is 20,000 to 80,000; The melt index of the polypropylene is 3～41g/10min; The melt index of the polyethylene is 3-41g/10min. 3. A PHBV-containing bio-based chemical fiber as claimed in claim 1, characterized in that the mass parts of each component in the bio-based chemical fiber is 100 parts by mass: PHBV 1～9 parts The second component polymer 91～99 parts. 4. A method for preparing bio-based chemical fibers containing PHBV as claimed in claim 2, characterized in that the mass parts of PHBV and the second component polymer in the mixture of 100 parts by mass are: PHBV 1～9 parts The second component polymer 91～99 parts.