Fully-degradable non-woven fabric produced by melt-blowing method and application thereof in medical mask
1. The fully-degradable non-woven fabric produced by the melt-blowing method is characterized by comprising the following steps:
s1, preparation of caprolactone-lactic acid random copolymer (P (CL-co-LA)):
weighing lactic acid (L-LA) and epsilon-caprolactone (epsilon-CL) and adding the lactic acid (L-LA) and the epsilon-caprolactone into a reaction vessel to obtain a reaction system, wherein the weight ratio of the lactic acid (L-LA) to the epsilon-caprolactone (epsilon-CL) in the reaction system is 1: (2-4);
adding a catalyst accounting for 0.1-0.2% of the weight of the reaction system into the reaction system, and then reacting for 18-24h at 130-140 ℃ under a vacuum condition to obtain a copolymer crude product;
purifying the crude copolymer product to finally obtain the caprolactone-lactic acid random copolymer (P (CL-co-LA));
s2, preparation of copolymerization modified PLA:
drying polylactic acid (PLA);
uniformly mixing the dried PLA and the dried P (CL-co-LA), and then carrying out melt blending at the temperature of 180 ℃ and the rotation speed of 50-100r/min to obtain a blend; wherein the mass ratio of the PLA to the (P (CL-co-LA)) is (9-99): 1, the blending time is 5-10 min;
the blend is placed at the temperature of 190 ℃ of 180 ℃ and under the pressure of 8-10MPa for compression molding, and the copolymerization modified PLA is finally obtained;
s3, preparing non-woven fabric by a melt-blowing method:
taking copolymerization modified PLA, PHBV and nano SiO2Blending a compatibilizer and a chain extender to obtain a melt-blown blend; wherein, according to the mass ratio, the copolymerization modified PLA: PHBV: nano SiO2: a compatilizer: chain extender ═ 80-95: (1-5): (0.1-0.2): (0.001-0.005): (0.001-0.01);
adding the melt-blown blend into a screw extruder, and performing melt extrusion granulation at the temperature of 160-;
adding the blended granules into a screw extruder for extrusion, melting and plasticizing, then conveying to a spinneret assembly, spraying from spinneret holes of a die head of the spinneret assembly, cooling and drawing by hot air flow to form melt-blown non-woven materials on a collecting device, and performing electret treatment on the melt-blown non-woven materials to finally obtain the fully-degradable non-woven fabric.
2. The fully degradable nonwoven fabric of claim 1, wherein the step of purifying the crude product in step S1 comprises:
s11, carrying out ultrasonic treatment and/or microwave treatment on the crude product, and precipitating the obtained product by using ethanol with the volume fraction of 90%;
s12, repeating the step S111-2 times, and finally obtaining the purified product.
3. The fully degradable nonwoven fabric of claim 2 wherein the ultrasonic treatment conditions are: the ultrasonic power is 200-; the microwave treatment conditions are as follows: the ultrasonic power is 200-300W, and the treatment time is 0.5-1 h.
4. The fully degradable nonwoven fabric of claim 1, wherein in step S3, the compatibilizer is one or more of maleic anhydride, butyric anhydride, stearic anhydride, and tannic acid.
5. The fully-degradable nonwoven fabric of claim 4, wherein the compatilizer is composed of maleic anhydride, butyric anhydride, stearic anhydride and tannic acid, and the mass ratio of maleic anhydride: butyric anhydride: stearic anhydride: tannic acid 1:1:1: 1.
6. The fully degradable nonwoven fabric of claim 1, wherein in step S3, the receiving distance from the die orifice of the spinneret assembly to the collecting device is 30-50cm, the extrusion frequency of the die orifice is 1.5Hz-2.5Hz, and the temperature of the hot air stream is 240-260 ℃.
7. The fully degradable nonwoven fabric of claim 1, wherein in step S2, the melt index of PLA at 210 ℃ is 20-40g/10 min.
8. The fully degradable nonwoven fabric of claim 1, wherein in step S3, the electret material for the electret treatment is obtained by corona electret, and the electret voltage is 30-40kV, the electret distance is 2-4cm, and the electret time is 1-2 min.
9. The fully degradable nonwoven fabric of claim 1, wherein in step S3, the co-polymerized modified PLA is sliced and dried at 60 ℃ for 24-48h before blending.
10. Use of the fully degradable nonwoven fabric according to any one of claims 1 to 9 for the manufacture of a medical mask.
Background
The non-woven fabric is also called non-woven fabric, is formed by oriented or random fibers, belongs to a new generation of environment-friendly materials, and has the characteristics of ventilation, lightness, thinness, good flexibility, no combustion supporting, no toxicity, no irritation, low price and the like.
The melt-blowing method is a non-woven fabric processing technology for directly preparing a polymer into a net, and the main action principle of the melt-blowing method is to gradually solidify a polymer melt into a melt trickle by utilizing high-speed and high-temperature air flow blowing so as to obtain superfine fibers, and the melt-blowing method is widely applied to the manufacturing process of non-woven fabrics.
However, the existing melt-blown nonwoven fabric mainly uses polypropylene as a raw material, and is not degradable after being discarded, which easily causes environmental pollution, for this reason, a scheme for preparing the melt-blown nonwoven fabric by using a degradable material has appeared in the prior art, such as 202011528027.X, "a degradable melt-blown nonwoven fabric for masks", but it only provides the raw material composition of the nonwoven fabric, and does not provide a specific process flow for preparing the raw material into the nonwoven fabric by using a melt-blowing method, so that it is unknown whether the raw material can be actually processed into masks by using the melt-blowing method.
Disclosure of Invention
The invention aims to provide a fully-degradable non-woven fabric produced by a melt-blowing method and application thereof in a medical mask.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a fully degradable non-woven fabric produced by a melt-blowing method is provided, and the production of the non-woven fabric comprises the following steps:
s1, preparation of caprolactone-lactic acid random copolymer (P (CL-co-LA)):
weighing lactic acid (L-LA) and epsilon-caprolactone (epsilon-CL) and adding the lactic acid (L-LA) and the epsilon-caprolactone into a reaction vessel to obtain a reaction system, wherein the weight ratio of the lactic acid (L-LA) to the epsilon-caprolactone (epsilon-CL) in the reaction system is 1: (2-4), preferably, the weight ratio of the lactic acid (L-LA) to the epsilon-caprolactone (epsilon-CL) is 1: 3;
adding a catalyst accounting for 0.1-0.2% of the weight of the reaction system into the reaction system, and then reacting for 18-24h at 130-140 ℃ under a vacuum condition to obtain a copolymer crude product; preferably, the catalyst comprises a nitrogen-donor zinc guanidine catalyst;
purifying the crude product, and drying the purified product in a vacuum drying oven at 40-50 ℃ to finally obtain the caprolactone-lactic acid random copolymer (P (CL-co-LA));
s2, preparation of copolymerization modified PLA:
drying PLA;
uniformly mixing the dried PLA and P (CL-co-LA), and then carrying out melt blending at the temperature of 180 ℃ and the rotation speed of 50-100r/min to obtain a blend; wherein the mass ratio of the PLA to the P (CL-co-LA) is (9-99): 1, the blending time is 5-10min (preferably 8 min);
the blend is placed at the temperature of 190 ℃ of 180 ℃ and under the pressure of 8-10MPa for compression molding, and the copolymerization modified PLA is finally obtained;
s3, preparing non-woven fabric by a melt-blowing method:
taking copolymerization modified PLA and PHBV (3)-copolymer of hydroxybutyrate and 3-hydroxyvalerate), nano SiO2Blending a compatibilizer and a chain extender to obtain a melt-blown blend; wherein, according to the mass ratio, the copolymerization modified PLA: PHBV: nano SiO2: a compatilizer: chain extender ═ 80-90: (1-3): (0.2-0.3): (0.005-0.01): (0.001-0.005); before blending, slicing the copolymerization modified PLA, and drying for 24-48h at 60 ℃ to reduce the water content to be below 0.025%;
adding the melt-blown blend into a screw extruder, and performing melt extrusion granulation at the temperature of 160-;
adding the blended granules into a screw extruder for extrusion, melting and plasticizing, accurately metering by a metering pump, conveying to a spinneret assembly, spraying from spinneret holes of a die head of the spinneret assembly, cooling and drawing by high-speed and high-pressure hot air flow to form a melt-blown non-woven material on a collecting device (such as a receiving plate), performing electret treatment on the melt-blown non-woven material, and performing edge cutting and winding forming to finally obtain the fully-degradable non-woven fabric.
Preferably, in step S1, the step of purifying the crude product comprises:
s11, carrying out ultrasonic treatment and/or microwave treatment on the crude product, and precipitating the obtained product by using ethanol with the volume fraction of 90%;
s12, repeating the step S111-2 times, and finally obtaining the purified product.
Preferably, the ultrasonic treatment conditions are as follows: the ultrasonic power is 200-;
the microwave treatment conditions are as follows: the ultrasonic power is 200-300W, and the treatment time is 0.5-1 h.
Preferably, in step S3, the compatibilizer is one or more of maleic anhydride, butyric anhydride, stearic anhydride, and tannic acid.
Preferably, the compatilizer consists of maleic anhydride, butyric anhydride, stearic anhydride and tannic acid, and the mass ratio of the maleic anhydride: butyric anhydride: stearic anhydride: tannic acid 1:2:2: 1.
Preferably, in step S3, the chain extender is an ADR chain extender (i.e., a multi-epoxy chain extender).
Preferably, in step S3, the distance between the die orifice of the spinneret assembly and the collection device is 30-50 cm.
Preferably, in step S3, the extrusion frequency of the spinneret orifices of the die head is 1.5Hz-2.5 Hz.
Preferably, in step S3, the temperature of the hot air stream is 240-260 ℃.
Preferably, in step S2, the melt index of the PLA at 210 ℃ is 20-40g/10 min.
Preferably, in step S3, the electret material for electret treatment is obtained by corona electret, and during electret treatment, the electret voltage is 30-40kV, the electret distance is 2-4cm, and the electret time is 1-2 min.
On the other hand, the application of the fully-degradable non-woven fabric in preparing a medical mask is also provided.
The invention has the beneficial effects that:
the raw materials for manufacturing the non-woven fabric are all fully degradable raw materials, so that the environment cannot be polluted after the non-woven fabric is discarded after use; meanwhile, the PLA is subjected to gradient multiple modification, namely, blending modification is firstly performed, and then blending modification and chain extension modification are performed, so that the PLA polylactic acid structure is changed, the polymer performance is changed, ultrasonic/microwave treatment and electret treatment are added in the modification process, and various melt-blown parameters are optimally set, so that various performance indexes of the finally obtained non-woven fabric are improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are further described below.
Example 1:
the embodiment provides a fully degradable non-woven fabric produced by a melt-blowing method, and the production of the fully degradable non-woven fabric comprises the following steps:
s1, preparation of caprolactone-lactic acid random copolymer (P (CL-co-LA)):
weighing lactic acid (L-LA) and epsilon-caprolactone (epsilon-CL) and adding the lactic acid (L-LA) and the epsilon-caprolactone into a reaction vessel to obtain a reaction system, wherein the weight ratio of the lactic acid (L-LA) to the epsilon-caprolactone (epsilon-CL) in the reaction system is 1: (2-4), preferably, the weight ratio of the lactic acid (L-LA) to the epsilon-caprolactone (epsilon-CL) is 1: 3;
adding a catalyst accounting for 0.1-0.2% of the weight of the reaction system into the reaction system, and then reacting for 18-24h at 130-140 ℃ under a vacuum condition to obtain a copolymer crude product; preferably, the catalyst comprises a nitrogen-nitrogen donor guanidine zinc catalyst, which has the advantages of no toxicity, simple synthesis method and the like, and compared with the common catalyst, namely stannous octoate, in the existing polylactic acid production, the catalyst has better ultrahigh molecular activity and faster catalytic reaction rate, and the produced polymer has better material stability and high molecular weight;
purifying the crude copolymer product, and drying the purified product in a vacuum drying oven at 40-50 ℃ (preferably 45 ℃), so as to finally obtain the caprolactone-lactic acid random copolymer (P (CL-co-LA)); wherein the step of purifying the crude product comprises: s11, carrying out ultrasonic treatment and/or microwave treatment on the crude product, and precipitating the obtained product by using ethanol with the volume fraction of 90%; s12, repeating the step S111-2 times to finally obtain the purified product, wherein the ultrasonic treatment conditions are as follows: the ultrasonic power is 200-; the microwave treatment conditions are as follows: the microwave power is 200-; thereby, the melt flow ability of the polylactic acid (PLA) is improved by the copolymerization modification of step S1.
S2, preparation of copolymerization modified PLA:
drying PLA; and the melt index of the PLA at 210 ℃ is 20-40g/10 min;
uniformly mixing the dried PLA and P (CL-co-LA), and then carrying out melt blending at the temperature of 180 ℃ and the rotation speed of 50-100r/min to obtain a blend; wherein the mass ratio of the PLA to the P (CL-co-LA) is (9-99): 1, the blending time is 5-10 min;
the blend is placed at the temperature of 190 ℃ of 180 ℃ and under the pressure of 8-10MPa for compression molding, and the copolymerization modified PLA is finally obtained;
s3, preparing non-woven fabric by a melt-blowing method:
taking copolymerization modified PLA, PHBV (copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate) and nano SiO2Blending a compatibilizer and a chain extender to obtain a melt-blown blend; wherein, according to the mass portion, the copolymerization modified PLA: PHBV: nano SiO2: a compatilizer: chain extender ═ 80-95: (1-5): (0.1-0.2): (0.001-0.005): (0.001-0.01); before blending, slicing the copolymerization modified PLA, and drying for 24-48h at 60 ℃ to reduce the water content to be below 0.025%; wherein the compatilizer is composed of one or more of maleic anhydride, butyric anhydride, stearic anhydride and tannic acid, preferably, the compatilizer is composed of maleic anhydride, butyric anhydride, stearic anhydride and tannic acid, and the mass ratio of maleic anhydride: butyric anhydride: stearic anhydride: the tannin is 1:1:1:1, and the chain extender is an ADR chain extender (namely a multi-epoxy chain extender);
adding the melt-blown blend into a screw extruder, and performing melt extrusion granulation at the temperature of 160-;
adding the blended granules into a screw extruder for extrusion, melting and plasticizing, accurately metering by a metering pump, conveying to a spinneret assembly, spraying from spinneret holes of a die head of the spinneret assembly, cooling and drawing by high-speed and high-pressure hot air flow to form a melt-blown non-woven material on a collecting device (such as a receiving plate), performing electret treatment on the melt-blown non-woven material, and performing edge cutting and winding forming to finally obtain a fully-degradable non-woven fabric; wherein the receiving distance from a die head spinneret orifice of the spinneret assembly to the collecting device is 30-50cm, the extrusion frequency of the die head spinneret orifice is 1.5Hz-2.5Hz, and the temperature of the hot air flow is 240-260 ℃; the electret material used for electret treatment is obtained by corona electret, and during the electret treatment, the electret voltage is 30-40kV, the electret distance is 2-4cm, and the electret time is 1-2 min.
In step S1 of this example, the crude product may be subjected to ultrasonic treatment and/or microwave treatment to perform assisted purification, thereby increasing the yield of the copolymerization modified product, i.e., P (CL-co-LA). The crude product is optimized for the secondary purification step by setting different purification modes and conditions for the crude product, and the specific settings are shown in table 1.
TABLE 1 influence of different auxiliary purification conditions on P (CL-co-LA) yield
Auxiliary purification conditions
Average yield (% of P (CL-co-LA))
-
81％
Ultrasonic treatment (power 300W, treatment time 1h)
92％
Microwave treatment (Power 250W, treatment time 1h)
85％
Ultrasonic treatment + microwave treatment
95％
Note: "-" indicates that the crude product was used as P (CL-co-LA) without any additional purification treatment.
As can be seen from table 1, when no auxiliary purification method is used, the average yield of the caprolactone-lactic acid random copolymer P (CL-co-LA) is only about 81%, the ultrasonic treatment or the microwave treatment can improve the yield of the product to some extent, and the product yield is the highest after the ultrasonic treatment or the microwave treatment are performed together, therefore, in step S11, the crude product is preferably subjected to the ultrasonic treatment and the microwave treatment, and the ultrasonic treatment conditions are as follows: the ultrasonic power is 300W respectively, and the processing time is 1 h; the microwave treatment conditions were: the microwave power is 250W, and the processing time is 1 h.
Further, this example also optimizes the mass ratio of PLA and P (CL-co-LA) (i.e., PLA/P (CL-co-LA)) in step S2, thereby discussing the effects thereof on the tensile strength and glass transition temperature of the co-modified PLA to obtain the co-modified PLA with the best performance, and the optimal arrangement is shown in table 2. Wherein, the tensile strength of the copolymerization modified PLA is tested according to the tensile strength test mode of GB/T1040-2006, the tensile rate is 10mm/min, and the glass transition temperature of the copolymerization modified PLA is tested by adopting a DMA test method, namely a film tensile mode, the frequency is 1Hz, the heating rate is 3 ℃/min, and the amplitude is 15 mu m.
TABLE 2 influence of PLA/P (CL-co-LA) on the Co-modified PLA
PLA/P(CL-coLA)
Tensile Strength (MPa)
Glass transition temperature (. degree. C.)
100/0
61
81
99/1
73
65
97/3
66
72
95/5
60
73
90/10
51
81
As can be seen from Table 2, as the P (CL-co-LA) content increased, the tensile strength of the blend increased first and then decreased. When the mass fraction of P (CL-co-LA) is less (1%), the P (CL-co-LA) is uniformly dispersed among PLA molecular chains, occupies gaps among the PLA molecular chains, and molecular chains are more tightly stacked, so that the tensile strength of the copolymerization modified PLA is improved; when the addition amount of P (CL-co-LA) continues to increase, P (CL-co-LA) coalesces, and the plasticizing effect plays a dominant role, so that the tensile strength of the co-modified PLA decreases with the increase in the addition amount of P (CL-co-LA). After the copolymerized PLA is tested by using DMA, the tendency that the glass transition temperature of the copolymerized PLA is firstly reduced and then increased is obtained, and when the mass ratio of P (CL-co-LA) is 99/1, the glass transition temperature is the lowest, which shows that the addition of a small amount of P (CL-co-LA) can play a role in internal lubrication, the glass transition temperature is reduced, and the result is consistent with the stretching result. In summary, in step S2, PLA and P (CL-co-LA) are mixed in a mass ratio of 99: 1, mixing uniformly.
Further, in step S3, since PLA molecules contain hydrophilic ester groups and have a water content of 0.4% to 0.6%, the molten PLA is degraded in the presence of water at a very high rate, which further causes the molecular weight of PLA to decrease and the molecular weight distribution to widen, thereby producing a molecular weight and a distribution thereof that are not suitable for spinning. On the other hand, the polymer fluid channel is closed in the melt spinning process, when the polymer is heated and melted, the presence of moisture not only affects the viscosity of the melted polymer and the extrusion state of the fluid, but also may form many tiny bubbles in the polymer, and these bubbles may cause filament breakage in the drawing process, and at the same time, have extremely adverse effects on the mechanical properties of the product, the fiber diameter and the like.
The water content of the slices, the drying time and the drying temperature are main factors influencing the thermal degradation of the PLA, and the higher the water content of the slices is, the higher the degradation degree is and the higher the degradation speed is; the longer the drying time, the greater the degree of degradation; the higher the drying temperature, the faster the degradation rate and the greater the degree of degradation. Therefore, in step S3, before blending, the co-modified PLA is dried to reduce its water content, and table 3 shows the optimal setting of the slicing and drying conditions for the co-modified PLA at a drying temperature of 60 ℃.
TABLE influence of different drying times at 360 ℃ on the Water content of the Co-modified PLA pellets
Drying time (h)
Average water content of copolymerized and modified PLA (polylactic acid) slices
12
0.135％
24
0.073％
36
0.057％
48
0.015％
Thus, in step S3, the co-modified PLA pellets are preferably dried at 60 ℃ for 48 hours to reduce their water content to 0.025% while avoiding thermal degradation.
Meanwhile, in step S3, copolymerization modified PLA, PHBV (3-hydroxybutyrate and 3-hydroxyvalerate) are addedCopolymer of ester), nano SiO2The compatilizer and the chain extender are blended to perform blending modification and chain extension modification, and in the process of further obtaining the melt-blown blend, the embodiment also optimizes the proportion of the components to investigate the influence of the components on the performance of the finally obtained fully-degradable non-woven fabric, wherein table 4 shows the influence of the mass ratio of the copolymerized modified PLA and the PHBV on the performance of the fully-degradable non-woven fabric.
TABLE 4 copolymerization modified PLA/PHBV/compatibilizer/chain extender/SiO2Mass ratio of
Numbering
Copolymerization modified PLA
PHBV
Compatilizer
Chain extender
Nano SiO2
1
100
-
-
-
-
2
95
5
0.005
0.01
0.2
3
90
4
0.005
0.01
0.2
4
85
3
0.005
0.01
0.2
5
80
1
0.005
0.01
0.2
On the basis, the mechanical properties of the finally obtained fully-degradable nonwoven fabric were measured by using a model YG028-500 brute force machine, and the results are shown in Table 5.
TABLE 5 influence of the mass ratio of the copolymerized modified PLA and PHBV on the mechanical properties of the fully-degradable nonwoven fabrics
Sample sequenceNumber (C)
Longitudinal strength (N)
Transverse strength (N)
Longitudinal elongation (%)
Transverse elongation (%)
1
12.04
7.61
15.08
17.40
2
11.78
7.54
27.16
32.78
3
11.54
7.53
45.44
47.57
4
11.24
7.14
51.27
49.48
5
10.24
6.98
67.15
61.28
In the processing procedures of mixing, extruding, injection molding, spinning and the like, due to the action of heat, moisture and impurities, the macromolecular chains of PLA can be broken, so that the performance of the material is reduced, and active groups (terminal carboxyl groups and terminal hydroxyl groups) are generated at the broken parts of the PLA molecular chains. The chain extender can generate coupling and branching reaction with an active end group generated at a molecular chain fracture position by depending on an active epoxy group of the chain extender, so that the length of a molecular chain is increased, more long-chain branches are obtained, and the processing stability of PLA is improved.
As can be seen from Table 5, with the addition of PHBV, the transverse strength and the longitudinal strength of the fully degradable nonwoven fabric are slightly reduced, but the longitudinal elongation and the transverse elongation are greatly improved, which indicates that the blending of PHBV and copolymerized modified PLA can exert respective performance advantages. Simultaneously adding a small amount of nano SiO with good dispersibility2Can play a good role in strengthening and toughening. From the point of micromechanics, the rigid nano particles can be uniformly dispersed in the polymer, when the polymer is subjected to an external force, a stress concentration effect is generated due to the existence of the rigid inorganic particles, the surrounding polymer is easily excited to generate micro cracks (or silver lines) to absorb certain deformation work, meanwhile, the polymer among the particles also generates yield and plastic deformation to absorb impact energy, and in addition, the existence of the rigid particles enables the crack of the polymer to be blocked and passivated and finally stopped without being developed into destructive cracking, so that the reinforcing and toughening effect is generated. In summary, in the melt-blown blend of step S3, the mass ratio of the copolymerized modified PLA to PHBV is preferably 80: 1.
Further, in the copolymerization modified PLA: PHBV: nano SiO2: chain extender 80: 1: 0.2: on the premise of 0.01, the influence of different compatilizers on the mechanical properties of the fully-degradable non-woven fabric is examined, the test process of the mechanical properties of the fully-degradable non-woven fabric is the same as that of the fully-degradable non-woven fabric, and the results are shown in table 6.
TABLE 6 influence of different compatibilizer compositions on mechanical Properties of fully degradable nonwoven fabrics
Most of the compatilizer contains polar groups, and the polar groups in the compatilizer can be subjected to esterification reaction or hydrogen bond formation, so that the polarity and the hygroscopicity of the filler are reduced. And the compatilizer also contains a nonpolar chain segment with good compatibility with the polymer, and plays a role similar to a bridge, so as to effectively bond the filler and the polymer together and improve the interface bonding performance of the filler and the polymer. As can be seen from table 6 above, the optimal ratio of the compatibilizer is, by mass, maleic anhydride: butyric anhydride: stearic anhydride: under the condition that tannic acid is 1:1:1:1, the longitudinal strength, the transverse strength, the longitudinal elongation and the transverse elongation of the fully-degradable non-woven fabric are maximum values.
As can be analyzed from tables 4-6, PHBV has low tensile strength and modulus, and PLA has the characteristics of high strength and high modulus, but due to inherent brittleness, low elongation at break, low impact strength, easy bending deformation and the like, the toughness of the non-woven fabric can be improved while the degradation performance of the material is maintained after the PHBV is blended with the copolymerization modified PLA. Meanwhile, in order to further increase the two-phase structure of the copolymerization modified PLA and PHBV blend, a compatilizer (one or more of maleic anhydride, butyric anhydride, stearic anhydride and tannic acid) is added into a PLA/PHBV blend system, so that the PLA and the PHBV can be better blended, and the respective performance advantages are exerted. In addition, PLA belongs to a crystalline polymer, long chain branches in a molecular chain are few, the branching degree is low, a PLA melt is sensitive to temperature, thermal oxidative degradation or hydrolysis is easy to occur in the processing process, molecular chain breakage is caused, all the factors cause that the melt viscosity and the melt strength of the PLA are low, the melt viscoelasticity is poor, strain hardening is insufficient, and the processing technology of the PLA is limited, so that the relative molecular quality of the PLA can be improved by adding a chain extender, and on the other hand, a long chain branch structure is introduced into the PLA molecule, so that the melt strength of the PLA is improved, and the processing performances of film blowing, blow molding, foaming and the like of the PLA are improved.
Further, in the copolymerization modified PLA: PHBV: nano SiO2: a compatilizer: chain extender 80: 1: 0.2: 0.003: on the premise of 0.01, the embodiment also optimizes the relevant melt-blown parametersIncluding the receiving distance of the die orifice of the orifice assembly to the collection device (i.e., "receiving distance"), the extrusion frequency of the die orifice (i.e., "extrusion frequency"), the temperature of the hot air stream (i.e., "hot air temperature"), are set in the manner specified in table 7, to examine the effect thereof on the properties of the meltblown product.
TABLE 7 optimized setting of receiving distance, extrusion frequency and hot air temperature
The effect of different take-up distances, hot air temperatures, extrusion frequencies on the diameter of the meltblown fibers was examined on the basis of table 7.
Fiber diameter testing: the size of the fiber diameter and its distribution directly affect the nonwoven pore size and pore size distribution and thus the filtration performance (filtration efficiency and filtration resistance) of the material. The fiber diameter is difficult to directly measure, and Smile-view software is adopted to measure the diameter of the fibers shot by a non-woven fabric scanning electron microscope to obtain the size and the distribution of the fiber diameter. Fiber diameters were first measured at 50 different locations in each specimen and averaged to reduce test error.
Effect of take-up distance on melt blown nonwoven fiber diameter
The parameter setting method and the test results are shown in Table 8.
TABLE 8 influence of different take-up distances on the fiber diameter of meltblown nonwovens
Receiving distance (cm)
Average diameter (μm)
CV value (%)
30
2.4
27.9
40
1.2
26.4
50
1.0
21.6
The nonwoven fabric fibers produced by melt blowing in step S3 have a three-dimensional cross distribution, and as can be seen from table 8, the larger the receiving distance, the smaller the fiber diameter, and when the receiving distance is increased from 30cm to 50cm, the average diameter of the fibers is decreased from 2.4 μm to 1.0 μm, mainly because when the receiving distance is smaller, the fibers are not effectively drawn and not sufficiently cooled, the degree of fiber entanglement increases, and a doubling phenomenon occurs, and the longer the drawing time of the fibers from the spinneret to the cylinder increases the receiving distance, the lower the fiber-to-fiber bonding force becomes, and the fibers can be sufficiently drawn and cooled, so that the fiber fineness decreases and the doubling phenomenon decreases. In summary, in step S3, the receiving distance from the spinneret orifice of the die head of the spinneret assembly to the collecting device is preferably 40-50 cm.
Effect of Hot air temperature on melt-blown nonwoven fiber diameter
The parameter setting method and the test results are shown in Table 9.
TABLE 9 influence of different hot air temperatures on the fiber diameter of meltblown nonwoven
Temperature of Hot air (. degree. C.)
Average diameter (μm)
CV value (%)
240
2.5
26.9
250
1.2
26.4
260
1.9
28.9
In the melt-blowing process, the temperature of the hot air is generally set to be slightly higher than the temperature of the die head in order to avoid the rapid temperature drop of the fibers after the fibers are sprayed from the spinneret orifices, so that the fibers cannot be further drawn. As can be seen from table 9, the fiber diameter of the fiber was large as a whole at a hot air temperature of 240 ℃, while the fiber diameters at 250 ℃ and 260 ℃ were relatively small, and tended to decrease and then increase. On one hand, the proper increase of the temperature of the hot air can prolong the cooling time of the fiber in the air, which is beneficial to better drafting; on the other hand, as the temperature increases, the viscosity of the melt gradually decreases, and the melt is more likely to be drawn down to be thinner, so that the fiber diameter is reduced. When the temperature of the hot air is continuously increased, although the fineness of a single fiber is reduced by the drafting effect, the activity degree of molecular chains of the fiber is intensified at the moment, and the fiber is doubled in the drafting process, so that the average diameter of the fiber is slightly increased. In summary, in step S3, the temperature of the hot air stream is preferably 250 ℃.
Extrusion frequency vs. melt blown nonwoven fibersInfluence of dimensional diameter
The parameter setting method and the test results are shown in Table 10.
TABLE 10 Effect of different extrusion frequencies on melt blown nonwoven fiber diameter
Extrusion frequency (Hz)
Average diameter (μm)
CV value (%)
1.5
1.1
25.8
2
1.2
26.4
2.5
2.1
33.1
As can be seen from table 10, when the extrusion frequency is 2.5Hz, the diameter of the fiber is large and the fiber is not uniformly distributed, mainly because the increase of the extrusion frequency increases the amount of the fiber ejected from the spinneret orifice, and the fiber is not uniformly drawn during the drawing process, which leads to serious differentiation of the fiber thickness. When the extrusion frequency was increased from 1.5Hz to 2.5Hz, the fiber diameter was increased from 1.1 μm to 2.1. mu.m, mainly because the amount of melt stored in the extruder per unit time was increased and the melt was not completely melted in the extruder, resulting in an increase in the fiber diameter as the extrusion frequency was increased. In view of this, in step S3, the extrusion frequency of the die orifice is preferably 1.5 to 2 Hz.
The influence of different receiving distances, hot air temperatures and extrusion frequencies on the air permeability and average pore size and thickness of the fully-degraded non-woven fabric obtained by melt-blowing is examined on the basis of table 7, wherein relevant tests can be performed by reference to standards such as GB/T24218.15-2018, GB/T24218.2-2009 and the like.
The effect of different take-up distances, hot air temperatures, extrusion frequencies on the air permeability and average pore size of the fully degraded nonwovens obtained by melt blowing is shown in table 11.
TABLE 11 influence of acceptance distance, Hot air temperature, extrusion frequency on air Permeability and average pore size of fully-degradable nonwoven fabrics
When a disposable mask is manufactured using a nonwoven fabric, the mask is required to have good air permeability. As can be seen from table 11, the nonwoven fabric finally obtained had a larger air permeability and a smaller average pore diameter under any conditions.
The effect of different take-up distances, hot air temperatures, extrusion frequencies on the thickness of the fully degraded nonwoven obtained by melt blowing is shown in table 12.
TABLE 12 influence of receiving distance, hot air temperature, extrusion frequency on thickness of fully degradable nonwoven fabrics
As can be seen from table 12, the thickness of the nonwoven fabric increases with increasing take-up distance, which is mainly related to the fiber diameter and the bulk of the web. The thickness of the non-woven fabric is slightly increased along with the increase of the temperature of the hot air, because the bonding effect among the fibers is strong when the temperature is lower, the fiber web structure is compact and small, the temperature is increased, the bonding effect among the fibers is weak, and the fiber web structure is fluffy and has larger thickness. As the frequency of extrusion increases, the thickness of the nonwoven increases because the frequency of extrusion causes poor fiber bonding and the web becomes lofty and increases in thickness.
Further, the filtration efficiency of the non-woven fabric can be improved through the electret, and therefore, the present embodiment also considers the influence of the electret treatment conditions on the filtration performance of the non-woven fabric, wherein 3 experimental groups are set to prepare the fully-degradable non-woven fabric by referring to the melt-blown method in the present embodiment, except that in the melt-blown blend corresponding to the experimental group 1, the experimental group 2 and the experimental group 3, the copolymerization modified PLA: PHBV: nano SiO2: a compatilizer: the chain extenders are respectively 80: 1: 0: 0.003: 0.01, 80: 1: 0.1: 0.003: 0.01, 80: 1: 0.2: 0.003: 0.01, and when each experimental group carries out the step S3 in the process of producing the fully-degradable non-woven fabric, taking part of the melt-blown non-woven material to carry out electret treatment, and not carrying out the electret treatment on the rest part, wherein the conditions of the electret treatment are set as follows: the electret voltage is 40kV, the electret distance is 3cm, the electret time is 1min, and other residual conditions are set to be the same.
And then, carrying out electrostatic potential test on the surface of the fully-degradable non-woven fabric finally obtained by each experimental group by using a YG401 fabric induction type electrostatic tester, wherein the number of samples of the non-woven fabric obtained without electret treatment and the non-woven fabric obtained after the electret treatment is 5, the distance between a probe and a test sample is 15mm, the rotating speed of a turntable is 1500rpm, and the test results are shown in Table 13.
TABLE 13 filtration Performance of fully degradable nonwoven fabrics
As can be seen from table 13 above, the filtration efficiency of the nonwoven fabric obtained without electret treatment is only about 40% through testing, and the filtration efficiency of the nonwoven fabric obtained through electret treatment can reach more than 90%. Therefore, after electret treatment, the filtration efficiency is obviously improved due to the increase of the surface charge of the melt-blown fiber net. Meanwhile, as can be seen from the test results, experimental group 3 has better filtration performance, which indicates that when the melt-blown blend is copolymerized with modified PLA: PHBV: nano SiO2: a compatilizer: the chain extender is 80: 1: 0.2: 0.003: 0.01 time the nonwoven fabric has the best filtering performance。
Furthermore, the non-woven fabrics after electret treatment in each group are taken and subjected to heating and water soaking treatment at room temperature, the charge intensity and the filtering efficiency are not reduced, and the filtering efficiency does not decay with time.
After detection, the non-woven fabric subjected to electret treatment in the embodiment is taken, and the number of the superposed layers is increased from 1 layer to 3 layers, so that the particle filtering efficiency is increased from 90% to 99.99%, and the 3-grade standard of the medical mask can be completely met. The number of the superimposed layers is increased from 1 to 3, the airflow resistance is increased from 78.6Pa to 247.1 under the condition that the gas flow is 85L/min, and the air suction resistance of the medical mask is not more than 343.2Pa (35mm H)2O). It can be seen that the filtration efficiency can be increased by superimposing the number of layers of the nonwoven fabric obtained by the electret treatment in this example.
Example 2:
this example also provides an application of the fully degradable non-woven fabric of example 1 in the preparation of a medical mask, that is, the medical mask is prepared from the fully degradable non-woven fabric of example 1, and the medical surgical mask may have a plurality of layers, wherein the innermost layer and the outermost layer are both made of non-woven fabric, and at least one layer of the non-woven fabric produced by the melt-blown method of example 1 is provided in the middle as a filter layer.
Further, the performance of the medical mask was evaluated according to the following criteria.
1. Efficiency of filtration
Under the condition that the gas flow is 85L/min, the filtering efficiency of the mask on the non-oily particles meets the requirement of the table 14.
TABLE 14 grading of non-oily particle filtration efficiency by mask
Grade
The filtration efficiency%
Level 1
≥95
Stage 2
≥99
Grade 3
≥99.97
2. Resistance to airflow
When the gas flow rate is 85L/min, the air suction resistance of the mask should not exceed 343.2Pa (35mm H)2O)。
3. Synthetic blood penetration
2mL of the synthetic blood was sprayed at a pressure of 10.7kPa (80mm Hg) onto the mask, and no permeation should occur inside the mask.
4. Surface moisture resistance
The water-spreading grade of the mask surface is not lower than the 3-grade regulation in GB/T4745-1997, namely the showered surface is wetted by unconnected small areas.
5. Flame retardant properties
The material should not have flammability and the afterflame time should not exceed 5 s.
6. Skin irritation
The primary stimulation integral of the mask material should not exceed 1.
7. Adhesion Property
The mask design should provide good fit, and the mask overall fit factor should be no less than 100.
Through detection, the performance of the medical mask in the embodiment can meet the requirements.
In summary, the nonwoven fabric of the present application is made of materials such as PLA, PHBV, and SiO nanoparticles2The compatilizer, the chain extender and the like are all fully degradable raw materials, so that the finally obtained non-woven fabric can be fully degraded and can be used for manufacturing medical consumables such as medical masks, and the environment cannot be polluted after the non-woven fabric is used and discarded; meanwhile, the PLA is subjected to gradient multiple modification, namely, the PLA and the epsilon-caprolactone are subjected to co-modificationPoly-modification, the obtained product is further mixed with PHBV and nano SiO2The method comprises the following steps of mixing a compatilizer and a chain extender to perform blending modification and chain extension modification, so that the structure of PLA polylactic acid is changed, the performance of a polymer is changed, ultrasonic/microwave treatment and electret treatment are added in the modification process, and various melt-blown parameters (such as receiving distance, hot air temperature, extrusion frequency and the like) are optimally set, so that various performance indexes of finally obtained non-woven fabrics are improved, such as mechanical property, air permeability, fiber strength, filtering efficiency and the like are improved, and the quality standard of consumables such as medical masks is met.
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
