CN115716977A - Preparation method of full-biodegradable nano composite material, product and application thereof - Google Patents
Preparation method of full-biodegradable nano composite material, product and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a full-biodegradable nano composite material, which comprises the following steps: s1: mixing rigid biodegradable polyester and a composite polyester modifier, and performing extrusion granulation to obtain modified rigid biodegradable polyester; the composite polyester modifier comprises epoxidized linseed oil and maleated linseed oil; s2: mixing the nano filler and the filler modifier uniformly, and carrying out intercalation treatment to obtain a modified nano filler; the filler modifier is selected from dihydrogenated tallow dimethyl ammonium chloride; s3: uniformly mixing the flexible biodegradable polyester, the modified rigid biodegradable polyester, the modified nano filler, the compatibilizer and the selectively added processing aid, and then extruding and granulating to obtain the fully biodegradable nano composite material. The fully biodegradable nano composite material prepared by the invention has the advantages of bending strength and bending modulus comparable to those of nylon, excellent toughness, complete biodegradation and capability of being used for preparing grass mowing ropes and being used in the field of handheld weeders.
Description
Technical Field
The invention relates to the technical field of full-biodegradable materials, in particular to a preparation method of a full-biodegradable nano composite material, a product thereof and application of the full-biodegradable nano composite material as a grass rope.
Background
The handheld weeding machine is widely used in the fields of landscaping and agriculture, realizes agricultural mechanization and improves agricultural production efficiency. The electric grass mowing machine has the working principle that a rotating shaft driven by electric power drives a special high-polymer wire (grass mowing rope) rope arranged on a rotating disc to rotate at a high speed, the grass mowing rope is driven by the electric power to drive the grass mowing rotating disc to rotate at a high speed through a transmission system, the grass mowing rope is synchronously adjusted and rotated, cutting-off weeds is achieved by the cutting force, and the effect of weeding is achieved.
Based on the working principle, the grass mowing rope is required to have excellent mechanical strength and high toughness, the existing grass mowing rope material is usually selected from nylon, the grass mowing rope made of large-batch nylon can be randomly broken in the field along with the increase of the using time, the degradation period of the nylon is long and is about 30-40 years, the micro plastic formed by disintegration of the nylon can become a transport carrier of pollutants, pathogenic bacteria and harmful microorganisms and is further fixed in soil, and the nutrient exchange between the soil and plants is blocked to influence the biological diversity of the soil, and the function of a land ecosystem is seriously or even influenced.
Therefore, it is highly desirable to develop a material with material properties comparable to those of nylon and complete biodegradability for the preparation of grass ropes.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a full-biodegradable nano composite material, the bending strength and the bending modulus of the prepared product can be comparable to those of nylon, and the product has excellent toughness, can realize full biodegradation, and can be used for preparing a grass mowing rope for the field of handheld weeders.
The specific technical scheme is as follows:
a preparation method of a full-biodegradable nano composite material comprises the following steps:
s1: mixing rigid biodegradable polyester and a composite polyester modifier, and performing extrusion granulation to obtain modified rigid biodegradable polyester;
the rigid biodegradable polyester is selected from polylactic acid and/or polyglycolic acid;
the composite polyester modifier comprises epoxidized linseed oil and maleated linseed oil;
s2: mixing the nano filler and the filler modifier uniformly, and performing intercalation treatment to obtain a modified nano filler;
the nano filler is selected from one or more of organic nano montmorillonite, nano bentonite and nano diatomite;
the filler modifier is selected from dihydrogenated tallow dimethyl ammonium chloride;
s3: uniformly mixing flexible biodegradable polyester, modified rigid biodegradable polyester, modified nano filler, compatibilizer and optionally added processing aid, and then extruding and granulating to obtain the fully biodegradable nano composite material;
the flexible biodegradable polyester is selected from polybutylene succinate and/or polybutylene succinate-adipate.
The invention discloses a preparation method of a full-biodegradable nano composite material, which comprises the steps of respectively carrying out special modification treatment on rigid biodegradable polyester and nano filler, then carrying out blending, extrusion granulation with other raw materials such as flexible biodegradable polyester and the like. Tests show that the two-step modification treatment is particularly critical, in the step S1, a composite polyester modifier with special composition is adopted, and if the composite polyester modifier is changed into a single component or the two components are replaced by conventional choices in the field, such as the compounding of epoxidized soybean oil and maleated soybean oil, the mechanical property of the finally prepared product can be influenced; in the step S2, a special filler modifier, namely dihydrogenated tallow dimethyl ammonium chloride is adopted, and tests show that the nano filler modified by the special filler modifier has a proper interlayer spacing (3.0-3.4 nm) and the mechanical property of the finally prepared product is better; without modification of the nanofiller or with an intercalating agent as is conventional in the art, such as cetyltrimethylammonium salt, the interlayer spacing does not meet the above requirements.
In step S1:
the mass ratio of the rigid biodegradable polyester to the composite polyester modifier is 1.5-3: 1;
the mass ratio of the epoxidized linseed oil to the maleated linseed oil is 1-3: 1.
in the step S1, the modification degree of the composite polyester modifier to the rigid biodegradable polyester is proper by adopting lower extruder temperature and matching weak shearing action.
Preferably:
the extrusion granulation is carried out, the extrusion temperature is 130-150 ℃, the screw rotating speed is 500-800 rpm, and the length-diameter ratio is 40-50;
the melt index of the modified rigid biodegradable polyester obtained after extrusion granulation is not higher than 1g/10min.
Tests show that if the processing technology is not appropriate, the mechanical property of the finally prepared product can be obviously influenced.
In step S2:
tests show that the interlayer spacing of the nano filler can be enlarged to 3.0nm or more by adopting the special filler modifier; the interlayer spacing increases with the amount of filler modifier or the mixing temperature. When tested, it was also found that if the layer spacing is too large, this may lead to a reduction in the degradation properties of the final product. Therefore, it is preferable to control the interlayer distance of the modified nanofiller to be between 3.0 and 3.4.
Preferably, the mass ratio of the nano filler to the filler modifier is 4-9: 1; more preferably 4 to 7:1.
if the kneading temperature is too high, side reactions may occur, and it is preferable to control the kneading temperature to 150 to 180 ℃.
Tests also show that the interlayer spacing of the modified nano-filler prepared by adopting the intercalation agent variety commonly used in the field, such as hexadecyl trimethyl ammonium salt, is still less than 3.0nm even if the mixing temperature is increased to 180 ℃.
Preferably, the nanofiller is selected from organic nanomontmorillonites.
In the step S3, the fully biodegradable nano composite material comprises the following raw materials in parts by weight:
in the step S3, the slightly higher temperature of the extruder is adopted, and the extruder is matched with equipment with medium shearing action and larger length-diameter ratio, so that the retention time of the materials is increased, and the crosslinking reaction is more sufficient.
Preferably, the following components:
the temperature of the extruder is 160-180 ℃, the rotating speed of the screw is 200-500 rpm, and the length-diameter ratio is 50-64.
In step S3:
the reactive compatibilizer is selected from diphenylmethane diisocyanate and/or lysine triisocyanate.
Tests show that the addition of the reactive compatibilizer can control the crosslinking degree of the system, has certain influence on mechanical properties, and more importantly, the degradation time of the material can be adjusted to meet market demands.
According to actual production conditions, different processing aids such as lubricants, nucleating agents, antioxidants and the like can be selectively added. Are selected from the conventional types in the field and have no special requirement.
On the basis of the above preferred raw material types, preferably, the raw material composition of the fully biodegradable nanocomposite material comprises:
tests show that the fully biodegradable nano composite material prepared by the weight parts has excellent impact strength, bending strength and bending modulus, and can be completely degraded by microorganisms in a soil environment.
Further preferably, the raw materials comprise:
more preferably, the raw material composition comprises:
with the continuous optimization of the raw material composition, the prepared fully biodegradable nano composite material has more excellent performance.
The invention also discloses the full-biodegradable nano composite material prepared by the method, and tests show that the flexural modulus, the flexural strength and the notch impact strength of the product are respectively not lower than 2200MPa, 45MPa and 30KJ/m 2 . When the grass-mowing rope prepared by the full-biodegradable nano composite material meeting the mechanical property requirements is used for a handheld weeding machine, the grass-mowing rope can be ensured not to break after being continuously used for 60 min. In the application of the full-biodegradable nano composite material disclosed by the invention as a grass cutting rope, the bending modulus, the bending strength and the notch impact strength are most concerned; when the notch impact strength is not lower than 30KJ/m 2 The higher the flexural modulus and the higher the flexural strength, the better.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a full-biodegradable nano composite material, which respectively modifies rigid biodegradable polyester and nano filler through a special modification treatment process. The prepared full-biodegradable nano composite material has excellent mechanical property, can be compared favorably with nylon, and can realize complete biodegradation. Is hopeful to be used for preparing the grass mowing rope for the field of handheld weeders.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
The following examples and comparative examples each employ the following test methods.
Notched impact strength: ASTM D256-2010E1;
bending strength: GB/T9341-2008;
flexural modulus: GB/T9341-2008;
degradation rate: GB/T41010-2021;
in the present invention, all the raw materials are in terms of mass unless otherwise specified.
Example 1
S1, drying 25 parts of polylactic acid (Fengyuan group, FY 801) in a vacuum oven at 90 ℃ for 12 hours to avoid hydrolysis, adding a mixture of 5 parts of epoxidized linseed oil and 5 parts of maleated linseed oil into a stirrer, uniformly stirring to obtain a mixed product, adding the mixed product into a double-screw extruder from a main feed, matching the temperature of the extruder and a weak shearing action, controlling the temperature of a first zone to a tenth zone of the extruder to be 130-150 ℃, controlling the temperature of a die head to be 150 ℃, controlling the rotating speed of a screw to be 800rpm and controlling the length-diameter ratio to be 40, obtaining modified polylactic acid after extrusion, and testing to obtain the modified polylactic acid with the melt index of 0.6g/10min (the testing condition is 190 ℃/2.16 kg);
s2, uniformly mixing 12 parts of organic nano montmorillonite and 3 parts of dihydrogenated tallow dimethyl ammonium chloride, shearing and mixing at the temperature of 150 ℃ to obtain powdery modified nano montmorillonite, and performing X-ray diffraction test analysis and Bragg equation calculation to obtain the interlayer spacing of 3.2nm;
s3, uniformly mixing 50 parts of poly (butylene succinate-butylene succinate) (TH 803S), 35 parts of modified polylactic acid prepared in the step S1, 15 parts of modified nano montmorillonite prepared in the step S2, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide, adding the mixture from a main feed inlet of a double-screw extruder, and matching the temperature of the extruder and the medium shearing action, wherein the temperature of a region I to a region 16 of the extruder is 160-180 ℃, the die head temperature is 170 ℃, the screw rotating speed is 300rpm, and the length-diameter ratio is 64, so as to obtain the fully biodegradable nano composite material after extrusion.
Comparative example 1
The preparation process is substantially the same as that in example 1, except that in step S1, 10 parts of epoxidized linseed oil is used instead of the composite polyester modifier consisting of 5 parts of epoxidized linseed oil and 5 parts of maleated linseed oil.
Comparative example 2
The preparation process is substantially the same as that in example 1, except that in step S1, 10 parts of maleated linseed oil is used instead of the composite polyester modifier consisting of 5 parts of epoxidized linseed oil and 5 parts of maleated linseed oil.
Comparative example 3
The preparation process was substantially the same as in example 1 except that in step S1, 5 parts of epoxidized soybean oil and 5 parts of maleated soybean oil were used instead of the original composite polyester modifier.
Comparative example 4
The preparation process is essentially the same as in example 1, except that in step S1, the twin-screw extruder process parameters are replaced by: the temperature of the first zone to the fifteenth zone of the extruder is 160-180 ℃, the die head temperature is 180 ℃, the screw rotating speed is 300rpm, and the length-diameter ratio is 60.
Comparative example 5
Step S1 is exactly the same as in example 1;
s2: 50 parts of poly (butylene succinate) (TH 803S) and 35 parts of modified polylactic acid prepared in the step S1, 15 parts of nano montmorillonite, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide are uniformly mixed and then added from a main feeding port of a double-screw extruder, the temperature of the extruder and the temperature of a region I to a region 16 are matched with the temperature and the medium shearing action of the extruder, the temperature of a die head is 170 ℃, the rotating speed of the screw is 300rpm, the length-diameter ratio is 64, and the fully biodegradable nano composite material is obtained after extrusion.
Comparative example 6
The preparation process was substantially the same as in example 1 except that, in step S2, dihydrogenated tallow dimethyl ammonium chloride was replaced with an equal mass part of hexadecyl trimethyl ammonium salt. The interlayer spacing of the prepared modified nano filler is 2.4nm through X-ray diffraction test analysis and Bragg equation calculation.
Comparative example 7
The preparation process was substantially the same as in example 1 except that in step S2, dihydrogenated tallow dimethyl ammonium chloride was replaced with an equal mass part of hexadecyl trimethyl ammonium salt while the mixing temperature was increased to 180 ℃. The interlayer spacing of the prepared modified nano filler is 2.5nm through X-ray diffraction test analysis and Bragg equation calculation.
Comparative example 8
S1, uniformly mixing 12 parts of organic nano montmorillonite and 3 parts of dihydrotallow dimethyl ammonium chloride, and shearing and mixing at the temperature of 150 ℃ to obtain powdery modified nano montmorillonite;
s2, uniformly mixing 50 parts of polybutylene succinate (Tunhe group, TH 803S), 25 parts of polylactic acid (Fengyuan group, FY 801), 5 parts of epoxidized linseed oil, 5 parts of maleated linseed oil, 15 parts of modified nano montmorillonite prepared in the step S1, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide, adding the mixture from a main feeding port of a double-screw extruder, matching with the temperature of the extruder and medium shearing action, wherein the temperature of a first zone to a 16 zone of the extruder is 160-180 ℃, the temperature of a die head is 170 ℃, the rotating speed of a screw is 300rpm, the length-diameter ratio is 64, and extruding to obtain the fully biodegradable nano composite material.
Comparative example 9
50 parts of poly (butylene succinate) (TH 803S) group, 25 parts of polylactic acid (Fengyuan group, FY 801), 5 parts of epoxidized linseed oil, 5 parts of maleated linseed oil, 15 parts of nano montmorillonite, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide are uniformly mixed and then added from a main feeding port of a double-screw extruder, the temperature of the extruder and the medium shearing action are matched, the temperature of a region I to a region 16 of the extruder is 160-180 ℃, the temperature of a die head is 170 ℃, the rotating speed of the screw is 300rpm, the length-diameter ratio is 64, and the fully biodegradable nano composite material is obtained after extrusion.
Example 2
The preparation process is substantially the same as in example 1, except that in step S1, the amount of epoxidized linseed oil is replaced by 7.5 parts, and the amount of maleated linseed oil is replaced by 2.5 parts.
Example 3
In the step S1, the usage amount of the polylactic acid is replaced by 18 parts, the usage amount of the epoxidized linseed oil is replaced by 6 parts, the usage amount of the maleated linseed oil is replaced by 6 parts, and the process parameters of the extruder are completely the same as those in the example 1;
step S2 is the same as in example 1;
in step S3, 55 parts of polybutylene succinate (TH 803S), 30 parts of modified polylactic acid prepared in step S1, 15 parts of modified nano montmorillonite prepared in step S2, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide are uniformly mixed and then added from a main feeding port of a double-screw extruder, the temperature of the extruder is 170-180 ℃, the temperature of a die head is 180 ℃, the rotating speed of a screw is 300rpm and the length-diameter ratio is 64, and the fully biodegradable nano composite material is obtained after extrusion.
Example 4
S1, drying 30 parts of polylactic acid (Fengyuan group, FY 801) in a vacuum oven at 90 ℃ for 12 hours to avoid hydrolysis, adding a mixture of 6 parts of epoxidized linseed oil and 4 parts of maleated linseed oil into a stirrer, uniformly stirring to obtain a mixed product, adding the mixed product into a double-screw extruder from a main feed, matching the temperature of the extruder and a strong shearing action, controlling the temperature of an extruder from a first area to a thirteen area to be 130-150 ℃, controlling the temperature of a die head to be 150 ℃, controlling the rotation speed of a screw to be 500rpm and controlling the length-diameter ratio to be 50, obtaining modified polylactic acid after extrusion, and testing to obtain the modified polylactic acid with the melting index of 0.4g/10min (the testing condition is 190 ℃/2.16 kg);
step S2 is exactly the same as in example 1;
s3, uniformly mixing 45 parts of polybutylene succinate (TUNHEO group, TH 803S), 40 parts of modified polylactic acid prepared in the step S1, 15 parts of modified nano montmorillonite prepared in the step S2, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide, adding the mixture from a main feeding port of a double-screw extruder, and matching the temperature of the extruder and the medium shearing action, wherein the temperature of one zone to sixteen zones of the extruder is 170-180 ℃, the temperature of a die head is 180 ℃, the rotating speed of a screw is 300rpm, and the length-diameter ratio is 64, so as to obtain the fully biodegradable nano composite material after extrusion.
Examples 5 to 6
The preparation process is basically the same as that of example 1, except that in step S2, the nano montmorillonite is sequentially replaced by nano bentonite and nano diatomite of equal mass.
The interlayer spacing of the prepared modified nano filler is 3.0nm through X-ray diffraction test analysis and Bragg equation calculation.
Example 7
The preparation process is basically the same as that of example 1, except that in step S2, the mass of the nano montmorillonite is replaced by 13.5 parts, and the mass of the dihydrogenated tallow dimethyl ammonium chloride is replaced by 1.5 parts. The interlayer spacing of the prepared modified nano filler is 3.0nm through X-ray diffraction test analysis and Bragg equation calculation.
Example 8
The preparation process was substantially the same as in example 1 except that the kneading temperature was replaced with 180 ℃ in step S2. The interlayer spacing of the prepared modified nano filler is 3.4nm through X-ray diffraction test analysis and Bragg equation calculation.
Example 9
Step S1 is exactly the same as in example 1;
s2, uniformly mixing 17.5 parts of organic nano montmorillonite and 2.5 parts of dihydrogenated tallow dimethyl ammonium chloride, shearing and mixing at 180 ℃ to obtain powdery modified nano montmorillonite, and performing X-ray diffraction test analysis and Bragg equation calculation test to obtain a layer spacing of 3.1nm;
s3, uniformly mixing 45 parts of polybutylene succinate (Tunghe group, TH 803S), 35 parts of modified polylactic acid prepared in the step S1, 20 parts of modified nano montmorillonite prepared in the step S2, 3 parts of diphenylmethane diisocyanate and 0.3 part of lubricant erucamide, adding the mixture from a main feeding port of a double-screw extruder, matching the temperature of the extruder and medium shearing action, wherein the temperature of one zone to sixteen zones of the extruder is 170-180 ℃, the die temperature is 180 ℃, the rotating speed of a screw is 300rpm, and the length-diameter ratio is 64, and extruding to obtain the fully biodegradable nano composite material.
Example 10
The preparation process was substantially the same as in example 1 except that in step S3, 6 parts by mass of diphenylmethane diisocyanate was replaced.
Example 11
The preparation process was substantially the same as in example 1 except that in step S3, 8 parts by mass of diphenylmethane diisocyanate were replaced.
The data on the properties of the fully biodegradable nanocomposites prepared in each example and each comparative example are shown in the following table 1, and each data is an average value obtained after testing 5 groups.
TABLE 1
The above examples are intended to aid in the understanding of the method and key points of the invention. This summary should not be construed to limit the invention.
Claims (10)
1. A preparation method of a full-biodegradable nano composite material is characterized by comprising the following steps:
s1: mixing rigid biodegradable polyester and a composite polyester modifier, and performing extrusion granulation to obtain modified rigid biodegradable polyester;
the rigid biodegradable polyester is selected from polylactic acid and/or polyglycolic acid;
the composite polyester modifier comprises epoxidized linseed oil and maleated linseed oil;
s2: mixing the nano filler and the filler modifier uniformly, and carrying out intercalation treatment to obtain a modified nano filler;
the nano filler is selected from one or more of organic nano montmorillonite, nano bentonite and nano diatomite;
the filler modifier is selected from dihydrogenated tallow dimethyl ammonium chloride;
s3: uniformly mixing flexible biodegradable polyester, modified rigid biodegradable polyester, modified nano filler, compatibilizer and optionally added processing aid, and then extruding and granulating to obtain the fully biodegradable nano composite material;
the flexible biodegradable polyester is selected from polybutylene succinate and/or polybutylene succinate-adipate.
2. The method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein in step S1:
the mass ratio of the rigid biodegradable polyester to the composite polyester modifier is 1.5-3: 1;
the mass ratio of the epoxidized linseed oil to the maleated linseed oil is 1-3: 1.
3. the method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein the method comprises the following steps:
in the step S1, the extrusion granulation is carried out, wherein the extrusion temperature is 130-150 ℃, the screw rotation speed is 500-800 rpm, and the length-diameter ratio is 40-50;
the melt index of the modified rigid biodegradable polyester obtained after extrusion granulation is not higher than 1g/10min.
4. The method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein in step S2:
the mass ratio of the nano filler to the filler modifier is 4-9: 1;
the mixing temperature is 150-180 ℃.
5. The method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein in step S3, the fully biodegradable nanocomposite material comprises the following raw materials in parts by weight:
6. the method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein in step S3:
the temperature of the extruder is 160-180 ℃, the rotating speed of the screw is 200-500 rpm, and the length-diameter ratio is 50-64.
7. The method for preparing the fully biodegradable nanocomposite material according to claim 1, wherein in step S3:
the reactive compatibilizer is selected from diphenylmethane diisocyanate and/or lysine triisocyanate.
8. The preparation method of the full-biodegradable nano composite material according to claim 5, wherein the raw materials comprise, in parts by weight:
9. a fully biodegradable nanocomposite prepared according to the method of any one of claims 1 to 8.
10. Use of the fully biodegradable nanocomposite according to claim 9 as a grass rope.
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