CN115948035B - Biodegradable particles, preparation method and application - Google Patents
Biodegradable particles, preparation method and application Download PDFInfo
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- CN115948035B CN115948035B CN202310245029.5A CN202310245029A CN115948035B CN 115948035 B CN115948035 B CN 115948035B CN 202310245029 A CN202310245029 A CN 202310245029A CN 115948035 B CN115948035 B CN 115948035B
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- 239000002245 particle Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002667 nucleating agent Substances 0.000 claims abstract description 50
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 22
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 29
- 239000004626 polylactic acid Substances 0.000 claims description 20
- 229920000881 Modified starch Polymers 0.000 claims description 17
- 239000004368 Modified starch Substances 0.000 claims description 17
- 235000019426 modified starch Nutrition 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003094 microcapsule Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical group CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 229940059904 light mineral oil Drugs 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical group [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000007762 w/o emulsion Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000006065 biodegradation reaction Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 45
- 229920001707 polybutylene terephthalate Polymers 0.000 description 24
- 238000010096 film blowing Methods 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000001514 detection method Methods 0.000 description 9
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- YNLZFQPOEWEPTM-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid;terephthalic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 YNLZFQPOEWEPTM-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to degradable particles, in particular to biodegradable particles, a preparation method and application. The method is characterized in that: comprises, by weight, 70-100 parts of degradable polymer base material, 0.6-2.0 parts of modified nucleating agent, 0.5-1.5 parts of biological promoter, 1.0-2.0 parts of ultraviolet absorber and 0.5-2.0 parts of compatilizer. Compared with the prior art, the modified nucleating agent in the biodegradable particles provided by the invention is a polyvinyl alcohol coated fluorescent complex, and the modified nucleating agent exerts influence on the semi-crystallization time and the cold crystallization temperature of the polymer base material, so that the polymer base material is promoted to have better mechanical properties in the blending and melting stage, the crystal density is enhanced, and the crystallinity is increased. In addition, the modified nucleating agent contains polyvinyl alcohol, and provides more hydroxyl groups for ester bonds in the biodegradation stage, so that the biodegradable particles can be promoted to hydrolyze and degrade more quickly.
Description
Technical Field
The invention relates to degradable particles, in particular to biodegradable particles, a preparation method and application.
Background
Biodegradable particles are particles that can be broken down into small molecular compounds within a certain period of time under the action of microorganisms in nature. The specific degradation is divided into two stages, and after the degradation is carried out by hydrolysis reaction, the degradation is carried out by microorganisms. Hydrolysis occurs first in the natural environment, oligomers are hydrolyzed by labile ester bonds in the backbone, and then microorganisms enter the tissue and break down them into carbon dioxide and water.
Environmental pollution is now increasingly serious, and the preparation and application of biodegradable particles are becoming more important.
Polybutylene terephthalate (PBAT) is a petrochemical-based biodegradable plastic, and is prepared from 1, 4-Butanediol (BDO), adipic Acid (AA), terephthalic acid (PTA) or terephthalic acid glycol ester (DMT) as raw materials by a direct esterification or transesterification method. The waste PBAT material can be biodegraded and does not release any toxic gases to the environment. Polybutylene terephthalate-adipate (PBAT) has good ductility, elongation at break capability, heat resistance and impact resistance; but with lower crystallinity. In addition, the chemical structure of polybutylene terephthalate-adipate (PBAT) lacks reactive functional groups, and also does not have hydrophilicity, and the degradation rate needs to be controlled.
In the prior art, a Chinese patent document disclosed in CN109535670A describes a fully degradable simulation material and a preparation method thereof, wherein the fully degradable simulation material comprises polybutylene terephthalate-adipate (PBAT), polylactic acid (PLA), polyepsilon-caprolactone (PCL), plant fiber powder, mineral powder, a biodegradation accelerator, lubricating oil and an antioxidant. According to the invention, mineral powder and plant fiber powder are used as a main nucleating agent and a secondary nucleating agent, and the crystallization behavior and weather resistance of terephthalic acid-butanediol adipate (PBAT), polylactic acid (PLA) and poly epsilon-caprolactone (PCL) are influenced. The technical scheme has the technical defects that: 1. the preparation method has the advantages that the addition amount of the nucleating agent is large, benign wetting is avoided, uneven dispersion of powder is easy to occur, interface connection of the composite material is poor, the elongation at break is reduced, and the mechanical property is affected. 2. Terephthalic acid-adipic acid butanediol (PBAT), polylactic acid (PLA) and poly epsilon-caprolactone (PCL) belong to different types of polymers, and in the extrusion melting link, the blending system is easy to cause macroscopic phase separation, so that the application value is lost.
Disclosure of Invention
The invention provides a preparation method of a degradable polymer substrate, which aims at the problems of low crystallinity and slow degradation period of the current polybutylene terephthalate-adipate (PBAT). The melt strength of the mixed system is improved and the biodegradation rate is optimized by blending and modifying the degradable high polymer materials with different properties and the modified nucleating agent.
In order to solve the technical problems, the aim of the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a biodegradable particle comprising the following components in parts by weight:
70-100 parts of degradable polymer base material;
0.6-2.0 parts of modified nucleating agent;
0.5-1.5 parts of biological promoter;
1.0-2.0 parts of ultraviolet absorber;
0.5-2.0 parts of compatilizer.
Preferably, the degradable polymer substrate comprises any one or a mixture of two or more of modified starch, polylactic acid (PLA) and polybutylene terephthalate-adipate (PBAT). Preferably, the modified starch is one or more of TH801T manufactured by Lanshan river company, and HL-101 manufactured by Huali company; polylactic acid (PLA) and its polymers such as 2003D of the regeotm series produced by NatureWorks company; the polybutylene terephthalate-adipate (PBAT) can be one or more of C2332 and C1200 manufactured by Basoff company.
Preferably, the modified nucleating agent is a nucleating agent which adopts polyvinyl alcohol to coat the surface of the fluorescent complex.
In a second aspect, the invention provides a modified nucleating agent comprising the following components in parts by weight:
8-10 parts of polyvinyl alcohol
78-86 parts of deionized water
Fluorescent complex 5-10 parts
1.0 to 2.0 parts of surface auxiliary agent
Preferably, the coating resin is polyvinyl alcohol.
Preferably, the good solvent is one or more of deionized water, purified water and distilled water.
Preferably, the fluorescent complex comprises one or two of divalent europium complex and trivalent europium complex. Preferably, the divalent europium complex is Sr 2 Si 5 N 8 :Eu 2+ 、Ca 2 Si 5 N 8 : Eu 2+ 、CaAlSiN 3 :Eu 2+ One or more of the following; the trivalent europium complex is Y 2 O 3 :Eu 3+ 、Gd 2 Mo 3 O 9 : Eu 3+ One or more of the following.
Preferably, the surface auxiliary agent is sodium dodecyl benzene sulfonate.
In a third aspect, the present invention also provides a method for preparing a modified nucleating agent as described above, comprising the steps of:
adding deionized water into the fluorescent complex at the temperature of 30-40 ℃ to form 25% slurry; maintaining the temperature at 30-40 ℃ and adding 8-10% polyvinyl alcohol aqueous solution together with the surface auxiliary agent; adding the mixture into the light mineral oil with vigorous stirring to be redispersed into the light mineral oil to form water-in-oil emulsion; then cooling the mixture to 10-20deg.C, adding cold ethanol (-20deg.C), and making into polyvinyl alcohol coated microcapsule; the microcapsules were filtered and washed with n-hexane (-20 ℃) and finally dried in a fluid bed at a temperature of 5-10 ℃ to form microcapsule granules.
As a preferred embodiment, the fineness of the modified nucleating agent is 3-5. Mu.m.
Further, the biological promoter is one or more of calcium dihydrogen phosphate and N-acyl-methyl alanine.
Preferably, the ultraviolet absorbent is one or more of dihydroxybenzophenone and phenyl orthohydroxybenzoate.
Preferably, the compatilizer comprises one or more of an oxide compound, a phosphate compound and an isocyanate compound. Preferably, the peroxide compound is one or more of dibenzoyl peroxide, di-tert-butyl peroxide and azobisisobutyronitrile; the phosphate compound such as TPP produced by Langsheng company is used as a flame retardant, and is also used as a compatilizer based on special reaction in a system; the isocyanate compound is one or the combination of two of toluene diisocyanate and o-xylylene diisocyanate.
In a fourth aspect, the present invention also provides a method for preparing a biodegradable particle-modified composite material as described above, comprising the steps of:
s1: respectively drying the degradable polymer substrate, the modified nucleating agent, the biological accelerator, the ultraviolet absorber and the compatilizer, and uniformly mixing;
s2: the biodegradable particles are obtained through melt blending, extrusion granulation, cooling granulation and drying. Drying at 85-110deg.C for 1-3h.
As a preferable scheme, the melt blending is carried out in an internal mixer, the temperature of the melt blending is 120-200 ℃, the rotating speed is controlled at 60-90rpm, the top plug is arranged, and the pressure is 0.6-0.8MPa.
Preferably, the extrusion granulation is performed in a twin-screw extruder, the length-diameter ratio of the twin-screw extruder is 36:1, granulation is performed in a cold cutting mode, and the temperature of each section of screw barrel of the extruder from a feed opening to an extruder head is set as follows: the first screw barrel is 80-120 ℃, the second screw barrel is 110-130 ℃, the third to sixth screw barrels are 130-170 ℃, the seventh screw barrel is 120-140 ℃, and the screw speed is 200-300r/min.
The biodegradable particles made by the invention can also be used for commodity packages and agricultural films.
Compared with the prior art, the invention has the following advantages:
1. the biodegradable particles provided by the invention contain modified starch, polylactic acid (PLA) and polybutylene terephthalate-adipate which are all easily degradable components, and can be rapidly hydrolyzed and degraded in a short time in the degradation process compared with a non-degradable PVC, PE, PP material, so that environmental pollution is radically cured.
2. The modified nucleating agent in the biodegradable particles provided by the invention is a polyvinyl alcohol coated fluorescent complex, and the modified nucleating agent exerts influence on the semi-crystallization time and the cold crystallization temperature of the polymer base material, so that the polymer base material is promoted to have enhanced crystal density and increased crystallinity in the blending and melting stage, and the obtained biodegradable particles have better mechanical properties. In addition, the modified nucleating agent contains polyvinyl alcohol, and provides more hydroxyl groups for ester bonds in the biodegradation stage, so that the biodegradable particles can be promoted to hydrolyze and degrade more quickly.
3. The biodegradable particles provided by the invention contain a compatilizer, and the compatilizer enables various incompatible high polymer materials to be combined in blending processing by means of intermolecular bonding force, so that the mechanical property of a blending system is enhanced.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
A biodegradable particle comprising the following components in parts by weight:
70 parts of degradable polymer base material, 0.6 part of modified nucleating agent, 0.5 part of biological accelerator, 1 part of ultraviolet absorber and 0.5 part of compatilizer.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
Wherein, the modified starch adopts TH801T produced by blue mountain river company, density: 1.24g/cm, a melt flow index of 5.0g/10 min, and a test condition of 210 ℃ per 2.16 kg.
Wherein the polylactic acid (PLA) has a density of 2003D manufactured by Nature works Co., ltd: 1.24g/cm, melt flow index of 5-7.0g/10 min, and test condition of 210 ℃ per 2.16 kg.
Wherein the polybutylene terephthalate-adipate (PBAT) has a density of C1200 produced by basf corporation: 1.30g/cm, a melt flow index of 4.9g/10 min, and a test condition of 210℃/2.16 kg.
Preferably, the modified nucleating agent is a nucleating agent which adopts polyvinyl alcohol to coat the surface of the fluorescent complex.
The modified nucleating agent comprises the following components in parts by weight:
0.24 part of polyvinyl alcohol, 2.4 parts of deionized water, 0.3 part of fluorescent complex and 0.06 part of sodium dodecyl benzene sulfonate.
The fluorescent complex consists of 0.25 part of Sr 2 Si 5 N 8 :Eu 2+ 0.25 part Gd 2 Mo 3 O 9 :Eu 3+ Composition is prepared.
The preparation method of the modified nucleating agent comprises the following steps:
sr is added 2 Si 5 N 8 :Eu 2+ 、Gd 2 Mo 3 O 9 : Eu 3+ Adding deionized water at 30-40 ℃ to form 25% slurry; maintaining the temperature at 30-Adding 8-10% polyvinyl alcohol water solution together with sodium dodecyl benzene sulfonate at 40 ℃; stirring vigorously at a stirring speed of not less than 6000r/min, and adding the mixture to the light mineral oil to form water-in-oil emulsion; then cooling the mixture to 10-20deg.C, adding cold ethanol (-20deg.C), and making into polyvinyl alcohol coated microcapsule; the microcapsules were filtered and washed with n-hexane (-20 ℃) and finally dried in a fluid bed at a temperature of 5-10 ℃ to form microcapsule granules.
Wherein the biological promoter is calcium dihydrogen phosphate and N-acyl-methyl alanine 1:1 weight ratio of the composition.
Wherein the ultraviolet absorber is dihydroxybenzophenone.
Wherein the compatilizer is TPP produced by Langsheng company.
A method of preparing biodegradable particles comprising the steps of:
s1: 10 parts of modified starch, 20 parts of polylactic acid (PLA), 70 parts of polybutylene terephthalate-adipate (PBAT), 0.6 part of modified nucleating agent, 1 part of biological accelerator, 1 part of ultraviolet absorbent and 2 parts of compatilizer are put into a closed rubber mixing mill according to the sequence to be melt-blended, the temperature of the melt-blended mixture is 120 ℃, the rotating speed is controlled at 60rpm, and the pressure of the upper plug is 0.6MPa;
s2: and (3) carrying out melt blending, putting the sizing material into a double-screw extruder while the sizing material is hot, extruding and granulating, cooling and granulating, and drying to obtain biodegradable particles. The length-diameter ratio of the twin-screw extruder is 36:1, granulation is carried out in a cold cutting mode, and the temperature of each section of screw barrel of the extruder from the feed opening to the end of the extruder head is set as follows: the first screw barrel is 80 ℃, the second screw barrel is 110 ℃, the third to sixth screw barrels are 130 ℃, the seventh screw barrel is 120 ℃, the screw speed is 200r/min, and the feeding speed is 50 parts/h, so as to obtain the biodegradable particles.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 50.31 MPa, TD is 42.76 MPa;
crystallinity: 42.13%.
Example 2
A biodegradable particle comprising the following components in parts by weight:
85 parts of degradable polymer base material, 1.2 parts of modified nucleating agent, 1.5 parts of biological accelerator, 1 part of ultraviolet absorber and 2 parts of compatilizer.
The degradable polymer base material consists of 10 parts of modified starch, 15 parts of polylactic acid (PLA) and 60 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 51.25 MPa, TD is 43.69 MPa;
crystallinity: 43.58%.
Example 3
A biodegradable particle comprising the following components in parts by weight:
100 parts of degradable polymer base material, 2 parts of modified nucleating agent, 1 part of biological promoter, 2 parts of ultraviolet absorber and 2 parts of compatilizer. A biodegradable particulate material comprising the following components in parts by weight:
the degradable polymer substrate consists of 15 parts of modified starch, 20 parts of polylactic acid (PLA) and 65 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 52.62 MPa, TD is 44.69 MPa;
crystallinity: 44.53%.
Example 4
A biodegradable particle comprising the following components in parts by weight:
100 parts of degradable polymer base material, 1.2 parts of modified nucleating agent, 1 part of biological accelerator, 1 part of ultraviolet absorber and 2 parts of compatilizer.
The degradable polymer substrate consists of 18 parts of modified starch, 24 parts of polylactic acid (PLA) and 58 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 51.85 MPa, TD is 44.13 MPa;
crystallinity: 43.92%.
Comparative example 1
The biodegradable particles provided in this comparative example comprise the following components in parts by weight:
70 parts of degradable polymer base material, 1 part of biological promoter and 1 part of ultraviolet absorber.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 38.25 MPa, TD is 32.71 MPa;
crystallinity: 25.63%.
Comparative example 2
The biodegradable particles provided in this comparative example comprise the following components in parts by weight:
70 parts of degradable polymer base material, 2 parts of modified nucleating agent, 1 part of biological promoter and 1 part of ultraviolet absorber.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 39.31 MPa, TD is 33.43 MPa;
crystallinity: 27.19%.
Comparative example 3
This comparative example differs from example 1 in that talc was used instead of the modified nucleating agent, the remainder being identical.
The biodegradable particles provided in this comparative example comprise the following components in parts by weight:
70 parts of degradable polymer base material, 1 part of biological promoter, 1 part of ultraviolet absorber and 2 parts of compatilizer.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 41.43 MPa, TD is 34.64 MPa;
crystallinity: 31.75%.
Comparative example 4
This comparative example differs from example 3 in that talc was used instead of the modified nucleating agent, the remainder being identical.
The biodegradable particles provided in this comparative example comprise the following components in parts by weight:
70 parts of degradable polymer base material, 1.5 parts of modified nucleating agent, 1 part of biological accelerator, 1 part of ultraviolet absorber and 1.5 parts of compatilizer.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 45.61 MPa, TD is 37.48 MPa;
crystallinity: 37.64%.
Comparative example 5
This comparative example differs from example 3 in that no nucleating agent was added to the blend and the remainder was identical.
The biodegradable particles provided in this comparative example comprise the following components in parts by weight:
70 parts of degradable polymer base material, 1.5 parts of uncoated fluorescent complex, 1 part of biological accelerator, 1 part of ultraviolet absorber and 1.5 parts of compatilizer.
The degradable polymer substrate consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation method of the biodegradable particles is the same as in example 1.
And (3) putting the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film manufactured by the biodegradable particles, and carrying out relevant detection.
Tensile strength: MD is 46.14 MPa, TD is 38.65 MPa;
crystallinity: 38.21%.
The products obtained in inventive examples 1-4 and comparative examples 1-5 were tested for tensile properties of polymers according to ASTM D638, and polymers were tested for crystallinity according to ASTM F2778-09, with the following results:
TABLE 1
From table 1, the following conclusions can be drawn:
1. comparing the example with the comparative example 1, it can be seen that the tensile strength and crystallinity of the mixed system are significantly improved when the modified nucleating agent and the compatilizer are added for synergistic compatibility.
2. Comparing comparative example 1 with comparative example 2, it can be seen that the tensile strength and crystallinity of the mixed system are significantly increased when only the polyvinyl alcohol-coated fluorescent complex is used as a nucleating agent, but further improvement of the tensile strength and crystallinity of the mixed system is seen when the solubilizer TPP is added in comparative example 1 and comparative example 2.
3. Comparing comparative example 1 with comparative example 3, it can be seen that the tensile strength and crystallinity of the mixed system are improved to some extent in the presence of only the solubilizer TPP, but further improvement in the tensile strength and crystallinity of the mixed system can be seen in the case of comparative example 1 and comparative example 3, after the polyvinyl alcohol-coated fluorescent complex is added as a nucleating agent.
4. Comparing comparative example 1 with comparative example 4, it can be seen that the synergistic compatibility of the modified nucleating agent and the compatilizer is added, so that the blending process of the degradable high polymer material modified starch, polylactic acid (PLA) and polybutylene terephthalate-adipate (PBAT) is more fully fused, and the tensile strength and crystallinity of the mixed system are better.
5. Comparing comparative example 1 with comparative example 5, it can be seen that the synergistic compatibility of the nucleating agent and TPP compatilizer added with the uncoated fluorescent complex further ensures that the blending process of the degradable high polymer material modified starch, polylactic acid (PLA) and polybutylene terephthalate-adipate (PBAT) is fully fused, and the tensile strength and crystallinity of the mixed system are better.
The products obtained in examples 1-4 and comparative examples 1-5 of the present invention, the plastics or residual plastics after composting according to ASTM D5988-2003, were tested for aerobic biodegradation in soil as follows:
TABLE 2
From table 2, the following conclusions can be drawn:
1. comparing examples 1-4, it can be seen that the modified nucleating agent exerts an influence on the degradation period of the mixed system, and the cause is analyzed, because the outer shell of the nucleating agent coats the polyvinyl alcohol, the introduced hydroxyl groups enable the composite material to be more easily hydrolyzed, and the composite material is hydrolyzed into an oligomer through an unstable ester bond on the main chain, so that the composite material is completely degraded.
2. Comparing example 1 with comparative example 1, it can be seen that the degradation period of the mixed system is shorter when the modified nucleating agent is added.
3. Comparing comparative example 1 with comparative example 2, it can be seen that the degradation period of the mixed system is relatively shorter when only the polyvinyl alcohol coated fluorescent complex is used as a nucleating agent, but the degradation period of the mixed system is affected because no compatilizer is added in comparative example 2 when comparative example 1 and comparative example 2.
4. The degradation period of the mixed system is shorter than that of comparative example 1 and comparative example 3, and the analysis causes are caused by better blending compatibility of the degradable polymer materials, but in the case of comparative example 1 and comparative example 3, the degradation period of the mixed system is further shortened after the polyvinyl alcohol coated fluorescent complex is added as a nucleating agent.
5. Comparing comparative example 1 with comparative example 4, it can be seen that the synergistic compatibility of the modified nucleating agent and the compatilizer is added, so that the degradation period of the mixed system is shorter.
6. Comparing comparative example 4 with comparative example 5, it can be seen that the degradation period of the mixed system of comparative example 5 is longer than that of comparative example 4 after the nucleating agent and TPP compatilizer of uncoated fluorescent complex are added, and the reason is analyzed because the nucleating agent of comparative example 5 does not contain polyvinyl alcohol, can not promote hydrolysis, and further shortens the degradation period.
Finally, it is noted that the above-mentioned embodiments illustrate rather than limit the invention, and that those skilled in the art will be understood that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (4)
1. The preparation method of the biodegradable particles comprises 70-100 parts by weight of degradable polymer base material, 0.6-2.0 parts by weight of modified nucleating agent, 0.5-1.5 parts by weight of biological accelerator, 1.0-2.0 parts by weight of ultraviolet absorber and 0.5-2.0 parts by weight of compatilizer, and is characterized in that the preparation method of the modified nucleating agent comprises the following steps:
adding deionized water into the fluorescent complex at the temperature of 30-40 ℃ to form 25% slurry; maintaining the temperature at 30-40 ℃ and adding 8-10% polyvinyl alcohol aqueous solution together with the surface auxiliary agent; stirring vigorously, and dispersing into light mineral oil to form water-in-oil emulsion;
then cooling the mixture to 10-20 ℃, and adding cold ethanol at-20 ℃ to prepare the polyvinyl alcohol coated microcapsule;
filtering the microcapsule, washing with-20deg.C n-hexane, and drying at 5-10deg.C on a fluidized bed to obtain the modified nucleating agent;
the preparation method of the biodegradable particles comprises the following specific steps:
s1: respectively drying the degradable polymer substrate, the modified nucleating agent, the biological accelerator, the ultraviolet absorber and the compatilizer, and uniformly mixing;
s2: the biodegradable particles are obtained through melt blending, extrusion granulation, cooling granulation and drying;
the degradable polymer base material is a mixture of modified starch, polylactic acid and polybutylene terephthalate-adipate;
the biological promoter is calcium dihydrogen phosphate and N-acyl-methyl alanine;
the compatilizer is TPP produced by Langsheng company.
2. The method for producing biodegradable particles according to claim 1, characterized in that: the modified nucleating agent comprises, by weight, 8-10 parts of polyvinyl alcohol, 78-86 parts of deionized water, 5-10 parts of fluorescent complex and 1.0-2.0 parts of surface auxiliary agent.
3. The method for preparing biodegradable particles according to claim 1, wherein the fluorescent complex comprises one or more of a divalent europium complex and a trivalent europium complex.
4. The method for producing biodegradable particles according to claim 1, characterized in that: the ultraviolet absorbent is one or more of dihydroxybenzophenone and phenyl orthohydroxybenzoate.
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| CN1974645A (en) * | 2006-12-08 | 2007-06-06 | 郑州市腾飞实业有限责任公司 | Completely biodegradable plastic |
| CN101314641A (en) * | 2007-06-01 | 2008-12-03 | 中国科学院化学研究所 | Aliphatic polyester series microspheres, preparation and application thereof |
| CN104479304A (en) * | 2014-12-10 | 2015-04-01 | 金发科技股份有限公司 | Full-biodegradable composite as well as preparation method and application of full-biodegradable composite |
| CN113754992A (en) * | 2021-09-28 | 2021-12-07 | 河南工业大学 | Biodegradable plastic film and preparation method thereof |
| WO2022246778A1 (en) * | 2021-05-28 | 2022-12-01 | 蒋妙根 | Preparation method for special nano-modified polyethylene material for resisting aging |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1974645A (en) * | 2006-12-08 | 2007-06-06 | 郑州市腾飞实业有限责任公司 | Completely biodegradable plastic |
| CN101314641A (en) * | 2007-06-01 | 2008-12-03 | 中国科学院化学研究所 | Aliphatic polyester series microspheres, preparation and application thereof |
| CN104479304A (en) * | 2014-12-10 | 2015-04-01 | 金发科技股份有限公司 | Full-biodegradable composite as well as preparation method and application of full-biodegradable composite |
| WO2022246778A1 (en) * | 2021-05-28 | 2022-12-01 | 蒋妙根 | Preparation method for special nano-modified polyethylene material for resisting aging |
| CN113754992A (en) * | 2021-09-28 | 2021-12-07 | 河南工业大学 | Biodegradable plastic film and preparation method thereof |
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