CN115948035A - Biodegradable particles, preparation method and application - Google Patents
Biodegradable particles, preparation method and application Download PDFInfo
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- CN115948035A CN115948035A CN202310245029.5A CN202310245029A CN115948035A CN 115948035 A CN115948035 A CN 115948035A CN 202310245029 A CN202310245029 A CN 202310245029A CN 115948035 A CN115948035 A CN 115948035A
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- 239000002245 particle Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002667 nucleating agent Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 34
- 229920006237 degradable polymer Polymers 0.000 claims abstract description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 230000002745 absorbent Effects 0.000 claims abstract description 18
- 239000002250 absorbent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 27
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 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
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 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
- 239000000203 mixture Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 229940059904 light mineral oil Drugs 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007762 w/o emulsion Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 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 9
- 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 42
- 238000010096 film blowing Methods 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000001514 detection method Methods 0.000 description 9
- 229920001610 polycaprolactone Polymers 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 6
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 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
- 238000005520 cutting process Methods 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000010074 rubber mixing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- ZLPOWNUXKJLCFE-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione hexanedioic acid terephthalic acid Chemical compound C1(C2=CC=C(C(=O)OCCCCO1)C=C2)=O.C(C2=CC=C(C(=O)O)C=C2)(=O)O.C(CCCCC(=O)O)(=O)O ZLPOWNUXKJLCFE-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
- 229910019142 PO4 Inorganic materials 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
- 239000001506 calcium phosphate 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
- 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
- 239000003623 enhancer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 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
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010452 phosphate Substances 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
- 238000004088 simulation Methods 0.000 description 1
- 239000002689 soil 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
- 230000009466 transformation Effects 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 70 to 100 portions of degradable polymer base material, 0.6 to 2.0 portions of modified nucleating agent, 0.5 to 1.5 portions of biological promoter, 1.0 to 2.0 portions of ultraviolet absorbent and 0.5 to 2.0 portions 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 exerts influence on the semi-crystallization time and the cold crystallization temperature of the polymer base material, so that the crystal density and the crystallinity of the polymer base material are enhanced 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 a biodegradation stage, so that the biodegradable particles can be promoted to be hydrolyzed and degraded 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 molecule compounds under the action of microorganisms in nature for a certain period of time. The specific degradation is divided into two stages, and the degradation is carried out by microorganisms after hydrolysis reaction. In natural environment, hydrolysis occurs first, forming oligomers by hydrolysis of the labile ester bonds in the main chain, and then microorganisms enter the tissue mass, breaking it down into carbon dioxide and water.
The problem of environmental pollution is becoming more serious now, and the preparation and application of biodegradable particles are more and more emphasized.
Polybutylene terephthalate adipate (PBAT) is petrochemical-based biodegradable plastic and is prepared by taking 1,4-Butanediol (BDO), adipic Acid (AA), terephthalic acid (PTA) or glycol terephthalate (DMT) as raw materials through a direct esterification or ester exchange method. The PBAT material can be biodegraded after disposal without releasing any toxic gases to the environment. The polybutylene terephthalate-adipate (PBAT) has good ductility, elongation at break capability, heat resistance and impact resistance; but the crystallinity is low. In addition, the chemical structure of the polybutylene terephthalate adipate (PBAT) lacks reactive functional groups and has no hydrophilicity, and the degradation speed needs to be controlled.
In the prior art, CN109535670a discloses a chinese patent document, which describes a fully degradable simulation material and a preparation method thereof, including polybutylene terephthalate-adipate-butylene glycol (PBAT), polylactic acid (PLA), poly epsilon-caprolactone (PCL), plant fiber powder, mineral powder, biodegradation accelerator, lubricating oil and antioxidant. The invention exerts influence on crystallization behavior and weather resistance of terephthalic acid-butanediol adipate (PBAT), polylactic acid (PLA) and poly epsilon-caprolactone (PCL) by using mineral powder and plant fiber powder as a main nucleating agent and a secondary nucleating agent. The technical scheme has the technical defects that: 1. in the preparation method, the addition amount of the nucleating agent is large, benign wetting is avoided, uneven powder dispersion is easily caused, the interface connection of the composite material is deteriorated, the elongation at break is reduced, and the mechanical property is influenced. 2. Terephthalic acid-butanediol adipate (PBAT), polylactic acid (PLA) and poly epsilon-caprolactone (PCL) belong to different types of high polymers, and in the link of extrusion and melting, a 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, aiming at the problems of low crystallinity and slow degradation period of the prior poly (butylene terephthalate-adipate-terephthalate) (PBAT). The melt strength of a mixed system is improved and the biodegradation rate is optimized by blending and modifying degradable high polymer materials with different properties and a modified nucleating agent.
In order to solve the technical problems, the purpose of the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a biodegradable particle, which comprises 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 absorbent;
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 selected from TH801T manufactured by Futun river of blue mountain, HL-101 manufactured by Huali corporation; such polylactic acid (PLA) and polymers thereof such as 2003D of the ingetom series manufactured by NatureWorks corporation; the polybutylene terephthalate-adipate (PBAT) is one or more of C2332 and C1200 produced by BASF corporation.
Preferably, the modified nucleating agent is a nucleating agent with the surface of the fluorescent complex coated by polyvinyl alcohol.
In a second aspect, the invention provides a modified nucleating agent, which comprises the following components in parts by weight:
8-10 parts of polyvinyl alcohol
78-86 parts of deionized water
5-10 parts of fluorescent complex
1.0-2.0 parts of surface additive
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 a divalent europium complex and a 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 above; the trivalent europium complex is Y 2 O 3 :Eu 3+ 、Gd 2 Mo 3 O 9 : Eu 3+ One or more of them.
Preferably, the surface auxiliary agent is sodium dodecyl benzene sulfonate.
In a third aspect, the invention also provides a preparation method of the modified nucleating agent, which comprises the following steps:
adding deionized water into the fluorescent complex at the temperature of 30-40 ℃ to form 25% slurry; keeping the temperature at 30-40 ℃, adding 8-10% polyvinyl alcohol aqueous solution together with the surface auxiliary agent; stirring vigorously, adding into light mineral oil, and dispersing to form water-in-oil emulsion; then cooling the mixture to 10-20 deg.C, adding cold ethanol (-20 deg.C), and making into microcapsule coated with polyvinyl alcohol; the microcapsules were filtered and washed with n-hexane (-20 deg.C) and finally dried to microcapsule particles on a fluid bed at a temperature of 5-10 deg.C.
Preferably, 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 dihydroxy benzophenone and phenyl ortho-hydroxybenzoate.
Preferably, the compatilizer comprises one or more of oxide compounds, phosphate compounds and isocyanate compounds. Preferably, the peroxide compound is one or more of dibenzoyl peroxide, di-tert-butyl peroxide and azobisisobutyronitrile; the phosphate ester compound such as TPP produced by Langsheng company is used as a flame retardant and also used as a compatilizer based on special reaction in a system; the isocyanate compound is one or a combination 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, which comprises the following steps:
s1: respectively drying the degradable polymer base material, the modified nucleating agent, the biological promoter, the ultraviolet absorbent and the compatilizer, and then uniformly mixing;
s2: and carrying out melt blending, extrusion granulation, cooling granulation and drying to obtain the biodegradable particles. The drying temperature is 85-110 ℃, and the drying time is 1-3h.
Preferably, the melt blending is carried out in an internal rubber mixing mill, the melt blending temperature is 120-200 ℃, the rotating speed is controlled at 60-90rpm, a 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, granulation is performed in a cold cutting mode, and the temperature of each section of screw cylinder of the extruder from a feed opening to an extruder head is set as follows: the first screw cylinder is 80-120 ℃, the second screw cylinder is 110-130 ℃, the third to sixth screw cylinders are 130-170 ℃, the seventh screw cylinder is 120-140 ℃, and the rotating speed of the screw is 200-300r/min.
The biodegradable particles prepared by the invention can also be used for commodity packaging 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, degraded in a short time and radically treat environmental pollution in the degradation process compared with non-degradable PVC, PE and PP materials.
2. The modified nucleating agent in the biodegradable particles provided by the invention is a polyvinyl alcohol coated fluorescent complex, and exerts influence on the semi-crystallization time and the cold crystallization temperature of the polymer base material, so that the crystal density of the polymer base material is enhanced and the crystallinity of the polymer base material is increased 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 a biodegradation stage, so that the biodegradable particles can be promoted to be hydrolyzed and degraded more quickly.
3. The biodegradable particles provided by the invention contain the compatilizer, and the compatilizer combines incompatible various high polymer materials in blending processing by virtue of intermolecular bonding force, so that the mechanical property of a blending system is enhanced.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Example 1
A biodegradable particle comprises 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 promoter, 1 part of ultraviolet absorbent and 0.5 part of compatilizer.
The degradable polymer base material 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 is TH801T produced by blue mountain Tunghe company, and the density is as follows: high speed up to 1.24g/cm, 5.0g/10 min, 210 deg.C/2.16 kg.
Wherein the polylactic acid (PLA) is produced by NatureWorks, 2003D, density: 1.24 And (3) carrying out g/cm high speed transformation, wherein the melt flow index is 5-7.0g/10 min, and the test condition is 210 ℃ per 2.16 kg.
Wherein the polybutylene terephthalate-adipate (PBAT) is prepared from C1200 manufactured by basf corporation, density: high speed up to 1.30g/cm, 4.9g/10 min, 210 deg.C/2.16 kg.
Preferably, the modified nucleating agent is a nucleating agent with the surface of the fluorescent complex coated by polyvinyl alcohol.
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 portion of Sr 2 Si 5 N 8 :Eu 2+ 0.25 part of Gd 2 Mo 3 O 9 :Eu 3+ And (4) forming.
The preparation method of the modified nucleating agent comprises the following steps:
sr is 2 Si 5 N 8 :Eu 2+ 、Gd 2 Mo 3 O 9 : Eu 3+ Adding deionized water at 30-40 deg.C to form 25% slurry; keeping the temperature at 30-40 ℃, adding 8-10% polyvinyl alcohol aqueous solution together with sodium dodecyl benzene sulfonate; stirring vigorously at a speed of not less than 6000r/min, and adding into light mineral oil to form water-in-oil emulsion; then cooling the mixture to 10-20 deg.C, adding cold ethanol (-20 deg.C), and making into microcapsule coated with polyvinyl alcohol; the microcapsules were filtered and washed with n-hexane (-20 deg.C) and finally dried to microcapsule particles on a fluid bed at a temperature of 5-10 deg.C.
Wherein the bio-enhancer is monocalcium phosphate and N-acyl-methylalanine 1:1 weight ratio of the composition.
Wherein the ultraviolet absorbent is dihydroxy benzophenone.
Wherein the compatilizer is TPP produced by Langshan company.
A method of making 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 promoter, 1 part of ultraviolet absorbent and 2 parts of compatilizer are sequentially placed into an internal rubber mixing mill for melt blending, the temperature for uniform mixing and melt blending is 120 ℃, the rotating speed is controlled at 60rpm, the top plug is arranged, and the pressure is 0.6MPa;
s2: and (3) carrying out melt blending, putting the hot rubber material into a double-screw extruder for extrusion granulation, cooling, granulating and drying to obtain biodegradable particles. The ratio of the length to the diameter of the twin-screw extruder was 36, and the pellets were granulated by cold cutting, and the temperatures of the respective sections of the screw barrel of the extruder from the feed opening to the extruder head were set as follows: the first screw cylinder is 80 ℃, the second screw cylinder is 110 ℃, the third to sixth screw cylinders are 130 ℃, the seventh screw cylinder is 120 ℃, the screw rotating speed is 200r/min, and the feeding speed is 50 parts/h, so as to obtain the biodegradable particles.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 50.31 MPa, TD is 42.76 MPa;
degree of crystallinity: 42.13 percent.
Example 2
A biodegradable particle comprises 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 promoter, 1 part of ultraviolet absorbent and 2 parts of compatilizer.
The degradable polymer base material is composed of 10 parts of modified starch, 15 parts of polylactic acid (PLA) and 60 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 51.25 MPa, TD is 43.69 MPa;
degree of crystallinity: 43.58%.
Example 3
A biodegradable particle comprises 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 absorbent and 2 parts of compatilizer. A biodegradable particle material comprises the following components in parts by weight:
the degradable polymer base material consists of 15 parts of modified starch, 20 parts of polylactic acid (PLA) and 65 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 52.62 MPa, TD is 44.69 MPa;
degree of crystallinity: 44.53 percent.
Example 4
A biodegradable particle comprises 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 promoter, 1 part of ultraviolet absorbent and 2 parts of compatilizer.
The degradable polymer base material consists of 18 parts of modified starch, 24 parts of polylactic acid (PLA) and 58 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 51.85 MPa, TD is 44.13 MPa;
degree of crystallinity: 43.92 percent.
Comparative example 1
The biodegradable particles provided by the 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 absorbent.
The degradable polymer base material consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 38.25 MPa, TD is 32.71 MPa;
degree of crystallinity: 25.63 percent.
Comparative example 2
The biodegradable particles provided by the 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 absorbent.
The degradable polymer base material consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 39.31 MPa, TD is 33.43 MPa;
degree of crystallinity: 27.19 percent.
Comparative example 3
This comparative example is identical to example 1 except that talc was used in place of the modified nucleating agent.
The biodegradable particles provided by the 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 absorbent and 2 parts of compatilizer.
The degradable polymer base material consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 41.43 MPa, TD is 34.64 MPa;
degree of crystallinity: 31.75 percent.
Comparative example 4
This comparative example is identical to example 3 except that talc was used in place of the modified nucleating agent.
The biodegradable particles provided by the 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 promoter, 1 part of ultraviolet absorbent and 1.5 parts of compatilizer.
The degradable polymer base material consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 45.61 MPa, TD is 37.48 MPa;
degree of crystallinity: 37.64 percent.
Comparative example 5
This comparative example is different from example 3 in that the blending system is identical except that no nucleating agent is added.
The biodegradable particles provided by the 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 promoter, 1 part of ultraviolet absorbent and 1.5 parts of compatilizer.
The degradable polymer base material consists of 5 parts of modified starch, 15 parts of polylactic acid (PLA) and 50 parts of polybutylene terephthalate-adipate (PBAT).
The preparation of the biodegradable particles was the same as in example 1.
And (3) placing the obtained biodegradable particles into a film blowing machine for film blowing to obtain a film made of the biodegradable particles, and carrying out related detection.
Tensile strength: MD is 46.14 MPa, TD is 38.65 MPa;
degree of crystallinity: 38.21 percent.
The tensile properties of the polymers obtained in inventive examples 1 to 4 and comparative test examples 1 to 5 were measured in accordance with ASTM D638, and the crystallinity of the polymers was measured in accordance with ASTM F2778-09, as follows:
TABLE 1
From table 1, the following conclusions can be drawn:
1. comparing the examples with comparative example 1, it can be seen that the tensile strength and crystallinity of the mixed system are significantly improved by adding the synergistic compatibility of the modified nucleating agent and the compatilizer.
2. Comparing comparative example 1 and 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 in comparing example 1 and comparative example 2, it can be seen that the tensile strength and crystallinity of the mixed system are further improved after the solubilizer TPP is added.
3. Comparing comparative example 1 and comparative example 3, it can be seen that the tensile strength and crystallinity of the mixed system are improved to some extent when only the solubilizer TPP is present, but in comparing example 1 and comparative example 3, it can be seen that the tensile strength and crystallinity of the mixed system are further improved after the polyvinyl alcohol-coated fluorescent complex is added as the nucleating agent.
4. Comparing comparative example 1 and 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 the crystallinity of the mixed system are better.
5. Comparing comparative example 1 and comparative example 5, it can be seen that the synergistic compatibility of the nucleating agent and the TPP compatibilizer added with the uncoated fluorescent complex further enables the blending process of the degradable high polymer material modified starch, polylactic acid (PLA), and polybutylene terephthalate-adipate (PBAT) to be fully fused, and the tensile strength and the crystallinity of the mixed system are better.
The products obtained in inventive examples 1 to 4 and comparative test examples 1 to 5 were subjected to aerobic biodegradation in soil of the composted plastics or residual plastics according to ASTM D5988-2003, with the following results:
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 cycle of the mixed system, and the cause of the analysis is that the shell of the nucleating agent is coated with polyvinyl alcohol, and the introduced hydroxyl groups make the composite material more susceptible to hydrolysis, and the composite material is hydrolyzed into oligomers through unstable ester bonds on the main chain, and then 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 and comparative example 2, it can be seen that the degradation cycle of the mixed system is relatively short when only the polyvinyl alcohol coated fluorescent complex is used as the nucleating agent, but in comparing example 1 and comparative example 2, the blending compatibility of the degradable high polymer material is poor due to no addition of the compatilizer in comparative example 2, and the degradation cycle of the mixed system is affected.
4. Compared with comparative example 1 and comparative example 3, the degradation period of the mixed system is shorter, and the analysis cause is that the blending compatibility of the degradable high polymer material is better, but in 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 the nucleating agent.
5. Comparing comparative example 1 and 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 and 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 the TPP compatibilizer which are not coated with the fluorescent complex are added, and the cause of the analysis is that the nucleating agent in comparative example 5 does not contain polyvinyl alcohol, so that the hydrolysis cannot be promoted, and the degradation period is shortened.
Finally, the embodiments described above are intended to illustrate rather than to limit the invention, and while the invention has been described in detail with reference to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.
Claims (8)
1. A preparation method of biodegradable particles comprises, by weight, 70-100 parts of a degradable polymer base material, 0.6-2.0 parts of a modified nucleating agent, 0.5-1.5 parts of a biological promoter, 1.0-2.0 parts of an ultraviolet absorbent and 0.5-2.0 parts of a compatilizer, and is characterized in that the preparation method of the modified nucleating agent by adopting polyvinyl alcohol to coat a fluorescent complex comprises the following steps: adding deionized water into the fluorescent complex at the temperature of 30-40 ℃ to form 25% slurry; keeping the temperature at 30-40 ℃, and adding 8-10% polyvinyl alcohol aqueous solution; stirring vigorously, and dispersing into light mineral oil to form water-in-oil emulsion; then cooling the mixture to 10-20 ℃, adding cold ethanol to-20 ℃ to prepare the microcapsule coated by the polyvinyl alcohol; filtering the microcapsule, washing with n-hexane at-20 deg.C, and drying in a fluidized bed at 5-10 deg.C to obtain the modified nucleating agent.
2. The method for preparing biodegradable particles according to claim 1, wherein: the degradable polymer base material comprises any one or a mixture of more than two of modified starch, polylactic acid and polybutylene terephthalate-adipate.
3. The method of claim 1, wherein the biodegradable particles are prepared by: the coating comprises, by weight, 8-10 parts of polyvinyl alcohol, 78-86 parts of deionized water, 5-10 parts of a fluorescent complex and 1.0-2.0 parts of a surface additive.
4. The method of claim 1, wherein the fluorescent complex comprises one or more of divalent europium complex and trivalent europium complex.
5. The method for preparing biodegradable particles according to claim 1, wherein: the biological promoter is one or more of calcium dihydrogen phosphate and N-acyl-methyl alanine.
6. The method of claim 1, wherein the biodegradable particles are prepared by: the ultraviolet absorbent is one or more of dihydroxy benzophenone and phenyl o-hydroxybenzoate.
7. The method for preparing biodegradable particles according to claim 1, wherein: the compatilizer comprises one or more of oxide compounds, phosphate compounds and isocyanate compounds.
8. A method for preparing biodegradable particles according to any one of claims 1-7, characterized by the following specific steps:
s1: respectively drying the degradable polymer base material, the modified nucleating agent, the biological promoter, the ultraviolet absorbent and the compatilizer, and then uniformly mixing;
s2: and carrying out melt blending, extrusion granulation, cooling granulation and drying to obtain the biodegradable particles.
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| 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 |
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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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Denomination of invention: A Biodegradable Particle, Preparation Method and Application Granted publication date: 20230630 Pledgee: Bank of Communications Co.,Ltd. Hebei Xiong'an Branch Pledgor: Hebei Liya Packaging Technology Co.,Ltd. Registration number: Y2024980001680 |