CN113999500B - Degradable composite material with lasting fragrance, preparation method and application - Google Patents
Degradable composite material with lasting fragrance, preparation method and application Download PDFInfo
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- CN113999500B CN113999500B CN202111441139.6A CN202111441139A CN113999500B CN 113999500 B CN113999500 B CN 113999500B CN 202111441139 A CN202111441139 A CN 202111441139A CN 113999500 B CN113999500 B CN 113999500B
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000003205 fragrance Substances 0.000 title claims abstract description 33
- 230000002045 lasting effect Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004005 microsphere Substances 0.000 claims abstract description 56
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 23
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims abstract description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical group CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229940073505 ethyl vanillin Drugs 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 230000005923 long-lasting effect Effects 0.000 claims 2
- 238000004898 kneading Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 9
- 239000000945 filler Substances 0.000 abstract description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 45
- 239000004626 polylactic acid Substances 0.000 description 45
- 239000000463 material Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000003995 emulsifying agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000341 volatile oil Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fats And Perfumes (AREA)
Abstract
The invention discloses a degradable composite material with lasting fragrance, a preparation method and application, wherein the degradable composite material is prepared from the following raw materials in parts by weight: 650-900 parts of PBAT, 50-200 parts of PLA porous microspheres embedded with essence, 50-300 parts of mineral powder and 1-10 parts of erucamide. According to the invention, the PBAT is taken as a matrix, and PLA porous microsphere filler is dispersed in the matrix to form a special sea-island structure, so that the modulus of the PBAT can be greatly improved on the premise of keeping high toughness of the PBAT. In addition, the hollow porous structure of the PLA porous microsphere can be used as a carrier of essence to hold the PLA porous microsphere, so that the essence is ensured to be stably existing in the composite material and not to be easily separated out, and the durability of the fragrance is maintained.
Description
Technical Field
The invention relates to a degradable composite material, in particular to a degradable composite material with lasting fragrance, a preparation method and application.
Background
In recent years, with the increasing urgent requirements of ecological environment protection and the increasing awareness of environmental protection, degradable materials gradually replace traditional plastics in disposable products, and market share is increasing. Considering the continuous improvement of the material use experience requirements of customers, the improvement of the mechanical property requirements of degradable plastic products is required, the injection molding products are required to have sufficient strength and firmness and durability in the service period, and meanwhile, the functional fragrance application is also started to develop, wherein the degradable plastic has natural advantages in the aspects of disposable fragrance products, such as holiday flowers, decorations and other consumables.
On one hand, the PBAT product is generally less applied to injection molding, and the strength of an injection molded part is difficult to ensure due to the fact that the PBAT product is soft and has insufficient rigidity; on the other hand, when the prior art is used for carrying out flavor modification on plastics, the essence components are mixed with the plastics in a direct blending mode, the distribution of the essence components is random, the migration and volatilization of the essence embedded in the deep part of the material needs too long, and even the usage period of the product is longer, so that the utilization rate of the essence is low; the essence is mostly small molecular component solid or liquid, diffuses under the concentration gradient, and the excessive addition can cause serious surface precipitation in the early stage, so that the use is affected, the fragrance dispersing rate is uneven, the fragrance degree is fast to reduce, the durability is insufficient, and the fragrance effect of the material is limited to a certain extent.
CN113308094a proposes a degradable composite filling material, which uses natural essential oil as fragrance and antibacterial ingredient and prepares the degradable material by direct blending method, the preparation method is simple, but the essential oil is liquid component, which has great difference with the physical property of solid matrix, it is difficult to mix uniformly by high mixer, it may cause uneven distribution of fragrance and antibacterial effect of the material, and it is difficult to ensure production stability; and the small molecular essential oil is directly filled into the matrix, so that the small molecular essential oil is easy to separate out and has poor fragrance retaining effect. In addition, the composite material is mainly applied to the field of films, and the larger surface area of the film can aggravate precipitation of small molecules and fragrance loss, and fragrance preservation treatment is more needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides a degradable composite material with lasting fragrance, a preparation method and application. According to the invention, the PBAT is taken as a matrix, and PLA porous microsphere filler is dispersed in the matrix to form a special sea-island structure, so that the modulus of the PBAT can be greatly improved on the premise of keeping high toughness of the PBAT. In addition, the hollow porous structure of the PLA porous microsphere can be used as a carrier of essence to hold the essence, so that the essence is ensured to be stably existing in the composite material and is not easy to separate out, and the durability of the fragrance is maintained, thereby completing the invention.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the degradable composite material with lasting fragrance is prepared from the following raw materials in parts by weight:
further, the degradable composite material with lasting fragrance is prepared from the following raw materials in parts by weight:
further, the PBAT refers to poly (butylene adipate/terephthalate), preferably a commercial product of PBAT having a melt index (190 ℃ C./2.16 kg) in the range of 2-15g/10 min.
Further, the essence is one or more of vanillin, ethyl vanillin and milk essence.
Further, the plat of the PLA porous microsphere
Further, the embedding amount of the essence in the PLA porous microsphere is 5-35%.
Further, the PLA porous microsphere has an average particle diameter of 100-800 μm and a porosity of 30-90%.
In some examples of the invention, the PLA porous microspheres may be prepared with reference to the following methods, in particular:
NH is added to 4 HCO 3 Adding 30-70g/L into 125mL of water to prepare an aqueous solution. The aqueous solution was added to 400mL of an organic solution containing 5-20g pla (polylactic acid) and emulsified into a main emulsifier. The main emulsifier is immediately poured into 15L of PVA (polyvinyl alcohol) aqueous solution containing 0.5-3g/L, and stirred at 25 ℃ to form double emulsion. Wherein the organic solvent is volatilized during the stirring. Stirring was continued at 25℃for at least 4h to allow complete evaporation of the organic solvent. And separating filtrate by using a 170-mesh filter screen, and finally washing the PLA microspheres with deionized water for 3 times and freeze-drying for later use. Wherein, the organic solvent can be selected from: dichloromethane, chloroform, ethyl acetate, and the like. Of course, the PLA porous microspheres may also be prepared by other methods or purchased or customized directly, and the invention is not limited to the process and source of preparing the PLA porous microspheres.
Further, the mineral powder is one or more of calcium carbonate, mica and talcum powder.
A method of preparing a durable fragrance degradable composite material as hereinbefore defined comprising the steps of:
according to the weight parts, the PBAT, the mineral powder and the erucamide are added from a main feeding port of a double-screw extruder after being uniformly mixed, PLA porous microspheres embedded with essence are added from a side feeding port, and the degradable composite material is obtained through melt mixing and extrusion.
Further, the melting and mixing temperature is 150-170 ℃, and the rotating speed is 100-300r/min.
Further, the preparation method of the PLA porous microsphere embedded with essence comprises the following steps:
and (3) putting the PLA porous microspheres into the essence after being fully melted, stirring for 3-5 hours under the conditions of 0.8-1.2MPa and 90-120 ℃, filtering to obtain a solid, cooling and drying to obtain the PLA porous microspheres embedded with the essence.
Use of a durable fragrance-emitting degradable composite as described hereinbefore or a durable fragrance-emitting degradable composite prepared by a process as described hereinbefore for the manufacture of an injection molded article.
Compared with the prior art, the invention has the following beneficial effects:
1) The essence is tightly confined in the degradable composite material through the PLA porous microsphere, the fragrance is stable and durable, the environment is friendly, no harmful components are generated, the essence can be applied to disposable fragrance consumables, and the essence is particularly suitable for holidays, celebrations, artificial flowers, decorations and the like.
2) The PLA porous microsphere and the PBAT matrix have certain density difference and thermodynamic difference, and the PLA porous microsphere embedded with essence after injection molding of the product tends to be distributed to the surface layer of the material, thereby being beneficial to shortening the migration path of the essence, ensuring more sufficient fragrance dispersing effect and improving the utilization rate of the essence.
3) The PLA porous microsphere and the PBAT degradable material realize functional compounding, and can greatly improve the modulus of the PBAT degradable material on the premise of keeping the high toughness of the PBAT, so as to obtain the degradable composite material with excellent mechanical properties, and greatly widen the application of the degradable material in injection molding so as to popularize and replace the traditional polyolefin material.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The main raw material information is as follows:
PLA: polylactic acid, BASF, germany, ecover IS1335, technical grade
PVA: polyvinyl alcohol, shanghai Meilin Biochemical technologies Co., ltd., model 2488, alcoholysis degree: 87.0-89.0% (mol/mol)
PBAT: techmer PM, hiFill PBAT BF30, injection grade
Vanillin: shanghai Yao spice Co.Ltd., industrial grade
Ethyl vanillin: shanghai Yao spice Co.Ltd., industrial grade
Milk-flavored essence: dongguan Ten chemical Co., ltd., industrial grade
Mineral powder: calcium carbonate, nanjing Chendong New Material Co., ltd., Q-1250, 1250 mesh
Talc powder: nanjing Chendong New Material Co., ltd., H-1250, 1250 mesh
Mica: chuzhou Mo Qiaojuan mica Co., ltd, CJ-A6, 2000 mesh
Erucamide: PMC, armoslip E, technical grade.
The main testing method comprises the following steps:
(1) Average particle size of PLA porous microspheres: measurement statistics were performed using a scanning electron microscope (QUANTA 450, FEI company, usa), and 100 microspheres were tested to average;
(2) PLA porous microsphere porosity: testing of the apparent density ρ of porous microspheres according to standard GB/T1636 B The method comprises the steps of carrying out a first treatment on the surface of the Testing specific pore volume V of porous microspheres by mercury porosimetry according to standard GB/T21650.1 g And recording the inter-particle mercury filling volume V of the porous microsphere with the mass of m in the test process i And then by the formula: ρ P ＝m/(m/ρ B -V i ) Calculating the particle density ρ of the porous microspheres P Finally by p=v g ·ρ P The porosity P of the porous microspheres was calculated.
(3) Tensile test: according to standard ASTM D638;
(4) Bending test: according to standard ASTM D790;
(5) Cantilever notched impact (23 ℃) test: according to standard ASTM D256;
(6) Load heat distortion temperature (0.45 MPa): according to standard ASTM D648;
(7) TVOC test (performed on perfume-containing samples only): according to standard VDA 277;
(8) Fragrance grade test (for fragrance-containing samples only): the ambient temperature was chosen to be 23.+ -. 2 ℃ according to standard VDA270 and the odor score scale meaning is referred to in Table 1.
Table 1, odor score rating
Preparation of PLA porous microsphere A [ preparation example 1 ]
NH is added to 4 HCO 3 Added to 125mL of water at a concentration of 50g/L to prepare an aqueous solution. The aqueous solution was added to 400mL of chloroform solution containing 12.5g of PLA and emulsified as the main emulsifier. The main emulsifier was immediately poured into 15L of PVA aqueous solution containing 1g/L to form a double emulsion, which was stirred at 25℃for 8 hours. And separating filtrate by using a 170-mesh filter screen, washing the obtained PLA porous microsphere A with deionized water for 3 times, and freeze-drying for later use. As a result of examination, the average particle diameter of the PLA porous microsphere A was 160. Mu.m, and the porosity was 77%.
Preparation of PLA porous microsphere B [ preparation example 2 ]
NH is added to 4 HCO 3 Added to 125mL of water at a concentration of 30g/L to prepare an aqueous solution. The aqueous solution was added to 400mL ethyl acetate solution containing 5g PLA and emulsified as the main emulsifier. The main emulsifier was immediately poured into 15L of PVA aqueous solution containing 0.5g/L to form a double emulsion, which was stirred at 25℃for 5h. And separating filtrate by using a 170-mesh filter screen, washing the obtained PLA porous microsphere A with deionized water for 3 times, and freeze-drying for later use. As a result of examination, the average particle diameter of the PLA porous microsphere A was 105. Mu.m, and the porosity was 34%.
Preparation of PLA porous microsphere C
NH is added to 4 HCO 3 To 125mL of water was added 70g/L to prepare an aqueous solution. This aqueous solution was added to 400mL of methylene chloride solution containing 20g of PLA and emulsified as the main emulsifier. The main emulsifier was immediately poured into 15L of PVA aqueous solution containing 3g/L to form a double emulsion, which was stirred at 25℃for 5h. And separating filtrate by using a 170-mesh filter screen, washing the obtained PLA porous microsphere A with deionized water for 3 times, and freeze-drying for later use. As a result of examination, the average particle diameter of the PLA porous microsphere A was 570. Mu.m, and the porosity was 86%.
[ example 1 ]
(1) PLA porous microsphere for preparing embedded essence
100g of ethyl vanillin is heated to 100 ℃ to be fully melted, 5g of PLA porous microsphere A is added into the mixture, the environment vacuum degree is regulated to be 1.2MPa, the mixture is stirred for 5 hours at a low speed of 100rpm by using mechanical stirring, then the mixture is filtered by a filter screen with a thickness of 70 mu m, and the filtrate is cooled, dried and weighed to obtain 6.35g of PLA porous microsphere embedded with essence (weight gain of 27%).
(2) Preparation of degradable composite materials
650g of PBAT, 100g of mica and 2g of erucamide are mixed uniformly and poured into a main feeding port of an extruder. 100g of the essence-embedded PLA porous microsphere prepared above was poured into a side feeding port. The parameters of the twin screw were set as: the temperature of the first area is 150-160 ℃, the temperature of the second area is 160-170 ℃, the temperature of the third area is 160-170 ℃, the temperature of the fourth area is 150-160 ℃, the rotating speed of the extruder is 100r/min, and the degradable composite material is obtained through melt extrusion, cooling and granulation in the extruder.
[ examples 2 to 5 ]
A degradable composite material was produced in substantially the same manner as in example 1 except that the reaction conditions in examples 2 to 5 were as shown in Table 2, respectively.
Table 2, examples 1-5 differentiate the reaction conditions
Comparative example 1
A degradable material was produced in substantially the same manner as in example 1 except that the essence-embedded PLA porous microsphere added in step (2) was replaced with 21.3g of ethyl vanillin.
Comparative example 2
A degradable material was prepared in substantially the same manner as in example 1 except that the essence-embedded PLA porous microsphere in step (2) was replaced with 100g of PLA pellets and adjusted to be added to the main feeding port in consideration of difficulty in mixing the PLA pellets.
[ comparative example 3 ]
A degradable material was prepared in substantially the same manner as in example 1 except that PLA porous microspheres having no essence embedded therein were added in the step (2).
[ comparative example 4 ]
A degradable material was produced in substantially the same manner as in example 1 except that the essence-embedded PLA porous microsphere in step (2) was replaced with 100g of essence-free PLA porous microsphere A.
The degradable material particles prepared above were dried at 60 ℃ for 3 hours, and injection molded at 180 ℃ using an injection molding machine, and tested for tensile strength, flexural modulus, impact strength, heat distortion temperature under load, TVOC, and flavor grade, respectively, and the results are shown in table 3.
TABLE 3 Performance test results
As can be seen from the data of the examples and the comparative examples, the degradable composite material prepared by the invention has obviously improved product rigidity, and the porous microsphere structure prepared by PLA is dispersed in the PBAT matrix, so that the improvement on the product rigidity is more obvious compared with the direct blending of PLA and PBAT. And the PLA porous microsphere can maintain the advantage of high toughness of the PBAT matrix while improving the rigidity of the product. The essence is filled in the PLA microsphere pores, so that the problem that the essence is separated out on the surface of the plastic can be avoided, and the fragrance dispersing effect is obvious, durable and stable.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. The degradable composite material with lasting fragrance is characterized by comprising the following raw materials in parts by weight:
2. the long lasting, biodegradable composite material according to claim 1, characterized in that it comprises the following raw materials in parts by weight:
3. the durable, biodegradable composite of claim 1 or 2, wherein the fragrance is one or more of vanillin, ethyl vanillin, milk fragrance.
4. A durable fragrance degradable composite according to claim 3, characterized in that the essence is embedded in the PLA porous microspheres in an amount of 5-35%.
5. The long lasting, degradable composite according to claim 4, wherein the PLA porous microspheres have an average particle size of 100-800 μm and a porosity of 30-90%.
6. A durable fragrance-degradable composite according to claim 1 or 2, characterized in that the mineral powder is one or more of calcium carbonate, mica, talc.
7. A method of preparing a durable fragrance degradable composite material according to any one of claims 1-6, comprising the steps of:
according to the weight parts, the PBAT, the mineral powder and the erucamide are added from a main feeding port of a double-screw extruder after being uniformly mixed, PLA porous microspheres embedded with essence are added from a side feeding port, and the degradable composite material is obtained through melt mixing and extrusion.
8. The method for preparing a durable fragrance degradable composite material according to claim 7, wherein the melt-kneading temperature is 150-170 ℃ and the rotational speed is 100-300r/min.
9. The method for preparing the biodegradable composite material with lasting fragrance according to claim 7 or 8, wherein the method for preparing the essence-embedded PLA porous microspheres comprises the following steps:
and (3) putting the PLA porous microspheres into the essence after being fully melted, stirring for 3-5 hours under the conditions of 0.8-1.2MPa and 90-120 ℃, filtering to obtain a solid, cooling and drying to obtain the PLA porous microspheres embedded with the essence.
10. Use of a durable fragrance-degradable composite material according to any one of claims 1 to 6 or a durable fragrance-degradable composite material prepared by a method according to any one of claims 7 to 9 for the manufacture of injection molded articles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441139.6A CN113999500B (en) | 2021-11-30 | 2021-11-30 | Degradable composite material with lasting fragrance, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111441139.6A CN113999500B (en) | 2021-11-30 | 2021-11-30 | Degradable composite material with lasting fragrance, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113999500A CN113999500A (en) | 2022-02-01 |
| CN113999500B true CN113999500B (en) | 2023-05-26 |
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