CN116554711B - Organic modified mica and preparation method and application thereof - Google Patents
Organic modified mica and preparation method and application thereof Download PDFInfo
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- CN116554711B CN116554711B CN202310487529.XA CN202310487529A CN116554711B CN 116554711 B CN116554711 B CN 116554711B CN 202310487529 A CN202310487529 A CN 202310487529A CN 116554711 B CN116554711 B CN 116554711B
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- 239000010445 mica Substances 0.000 title claims abstract description 116
- 229910052618 mica group Inorganic materials 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 54
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 17
- 229930195729 fatty acid Natural products 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 26
- -1 polybutylene adipate terephthalate Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 11
- 239000004626 polylactic acid Substances 0.000 claims description 11
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical group CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 3
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005469 granulation Methods 0.000 description 10
- 230000003179 granulation Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 150000001263 acyl chlorides Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- 229910052627 muscovite Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention provides an organic modified mica, a preparation method and application thereof. A process for preparing the organically modified mica includes such steps as dispersing mica in toluene, adding fatty acid chloride, stirring, sequentially dripping triethylamine and imidazole, stirring, cooling, filtering to obtain coarse modified mica, and drying. The preparation method of the organic modified mica is simple, mild in condition, easy to obtain raw materials, low in price, easy to realize, high in reaction efficiency and yield, capable of being applied to industrial production on a large scale, good in processability, high in mechanical strength, low in oxygen permeability and water vapor permeability when being blended with the full-biodegradable material, and capable of being applied to blown films.
Description
Technical Field
The invention relates to the technical field of silicate mineral materials, in particular to organic modified mica, a preparation method and application thereof.
Background
Mica belongs to silicate minerals, is rich in resources in China, can be used as a filling material of a polymer, reduces cost, and improves the performances of heat, mechanics, aging resistance and the like. Sericite is a heterogeneous muscovite which is in a superfine scale shape in mica, is called as fine scale-shaped muscovite, and has fine particles, high water content, firm layer combination and good dispersion suspension property. Such a layered structure is very suitable for use as a gas barrier material due to its scaly structure. However, when sericite is used as a gas barrier material, if the laminated lamellar structure can be separated by intercalation or exfoliation, a lamellar structure of more single layers can be obtained, and the barrier properties can be further improved. Meanwhile, the highest filling amount of the filling material restricts the performance of the material, and sericite with high content is easy to agglomerate, so that the barrier, thermal and mechanical properties of the material are reduced, and the use is influenced.
In order to obtain intercalated or exfoliated sericite, and simultaneously realize efficient dispersion in a polymer, agglomeration is reduced, a surface modification method is often adopted. The organic modified mica material is obtained by modifying the surface of sericite with a large number of hydroxyl (-OH) groups on the surface by a silane coupling agent and the like. Or reducing the bonding force between the layers through activation treatment, and then mixing and intercalating the mica and the organic reagent to obtain the organic modified mica material. However, these modifying methods have limited modifying effects on sericite and do not function well.
Disclosure of Invention
The invention aims to provide an organic modified mica, a preparation method and application thereof, and the preparation method provided by the invention realizes surface modification of sericite and intercalation and stripping of a lamellar structure, can improve interfacial compatibility between mica and a polymer when being used as a filling material of a biodegradable polymer, reduces aggregation of the mica and the polymer, and improves comprehensive performance of the material.
The invention is realized by the following technical scheme:
A preparation method of organic modified mica is characterized by comprising the following steps of dispersing mica into toluene, adding fatty acid acyl chloride, stirring, sequentially dripping triethylamine and imidazole, continuously stirring uniformly, cooling and filtering to obtain coarse modified mica, and drying the coarse modified mica to obtain the organic modified mica. The drying temperature proposed by the present invention is 115℃to 125℃and more preferably 120 ℃.
In the preparation method of the organic modified mica, acyl chloride groups of fatty acid acyl chloride are affinitized with hydroxyl groups on the surface of the mica, adsorbed on the surface of the mica, chloridion is removed under the action of triethylamine, and the fatty acid acyl chloride reacts with the hydroxyl groups on the mica directly to bond with the mica under the catalysis of imidazole, or self-polymer of a dimer is obtained after self-polymerization, the self-polymer continuously interacts with the hydroxyl groups on the mica under the catalysis of imidazole, and the self-polymer is bonded or physically adsorbed on the surface of the mica to obtain the organic modified mica (shown in figure 1).
Preferably, the preparation method specifically comprises the following steps: dispersing 100 parts by mass of mica into 100-500 parts by mass of toluene, adding 1-50 parts by mass of fatty acid chloride, stirring for 1-5 min, sequentially dripping 0.05-5 parts by mass of triethylamine and 0.01-0.05 part by mass of imidazole, continuously stirring for 0.5-1 h, cooling and filtering to obtain coarse modified mica, and carrying out heat preservation and drying on the coarse modified mica for 3-12 h to obtain the organic modified mica.
Further preferably, the preparation method specifically comprises the following steps: dispersing 100 parts by mass of mica into 500 parts by mass of toluene, adding 10-30 parts by mass of fatty acid chloride, stirring for 1-5 min, sequentially dripping 1-2 parts by mass of triethylamine and 0.02-0.03 part by mass of imidazole, continuously stirring for 0.5-1 h, cooling and filtering to obtain coarse modified mica, and carrying out heat preservation and drying on the coarse modified mica for 3-12 h to obtain the organic modified mica.
Preferably, the mica is sericite, and the particle size is 400-10000 meshes. The invention prefers sericite, and modifies, intercalates and peels the surface of the sericite, reduces stronger binding force between the lamellar layers of the sericite and enhances interface compatibility between the sericite and the polymer.
Preferably, the fatty acid in the fatty acid chloride is a fatty chain segment with a carbon chain length of between 12 and 20 carbons. The fatty acid acyl chloride is preferably stearic acid acyl chloride with acyl chloride functional groups, a stearic acid chain segment on the stearic acid acyl chloride is a hydrophobic and oleophilic fatty chain segment which does not participate in the reaction, and can also be a fatty chain segment with the carbon chain length of 12 to 20 carbon atoms such as a palmitic acid chain segment and the like besides the stearic acid chain segment, wherein one end of the chain segment is acyl chloride.
Further preferably, the fatty acid chloride is lauric acid chloride, stearic acid chloride or palmitic acid chloride.
The invention also protects the organic modified mica prepared by the preparation method.
The invention also protects a full-biodegradation composition which is obtained by melt blending the organic modified mica and the full-biodegradation material, wherein the organic modified mica accounts for 3-50% of the total mass.
The organic modified mica and the full biodegradable material blend provided by the invention have good processability, higher mechanical strength, lower oxygen permeability and water vapor permeability, and can be applied to blown films.
Preferably, the blending temperature is 150 ℃ to 210 ℃. Further preferably, the blending temperature is 160℃to 190 ℃.
The organic modified mica obtained by the preparation method of the invention realizes the efficient dispersion of the mica in the polymer, and improves the mechanical strength and gas barrier property of the polymer, especially the biodegradable material.
Preferably, the organically modified mica comprises 20% of the total mass.
Preferably, the fully biodegradable material is selected from more than one of polybutylene adipate terephthalate, polylactic acid, polypropylene carbonate, polyhydroxyalkanoate and polyvinyl alcohol.
The invention also protects the application of the organically modified mica as a filling material in biodegradable materials.
Compared with the prior art, the invention has the beneficial effects that:
1. In order to obtain the surface modified and intercalated sericite, the invention selects the amphipathic surfactant material fatty acid acyl chloride with affinity to hydroxyl (-OH) and triethylamine with reactivity to fatty acid acyl chloride, and under the catalysis of imidazole, stearic acid acyl chloride entering the mica interlayer reacts with triethylamine, and the product has good adhesiveness on the surface of the sericite. The organically modified sericite has certain hydrophobicity.
2. The organically modified mica has improved compatibility with the polymeric material compared to unmodified mica. After the inorganic filler is used for filling the polymer material, the polymer still maintains higher mechanical property, and the gas barrier property is improved.
3. After the organic modified mica provided by the invention is blended with the biodegradable material, the gas barrier property of the material is improved, and especially the water vapor transmittance is further reduced.
Drawings
FIG. 1 is a schematic diagram of the modification of organically modified mica.
Detailed Description
The present invention will be described in further detail with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental methods without specific conditions noted in the examples below are generally in accordance with conventional conditions in the art or in accordance with manufacturer's recommendations; the raw materials, reagents and the like used, unless otherwise specified, are considered to be commercially available through conventional markets and the like. The mica in the following examples and comparative examples is sericite, and the particle size is 400 to 10000 mesh.
The organically modified mica or mica of the following examples or comparative examples was tested by thermogravimetry and glass transition temperature, contact angle, as follows:
thermogravimetric analysis: and (3) testing by a thermogravimetric analyzer, testing under a nitrogen atmosphere, wherein the heating speed is 10 ℃/min, and the highest temperature is 800 ℃.
Contact angle: the organically modified mica or mica powder was pressed into flakes under 20MPa with an infrared tabletting machine, and the contact angle of 2. Mu.L of water drops on the flakes at 30s was measured on a contact angle tester.
The full biodegradable composition prepared in the following examples or comparative examples was injection molded, and subjected to a tensile test, a bending test and a notched Izod impact test. And (3) hot-press molding the full-biodegradable composition, setting the temperature of a heating plate to 180 ℃, setting the pressure to 15MPa, hot-pressing for 3min, cooling a cooling plate, and performing oxygen transmittance test on a polyester film with the thickness of 0.22mm in a die. Oxygen transmission rate test: the oxygen transmittance of the film is tested by adopting a coulomb method sensor test method, the set temperature is 23 ℃, and the relative humidity in the cavity is 0%. The water vapor transmittance of the film is tested by adopting an infrared sensor test method, the set temperature is 23 ℃, and the relative humidity of two sides of the cavity is 50%.
Example 1
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 10 parts by mass of stearic acid acyl chloride is added and stirred for 2min, 1 part by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process for 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain the organically modified mica.
(2) Weighing 20 parts by weight of the organic modified mica obtained in the step (1), and carrying out melt blending granulation on the organic modified mica and 80 parts by weight of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
And (3) testing the organic modified mica obtained in the step (1), wherein the thermal weight loss of the modified mica is 5.35%, and the contact angle is 121 degrees.
The fully biodegradable composition prepared in this example was tested for a tensile strength of 73MPa, an elongation at break of 7%, a flexural strength of 84MPa, a flexural modulus of 2800MPa and an impact strength of 28.9J/m. Oxygen transmission rate 325 cc/(m 2.24 h), water vapor transmission rate 24.5 g/(m 2.24 h).
Example 2
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 20 parts by mass of stearic acid acyl chloride is added and stirred for 2min, 1 part by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process for 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain the organically modified mica.
(2) Weighing 20 parts by mass of the organic modified mica obtained in the step (1), and carrying out melt blending granulation on the organic modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The organic modified mica prepared in this example was tested for thermal weight loss of 5.70% and contact angle of 123 °. The fully biodegradable composition prepared in this example was tested for a tensile strength of 71MPa, an elongation at break of 8%, a flexural strength of 80MPa, a flexural modulus of 2780MPa, and an impact strength of 29.4J/m. Oxygen transmission rate 300 cc.mm/(m 2.24 h), water vapor transmission rate 20.2 g/(m 2.24 h).
Example 3
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 30 parts by mass of stearic acid acyl chloride is added and stirred for 2min, 2 parts by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process within 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain the organically modified mica.
(2) Weighing 20 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The organic modified mica prepared in this example was tested for thermal weight loss of 6.0% and contact angle of 125 °. The full-biodegradable composition prepared in this example was tested for a tensile strength of 70MPa, an elongation at break of 8%, a flexural strength of 78MPa, a flexural modulus of 2750MPa, and an impact strength of 32J/m. The oxygen transmission rate is 290 cc.mm/(m 2.24 h), and the water vapor transmission rate is 17.8 g/(m 2.24 h).
Example 4
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 10 parts by mass of stearic acid acyl chloride is added and stirred for 2min, 1 part by mass of triethylamine and 0.03 part by mass of imidazole are added dropwise in the stirring process for 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain modified mica.
(2) Weighing 20 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The modified mica prepared in this example was tested for thermal weight loss of 6.5% and contact angle of 135 °. The fully biodegradable composition prepared in this example was tested for a tensile strength of 73MPa, an elongation at break of 8%, a flexural strength of 74MPa, a flexural modulus of 2720MPa, and an impact strength of 33.2J/m. Oxygen transmission 315 cc.mm/(m 2.24 h), water vapor transmission 22.6 g/(m 2.24 h).
Example 5
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 10 parts by mass of palmitic acid chloride is added and stirred for 2min, 1 part by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process within 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain modified mica.
(2) Weighing 20 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The modified mica prepared by this example was tested for thermal weight loss of 5.4% and contact angle of 123 °. The fully biodegradable composition prepared in this example was tested for a tensile strength of 74MPa, an elongation at break of 7.8%, a flexural strength of 79MPa, a flexural modulus of 2790MPa and an impact strength of 33.5J/m. The oxygen transmission rate is 309 cc.mm/(m 2.24 h), and the water vapor transmission rate is 21.6 g/(m 2.24 h).
Example 6
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 30 parts by mass of lauroyl chloride is added and stirred for 2min, 2 parts by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process within 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain the organically modified mica.
(2) Weighing 20 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The organic modified mica prepared in this example was tested for thermal weight loss of 4.2% and contact angle of 109 °. The fully biodegradable composition prepared in this example was tested for tensile strength of 69MPa, elongation at break of 7%, flexural strength of 73MPa, flexural modulus of 2690MPa, and impact strength of 27.7J/m. The oxygen transmission rate is 350 cc.mm/(m 2.24 h), and the water vapor transmission rate is 22.9 g/(m 2.24 h).
Comparative example 1
100 Parts of polylactic acid are melted, blended and granulated in a double-screw extruder, and the mixing temperature is 190 ℃ to obtain the full-biodegradable composition.
The full-biodegradable composition prepared in this comparative example was tested for tensile strength of 64MPa, elongation at break of 9.1%, flexural strength of 63MPa, flexural modulus of 2650MPa, and impact strength of 27J/m. Oxygen transmission rate 555 cc.mm/(m 2.24 h), water vapor transmission rate 67 g/(m 2.24 h).
Comparative example 2
20 Parts by mass of mica and 80 parts by mass of polylactic acid are weighed by using unmodified common mica GM-6, and are subjected to melt blending granulation in a double-screw extruder, and the mixing temperature is 190 ℃ to obtain the full-biodegradable composition.
Mica has a thermal weight loss of 2.2% and a contact angle of 0 °.
The full-biodegradable composition prepared in this comparative example was tested for a tensile strength of 53MPa, an elongation at break of 3.1%, a flexural strength of 70MPa, a flexural modulus of 2900MPa, and an impact strength of 21J/m. The oxygen transmission rate is 450 cc.mm/(m 2.24 h), and the water vapor transmission rate is 59 g/(m 2.24 h).
Comparative example 3
(1) 100 Parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 10 parts by mass of benzoyl chloride is added and stirred for 2min, 1 part by mass of triethylamine and 0.02 part by mass of imidazole are added dropwise in the stirring process within 0.5h, stirring is continued for 1h, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 6h to obtain modified mica.
(2) Weighing 20 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 80 parts by mass of polylactic acid in a double-screw extruder, wherein the mixing temperature is 190 ℃, so as to obtain the full-biodegradable composition.
The modified mica prepared in this comparative example was tested for thermal weight loss of 2.9% and contact angle of 0 °.
The full-biodegradable composition prepared in this comparative example was tested for tensile strength of 55MPa, elongation at break of 5.1%, flexural strength of 72MPa, flexural modulus of 2930MPa, and impact strength of 23.5J/m. Oxygen transmission rate 440 cc.mm/(m 2.24 h), water vapor transmission rate 57 g/(m 2.24 h).
Example 7
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 100 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 1 part by mass of stearic acid acyl chloride is added and stirred for 1min, 0.05 part by mass of triethylamine and 0.01 part by mass of imidazole are added dropwise in the stirring process for 0.5h, stirring is continued for 0.5h, cooling and filtering are carried out, and a filter cake is taken out in an oven at 120 ℃ for 3h to obtain modified mica.
(2) Weighing 3 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 97 parts by mass of polybutylene adipate terephthalate in a double-screw extruder, wherein the mixing temperature is 180 ℃, so as to obtain the full-biodegradable composition.
Example 8
A full-biodegradable composition is prepared by the following steps:
(1) 100 parts by mass of mica is weighed into 500 parts by mass of toluene solution, stirred and dispersed in a three-hole flask, 50 parts by mass of palmitic acid chloride is added and stirred for 5 minutes, 5 parts by mass of triethylamine and 0.05 part by mass of imidazole are dropwise added in the stirring process within 0.5 hour, the stirring is continued for 1 hour, cooling and filtering are carried out, and a filter cake is taken out in a baking oven at 120 ℃ for 12 hours to obtain modified mica.
(2) Weighing 50 parts by mass of the modified mica obtained in the step (1), and carrying out melt blending granulation on the modified mica and 50 parts by mass of the polypropylene carbonate in a double-screw extruder, wherein the mixing temperature is 200 ℃, so as to obtain the full-biodegradable composition.
The above embodiments are only described to assist in understanding the technical solution of the present invention and its core idea, and it should be noted that it will be obvious to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (9)
1. The preparation method of the organic modified mica is characterized by comprising the following steps of: dispersing 100 parts by mass of mica into 100-500 parts by mass of toluene, adding 1-50 parts by mass of fatty acid chloride, stirring for 1-5 min, sequentially dripping 0.05-5 parts by mass of triethylamine and 0.01-0.05 part by mass of imidazole, continuously stirring for 0.5-1 h, cooling and filtering to obtain coarse modified mica, and carrying out heat preservation and drying on the coarse modified mica for 3-12 h to obtain the organic modified mica.
2. The preparation method according to claim 1, comprising the specific steps of: dispersing 100 parts by mass of mica into 500 parts by mass of toluene, adding 10-30 parts by mass of fatty acid chloride, stirring for 1-5 min, sequentially dripping 1-2 parts by mass of triethylamine and 0.02-0.03 part by mass of imidazole, continuously stirring for 0.5-1 h, cooling and filtering to obtain coarse modified mica, and carrying out heat preservation and drying on the coarse modified mica for 3-12 h to obtain the organic modified mica.
3. The preparation method according to claim 1 or 2, wherein the mica is sericite and has a particle size of 400-10000 meshes.
4. The method according to claim 1 or 2, wherein the fatty acid in the fatty acid chloride is a fatty segment having a carbon chain length of between 12 and 20 carbons.
5. The method according to claim 4, wherein the fatty acid chloride is lauric acid chloride, stearic acid chloride or palmitic acid chloride.
6. An organically modified mica prepared by the preparation method of claim 1 or 2.
7. A fully biodegradable composition is characterized by being obtained by melt blending the organic modified mica and a fully biodegradable material according to claim 6, wherein the organic modified mica accounts for 3% -50% of the total mass.
8. The composition of claim 7, wherein the fully biodegradable material is selected from the group consisting of polybutylene adipate terephthalate, polylactic acid, polypropylene carbonate, polyhydroxyalkanoates, and polyvinyl alcohol.
9. Use of the organically modified mica of claim 6 as a filler material in biodegradable materials.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156724A (en) * | 1996-12-19 | 1997-08-13 | 吴县市天马化工原料厂 | Process for producing alkyl ketene dipolymer |
| CN1337388A (en) * | 2000-08-07 | 2002-02-27 | 王景明 | Prepn of alkyl ketene dimer |
| CN1412184A (en) * | 2001-10-16 | 2003-04-23 | 田载扬 | Production process of alkyl ketene dimer |
| CN101879482A (en) * | 2010-06-17 | 2010-11-10 | 新疆有色金属研究所 | Novel mica inhibiting agent, and preparation method and use method thereof |
| CN102241877A (en) * | 2010-05-12 | 2011-11-16 | 邹俊 | Polylactic acid modified material, and preparation method and application thereof |
| CN107629303A (en) * | 2017-09-25 | 2018-01-26 | 佛山慧创正元新材料科技有限公司 | Add the preparation method of the degradable nano packaging film of modified nano montmorillonite |
| CN207523142U (en) * | 2017-07-07 | 2018-06-22 | 平江县盛盈云母工业有限公司 | A kind of high temperature resistant release paper based on mica paper base material |
| CN108329721A (en) * | 2018-02-07 | 2018-07-27 | 南京工业大学 | Modified mica and preparation method and application thereof |
| CN109749582A (en) * | 2019-01-22 | 2019-05-14 | 雷洪军 | A kind of graphene heat radiation coating and preparation method thereof |
| CN109929228A (en) * | 2019-04-17 | 2019-06-25 | 谷水英 | Green biodegradable plastics film and its processing technology |
| CN111485450A (en) * | 2020-04-28 | 2020-08-04 | 济宁明升新材料有限公司 | Preparation method of high-melting-point AKD sizing agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009026421B4 (en) * | 2008-05-23 | 2019-08-29 | Gelest Technologies, Inc. | Silanes with embedded hydrophilicity, dispersible particles derived therefrom and associated processes |
-
2023
- 2023-04-28 CN CN202310487529.XA patent/CN116554711B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156724A (en) * | 1996-12-19 | 1997-08-13 | 吴县市天马化工原料厂 | Process for producing alkyl ketene dipolymer |
| CN1337388A (en) * | 2000-08-07 | 2002-02-27 | 王景明 | Prepn of alkyl ketene dimer |
| CN1412184A (en) * | 2001-10-16 | 2003-04-23 | 田载扬 | Production process of alkyl ketene dimer |
| CN102241877A (en) * | 2010-05-12 | 2011-11-16 | 邹俊 | Polylactic acid modified material, and preparation method and application thereof |
| CN101879482A (en) * | 2010-06-17 | 2010-11-10 | 新疆有色金属研究所 | Novel mica inhibiting agent, and preparation method and use method thereof |
| CN207523142U (en) * | 2017-07-07 | 2018-06-22 | 平江县盛盈云母工业有限公司 | A kind of high temperature resistant release paper based on mica paper base material |
| CN107629303A (en) * | 2017-09-25 | 2018-01-26 | 佛山慧创正元新材料科技有限公司 | Add the preparation method of the degradable nano packaging film of modified nano montmorillonite |
| CN108329721A (en) * | 2018-02-07 | 2018-07-27 | 南京工业大学 | Modified mica and preparation method and application thereof |
| CN109749582A (en) * | 2019-01-22 | 2019-05-14 | 雷洪军 | A kind of graphene heat radiation coating and preparation method thereof |
| CN109929228A (en) * | 2019-04-17 | 2019-06-25 | 谷水英 | Green biodegradable plastics film and its processing technology |
| CN111485450A (en) * | 2020-04-28 | 2020-08-04 | 济宁明升新材料有限公司 | Preparation method of high-melting-point AKD sizing agent |
Non-Patent Citations (6)
| Title |
|---|
| AKD对滑石粉和绢云母的改性效果与作用机理;杨德清 等;中国造纸(第04期);1-7 * |
| AKD改性填料的表面施胶性能;杨德清 等;中华纸业;第30卷(第20期);47-50 * |
| PLA/PBAT/ 绢云母复合材料制备与性能;张震 等;工程塑料应用;第50卷(第2期);33-38 * |
| 电气石粉体表面有机化改性探讨;边静;中国优秀硕士学位论文全文数据库;1-66 * |
| 疏水改性填料用于纸张施胶;杨德清;中国优秀硕士学位论文全文数据库;1-92 * |
| 绢云母表面改性的研究进展;梁玉 等;中国非金属矿工业导刊(第01期);5-8 * |
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