CN113652068A - Nano composite plastic, preparation method thereof and three-dimensional mark - Google Patents
Nano composite plastic, preparation method thereof and three-dimensional mark Download PDFInfo
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- 229920003023 plastic Polymers 0.000 title claims abstract description 52
- 239000004033 plastic Substances 0.000 title claims abstract description 52
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 66
- 239000002121 nanofiber Substances 0.000 claims abstract description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 29
- 229920002678 cellulose Polymers 0.000 claims abstract description 26
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 19
- 239000004814 polyurethane Substances 0.000 claims abstract description 19
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 19
- 239000002159 nanocrystal Substances 0.000 claims abstract description 13
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 12
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003365 glass fiber Substances 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 16
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 11
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 11
- 241001330002 Bambuseae Species 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 11
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 11
- 239000011425 bamboo Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 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 claims description 7
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- 235000019359 magnesium stearate Nutrition 0.000 claims description 7
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000001350 alkyl halides Chemical class 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 235000010216 calcium carbonate Nutrition 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 235000012222 talc Nutrition 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 125000001309 chloro group Chemical group Cl* 0.000 description 17
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
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- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 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 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004526 silane-modified polyether Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000009629 microbiological culture Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000012138 yeast extract Substances 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
- C08L67/06—Unsaturated polyesters
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a nano composite plastic, a preparation method thereof and a three-dimensional mark. The nano composite plastic comprises the following components in parts by weight: 53-68 parts of unsaturated polyester resin, 20-32 parts of polyurethane, 5-11 parts of halogenated group substituted hydroxyl modified nano fiber, 3-6 parts of natural fiber, and an auxiliary agent and a filler for plastics; the nano-fiber comprises the following components in parts by weight: 3-5 parts of cellulose nanocrystals, 1-3 parts of cellulose nanofibrils, 3-6 parts of carbon nanofibers and 5-9 parts of glass fibers. The nano composite plastic has excellent mechanical performance, deformation resistance and degradability. The invention also provides a preparation method of the nano composite plastic and a three-dimensional mark comprising the nano composite plastic.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nano composite plastic, a preparation method thereof and a three-dimensional mark.
Background
The base material used for manufacturing enterprise marks, car body marks and the like is usually ABS resin, High Density Polyethylene (HDPE), polypropylene (PP) and the like. However, these materials have certain defects and are difficult to be applied, for example, the aging resistance, the environmental cracking resistance, the low temperature impact resistance and the like are poor, and the materials are difficult to resist oxidation, acid and alkali corrosion and the like in the outdoor environment for a long time.
Disclosure of Invention
Based on the above, the invention provides a heat-resistant, cold-deformation-resistant and high-strength nano composite plastic, which comprises the following components in parts by weight:
53-68 parts of unsaturated polyester resin, 20-32 parts of polyurethane, 5-11 parts of halogenated group substituted hydroxyl modified nano fiber, 3-6 parts of natural fiber, and an auxiliary agent and a filler for plastics;
the nano-fiber comprises the following components in parts by weight:
3-5 parts of cellulose nanocrystals, 1-3 parts of cellulose nanofibrils, 3-6 parts of carbon nanofibers and 5-9 parts of glass fibers.
Optionally, as described in the above nanocomposite plastic, the natural fiber comprises the following components in parts by weight: 1-3.5 parts of bamboo fiber and 1-11 parts of cotton fiber.
Optionally, in the nanocomposite plastic described above, the filler includes at least one of nano kaolin, talc, calcium carbonate, and magnesium stearate.
Optionally, in the nanocomposite plastic described above, the filler includes at least one of nano kaolin, talc, calcium carbonate, and magnesium stearate.
Optionally, as described in the above nanocomposite plastic, the auxiliary agent includes at least one of a compatibilizer, a flame retardant, an anti-ultraviolet agent, and an antioxidant.
Optionally, as described in the above nanocomposite plastic, the compatibilizer includes at least one of polyethylene glycol, a silane coupling agent, aluminum titanate, and titanate; and/or
The flame retardant comprises at least one of antimony trioxide, aluminum hydroxide and magnesium hydroxide.
Optionally, as in the nanocomposite plastic described above, the anti-ultraviolet agent includes nano titanium dioxide and/or nano zinc oxide.
In one aspect of the present invention, there is also provided a method for preparing the nanocomposite plastic, including the following steps:
and mixing and heating the unsaturated polyester resin, the polyurethane, the halogen-substituted hydroxyl modified nano-fiber, the natural fiber, the filler and the plastic auxiliary agent to form molten liquid, and plasticizing the molten liquid in a mold.
Optionally, as described in the above preparation method of nanocomposite plastic, the preparation method of the halo-substituted hydroxyl-modified nanofiber includes the following steps:
mixing the nanofiber with alkyl halide and thionyl chloride, heating and refluxing, adding 2-propylene-1-alcohol, heating, centrifugally separating, drying the obtained solid, and preparing the halo-substituted hydroxyl modified nanofiber.
Optionally, in the preparation method of the nanocomposite plastic, the mass ratio of the nanofiber to dichloroethane, thionyl chloride and 2-propen-1-ol is (5-11): (3-8): (2-3).
In another aspect of the present invention, there is further provided a three-dimensional emblem including a vehicle body emblem or an enterprise emblem, comprising the nanocomposite plastic as described above.
According to research, the invention discovers that the mechanical strength of the whole plastic matrix is enhanced by modifying the nano-fibers and grafting the nano-fibers into the unsaturated polyester resin. The natural fiber further enhances the strength of the composite material on the basis of improving the antistatic property of the plastic. In addition, the composite plastic prepared by the invention also has degradability, cold resistance and heat resistance. The polyurethane and the unsaturated polyester can form an interpenetrating network structure, so that the toughness of the nano composite plastic is ensured, and the bending strength and the impact strength of the nano composite plastic are improved.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
On one hand, the invention provides a nano composite plastic which comprises the following components in parts by weight:
53-68 parts of unsaturated polyester resin, 20-32 parts of polyurethane, 5-11 parts of halogenated group substituted hydroxyl modified nano fiber, 3-6 parts of natural fiber, and an auxiliary agent and a filler for plastics;
the nano-fiber comprises the following components in parts by weight:
3-5 parts of cellulose nanocrystals, 1-3 parts of cellulose nanofibrils, 3-6 parts of carbon nanofibers and 5-9 parts of glass fibers.
In some embodiments, the natural fibers comprise the following components in parts by weight: 1-3.5 parts of bamboo fiber and 1-11 parts of cotton fiber.
The introduction of the natural fiber can enable the nano composite plastic to have the characteristics of excellent mechanical property, acid and alkali corrosion resistance, difficult deformation and long service life on the basis of enabling the nano composite plastic to have the antistatic property.
In some embodiments, the filler comprises at least one of nano kaolin, talc, calcium carbonate, and magnesium stearate.
In some embodiments, the filler is added in an amount of 2 to 5 parts.
In some embodiments, the adjuvant comprises at least one of a compatibilizing agent, a flame retardant, an anti-ultraviolet agent, and an antioxidant.
In some embodiments, the compatibilizing agent comprises at least one of polyethylene glycol, a silane coupling agent, an aluminum titanate, and a titanate; and/or
The flame retardant comprises at least one of antimony trioxide, aluminum hydroxide and magnesium hydroxide.
In some embodiments, the silane coupling agent may be any one commonly used in the art, including but not limited to, KH-550 silane coupling agent, KH-570 silane coupling agent, HD-a151 silane coupling agent, and the like.
In some embodiments, the compatibilizer is added in an amount of 1 to 3 parts and the flame retardant is added in an amount of 2 to 7 parts.
In some embodiments, the anti-uv agent comprises nano titanium dioxide and/or nano zinc oxide. Preferably, the uvioresistant agent is nano titanium dioxide.
In some embodiments, the anti-ultraviolet agent is added in an amount of 3 to 7 parts, and the antioxidant is added in an amount of 0.5 to 1.5 parts.
In another aspect of the present invention, a method for preparing the above nanocomposite plastic is also provided, which comprises the following steps:
unsaturated polyester resin, polyurethane, halogen-substituted hydroxyl modified nano-fiber, natural fiber, filler and plastic are mixed and heated by using an auxiliary agent to form molten liquid, and the molten liquid is placed in a mold for plasticizing.
In some embodiments, the plasticizing is pressure plasticizing, the pressure of the pressure being 18MPa to 25 MPa.
In some embodiments, the method of making halo-substituted hydroxyl-modified nanofibers comprises the steps of:
mixing the nanofiber with alkyl halide and thionyl chloride, heating and refluxing, adding 2-propylene-1-alcohol, heating, centrifugally separating, drying the obtained solid, and preparing the halo-substituted hydroxyl modified nanofiber.
The hydroxyl on the nano reinforced fiber is activated by thionyl chloride, then the hydroxyl and chlorine atoms in dichloroethane generate substitution reaction, and the hydroxyl is grafted to unsaturated polyester resin under the action of 2-propylene-1-alcohol, so that the mechanical property of the unsaturated polyester resin is improved.
In some embodiments, the alkyl halide is any alkyl halide commonly used in the art, and may be, for example, dichloroethane.
In some embodiments, the temperature of the heating reflux is 70 ℃ to 80 ℃ for 5h to 6 h.
In some embodiments, after the 2-propen-1-ol is added and heated, the method further comprises the steps of stirring and washing, wherein the heating temperature is 60-70 ℃, the stirring time is 5-15 h, and the solvent used for washing is acetone or ethanol.
In some embodiments, the mass ratio of the nanofibers to dichloroethane, thionyl chloride, and 2-propen-1-ol is (5-11): (3-8): (2-3).
In still another aspect of the present invention, there is provided a three-dimensional emblem including a vehicle body emblem or an enterprise emblem, which includes the nanocomposite plastic described above.
In some embodiments, the method of making the three-dimensional emblem may be injection molding. The injection molding process has high production speed and high efficiency, and can realize automation in operation. The manufactured mark can be changed from a simple shape to a complex shape, the size can be changed from large to small, the size of the product is accurate, and the product is easy to update and can be changed into a product with a complex shape.
In some embodiments, the material of the mold used in the injection molding process may be any steel material commonly used in the art. The medium carbon alloy steel H13 is selected in the invention in consideration of the strength, toughness, wear resistance, thermal fatigue resistance, seizure resistance and the like of the die. The steel grade has excellent heat strength, corrosion resistance, hardenability and the like, and has lower cost.
In some embodiments, the injection molding machine used in the injection molding process may be any one commonly used in the art. Preferably, the injection molding machine used is a TOSIHIBA 2000 g 450 ton injection molding machine.
In some embodiments, the body sign is mounted to the vehicle by an adhesive, which may be a silicone adhesive, a silane modified polyether sealant, or a polyurethane adhesive. Can make automobile body sign install fast and dismantle through the binder, and can carry out the reutilization on the basis of guaranteeing that the product does not take place to warp. And the binder on the automobile body also can be cleared up fast, can not cause the damage to the automobile body anticorrosive coating. Preferably, the binder is a polyurethane glue or a silane modified polyether sealant. More preferably, the binder is a silane modified polyether sealant. The sealant has good cohesiveness, elasticity, weather resistance and paintability.
The nanocomposite plastic of the present invention, the preparation method thereof, and the three-dimensional symbols are further described in detail below with reference to specific examples and comparative examples.
Example 1
1) Uniformly mixing 3.6 parts of cellulose nanocrystals, 2.5 parts of cellulose nanofibrils, 3 parts of carbon nanofibers and 7.4 parts of glass fibers to prepare 16.5 parts of nano reinforced fibers;
2) and (3) uniformly mixing the 16.5 parts of nano reinforced fiber and 4.5 parts of dichloroethane, adding 4.2 parts of thionyl chloride, uniformly stirring, heating to 74.5 ℃, and refluxing for 5.5 hours. Cooling to room temperature, adding 6 parts of 2-propylene-1-ol, uniformly mixing, heating to 69 ℃, stirring for 8 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 6 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 4.8 parts of natural fibers (the mass ratio of the bamboo fibers to the cotton fibers is 7:5) in 2.1 parts of polyethylene glycol to prepare a natural fiber dispersion liquid;
4) mixing 6 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 53 parts of unsaturated polyester resin, 26 parts of polyurethane, 7 parts of nano-titanium dioxide, 2 parts of antimony trioxide, 3.5 parts of nano-kaolin and 1 part of antioxidant, and heating at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 2
1) Uniformly mixing 4.2 parts of cellulose nanocrystals, 1.9 parts of cellulose nanofibrils, 6 parts of carbon nanofibers and 6.2 parts of glass fibers to prepare 18.3 parts of nano reinforced fibers;
2) and (3) uniformly mixing 18.3 parts of nano reinforced fiber and 5.5 parts of dichloroethane, adding 2 parts of thionyl chloride, uniformly stirring, heating to 70 ℃, and refluxing for 6 hours. Cooling to room temperature, adding 4.3 parts of 2-propylene-1-ol, uniformly mixing, heating to 66 ℃, stirring for 14 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 9 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 6 parts of natural fibers (the mass ratio of the bamboo fibers to the cotton fibers is 7:5) in 1 part of KH550 to prepare a natural fiber dispersion liquid;
4) 9 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 61 parts of unsaturated polyester resin, 22 parts of polyurethane, 4.5 parts of nano-titanium dioxide, 4.2 parts of aluminum hydroxide, 2 parts of talcum powder and 0.5 part of antioxidant are mixed and heated at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 3
1) Uniformly mixing 4.8 parts of cellulose nanocrystals, 3 parts of cellulose nanofibrils, 3.4 parts of carbon nanofibers and 8 parts of glass fibers to prepare 19.2 parts of nano reinforced fibers;
2) and (3) uniformly mixing the 19.2 parts of nano reinforced fiber and 8 parts of dichloroethane, adding 3.6 parts of thionyl chloride, uniformly stirring, heating to 71.5 ℃, and refluxing for 6 hours. Cooling to room temperature, adding 5.2 parts of 2-propylene-1-ol, uniformly mixing, heating to 63 ℃, stirring for 11 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 8 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 4.5 parts of natural fibers (the mass ratio of the bamboo fibers to the cotton fibers is 2:1) in 1.6 parts of aluminum titanate to prepare a natural fiber dispersion liquid;
4) mixing 8 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 55 parts of unsaturated polyester resin, 30 parts of polyurethane, 3.2 parts of magnesium hydroxide, 3 parts of nano-titanium dioxide, 5 parts of calcium carbonate and 1.2 parts of antioxidant, and heating at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 4
1) Uniformly mixing 3 parts of cellulose nanocrystals, 1.3 parts of cellulose nanofibrils, 4.7 parts of carbon nanofibers and 8.5 parts of glass fibers to prepare 17.5 parts of nano reinforced fibers;
2) and (3) uniformly mixing the 17.5 parts of nano reinforced fiber and 7.2 parts of dichloroethane, adding 3 parts of thionyl chloride, uniformly stirring, heating to 71.5 ℃, and refluxing for 6 hours. Cooling to room temperature, adding 5.5 parts of 2-propylene-1-ol, uniformly mixing, heating to 63 ℃, stirring for 11 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 8.5 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 3 parts of natural fibers (the mass ratio of the bamboo fibers to the cotton fibers is 2:1) in 2.7 parts of titanate to prepare a natural fiber dispersion liquid;
4) mixing 8.5 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 65 parts of unsaturated polyester resin, 20 parts of polyurethane, 3.8 parts of a mixture of antimony trioxide and aluminum hydroxide (the mass ratio is 9.5:0.5), 5.6 parts of nano titanium dioxide, 4.8 parts of magnesium stearate and 0.6 part of antioxidant, and heating at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 5
1) Uniformly mixing 4.5 parts of cellulose nanocrystals, 1.6 parts of cellulose nanofibrils, 5.2 parts of carbon nanofibers and 5 parts of glass fibers to prepare 16.3 parts of nano reinforced fibers;
2) and uniformly mixing the 16.3 parts of nano reinforced fiber and 6 parts of dichloroethane, adding 6 parts of thionyl chloride, uniformly stirring, heating to 73 ℃, and refluxing for 5.5 hours. Cooling to room temperature, adding 4.9 parts of 2-propylene-1-ol, uniformly mixing, heating to 70 ℃, stirring for 5 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 11 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 3.5 parts of natural fibers (the mass ratio of the bamboo fibers to the cotton fibers is 4:3) in 2.4 parts of a mixture (the mass ratio is 2:8) of polyethylene glycol and a silane coupling agent to prepare a natural fiber dispersion liquid;
4) 11 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 68 parts of unsaturated polyester resin, 28 parts of polyurethane, 5.4 parts of a mixture of aluminum hydroxide and magnesium hydroxide (the mass ratio is 3:7), 4 parts of nano titanium dioxide, 2.5 parts of a mixture of nano kaolin and talcum powder (the mass ratio is 8:2) and 1.5 parts of antioxidant are mixed and heated at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 6
1) Uniformly mixing 5 parts of cellulose nanocrystals, 2.8 parts of cellulose nanofibrils, 4.2 parts of carbon nanofibers and 9 parts of glass fibers to prepare 21 parts of nano reinforced fibers;
2) and (3) uniformly mixing the 21 parts of nano reinforced fiber and 4 parts of dichloroethane, adding 2.5 parts of thionyl chloride, uniformly stirring, heating to 76 ℃, and refluxing for 5 hours. Cooling to room temperature, adding 5.8 parts of 2-propylene-1-ol, uniformly mixing, heating to 60 ℃, stirring for 15 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 7 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 5.5 parts of natural fibers (the mass ratio of bamboo fibers to cotton fibers is 6:5) in 3 parts of a mixture of KH-550 and aluminum titanate (the mass ratio is 9:1) to prepare a natural fiber dispersion liquid;
4) 7 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 57 parts of unsaturated polyester resin, 32 parts of polyurethane, 2.6 parts of a mixture of antimony trioxide and magnesium hydroxide (the mass ratio is 3:7), 5 parts of nano titanium dioxide, 4.5 parts of a mixture of calcium carbonate and magnesium stearate (the mass ratio is 5:4.5:0.5) and 1.3 parts of antioxidant are mixed and heated at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 7
1) Uniformly mixing 3.3 parts of cellulose nanocrystals, 2.2 parts of cellulose nanofibrils, 3.8 parts of carbon nanofibers and 5.6 parts of glass fibers to prepare 14.9 parts of nano reinforced fibers;
2) and (3) uniformly mixing 14.9 parts of nano reinforced fiber and 6.6 parts of dichloroethane, adding 5.5 parts of thionyl chloride, uniformly stirring, heating to 77.5 ℃, and refluxing for 5 hours. Cooling to room temperature, adding 4.6 parts of 2-propylene-1-ol, uniformly mixing, heating to 67 ℃, stirring for 9.5 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 5 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 4 parts of natural fibers (the mass ratio of bamboo fibers to cotton fibers is 3:2) in 1.9 parts of a mixture of aluminum titanate and titanate (the mass ratio is 7:3) to prepare a natural fiber dispersion liquid;
4) 5 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 63 parts of unsaturated polyester resin, 24 parts of polyurethane, 7 parts of antimony trioxide, a mixture of aluminum hydroxide and magnesium hydroxide (the mass ratio is 6:4:1), 3.5 parts of nano titanium dioxide, 4 parts of a mixture of talcum powder and calcium carbonate (the mass ratio is 9:1) and 0.9 part of antioxidant are mixed and heated at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Example 8
1) Uniformly mixing 3.9 parts of cellulose nanocrystals, 1 part of cellulose nanofibrils, 5.7 parts of carbon nanofibers and 6.8 parts of glass fibers to prepare 17.4 parts of nano reinforced fibers;
2) and (3) uniformly mixing the 17.4 parts of nano reinforced fiber and 5 parts of dichloroethane, adding 5 parts of thionyl chloride, uniformly stirring, heating to 80 ℃, and refluxing for 5 hours. Cooling to room temperature, adding 4 parts of 2-propylene-1-ol, uniformly mixing, heating to 64.5 ℃, stirring for 6.5 hours, washing with acetone, centrifuging, taking the solid, drying in vacuum, and cooling to room temperature to obtain 10 parts of chlorine atom substituted hydroxyl modified nanofiber;
3) dispersing 5 parts of natural fibers (the mass ratio of bamboo fibers to cotton fibers is 3:2) in 1.3 parts of a mixture of aluminum titanate and titanate (the mass ratio is 7:3) to prepare a natural fiber dispersion liquid;
4) mixing 10 parts of chlorine atom substituted hydroxyl modified nano-fiber, natural fiber dispersion liquid, 59 parts of unsaturated polyester resin, 31 parts of polyurethane, 4.8 parts of antimony trioxide, 6.2 parts of nano-titanium dioxide, 3 parts of nano-kaolin, a mixture of calcium carbonate and magnesium stearate (the mass ratio is 6:3:1) and 0.8 part of antioxidant, and heating at 320 ℃ for 3 hours. And then placing the melted mixed solution in a mold, pressing for 2 hours at 20MPa, and naturally cooling.
Comparative example 1
Comparative example 1 was prepared substantially the same as example 1, except that: the addition amount of the unsaturated polyester resin is 50 parts.
Comparative example 2
Comparative example 2 was prepared substantially the same as example 1, except that: the amount of polyurethane added was 15 parts.
Comparative example 3
Comparative example 3 is prepared substantially the same as example 1, except that: a method for preparing nano reinforced fiber. The method comprises the following specific steps:
and 3.6 parts of cellulose nanocrystals and 2.5 parts of cellulose nanofibrils are uniformly mixed to prepare 6.1 parts of nano reinforced fiber.
Performance testing
The nano composite plastics prepared in examples 1 to 8 and comparative examples 1 to 3 were subjected to related performance tests, and the test results are shown in table 1:
degradability: the nanocomposite plastics prepared in each example and comparative example, which were of the same mass, were placed in a microbiological culture medium consisting of tryptone, yeast extract, glucose and agar in a mass ratio of 15:5:2:27, respectively, for observation of degradability, and the degradation time was recorded.
TABLE 1 relevant Performance test of nanocomposite plastics prepared in examples 1 to 8 and comparative examples 1 to 3
From the test results in the table above, it can be seen that the nanocomposite plastic prepared by the invention has good heat resistance and cold resistance, and has higher strength and excellent toughness, so that the product has higher impact resistance while having tensile resistance and bending resistance. In addition, the nano composite plastic also has biodegradability and is relatively environment-friendly.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The nano composite plastic is characterized by comprising the following components in parts by weight:
53-68 parts of unsaturated polyester resin, 20-32 parts of polyurethane, 5-11 parts of halogenated group substituted hydroxyl modified nano fiber, 3-6 parts of natural fiber, and an auxiliary agent and a filler for plastics;
the nano-fiber comprises the following components in parts by weight:
3-5 parts of cellulose nanocrystals, 1-3 parts of cellulose nanofibrils, 3-6 parts of carbon nanofibers and 5-9 parts of glass fibers.
2. The nanocomposite plastic according to claim 1, wherein the natural fibers comprise the following components in parts by weight: 1-3.5 parts of bamboo fiber and 1-11 parts of cotton fiber.
3. The nanocomposite plastic of claim 1, wherein the filler comprises at least one of nano kaolin, talc, calcium carbonate, and magnesium stearate.
4. The nanocomposite plastic of claim 1, wherein the auxiliary agent comprises at least one of a compatibilizer, a flame retardant, an anti-ultraviolet agent, and an antioxidant.
5. The nanocomposite plastic of claim 4, wherein the compatibilizer comprises at least one of polyethylene glycol, a silane coupling agent, aluminum titanate, and titanate; and/or
The flame retardant comprises at least one of antimony trioxide, aluminum hydroxide and magnesium hydroxide.
6. The nanocomposite plastic according to claim 4, wherein the anti-ultraviolet agent comprises nano titanium dioxide and/or nano zinc oxide.
7. A method for preparing a nanocomposite plastic according to any one of claims 1 to 6, comprising the steps of:
and mixing and heating the unsaturated polyester resin, the polyurethane, the halogen-substituted hydroxyl modified nano-fiber, the natural fiber, the filler and the plastic auxiliary agent to form molten liquid, and plasticizing the molten liquid in a mold.
8. The nanocomposite plastic according to claim 7, wherein the preparation method of the halo-substituted hydroxyl-modified nanofiber comprises the following steps:
mixing the nanofiber with alkyl halide and thionyl chloride, heating and refluxing, adding 2-propylene-1-alcohol, heating, centrifugally separating, drying the obtained solid, and preparing the halo-substituted hydroxyl modified nanofiber.
9. The nanocomposite plastic according to claim 8, wherein the mass ratio of the nanofibers to dichloroethane, thionyl chloride and 2-propen-1-ol is (5-11): (3-8): (2-3).
10. A three-dimensional emblem, including a vehicle body emblem or an enterprise emblem, comprising the nanocomposite plastic of any of claims 1-6.
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