CN110643113B - Low-VOCs (volatile organic compounds) bamboo fiber modified plastic and preparation method thereof - Google Patents

Low-VOCs (volatile organic compounds) bamboo fiber modified plastic and preparation method thereof Download PDF

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CN110643113B
CN110643113B CN201910908098.3A CN201910908098A CN110643113B CN 110643113 B CN110643113 B CN 110643113B CN 201910908098 A CN201910908098 A CN 201910908098A CN 110643113 B CN110643113 B CN 110643113B
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bamboo fiber
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bamboo
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CN110643113A (en
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王利军
曹颖
黎晨欣
郭维林
宋贤震
陈胜文
罗立立
李章民
曾静
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Ningbo Jucai New Material Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
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Abstract

The low-VOCs bamboo fiber modified plastic comprises the following components in parts by weight: 100 parts of thermoplastic plastic, 1-20 parts of modified bamboo fiber and 0.5-2 parts of toughening agent. The modified bamboo fiber is obtained by a preparation method comprising the following process steps: (1) raw bamboo treatment: cutting bamboo blocks into slices, and then crushing and sieving to obtain bamboo fiber raw powder; (2) soaking the bamboo fiber raw powder in NaOH solution, centrifuging to obtain precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying to obtain bamboo fiber; (3) and soaking the bamboo fiber in a modified heavy calcium carbonate solution for ultrasonic treatment, centrifuging and drying to obtain the modified bamboo fiber. The modified bamboo fiber is applied to the thermoplastic plastics, so that the mechanical property is greatly improved, the VOCs content of the thermoplastic plastics can be reduced, and the modified bamboo fiber is more environment-friendly.

Description

Low-VOCs (volatile organic compounds) bamboo fiber modified plastic and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a low-VOCs (volatile organic compounds) bamboo fiber modified plastic and a preparation method thereof.
Background
Polypropylene (PP) is widely used due to its superior properties and low price, but due to the influence of polymerization process, catalyst, oxide residue, short chain oligomers, etc., PP material may release harmful Volatile Organic Compounds (VOCs) to various degrees during high temperature processing and use. Along with the continuous enhancement of environmental protection consciousness and health consciousness of people, the requirements of daily products are more green and environment-friendly, a certain part of daily products are prepared by modified PP materials, in the preparation process of the modified PP materials, in order to achieve the performance required by products, other auxiliary materials such as fillers, toughening agents, coupling agents, lubricants, stabilizers and the like are often required to be added, and the materials can bring harmful VOCs, so that the harm is brought to people using the materials in a relatively closed environment. Therefore, the development of the polypropylene composite material with advanced technology, low VOCs emission, energy conservation and environmental protection has great importance.
Bamboo fiber, as a natural fiber, has unique ecological characteristics: strong reproduction capability, high yield and short wood forming period, and is an excellent renewable resource. Compared with artificial fiber, the plant fiber has the characteristics of natural growth, recoverability, lighter weight and the like, and is basically free of VOCs release and the like. The bamboo fiber is used as a reinforcing agent to replace other auxiliary materials and applied to the plastic, so that the release of VOCs in the plastic can be reduced. For example, chinese patent application CN109304778A discloses a method for manufacturing high performance bamboo garden fiber reinforced plastic and a product thereof, which adopts long fibers as reinforcing fibers to fuse with plastic, and sends the long bamboo fibers dried by hot air into a winding machine, and winds the long bamboo fibers on a solid plastic rod, and obtains the bamboo fiber reinforced plastic through a hot pressing and cooling method; the invention adopts a mechanical method to prepare the bamboo fiber, and the short fiber generated by excessive processing in the extraction process can be changed into powder. The bamboo fiber is directly wound on the plastic, and a large part of the bamboo fiber is fused with the plastic on the surface in the hot pressing process, so that the reinforced plastic has large individual difference in performance and low reproduction rate. Chinese patent CN105482480B discloses a bamboo fiber reinforced thermoplastic, which adopts a steam explosion device, the hydroxyl distribution on the surface of the fiber is changed in a violent explosion environment, and hydrogen bonds are destroyed, so that the compatibility between the bamboo fiber and the polymer is improved, but the modification method has expensive equipment, difficult control of the obtained fiber length and low production efficiency, and is difficult to adapt to large-scale production.
The compounding of bamboo fiber and plastic still faces many technical difficulties, for example, the surface of bamboo fiber contains a large amount of polar hydroxyl and phenolic hydroxyl functional groups, so that the surface of bamboo fiber shows stronger chemical polarity, but the plastic is nonpolar and has strong hydrophobicity, so that the compatibility between the bamboo fiber and the plastic is poor, the interface bonding performance is poor, and the comprehensive performance of the material is deteriorated.
Disclosure of Invention
The invention provides a technical scheme of a low-VOCs bamboo fiber modified plastic aiming at the defect that the existing plastic contains high VOCs.
One purpose of the invention is realized by the following technical scheme: the low-VOCs bamboo fiber modified plastic comprises the following components in parts by weight: 100 parts of thermoplastic plastic, 1-20 parts of modified bamboo fiber and 0.5-2 parts of toughening agent.
The modified bamboo fiber is adopted to act on the thermoplastic, the content of VOCs (volatile organic compounds) in the bamboo fiber is extremely low compared with other additives commonly used for reinforcing and toughening the thermoplastic, the release of VOCs is basically avoided, the compatibility of the bamboo fiber with the thermoplastic is greatly improved after the bamboo fiber is modified, and the reinforcing effect on the thermoplastic is more remarkable, so that the content of VOCs in the thermoplastic can be reduced when the modified bamboo fiber is applied to the thermoplastic, the mechanical property is greatly improved, and the environment is protected.
The content of the modified bamboo fibers in the thermoplastic plastic needs to be limited, and if the content of the modified bamboo fibers is too small, the thermoplastic plastic is not obviously reinforced; the excessive content of the modified bamboo fiber greatly increases the rigidity of the thermoplastic plastic, but reduces the impact strength.
The thermoplastic plastic is selected from one or more of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyformaldehyde, polycarbonate, polyamide and acrylic plastics.
Preferably, the modified plastic comprises the following components in parts by weight: 100 parts of thermoplastic plastic, 15 parts of modified bamboo fiber and 0.5-2 parts of toughening agent.
In a preferred embodiment of the present invention, the modified bamboo fiber is obtained by a preparation method comprising the following process steps:
(1) raw bamboo treatment: cutting bamboo blocks into slices, and then crushing and sieving to obtain bamboo fiber raw powder;
(2) soaking the bamboo fiber raw powder in NaOH solution, centrifuging to obtain precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying to obtain bamboo fiber;
(3) and soaking the bamboo fiber in a modified heavy calcium carbonate solution for ultrasonic treatment, centrifuging and drying to obtain the modified bamboo fiber.
The bamboo block is a hollow cylinder, preferably a hollow cylinder with the length of 30-60mm and the diameter of 100-200 mm.
Firstly, cutting hollow cylindrical bamboo blocks into hollow slices along the longitudinal direction of fibers, wherein the length range of the hollow slices is 0.5-2mm, then cutting the hollow slices into small slices along the radial direction, and crushing the small slices of bamboo in a high-speed crushing mixer. The rotation speed of the high-speed mixer is 10000-80000r/min, the temperature of the crushing environment is room temperature and the humidity is below 35%, the crushed materials are sieved, a 90-110-mesh sieve is adopted for sieving, small fiber impurities in the crushed materials are removed, the oversize materials are sieved by a 30-50-mesh sieve, the undersize materials are reserved, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
The bamboo fiber raw powder is soaked in a sodium hydroxide solution and treated by sodium hydroxide, a plurality of combined loose single fibers can be separated from a fiber bundle of the bamboo fiber to obtain the single fibers, impurities among the fibers can be removed due to the obtaining of the single fibers, and extremely small benzene and aldehyde substances contained in lignin and hemicellulose which are additionally included can also be removed, so that the content of VOCs is reduced. After the bamboo fiber is subjected to alkali treatment, part of impurities such as pectin, lignin, hemicellulose and the like on the surface of the bamboo fiber are dissolved, so that the surface becomes rough.
Preferably, the mass concentration of the NaOH solution is 0.5-5%, the soaking temperature is 75-85 ℃, and the soaking time is 8-12 h. The technological conditions of alkali treatment need to be controlled within a certain range, if the concentration, the treatment time and the temperature of the alkali solution are too small, the alkali treatment strength is not large, the modification degree of the bamboo fiber is too small, and the performance is not favorably exerted; and the concentration of the alkali solution is too high, the treatment time is too long, and the temperature is too high, so that the cellulose is possibly subjected to alkaline degradation, and the strength of the fiber is reduced.
Centrifuging the cellulose treated by alkali to obtain a precipitate, then washing with water, centrifuging, repeating the operation until the solution is neutral after water is added, centrifuging, and drying.
The bamboo fiber after the alkali treatment is placed in a modified heavy calcium carbonate solution for ultrasonic treatment, wherein the mass concentration of the modified heavy calcium carbonate solution is preferably 1-5%.
Preferably, the preparation method of the modified heavy calcium carbonate comprises the following steps: mixing heavy calcium carbonate and water to prepare emulsion, pressurizing and stirring for 3-6h under inert atmosphere, centrifugally filtering, and drying filter cakes to obtain the modified heavy calcium carbonate. The inert atmosphere is one or more of carbon dioxide, nitrogen, helium and argon. Preferably, the ratio of the heavy calcium carbonate to the water is 1: (8-15), wherein the pressure is 0.8-1.5 MPa. Stirring the heavy calcium carbonate emulsion in an inert atmosphere at a pressure of 0.8-1.5MPa to obtain a rougher surface with a smaller particle size, wherein the specific surface area of the modified heavy calcium carbonate is 17-20m2/g。
The rough modified heavy calcium carbonate is deposited on the rough surface of the bamboo fiber under ultrasonic treatment, and the bonding force of the two is greatly enhanced because the two have rough surfaces. The rough surface of the modified heavy calcium carbonate also increases the binding force with the plastic matrix, so the modified heavy calcium carbonate plays a role of a bridge and is beneficial to the binding of the bamboo fiber and the plastic matrix.
The ultrasonic power in the step (3) is 200-.
The other purpose of the invention is realized by the following technical scheme: a preparation method of low-VOCs bamboo fiber modified plastic comprises the following steps:
mixing 100 parts of thermoplastic plastic, 1-20 parts of modified fiber and 0.5-2 parts of toughening agent by using a high-speed mixer, and adding the mixture into a double-screw extruder for granulation to obtain the low-VOCs bamboo fiber modified plastic.
The screw rotating speed of the double-screw extruder is 60-80r/min, and the temperature ranges of all sections of the double-screw extruder are respectively as follows: 190 ℃ at 180 ℃, 185 ℃ at 195 ℃, 190 ℃ at 200 ℃, 195 ℃ at 205 ℃ at 195 ℃ at 205 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the alkali treatment method to extract the bamboo fiber, under the alkaline condition, partial single fiber is separated from the fiber bundle, the contact area with the plastic matrix is increased, the components such as pectin or hemicellulose on the surface are removed, and the roughness of the fiber surface is increased. And then, under the action of ultrasonic cavitation, the bamboo fiber is subjected to surface treatment by utilizing the structural characteristics of rough surface and small particle size of the modified heavy calcium carbonate, the rough modified heavy calcium carbonate increases the binding force with the rough surface of the bamboo fiber and a matrix, and the modified heavy calcium carbonate serves as a bridge to improve the bonding property of a two-phase interface of the bamboo fiber and the matrix. The raw materials are easy to obtain, the process is simple, the adhesion between the modified bamboo fiber and the plastic is enhanced, the interface compatibility is improved, the mechanical property is good, and the emission of VOCs is effectively reduced because the auxiliary agent with the content of VOCs is not added.
Drawings
FIG. 1 is an electron microscope photograph of a bamboo fiber obtained after alkali treatment in example 1.
Detailed Description
Hereinafter, the technical solution of the present invention will be further described and illustrated by specific embodiments and drawings, however, these embodiments are exemplary and the present disclosure is not limited thereto. And the drawings used herein are for the purpose of illustrating the disclosure better and are not intended to limit the scope of the invention. Unless otherwise specified, the raw materials used in the following specific examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art.
The bamboo blocks used hereinafter were purchased from an amjid idea bamboo processing plant, hollow cylindrical, 40mm in length and 150mm in diameter. The polypropylene is purchased from China petrochemical, the melt flow rate is 1g/min, and the density is 0.905g/cm3The Rockwell hardness is more than or equal to 100R. The toughener, ENGAGE, was purchased from Dow chemistry. The modified heavy calcium carbonate is self-made and is obtained by the following preparation method: mixing heavy calcium carbonate (purchased from Wuhuan development industry Co., Ltd., Guilin city, with a mesh size of 400) and deionized water according to a weight ratio of 1: 10 to prepare emulsion, then pressurizing and stirring the emulsion in the atmosphere of 10 atmospheric pressure carbon dioxide, keeping the mixture for 4 hours, taking the mixture out, centrifuging and filtering the mixture, and drying a filter cake at 120 ℃ to obtain the modified heavy calcium carbonate. The specific surface area of the obtained modified ground calcium carbonate is 18m2(g) the average particle diameter was 15 μm.
Example 1
The low-VOCs bamboo fiber modified plastic of the embodiment 1 comprises the following components in parts by weight: 100 parts of polypropylene, 15 parts of modified bamboo fiber and 1 part of toughening agent ENGAGE.
The modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) The bamboo fiber raw powder is placed into NaOH solution with the mass concentration of 1% to be soaked for 10 hours, and the temperature of the alkali solution is controlled to be 80 ℃. And after soaking, centrifuging to obtain a precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying for later use. The electron microscopic image of the bamboo fiber obtained after the alkali treatment is shown in fig. 1, and the surface of the bamboo fiber is very rough.
(3) Soaking the bamboo fiber powder in a modified heavy calcium carbonate solution with the mass concentration of 1% by using an ultrasonic induction mode for ultrasonic treatment, wherein the ultrasonic power is 500W, the treatment temperature is 40 ℃, the ultrasonic time is 60min, centrifuging and drying for later use.
Mixing 100 Parts of Polypropylene (PP), 15 parts of modified bamboo fiber and 1 part of toughening agent ENGAGE by using a high-speed mixer, and granulating by using a double-screw extruder, wherein the rotating speed of a screw is 80r/min, and the temperature ranges of all sections set by the double-screw extruder are respectively as follows: 180 deg.C, 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C. And (5) granulating to obtain the low-VOCs bamboo fiber modified plastic.
Example 2
The low-VOCs bamboo fiber modified plastic of the embodiment 1 comprises the following components in parts by weight: 100 parts of polypropylene, 15 parts of modified bamboo fiber and 0.8 part of toughening agent ENGAGE.
The modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) The bamboo fiber raw powder is placed into NaOH solution with the mass concentration of 2% to be soaked for 9 hours, and the temperature of the alkali solution is controlled to be 80 ℃. And after soaking, centrifuging to obtain a precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying for later use.
(3) Soaking the bamboo fiber powder in a modified heavy calcium carbonate solution with the mass concentration of 2% by using an ultrasonic induction mode for ultrasonic treatment, wherein the ultrasonic power is 600W, the treatment temperature is 50 ℃, the ultrasonic time is 70min, centrifuging and drying for later use.
Mixing 100 Parts of Polypropylene (PP), 15 parts of modified bamboo fiber and 0.8 part of toughening agent ENGAGE by using a high-speed mixer, and granulating by using a double-screw extruder, wherein the rotating speed of the screw is 70r/min, and the temperature ranges of all sections set by the double-screw extruder are respectively as follows: 185 deg.C, 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C. And (5) granulating to obtain the low-VOCs bamboo fiber modified plastic.
Example 3
Example 3 is different from example 1 only in that the modified bamboo fiber of example 3 is 5 parts, and the other parts are the same as example 1.
Example 4
Example 4 is different from example 1 only in that the modified bamboo fiber of example 4 is 10 parts, and the rest is the same as example 1.
Example 5
Example 5 is different from example 1 only in that the modified bamboo fiber of example 5 is 20 parts, and the rest is the same as example 1.
In order to verify the beneficial effects of the technical scheme of the invention, the following comparative experiment is designed.
Comparative example 1
Comparative example 1 is different from example 1 in that the modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) Soaking the bamboo fiber raw powder in a modified heavy calcium carbonate solution with the mass concentration of 1% in an ultrasonic induction mode for ultrasonic treatment, wherein the ultrasonic power is 500W, the treatment temperature is 40 ℃, the ultrasonic time is 60min, centrifuging and drying for later use.
The rest is the same as in example 1.
Comparative example 2
Comparative example 2 is different from example 1 in that the modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) The bamboo fiber raw powder is placed into NaOH solution with the mass concentration of 1% to be soaked for 10 hours, and the temperature of the alkali solution is controlled to be 80 ℃. And after soaking, centrifuging to obtain a precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying for later use.
The rest is the same as in example 1.
Comparative example 3
Comparative example 3 differs from example 1 in that the modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) The bamboo fiber raw powder is placed into NaOH solution with the mass concentration of 1% to be soaked for 10 hours, and the temperature of the alkali solution is controlled to be 80 ℃. And after soaking, centrifuging to obtain a precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying for later use.
(3) Soaking the bamboo fiber powder in a solution of 1% by mass of ground calcium carbonate (purchased from Jiangxiefeng Leizihe chemical industry, 800 meshes) without modification treatment by using an ultrasonic induction mode to perform ultrasonic treatment, wherein the ultrasonic power is 500W, the treatment temperature is 40 ℃, the ultrasonic time is 60min, and centrifuging and drying are performed for later use.
The rest is the same as in example 1.
Comparative example 4
Comparative example 4 is different from example 1 in that the modified bamboo fiber is prepared by the following process steps:
(1) cutting bamboo blocks into hollow slices along the longitudinal direction of fibers, then cutting the hollow slices into small slices along the radial direction, putting the small slices of bamboo into a high-speed crushing mixer for crushing, sieving and sorting, wherein the powder sieve specification is 100 meshes and 40 meshes, firstly removing small fiber impurities in crushed materials by adopting a 100-mesh sieve, then sieving oversize materials by adopting a 40-mesh sieve to retain undersize materials, and the undersize materials are bamboo fiber raw powder with the length-diameter ratio of 5-8.
(2) The bamboo fiber raw powder is placed into NaOH solution with the mass concentration of 1% to be soaked for 10 hours, and the temperature of the alkali solution is controlled to be 80 ℃. And after soaking, centrifuging to obtain a precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying for later use.
(3) Soaking the bamboo fiber powder in a modified heavy calcium carbonate solution with the mass concentration of 1% to perform stirring reaction at the reaction temperature of 40 ℃ for 60min, centrifuging and drying for later use.
The rest is the same as in example 1.
Comparative example 5
Comparative example 5 is different from example 1 in that the modified bamboo fiber of comparative example 5 is 25 parts, and the rest is the same as example 1.
Comparative example 6
Comparative example 6 is different from example 1 in that the modified bamboo fiber of comparative example 6 is 0.5 parts, and the rest is the same as example 1.
The plastic pellets of examples 1-5 and comparative examples 1-6 were baked in an oven at 80 ℃ for 2 hours to remove free water from the pellets so that the presence of moisture during injection molding into test bars did not affect the performance of the plastic bars. And then, injection molding the dried plastic particles into a test sample strip by using an MA900/260 plastic sample strip injection molding machine, wherein the injection molding temperature is set as a step temperature, and the temperature of each section is as follows: 190 deg.C, 195 deg.C, 200 deg.C, 205 deg.C. After being placed at room temperature for 24 hours, the performance of the sample is tested by using a ZBC7000 pendulum impact tester and an INSTRON3369 tensile material tester according to the GB1843-2008 plastic cantilever beam impact test method and the GB/T1040-. Each example was tested using 10 test bars, the values in Table 1 being the average of 10 test bars.
TABLE 1 spline Performance data for examples 1-5 and comparative examples 1-6
Figure BDA0002213880590000091
As can be seen from table 1: according to the performance data of examples 1, 3-5, it is shown that as the content of the modified bamboo fiber increases, the tensile strength of the polypropylene material gradually increases, and the impact strength gradually decreases. However, example 1 in which 15 parts of modified bamboo fiber was added had a 59.5% increase in tensile strength and only a 5% decrease in impact strength, compared to example 4 in which 10 parts of modified bamboo fiber was added, and example 1 had an 49% increase in impact strength and only an 8.4% decrease in tensile strength, compared to example 5 in which 20 parts of modified bamboo fiber was added. The fact that when the addition part of the modified bamboo fiber is 15 parts, the impact strength and the tensile strength tend to be balanced, and the performance is optimal is shown. When the modified bamboo fiber is increased to 25 parts, see comparative example 5, the tensile strength is increased by only 5.2% compared to example 5 in which 20 parts of the modified bamboo fiber is used, but the impact strength is decreased by 24.5%, indicating that the performance is not benefited by continuously increasing the content of the modified bamboo fiber.
Comparative example 1 with respect to example 1, the modified cellulose was not subjected to sodium hydroxide modification before the modified ground calcium carbonate was subjected to ultrasonic treatment, the bamboo fibers which were not subjected to sodium hydroxide treatment were still present in the form of bamboo fiber bundles, the contact area with the polypropylene matrix was greatly reduced, and it was difficult to load the modified ground calcium carbonate particles on the surface, and the modified ground calcium carbonate was merely physically and simply mixed with the bamboo fibers, so that the compatibility of the bamboo fibers with the polypropylene matrix was greatly reduced as compared with example 1, showing a reduction in tensile strength and impact strength. Comparative example 2 with respect to example 1, the modified cellulose treated with sodium hydroxide was not subjected to ultrasonic treatment with modified ground calcium carbonate, which acts as a "bridge" between the bamboo fibers and the polypropylene matrix, and when the rough surface of the bamboo fibers did not deposit modified ground calcium carbonate particles, it was not favorable for compatible mixing of the bamboo fibers and the polypropylene matrix. Compared with the embodiment 1, the modified common ground calcium carbonate is adopted to treat the bamboo fiber, the ground calcium carbonate can obtain a rough surface after being modified, the bonding force between the ground calcium carbonate and the rough bamboo fiber is improved, the 'bridge' effect can be exerted, the compatibility between the bamboo fiber and the substrate is improved, when the ground calcium carbonate is not modified, the unmodified ground calcium carbonate is difficult to deposit on the surface of the bamboo fiber, and the compatibility between the bamboo fiber and the polypropylene substrate is reduced. Comparative example 4 compared to example 1, no sonication was added, but instead a conventional stirring reaction. The ultrasonic treatment is beneficial to the deposition and bonding of the modified heavy calcium carbonate on the surface of the bamboo fiber, and when the ultrasonic treatment is lacked, the modified heavy calcium carbonate particles deposited on the surface of the bamboo fiber are fewer in number and lower in bonding force, so that the tensile strength and the impact strength of the comparative example 4 are lower than those of the example 1.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (8)

1. The low-VOCs bamboo fiber modified plastic is characterized by comprising the following components in parts by weight: 100 parts of thermoplastic plastic, 1-20 parts of modified bamboo fiber and 0.5-2 parts of toughening agent; the modified bamboo fiber is obtained by a preparation method comprising the following process steps:
(1) raw bamboo treatment: cutting bamboo blocks into slices, and then crushing and sieving to obtain bamboo fiber raw powder;
(2) soaking the bamboo fiber raw powder in NaOH solution, centrifuging to obtain precipitate, repeatedly washing the precipitate with water until the solution is neutral, centrifuging, and drying to obtain bamboo fiber;
(3) soaking bamboo fibers in a modified heavy calcium carbonate solution for ultrasonic treatment, centrifuging and drying to obtain modified bamboo fibers;
the preparation method of the modified heavy calcium carbonate comprises the following steps: mixing heavy calcium carbonate and water to prepare emulsion, pressurizing and stirring for 3-6h under the atmosphere of carbon dioxide, centrifugally filtering, and drying a filter cake to obtain the modified heavy calcium carbonate.
2. The low-VOCs bamboo fiber modified plastic of claim 1, wherein the crushed material in step (1) is sieved by a 90-110 mesh sieve, the oversize material is sieved by a 30-50 mesh sieve, and the obtained undersize material is bamboo fiber raw powder.
3. The low-VOCs bamboo fiber modified plastic of claim 1, wherein the mass concentration of the NaOH solution in step (2) is 0.5% -5%, the soaking temperature is 75-85 ℃, and the soaking time is 8-12 h.
4. The low-VOCs bamboo fiber modified plastic according to claim 1, wherein the mass concentration of the modified heavy calcium carbonate solution in the step (3) is 1-5%.
5. The low-VOCs bamboo fiber modified plastic as claimed in claim 1, wherein the ultrasonic power in step (3) is 200- "1000W, the treatment temperature is 20-60 ℃, and the ultrasonic time is 30-150 min.
6. The low-VOCs bamboo fiber modified plastic according to claim 1, wherein the ratio of the ground calcium carbonate to the water is 1: (8-15), wherein the pressure is 0.8-1.5 MPa.
7. The preparation method of the low-VOCs bamboo fiber modified plastic as claimed in claim 1, wherein the preparation method comprises the following steps:
mixing 100 parts of thermoplastic plastic, 1-20 parts of modified fiber and 0.5-2 parts of toughening agent by using a high-speed mixer, and adding the mixture into a double-screw extruder for granulation to obtain the low-VOCs bamboo fiber modified plastic.
8. The preparation method of the low-VOCs bamboo fiber modified plastic as claimed in claim 7, wherein the screw rotation speed of the twin-screw extruder is 60-80r/min, and the temperature ranges of the sections set by the twin-screw extruder are respectively as follows: 190 ℃ at 180 ℃, 185 ℃ at 195 ℃, 190 ℃ at 200 ℃, 195 ℃ at 205 ℃ at 195 ℃ at 205 ℃.
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