CN109054104A - A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing - Google Patents

A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing Download PDF

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CN109054104A
CN109054104A CN201810722989.5A CN201810722989A CN109054104A CN 109054104 A CN109054104 A CN 109054104A CN 201810722989 A CN201810722989 A CN 201810722989A CN 109054104 A CN109054104 A CN 109054104A
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bamboo powder
parts
cornstarch
starch
disperse
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王家阳
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ANHUI SHUCHENG HUAZHU INDUSTRY Co Ltd
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ANHUI SHUCHENG HUAZHU INDUSTRY Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C08J9/103—Azodicarbonamide
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/009—Use of pretreated compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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    • 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
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a kind of preparation methods of the starch-based degradable composite foam material of bamboo powder filled enhancing, it is characterized in that, being refined being sieved after bamboo powder heat drying, put into high-speed mixer, even application KH560 coupling agent solution, stir evenly surface modification bamboo powder；It will disperse in ethanol, titanate coupling agent to be added to be stirred to react modification after nano grade silica particles heat drying, addition polymerization ethylene glycol ultrasonic disperse obtains the nano silica of disperse modified；Cornstarch after drying is placed in high speed blender after being blended with glycerol, dioctyl phthalate mixing plasticiser, obtains the modified cornstarch of plasticizing, closed sealing is stood；By polylactic acid, poly butylene succinate particle forced air drying, azodicarbonamide is mixed into obtain foaming agent with zinc oxide, by mixing in pretreated feedstock and compatilizer polyvinyl alcohol and front resulting material investment high speed blender, it takes out, with double screw extruder extrusion foaming, injection molding prepares sample.

Description

A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing
Technical field
The present invention relates to bamboo and wood products' Material Fields, and in particular to a kind of starch-based degradable of bamboo powder filled enhancing is compound The preparation method of foamed material.
Background technique
China is the country of poor forest resources, no matter forest coverage rate or occupancy volume per person to be below the world average The domestic high-quality major diameter timber resources of level, especially China is more in short supply, and artificial fast-growing forest timber, small dimension wood and saw lumber flaw-piece Etc. resources it is relatively abundant.In addition, also very abundant, area and yield occupy first place in the world the bamboo resource in China.How very well These resources abundant of comprehensive utilization to alleviate China's timber resources anxiety contradiction, promote the sustainable development of wood-based panel industry It has very important significance.
Bamboo wood has many advantages, such as that intensity is high, hardness is big, good toughness, wear-resisting, but also has the disadvantages such as diameter grade is small, utilization rate is low. And fast growing wood and small dimension wood have many advantages, such as handling ease, high production efficiency, but exist simultaneously that intensity is low, surface hardness is low, residual The disadvantages of residue stress is big.Therefore, by studying bamboo-wood composite material, bamboo wood can be played more scientific and reasonablely and timber is respective Advantage and characteristic, acquisition not only reduces production cost, but also guarantees in product in the double effects with presentation quality.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of starch-based degradable of bamboo powder filled enhancing is composite foamed The preparation method of material, the foamed material mechanical property prepared according to the technique are excellent, degradable.
A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing, which is characterized in that by with Lower step carries out:
(1) pretreatment of bamboo powder:
20-25 parts of bamboo powders are put into 80-82 DEG C of electric drying oven with forced convection and dry 7-8h, then heat 25- at 100-103 DEG C 30min makes moisture content lower than 5%, sieves with 100 mesh sieve, and puts into 60-62 DEG C of high-speed mixer after refinement；To 1-1.3 parts of coupling agents Glacial acetic acid aqueous solution is added in 1:5-6 in KH560, and dilution is made into coupling agent solution, the bamboo powder surface even application into mixing machine Coupling agent solution stirs evenly, and obtains the bamboo powder of KH560 surface modification；
(2) modification and dispersion of nano silica:
By 2-3 parts of nano grade silica particles, dry 20-24h, 1:50-100 disperse in ethanol, to be added at 104-106 DEG C After being stirred to react modified 70-80min at 60-62 DEG C, 0.1-0.2 parts of poly- second two are added in 0.05-0.07 parts of titanate coupling agents Alcohol, ultrasonic disperse 20-30min obtain the nano silica of disperse modified；
(3) plasticizing of cornstarch is modified:
95-105 parts of cornstarch are dried in 80-83 DEG C of thermostatic drying chamber, by 26-27 parts of glycerol and 2-3 parts of O-phthalics Dioctyl phthalate mixes to obtain plasticiser, the cornstarch after drying is placed in high speed blender with mixing plasticiser, 3-5min is blended Afterwards, the modified cornstarch of plasticizing is obtained, closed sealing stands 10-15h；
(4) preparation of degradable foam materials:
30-40 parts of polylactic acid, 25-35 parts of poly butylene succinate particles are dried into 10-12h in 80-82 DEG C of convection oven, 0.5-1 parts of azodicarbonamides are mixed into obtain foaming agent with 2-3 parts of zinc oxide, pretreated feedstock and 10-12 parts of compatilizers are gathered Vinyl alcohol and (1), (2), mixing 15-20min in resulting material investment high speed blender in (3), take out, use double screw extruder Extrusion foaming, injection molding prepare sample.
Wherein, the pH of glacial acetic acid aqueous solution is 3.5-5.5 in step (1).
Polyethylene glycol is polyethylene glycol 400 in step (2).
In step (4) extrusion temperature be 130-140 DEG C, extrusion pressure 70-80MPa, screw speed 10-12Hz；Machine barrel 115-135 DEG C of temperature, 45-50 DEG C of mold temperature, injection pressure 40-50MPa, dwell pressure 40-50MPa, injecting rate 10- 11g/s。
It is of the invention that the reaction mechanism is as follows:
Using cornstarch as matrix, thermoplastic modification is carried out to starch with glycerol and dioctyl phthalate, increases and stretches by force Degree, addition compatilizer polyvinyl alcohol can improve the interface compatibility between each component, further increase tensile strength；Bamboo powder is filling Enhance raw material, improves composite property after surface modification through coupling agent KH560, improve the crystallization temperature of material, bamboo powder pair Composite material plays the role of heterogeneous nucleation, and the addition of bamboo powder improves the degradation rate of material；Use titanate coupling agent modified Nano silica, then ultrasonic wave dispersion is carried out to it with polyethylene glycol, the nano silica for adding disperse modified can enhance The mechanical property of intermingling material improves the water absorbing properties and degradation property of intermingling material；With starch, polylactic acid, biodegradable Material poly butylene succinate is matrix, then is aided with the processing aids such as compatilizer, plasticiser, foaming agent, utilizes injection foaming Method is prepared for degradable composite foam material, and product cell size is moderate, and quantity is more, and is evenly distributed.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below Specific embodiment is closed, the present invention is further explained.
Embodiment
A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing, which is characterized in that by with Lower step carries out:
(1) pretreatment of bamboo powder:
20kg bamboo powder is put into 80-82 DEG C of electric drying oven with forced convection and dries 7h, then 25min is heated at 100-103 DEG C, makes Moisture content is lower than 5%, sieves with 100 mesh sieve, and puts into 60-62 DEG C of high-speed mixer after refinement；Into 1kg coupling agent KH560,1:6 adds Enter glacial acetic acid aqueous solution, dilution is made into coupling agent solution, the bamboo powder surface even application coupling agent solution into mixing machine, stirring Uniformly, the bamboo powder of KH560 surface modification is obtained；
(2) modification and dispersion of nano silica:
By 2kg nano grade silica particles, dry 20h, 1:50 disperse in ethanol, 0.05kg metatitanic acid to be added at 104-106 DEG C After being stirred to react modified 70min at 60-62 DEG C, 0.1kg polyethylene glycol is added in ester coupling agent, and ultrasonic disperse 20min is obtained The nano silica of disperse modified；
(3) plasticizing of cornstarch is modified:
95kg cornstarch is dried in 80-83 DEG C of thermostatic drying chamber, 26kg glycerol and 2kg dioctyl phthalate are mixed Plasticiser is closed to obtain, after being placed in the cornstarch after drying in high speed blender 5min is blended with mixing plasticiser, is plasticized Modified cornstarch, closed sealing stand 10h；
(4) preparation of degradable foam materials:
30kg polylactic acid, 25kg poly butylene succinate particle are dried into 10h in 80-82 DEG C of convection oven, by 0.5kg idol Nitrogen diformamide mixes to obtain foaming agent with 2kg zinc oxide, by pretreated feedstock and 10kg compatilizer polyvinyl alcohol and (1), (2), (3) mixing 20min in resulting material investment high speed blender, takes out, with double screw extruder extrusion foaming, injection molding system in Standby sample.
Wherein, the pH of glacial acetic acid aqueous solution is 3.5-4 in step (1).
Polyethylene glycol is polyethylene glycol 400 in step (2).
In step (4) extrusion temperature be 130-140 DEG C, extrusion pressure 70MPa, screw speed 10Hz；Barrel temperature 115-135 DEG C, 50 DEG C of mold temperature, injection pressure 40-50MPa, dwell pressure 40-50MPa, injecting rate 11g/s.

Claims (5)

1. a kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing, which is characterized in that by bamboo powder After heat drying be sieved refinement, put into high-speed mixer in, even application KH560 coupling agent solution, stir evenly surface is repaired The bamboo powder of decorations；It will disperse in ethanol, titanate coupling agent to be added to be stirred to react modification after nano grade silica particles heat drying, Addition polymerization ethylene glycol ultrasonic disperse, obtains the nano silica of disperse modified；By the cornstarch and glycerol, O-phthalic after drying Dioctyl phthalate mixing plasticiser, which is placed in high speed blender, after blending, obtains the modified cornstarch of plasticizing, and closed sealing is stood； Polylactic acid, poly butylene succinate particle is dry in convection oven, azodicarbonamide is mixed to obtain to hair with zinc oxide Infusion takes out mixing in pretreated feedstock and compatilizer polyvinyl alcohol and front resulting material investment high speed blender, with double Screw extruder extrusion foaming, injection molding prepare sample.
2. a kind of preparation side of the starch-based degradable composite foam material of bamboo powder filled enhancing according to claim 1 Method, which is characterized in that sequentially include the following steps:
(1) pretreatment of bamboo powder:
20-25 parts of bamboo powders are put into 80-82 DEG C of electric drying oven with forced convection and dry 7-8h, then heat 25- at 100-103 DEG C 30min makes moisture content lower than 5%, sieves with 100 mesh sieve, and puts into 60-62 DEG C of high-speed mixer after refinement；To 1-1.3 parts of coupling agents Glacial acetic acid aqueous solution is added in 1:5-6 in KH560, and dilution is made into coupling agent solution, the bamboo powder surface even application into mixing machine Coupling agent solution stirs evenly, and obtains the bamboo powder of KH560 surface modification；
(2) modification and dispersion of nano silica:
By 2-3 parts of nano grade silica particles, dry 20-24h, 1:50-100 disperse in ethanol, to be added at 104-106 DEG C After being stirred to react modified 70-80min at 60-62 DEG C, 0.1-0.2 parts of poly- second two are added in 0.05-0.07 parts of titanate coupling agents Alcohol, ultrasonic disperse 20-30min obtain the nano silica of disperse modified；
(3) plasticizing of cornstarch is modified:
95-105 parts of cornstarch are dried in 80-83 DEG C of thermostatic drying chamber, by 26-27 parts of glycerol and 2-3 parts of O-phthalics Dioctyl phthalate mixes to obtain plasticiser, the cornstarch after drying is placed in high speed blender with mixing plasticiser, 3-5min is blended Afterwards, the modified cornstarch of plasticizing is obtained, closed sealing stands 10-15h；
(4) preparation of degradable foam materials:
30-40 parts of polylactic acid, 25-35 parts of poly butylene succinate particles are dried into 10-12h in 80-82 DEG C of convection oven, 0.5-1 parts of azodicarbonamides are mixed into obtain foaming agent with 2-3 parts of zinc oxide, pretreated feedstock and 10-12 parts of compatilizers are gathered Vinyl alcohol and (1), (2), mixing 15-20min in resulting material investment high speed blender in (3), take out, use double screw extruder Extrusion foaming, injection molding prepare sample.
3. a kind of preparation side of the starch-based degradable composite foam material of bamboo powder filled enhancing according to claim 2 Method, which is characterized in that the pH of glacial acetic acid aqueous solution is 3.5-5.5 in step (1).
4. a kind of preparation side of the starch-based degradable composite foam material of bamboo powder filled enhancing according to claim 2 Method, which is characterized in that polyethylene glycol is polyethylene glycol 400 in step (2).
5. a kind of preparation side of the starch-based degradable composite foam material of bamboo powder filled enhancing according to claim 2 Method, which is characterized in that in step (4) extrusion temperature be 130-140 DEG C, extrusion pressure 70-80MPa, screw speed 10- 12Hz；115-135 DEG C of barrel temperature, 45-50 DEG C of mold temperature, injection pressure 40-50MPa, dwell pressure 40-50MPa, injection molding Rate is 10-11g/s.
CN201810722989.5A 2018-07-04 2018-07-04 A kind of preparation method of the starch-based degradable composite foam material of bamboo powder filled enhancing Pending CN109054104A (en)

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CN110330694A (en) * 2019-05-16 2019-10-15 湖南工业大学 A kind of starch base composite foam material freezing foaming and its preparation
CN111500037A (en) * 2020-06-03 2020-08-07 泉州陶纪塑胶有限公司 High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof
CN111909416A (en) * 2020-08-29 2020-11-10 福建省灿辉环保科技有限公司 Efficient EVA foaming fast curing agent and preparation method thereof
CN112961394A (en) * 2021-04-20 2021-06-15 浙江省林业科学研究院 Preparation method of degradable bamboo fiber straw
CN113980362A (en) * 2021-11-08 2022-01-28 蚌埠天成包装科技股份有限公司 Starch-based foaming composition and preparation method thereof
CN114031820A (en) * 2021-10-26 2022-02-11 南京五瑞生物降解新材料研究院有限公司 Heat-resistant biodegradable composite foam material and preparation method thereof
CN118325169A (en) * 2024-06-17 2024-07-12 山东科迈生物制浆有限公司 Degradable buffer material containing wheat straw biomechanical pulp fibers and preparation method thereof
CN118325169B (en) * 2024-06-17 2024-10-22 山东科迈生物制浆有限公司 Degradable buffer material containing wheat straw biomechanical pulp fibers and preparation method thereof

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330694A (en) * 2019-05-16 2019-10-15 湖南工业大学 A kind of starch base composite foam material freezing foaming and its preparation
CN110330694B (en) * 2019-05-16 2021-08-13 湖南工业大学 Freezing foaming method and starch-based composite foaming material prepared by freezing foaming method
CN111500037A (en) * 2020-06-03 2020-08-07 泉州陶纪塑胶有限公司 High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof
CN111500037B (en) * 2020-06-03 2022-04-22 中山市瑞邦红利塑料工业有限公司 High-density bamboo powder modified polylactic acid biodegradable plastic and preparation method thereof
CN111909416A (en) * 2020-08-29 2020-11-10 福建省灿辉环保科技有限公司 Efficient EVA foaming fast curing agent and preparation method thereof
CN112961394A (en) * 2021-04-20 2021-06-15 浙江省林业科学研究院 Preparation method of degradable bamboo fiber straw
CN112961394B (en) * 2021-04-20 2022-05-13 浙江省林业科学研究院 Preparation method of degradable bamboo fiber straw
CN114031820A (en) * 2021-10-26 2022-02-11 南京五瑞生物降解新材料研究院有限公司 Heat-resistant biodegradable composite foam material and preparation method thereof
CN113980362A (en) * 2021-11-08 2022-01-28 蚌埠天成包装科技股份有限公司 Starch-based foaming composition and preparation method thereof
CN118325169A (en) * 2024-06-17 2024-07-12 山东科迈生物制浆有限公司 Degradable buffer material containing wheat straw biomechanical pulp fibers and preparation method thereof
CN118325169B (en) * 2024-06-17 2024-10-22 山东科迈生物制浆有限公司 Degradable buffer material containing wheat straw biomechanical pulp fibers and preparation method thereof

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Application publication date: 20181221