CN109575543A - A kind of degradable wood bamboo modeling composite foam packaging material and preparation method - Google Patents
A kind of degradable wood bamboo modeling composite foam packaging material and preparation method Download PDFInfo
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- 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
- C08J9/04—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
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- 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
- C08J9/0061—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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- 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
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- 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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- 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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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The present invention relates to the technical fields of composite foam material, provide the degradable wood bamboo modeling composite foam packaging material of one kind and preparation method.This method first prepares wood bamboo composite powder with straw, Chinese medicine slag, bamboo scraps, sawdust, and esterification modification is carried out using stearic acid, then esterification modification is carried out to nano silica using stearic acid, PHBV, PLA, stearic acid grafted wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent are subjected to high speed blending, melt blending and foaming again, degradable wood bamboo modeling composite foam packaging material is made.It is compared with the traditional method, is modified due to carrying out chemical esterification to wood bamboo composite powder and nano grade silica particles using stearic acid, in powder surface grafting-(CH2)16CH3Long-chain keeps the compatibility between each component good, and powder dispersibility is good, and composite material has good mechanical property.
Description
Technical field
The invention belongs to the technical fields of composite foam material, provide a kind of degradable wood bamboo modeling composite foam packaging
Material and preparation method.
Background technique
The reduction of the forest reserves and the processing of plastic products junk gradually become major issue urgently to be resolved.Therefore,
Advanced composite material (ACM), i.e. wood moulding, bamboo-plastic composite material come into being.Such alternative corresponding Bamboo and wood product of product is saved a large amount of
The forest reserves, and dispose the waste generated in a large amount of waste plastic and timber, bamboo processing, be conducive to protection life
State environment.
Wood moulding, the application range of bamboo-plastic composite material are very extensive, are mainly used in the packet of building materials, auto industry, cargo
Ship defeated, warehousing industry, ornament materials and daily life tools etc..Due to the reproducibility of plant fiber, can be disappeared by environment
The property received, such composite material are a kind of green materials of great development prospect.
Wood bamboo plastic composite materials mainly have following characteristics: (1) containing a large amount of hydrophilic radical hydroxyl, plant fiber has
Very strong polarity, and common resin matrix is not usually nonpolar, hydrophilic, therefore the compatibility between plant fiber and resin matrix
Very poor, interface binding intensity is low, affects the mechanical performance of wood bamboo plastic composite materials；(2) it since hydrogen bond can be formed between hydroxyl, plants
There is very strong interaction between fibres, so that its dispersion in resin matrix is very poor, to reach evenly dispersed more tired
It is difficult；(3) plant stuffing degradable discoloration when processing and forming, at the same high molecular material also can thermal degradation, it is unsuitable with mix plus
Work technique will lead to the performance decline of wood bamboo plastic composite materials.Therefore, the key technology of production wood bamboo plastic composite materials product is
Under the premise of guaranteeing plant fiber high filler loading capacity, how to ensure the high processing fluidity of composite material, resin and wood powder, bamboo powder
Between excellent compatibility, to reach best mechanical property, finally with lower production cost produce have higher usability
The wood bamboo plastic composite materials product of energy.
Chinese invention patent application number 201110361264.6 discloses a kind of bamboo-plastic composite material, by including following heavy
Amount parts by weight component be made: 20 ~ 60 parts by weight of bamboo fibre, 30 ~ 70 parts by weight of thermoplastic, 0.5 ~ 2 parts by weight of coupling agent,
1.5 ~ 5 parts by weight of compatilizer, 0.5 ~ 2 parts by weight of nucleating agent, 0.5 ~ 2 parts by weight of lubricant, 2 ~ 5 parts by weight of mixed aid.The hair
It is bright to also disclose the preparation method of the bamboo-plastic composite material.The bamboo-plastic composite material of the invention is light-weight, good stability of the dimension, but
Bad dispersibility of the bamboo fibre added in composite material in plastic substrate, affects the mechanical property of composite material.
Chinese invention patent application number 201810018124.0 discloses a kind of wood plastic composite and preparation method thereof,
Belong to technical field of composite materials, which is prepared from the following materials, by weight percentage, raw material packet
It includes: 25 ~ 40 parts by weight of plastics, 40 ~ 60 parts by weight of wood-fibred, 8 ~ 25 parts by weight of ceramic powder, 1 ~ 3 parts by weight of lubricant, coupling agent 1
~ 3 parts by weight, 0.1 ~ 0.5 parts by weight of antioxidant, 0.1 ~ 0.5 parts by weight of mould inhibitor, 0.05 ~ 0.3 parts by weight of UV stabilizer, toner 1
~ 5 parts by weight.The defect of the invention is the poor compatibility of wood-fibred and plastic substrate, causes dispersion uneven, mechanical property is by shadow
It rings.
In conclusion in the wood bamboo plastic composite materials of the prior art, due to the compatibility of wood bamboo powder and plastic fraction compared with
Difference causes the dispersion of wood bamboo powder uneven, and the mechanical property of composite material is adversely affected, therefore it is good to prepare a kind of dispersibility
Good, good mechanical properties wood bamboo plastic composite materials, have great significance.
Summary of the invention
As it can be seen that, since the compatibility of wood bamboo powder and plastic fraction is poor, causing wood bamboo powder in wood bamboo plastic composite materials
Dispersion is uneven, and the mechanical property of composite material is adversely affected.In response to this, the present invention proposes a kind of degradable wood
Bamboo-plastic combined bubble wrap material and preparation method, it is modified by carrying out surface esterification to wood bamboo composite powder, make between each component
Compatibility it is good, powder dispersibility is good, composite material have good mechanical property.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of degradable wood bamboo modeling composite foam packaging material, the tool of the composite foam packaging material preparation
Steps are as follows for body:
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to be no more than 0.5% to moisture content, wood bamboo composite powder is made；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made.
Preferably, step (1) straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 2 ~ 5:2 ~ 5:1 ~ 2:1 ~ 2.
The straw be common crops stalk, cellulose rich in, for example, corn stover, wheat stalk,
Rice straw, broomcorn straw, rape stalk, cotton stalk, sugarcane stalk.
The Chinese medicine slag be vegetable drug Chinese medicine slag, vegetable drug can be preferably screwtree root, desmodium triquetrum, evodia lepta,
Pogostemon cablin, pithecellobium clypearia, sunset abelmoschus root.The main component of Chinese medicine slag is cellulose, can be used as fibre reinforcement and is used in plastics, simultaneously
Chinese medicine slag usually contains natural bacteriostatic substance, can assign composite material fungus-resistant function.
The leftover pieces of bamboo processing can be used in the bamboo scraps or the corner of timber processing can be used in discarded part, the sawdust
Material or discarded part.
In general, above-mentioned straw, Chinese medicine slag, bamboo scraps, sawdust are handled as solid waste, both cause resource unrestrained
Take, and pollute environment, the present invention is fully utilized, and has not only reduced the preparation cost of bubble wrap material, but also can be improved
The intensity of material.But since the cellulose that straw, Chinese medicine slag, bamboo scraps, sawdust are rich in has a large amount of hydroxyl, make powder
Last surface is in hydrophilic and oleophobic property, and polymer surfaces are hydrophobic oleophilic oils, therefore, wood bamboo composite powder and polymer obtained
Interface compatibility it is poor, composite powder be difficult to it is evenly dispersed, be also easy to produce in stress stress concentration, cannot effectively play cellulose
Humidification.In consideration of it, the present invention carries out chemical modification to composite powder, with other functional group's substituted hydroxies, hydrogen bond is reduced,
Weaken inter-molecular binding force, the crystalline texture of cellulose is destroyed, to assign composite powder certain thermoplasticity.We select
Stearic acid is selected to realize the chemical modification of cellulose, reacts to form ester group with hydroxyl by carboxyl, the introducing-on composite powder surface
(CH2)16CH3Long-chain assigns composite powder surface hydrophobic, realizes good compatible with polymer.
Preferably, the molar concentration of step (1) described sodium hydroxide solution is 15 ~ 20mol/L, and the temperature of alkali process is 50
~ 60 DEG C, the time is 15 ~ 20min.
Preferably, step (2) the wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:
200~250:3~5:0.3~0.5。
Preferably, the temperature of step (2) described esterification is 70 ~ 90 DEG C, and the time is 20 ~ 40min.
Preferably, step (3) dispersing agent be sodium methylene bis-naphthalene sulfonate, in dispersing agent MF extremely
Few one kind.
Preferably, step (3) nano grade silica particles, dispersing agent, deionized water, the weight of stearic acid, boric acid
Than for 100:2 ~ 4:150 ~ 200:2 ~ 4:0.3 ~ 0.5.
Preferably, the temperature of step (3) described esterification is 80 ~ 95 DEG C, and the time is 30 ~ 40min.
By existing research it is found that adding nano silica in the polymer, the strength of materials both can be improved, also can be improved
Toughness of material.And the surface of nano silica usually has hydroxyl, and due to nano effect, easily rolls into a ball in the polymer
It is poly-.Similar with the modification of above-mentioned wood bamboo composite powder, the present invention is reacted using stearic acid with the hydroxyl of nano-silica surface,
To be grafted upper-(CH in nanoparticle surface2)16CH3Group improves the compatibility of nano silica and plastics, the group of preventing
It is poly-, be conducive to the raising of the intensity and toughness of bubble wrap material.
It is good with nanometer powder to promote catalyst evenly dispersed in system in the selection of the catalyst of esterification
Good contact, and the active function of catalyst is played to the full extent, in the toluene dispersion of wood bamboo composite powder, select first
Base benzene sulfonic acid is as catalyst；In the deionized water dispersion of nano grade silica particles, select boric acid as catalyst.
Preferably, step (4) the PHBV, PLA, stearic acid grafted wood bamboo composite powder, stearic acid grafted nano-silica
SiClx powder, AC foaming agent weight ratio be 40 ~ 60:20 ~ 30:20 ~ 30:4 ~ 8:3 ~ 5.
The present invention also provides a kind of degradable wood bamboos that a kind of above-mentioned preparation method is prepared to mould composite foam packet
Package material.The bubble wrap material is first to be prepared wood bamboo composite powder with straw, Chinese medicine slag, bamboo scraps, sawdust, and used
Stearic acid carries out esterification modification, then carries out esterification modification to nano silica using stearic acid, then by PHBV, PLA, tristearin
Acid grafting wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent carry out high speed blending, melt blending and
Foaming and be made.
The present invention provides a kind of degradable wood bamboo modeling composite foam packaging materials and preparation method, with prior art phase
Than the feature and excellent effect protruded is:
1. the present invention with straw, Chinese medicine slag, bamboo scraps, sawdust produce wood bamboo composite powder to plastic foam carry out enhancing fill out
It fills, reduces the preparation cost of bubble wrap material, and chemical esterification is carried out to wood bamboo composite powder by stearic acid and is modified,
The certain mobility of powder is assigned in order to process, while assigning powder surface good hydrophobic oleophilic oil, realize with PHBV,
PLA's is good compatible, and wood bamboo modeling composite foam packaging material obtained has good mechanical strength.
It is modified 2. the present invention carries out activeness and quietness to plastic foam with nano grade silica particles, by stearic acid to nanometer
Silica carries out chemical esterification and is modified, and prevents the reunion of nanometer powder, improves the interface of nano silica and PHBV, PLA
In conjunction with being improved the intensity of wood bamboo modeling composite foam packaging material obtained and toughness.
3. primary raw material PHBV, PLA, straw, Chinese medicine slag, bamboo scraps, sawdust that the present invention uses all have good
Degradability, the feature of environmental protection are good.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.3%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 3:3:1:
2；The molar concentration of sodium hydroxide solution is 17mol/L, and the temperature of alkali process is 56 DEG C, time 17min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:230:4:
0.4；The temperature of esterification is 78 DEG C, time 28min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is sodium methylene bis-naphthalene sulfonate；Nano grade silica particles, dispersing agent, deionization
Water, stearic acid, boric acid weight ratio be 100:3:157:3:0.4；The temperature of esterification is 87 DEG C, time 36min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 48:26:24:5:4.
Embodiment 2
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.2%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 3:3:1:1；
The molar concentration of sodium hydroxide solution is 16mol/L, and the temperature of alkali process is 52 DEG C, time 19min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:210:3.5:
0.3；The temperature of esterification is 75 DEG C, time 35min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is dispersing agent MF；Nano grade silica particles, are gone dispersing agent
Ionized water, stearic acid, boric acid weight ratio be 100:2.5:160:2.5:0.35；The temperature of esterification is 83 DEG C, and the time is
37min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 45:23:22:5:3.
Embodiment 3
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.4%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 4:4:2:
2；The molar concentration of sodium hydroxide solution is 19mol/L, and the temperature of alkali process is 58 DEG C, time 16min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:240:4.5:
0.5；The temperature of esterification is 85 DEG C, time 25min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is sodium methylene bis-naphthalene sulfonate；Nano grade silica particles, dispersing agent, deionization
Water, stearic acid, boric acid weight ratio be 100:4:190:3.5:0.5；The temperature of esterification is 93 DEG C, time 32min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 55:28:28:7:4.5.
Embodiment 4
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.2%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 2:2:1:1；
The molar concentration of sodium hydroxide solution is 15mol/L, and the temperature of alkali process is 50 DEG C, time 20min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:200:3:
0.3；The temperature of esterification is 70 DEG C, time 40min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is dispersing agent MF；Nano grade silica particles, are gone dispersing agent
Ionized water, stearic acid, boric acid weight ratio be the temperature of 100:2:150:2:0.3 esterification be 80 DEG C, time 40min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 40:20:20:4:3.
Embodiment 5
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.5%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 5:5:2:
2；The molar concentration of sodium hydroxide solution is 20mol/L, and the temperature of alkali process is 60 DEG C, time 15min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:250:5:
0.5；The temperature of esterification is 90 DEG C, time 20min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is sodium methylene bis-naphthalene sulfonate；Nano grade silica particles, dispersing agent, deionization
Water, stearic acid, boric acid weight ratio be 100:4:200:4:0.5；The temperature of esterification is 95 DEG C, time 30min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 60:30:30:8:5.
Embodiment 6
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to moisture content be 0.4%, be made wood bamboo composite powder；Straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 4:4:1.5:
1.5；The molar concentration of sodium hydroxide solution is 18mol/L, and the temperature of alkali process is 55 DEG C, time 18min；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；Wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid weight ratio be 100:225:4:
0.4；The temperature of esterification is 80 DEG C, time 30min；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；Dispersing agent is dispersing agent MF；Nano grade silica particles, are gone dispersing agent
Ionized water, stearic acid, boric acid weight ratio be 100:3:180:3:0.4；The temperature of esterification is 88 DEG C, time 35min；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made；PHBV, PLA, stearic acid grafted
Wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC foaming agent weight ratio be 50:25:25:6:4.
Comparative example 1
In preparation process, stearic acid modified to the progress of wood bamboo composite powder, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, stearic acid modified to nano grade silica particles progress, other preparation conditions and embodiment 6 are consistent.
Comparative example 3
In preparation process, wood bamboo composite powder and nano grade silica particles do not carry out stearic acid modified, other preparation conditions
It is consistent with embodiment 6.
Performance test:
(1) referring to GB/T 1040-2006 standard, mark tensile strength: is made in wood bamboo produced by the present invention modeling composite foam material
Quasi- sample carries out tensile strength test using CMT6104 electronic universal tester, tests Environment-Greenhouse temperature, relative humidity 55
± 5%, test speed 5mm/min measure the tensile strength of sample；
(2) compressive strength: referring to GB/T 29418-2012 standard, wood bamboo produced by the present invention modeling composite foam material is made
Standard sample carries out axial compression strength test using CMT6104 electronic universal tester, tests Environment-Greenhouse temperature, relatively wet
Degree is 55 ± 5%, measures the compressive strength of sample；
(3) referring to GB/T 1043-2008 standard, wood bamboo produced by the present invention unnotched impact strength: is moulded into composite foam material
The standard non-notch of being made hits sample, carries out unnotched impact strength test using impact strength test machine, tests Environment-Greenhouse temperature,
Relative humidity is 55 ± 5%, measures the unnotched impact strength of sample.
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, which is characterized in that the composite foam packet
Specific step is as follows for package material preparation:
(1) straw, Chinese medicine slag, bamboo scraps, sawdust are cleaned with clear water respectively, is dried, mixed and grind in nano grinder
Grinds are subsequently placed in sodium hydroxide solution and carry out alkali process, remove small-molecule substance, then clean with clear water, and vacuum is dry
It is dry to be no more than 0.5% to moisture content, wood bamboo composite powder is made；
(2) it disperses wood bamboo composite powder made from step (1) in toluene, stearic acid and toluenesulfonic acid is added, heating makes
Stearic carboxyl and the hydroxyl on composite powder surface carry out esterification, are washed, are dried after reaction, and tristearin is made
Acid grafting wood bamboo composite powder；
(3) nano grade silica particles, dispersing agent are added in deionized water, stearic acid and boric acid is added, heating makes stearic acid
Carboxyl and nano-silica surface hydroxyl carry out esterification, washed, dried after reaction, be made stearic acid
Engrafted nanometer SiO 2 powder；
(4) by polyhydroxybutyrate valeric acid copolyesters (PHBV), polylactic acid (PLA), stearic acid grafted wood bamboo composite powder, stearic acid
Engrafted nanometer SiO 2 powder, AC foaming agent are uniformly mixed in a high speed mixer, then pass through twin-screw extrusion injection molding machine
Melt blending and foaming are carried out, degradable wood bamboo modeling composite foam packaging material is made.
2. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In: step (1) straw, Chinese medicine slag, bamboo scraps, the weight ratio of sawdust are 2 ~ 5:2 ~ 5:1 ~ 2:1 ~ 2.
3. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
It is 15 ~ 20mol/L in: the molar concentration of step (1) described sodium hydroxide solution, the temperature of alkali process is 50 ~ 60 DEG C, and the time is
15~20min。
4. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In the weight ratio of: step (2) the wood bamboo composite powder, toluene, stearic acid, toluenesulfonic acid be 100:200 ~ 250:3 ~ 5:
0.3~0.5。
5. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In: the temperature of step (2) described esterification is 70 ~ 90 DEG C, and the time is 20 ~ 40min.
6. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In: step (3) dispersing agent is at least one of sodium methylene bis-naphthalene sulfonate, dispersing agent MF.
7. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In the weight ratio of: step (3) nano grade silica particles, dispersing agent, deionized water, stearic acid, boric acid be 100:2 ~ 4:
150~200:2~4:0.3~0.5。
8. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In: the temperature of step (3) described esterification is 80 ~ 95 DEG C, and the time is 30 ~ 40min.
9. a kind of preparation method of degradable wood bamboo modeling composite foam packaging material, feature exist according to claim 1
In: step (4) the PHBV, PLA, stearic acid grafted wood bamboo composite powder, stearic acid grafted nano grade silica particles, AC hair
The weight ratio of infusion is 40 ~ 60:20 ~ 30:20 ~ 30:4 ~ 8:3 ~ 5.
10. the degradable wood bamboo modeling composite foam packaging of one kind that any one of claim 1 ~ 9 preparation method is prepared
Material.
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