CN106188842B - Polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method - Google Patents
Polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method Download PDFInfo
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- CN106188842B CN106188842B CN201610560604.0A CN201610560604A CN106188842B CN 106188842 B CN106188842 B CN 106188842B CN 201610560604 A CN201610560604 A CN 201610560604A CN 106188842 B CN106188842 B CN 106188842B
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- C—CHEMISTRY; METALLURGY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/16—Inorganic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
- B27K3/50—Mixtures of different organic impregnating agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K9/00—Chemical or physical treatment of reed, straw, or similar material
- B27K9/002—Cane, bamboo
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Abstract
The invention discloses a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method, includes the following steps: to carry out surface modification treatment 1), by bamboo particle using alkali process and silane coupling agent combination, obtain modified bamboo particle；2), ultra micro bamboo charcoal silane coupling agent surface modification treatment obtains modified ultra micro bamboo charcoal；3), raw material is composed of the following components in parts by weight: 65-70 parts of polypropylene, 0-30 parts of modified bamboo particle, 0-30 parts of modified ultra micro bamboo charcoal, 0-2 parts of talcum powder, 0-2 parts of antioxidant；Raw material is melted, is formed, polypropylene/bamboo particle/ultra micro bamboo charcoal composite material is obtained.The tensile property and bending property of behavior of polypropylene composites can be promoted using method of the invention, while improving the toughness of material.
Description
Technical field
The present invention relates to a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation methods, belong to composite material neck
Domain.
Background technique
Polypropylene is a kind of semi-crystalline thermoplastic's resin as prepared by propylene polymerization.Usually translucent colorless solid,
It is odorless nontoxic.Polypropylene such as can be squeezed out on general process equipment, be molded, blow bottle, thermoforming at the processing, be produced thin
Film, sheet material, bottle and various heat products, excellent hot property, processing performance become be most widely used at present it is big
Kind general-purpose plastics, yield are only smaller than polyethylene and occupy second, are widely used in the articles for daily use such as electric appliance, packaging, furniture
Field.However polypropylene material is because mobility is poor, mechanical strength is lower, polar polymer poor compatibility answers it due to the defects of
With being subject to certain restrictions.Therefore, to expand polyacrylic application field, it must be modified to enhance its performance.
Bamboo particle is a kind of renewable natural resources, has many advantages, such as resourceful, cheap and easy to get, higher force intensity.
China's bamboo wood cultivated area is wide, and a large amount of bamboo surplus material of processing is directly burned or abandoned, and cannot efficiently use and pollute
Environment, bamboo particle introducing polypropylene is prepared composite material can not only reinforcing material performance, moreover it is possible to it is dirty to solve the wasting of resources, environment
The problems such as dye.Since bamboo particle surface contains a large amount of hydrophilic hydroxy groups, when bamboo particle introduces polypropylene as reinforcement, it is made
Composite material in interface cohesion between hydrophobic polypropylene and hydrophilic bamboo particle material property is influenced it is especially heavy
It wants, surface chemical modification is carried out to bamboo particle by silane coupling agent, the molecule functional group of grafted hydrophobic, this can be effectively improved
The interface cohesion between polypropylene matrix.The behavior of polypropylene composites that introducing bamboo particle preparation obtains is compared with virgin pp material
Tensile strength, bending strength etc. have biggish promotion, but there are problems that tensile toughness decline, poor fluidity.Therefore it needs to introduce
The third high-intensitive, high-lubricity substance, further promotes the performances such as intensity, mobility, the tensile toughness of composite material.
Natural fiber reinforced polypropylene composite material has been achieved with extensive concern, and Chinese Patent Application No. is
201510586912.6 a kind of hard directly natural fiber reinforced polypropylene composite material and preparation method thereof is disclosed, wherein using boundary
Face modifying agent, rigid compatilizer and initiator improve the interface cohesion between natural fiber and polypropylene, but in reinforcing material
Mechanical strength while but significantly reduce the toughness of material so that material fragility is larger, while there is poor fluidity, interface
Compatibility is still bad.Chinese Patent Application No. discloses a kind of natural fiber enhancing thermoplastic composite for 201110253466.9
Material and its preparation method and application, using jute fiber reinforced polypropylene material, strength of materials enhancing less, application range compared with
It is small.Major part natural fiber enhancing polymer composites are that binary is compound at present, compatibility between reinforcement and matrix compared with
Difference, the strength of materials is poor, and the addition of natural fiber causes the mobility of material and toughness to have decline, and performance is bad.
Bamboo charcoal is solid product of the bamboo after Pintsch process under anaerobic environment, cheap because its is from a wealth of sources, performance
The advantages that unique, has a wide range of applications bamboo charcoal.Bamboo charcoal have good intensity, modulus, lubricity, abrasiveness, thermal insulation and
Stability, ultra micro bamboo charcoal are the powder bamboo charcoals that partial size is greater than 1000 mesh, and partial size is smaller, rough surface, has more gap, specific surface
Product is big, this is conducive to ultra micro bamboo charcoal material in conjunction with the surface between polymer material, and polypropylene matrix can be improved to bamboo particle
Between stress transfer, this give its field of compound material application potentiality.In addition, China's bamboo wood cultivated area is wide, add
Work ability is strong, and a large amount of bamboo surplus material of processing cannot efficiently use, if preparing ultra micro bamboo charcoal particle after charing, is applied to multiple
Condensation material field is excellent reinforcement material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparations
Method, which can promote the tensile property and bending property of behavior of polypropylene composites, while improve the toughness of material.
In order to solve the above technical problem, the present invention provides a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material systems
Preparation Method includes the following steps:
1), bamboo is granule modified:
Bamboo particle is subjected to surface modification treatment using alkali process and silane coupling agent combination, obtains modified bamboo particle；
2), ultra micro is bamboo charcoal modified:
Ultra micro bamboo charcoal silane coupling agent surface modification treatment obtains modified ultra micro bamboo charcoal；
3), raw material is composed of the following components in parts by weight: 65-70 parts of polypropylene, 0-30 parts of modified bamboo particle, modified
0-30 parts of ultra micro bamboo charcoal, 0-2 parts of talcum powder, 0-2 parts of antioxidant；
Raw material is melted, is formed, polypropylene/bamboo particle/ultra micro bamboo charcoal composite material is obtained.
As the improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
The bamboo of the step 1) it is granule modified the following steps are included:
1., by bamboo particle immerse 3~5wt% aqueous slkali in, bath raio be 1kg:20~30L, 60~80 DEG C of water bath processings
Then 20~28h washes, is dry, obtaining bamboo particle after alkali process；
2., silane coupling agent as surface modifier, adjusting pH to 4~5, in 40~60 are added in alcohol/aqueous solution
DEG C stirring hydrolysis 30-60min, silane coupler solution after must hydrolyzing；The silane coupling agent is with alcohol/aqueous solution solid-liquid ratio
1kg/10-25L；In the alcohol/aqueous solution, alcohol/water: 80/20 (volume ratio)；
3., according to silane coupling agent: bamboo particle be 0.5%-3% weight ratio, will be added in bamboo particle after alkali process to
After hydrolysis in silane coupler solution, continues 2~3h of stirring under the conditions of 40~60 DEG C and (sufficiently achieve coupling agent grafting bamboo particle table
The effect in face), it is dry after washing, obtain modified bamboo particle (that is, silane coupling agent treated bamboo particle).
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
Silane coupling agent in the step 1) be it is following any one: A-151, KH-550, KH-570, KH-590；
When silane coupling agent be KH-570 or KH-590 when, the step 1) 2. in alcohol/aqueous solution be methanol/water it is molten
Liquid；
When silane coupling agent be A-151 or KH-550 when, the step 1) 2. in alcohol/aqueous solution be ethanol/water it is molten
Liquid.
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
In the step 1),
Step 2., using second acid for adjusting pH；
Step 1. in drying be 100~110 DEG C of drying (to constant weight), step 3. in drying be in 60~90 DEG C drying
(to constant weight).
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
The ultra micro of the step 2) is bamboo charcoal modified be the following steps are included:
1., by ultra micro bamboo charcoal particle benzene alcoholic solution 6~10h of soxhlet type, dry, ultra micro bamboo charcoal particle after must drying；
In the benzene alcoholic solution, benzene/alcohol: 80/20 (volume ratio)；
2., silane coupling agent as surface modifier, adjusting pH to 4~5, in 40~60 are added in alcohol/aqueous solution
DEG C (preferably 50 DEG C) stirring 30~50min of hydrolysis, silane coupler solution after must hydrolyzing；The silane coupling agent and alcohol/water
The solid-liquid ratio of solution is 1kg/10-25L；In the alcohol/aqueous solution, alcohol/water: 80/20；
3., according to silane coupling agent: the weight ratio of micro- bamboo charcoal particle=0.5%-3%, silane coupling agent is molten after hydrolyzing
Ultra micro bamboo charcoal particle after drying is added in liquid, continues 2~3h of stirring under the conditions of 40~60 DEG C, it is dry after washing, it obtains modified super
Micro- bamboo charcoal particle (that is, ultra micro bamboo charcoal particle of silylation).
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
Silane coupling agent in the step 2) be it is following any one: A-151, KH-550, KH-570, KH-590；
When silane coupling agent be KH-570 or KH-590 when, the step 2) 2. in alcohol/aqueous solution be methanol/water it is molten
Liquid；
When silane coupling agent be A-151 or KH-550 when, the step 1) 2. in alcohol/aqueous solution be ethanol/water it is molten
Liquid.
Remarks explanation: the step 1) and the silane coupling agent in step 2) can be it is same, can also difference.
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
In the step 2),
Step 1. in, the solid-liquid ratio of ultra micro bamboo charcoal particle and benzene alcoholic solution is 1kg/10-25L；The grain of the ultra micro bamboo charcoal
Diameter is 1000-5000 mesh；
Step 2. in, using second acid for adjusting pH；
The step 1. in drying be in 100~110 DEG C of dryings (to constant weight)；The step 3. in drying be in 70
~80 DEG C of drying (to constant weight).
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
Any one following mode is selected in melting, the molding of the step 3):
It is mode one, melting mixing, hot-forming:
By raw material in kneading machine after melting mixing it is hot-forming, obtain composite material；
Mode two, melting extrusion granulation, injection molding:
By raw material in high-speed mixer after mixing, add twin-screw extrude melting extrusion molding, tie rod is cold
But, it is granulated, then injection molding obtains composite material in injection molding machine.
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
In mode one, 6-12min, screw speed 40-60r/min, kneading machine are kneaded in kneading machine after raw material mixing
There are three section is heated, temperature range is 170-195 DEG C；Hot-forming temperature is 175-200 DEG C, pressure 2-4MPa, hot pressing 4-
Polypropylene/bamboo particle/ultra micro bamboo charcoal composite material is obtained after pressure maintaining is cooling after 6min；
In mode two, raw material is uniformly mixed in high-speed mixer, and adding twin-screw extrude heating temperature is 170-
195 DEG C, rear extrusion molding, tie rod is cooling, is granulated, injection molding in composite particles injection molding machine, injection temperature 175-
200℃。
As the further improvement of polypropylene of the invention/bamboo particle/ultra micro bamboo charcoal composite material preparation method:
The antioxidant is antioxidant 1010.
In the present invention, preferred version are as follows:
Silane coupling agent: the weight ratio that bamboo particle is 2%, silane coupling agent: the weight ratio of ultra micro bamboo charcoal particle=2%,
Silane coupling agent in step 1) and step 2) is KH-590 coupling agent；Weigh 69 parts of polypropylene, 5 parts of modified bamboo particles,
25 parts of modified ultra micro bamboo charcoals, 0.5 part of talcum powder and 0.5 part of antioxidant 1010 are as raw material.
In the present invention, bamboo particle is ground into the particle of 40 mesh using bamboo surplus material of processing as raw material.The present invention is using at alkali
Reason removal is handled as extract, the impurity in the bamboo particle of raw material, then by silane coupling agent, and silane coupling agent is dissolved in
It in alcohol/aqueous solution, is uniformly mixed with bamboo particle and is placed on solvent flashing in ventilation device, group is grafted on into bamboo particle surface.
The ultra micro bamboo charcoal is the bamboo charcoal of 1000 mesh of partial size or more, commercially available acquisition.
Silane coupling agent can be vinyltriethoxysilane (A-151), 3- aminopropyl triethoxysilane (KH-
550), 3- isobutene acyl-oxygen) propyl trimethoxy silicane (KH-570) and (3- mercaptopropyi) trimethoxy silane (KH-590).
The present invention has following technical advantage:
(1) the modified bamboo reinforced particulate in surface is introduced into polypropylene matrix, it can the tensile strength of reinforcing material, bending
Intensity solves the problems, such as polypropylene material poor mechanical property.
(2) ultra micro bamboo charcoal is introduced into bamboo particle and polypropylene mixed system, binary complex system is carried out with ultra micro bamboo charcoal
Enhancing, can promote the mechanical strength of material, while the mobility of reinforcing material.
(3) present invention can reduce nondegradable plastics poly- third by the bamboo particle and ultra micro bamboo charcoal of introducing natural reproducible
The dosage of alkene, while reducing cost.
In conclusion to bamboo particle and surpassing present invention introduces ultra micro bamboo charcoals more than 1000 mesh, and using silane coupling agent
Micro- bamboo charcoal is modified processing, and the melting mixing in kneading machine is mixed and add after the auxiliary agents such as talcum powder, antioxidant with polypropylene,
Reprocessing molding prepares polypropylene/bamboo particle/ultra micro bamboo charcoal composite material, this method further expansion benefit of bamboo timber resource
With not only having played the humidification of bamboo fiber, but also the lubrication using ultra micro bamboo charcoal, toughening effect, and obtained good mechanical performance
Behavior of polypropylene composites.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 be comparative example 1-1~1-7 polypropylene/bamboo particle/ultra micro bamboo charcoal composite material tensile strength, stretch modulus and
Tension fracture elongation rate figure；
Fig. 2 be embodiment 1-1~1-7 polypropylene/bamboo particle/ultra micro bamboo charcoal composite material bending strength, bending modulus and
It is broken bending strain figure；
Fig. 3 is embodiment 1-1~1-7 polypropylene/bamboo particle/ultra micro bamboo charcoal composite material anti humility performance figure；
Fig. 4 is embodiment 1-1 polypropylene/bamboo particle/ultra micro bamboo charcoal (69/5/25) fracture of composite materials face form SEM figure；
Fig. 5 is polypropylene/bamboo particle/ultra micro bamboo charcoal (69/15/15) fracture of composite materials face form SEM of embodiment 2
Figure；
Fig. 6 is the polypropylene material fracture behavior SEM figure of comparative example 2；
Fig. 7 is polypropylene/bamboo particulate composite fracture behavior SEM figure of comparative example 1-1.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1-1, a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method, are successively walked as follows
It is rapid:
1), bamboo is granule modified:
1., 40 mesh bamboo particles immerse the NaOH solution of 4wt%, bath raio 1kg:25L, 80 DEG C of water bath processings are for 24 hours afterwards with clear
Water rinses, and removes extra lye, until pH is 7 or so, 105 DEG C, drying to constant weight.
2., in methanol/water solution (silane coupling agent -- KH- as surface modifier methanol/water: is added in 80/20)
590 coupling agents hydrolyze 30~60min in 50 DEG C of magnetic agitations, silane coupling agent is molten after must hydrolyzing with second acid for adjusting pH to 4~5
Liquid；The silane coupling agent and alcohol/aqueous solution solid-liquid ratio are 1kg/25L；
3., according to silane coupling agent: bamboo particle be 2% weight ratio, will after alkali process in bamboo particle be added to hydrolyze after
Continue 2~3h of magnetic agitation in silane coupler solution, under the conditions of 50 DEG C and (sufficiently achieves the effect of coupling agent grafting bamboo particle surface
Fruit), after washing, 75 DEG C drying to constant weight, obtains modified bamboo particle (that is, silane coupling agent treated bamboo particle, silylation
Bamboo particle).
2), ultra micro is bamboo charcoal modified:
1., by 1000 mesh ultra micro bamboo charcoal particle of granularity benzene alcoholic solution (benzene: ethyl alcohol=80/20, volume ratio) soxhlet type
6h (room temperature), 105 DEG C of dryings to constant weight, ultra micro bamboo charcoal particle after must drying；The solid-liquid ratio of ultra micro bamboo charcoal particle and benzene alcoholic solution
For 1kg/25L；
2., be added as the silane coupled of surface modifier in methanol/water solution (methanol/water: 80/20, volume ratio)
Agent -- KH-590 coupling agent hydrolyzes 30~50min, silane after must hydrolyzing in 50 DEG C of magnetic agitations with second acid for adjusting pH to 4~5
Coupling agent solution；The silane coupling agent and alcohol/aqueous solution solid-liquid ratio are 1kg/25L；
4., according to silane coupling agent: the weight ratio of ultra micro bamboo charcoal particle=2%, after hydrolyzing in silane coupler solution
Ultra micro bamboo charcoal particle after addition is dry, heat preservation continue 2~3h of stirring, and after washing, 75 DEG C drying to constant weight, obtains modified ultra micro bamboo
Charcoal particle (that is, ultra micro bamboo charcoal particle of silylation).
3) 69 parts of polypropylene, 5 parts of modified bamboo particles, 25 parts of modified ultra micro bamboo charcoals, 0.5 part of talcum powder and 0.5, are weighed
Part antioxidant 1010 is as raw material；Raw material is kneaded 10min, screw speed 60r/min in kneading machine after mixing, is mixed
There are three bringing-up section, temperature to be respectively as follows: I section 190 DEG C, II section 185 DEG C, III section 190 DEG C for mill.Taking-up mixture, which is placed in, to be hot pressed into
In mold on type machine, molding temperature is 195 DEG C, preheats 15min, pressure 3MPa, hot pressing 5min, is made poly- after pressure maintaining is cooling
Propylene/bamboo particle/ultra micro bamboo charcoal composite material.
Referring to ASTM testing standard, every group is at least tested 3 samples for sample Mechanics Performance Testing, take sample tensile strength,
The average value of stretch modulus and elongation at break, respectively 29.69MPa, 559.52MPa and 7.81%, fracture behavior
Scanning electron microscope (SEM) photograph is as shown in Figure 4.
Sample bent intensity and bending modulus average value are respectively 54.14 and 2450.96MPa；
For the test of sample moisture blocking property referring to GB/T 1034-2008 testing standard, every group is at least tested 3 samples, takes sample
The average value of hydroscopicity is 0.05%.
Embodiment 1-2~embodiment 1-7,
By the number 69/5/25 of polypropylene/modified rear bamboo particle/modified ultra micro bamboo charcoal in embodiment 1-1, change respectively
At as follows:
69/30/0,69/25/5,69/20/10,69/15/15,69/10/20,69/0/30.Remaining is equal to embodiment 1-
1；To obtain embodiment 1-2~embodiment 1-7 accordingly.
Gained composite material is detected according to the method described above, bending strength, bending modulus and fracture bending strain figure
As described in Figure 2.Its hydroscopicity is as described in Figure 3.
Comparative example 1-1~comparative example 1-7,
Cancel the modification of embodiment 1-1~embodiment 1-7 step 1) and step 2), that is, by embodiment 1-1~reality
" the modified bamboo particle " applied in a 1-7 is changed to " bamboo particle ", and " modified ultra micro bamboo charcoal " is changed to " ultra micro bamboo charcoal "；It is former simultaneously
Talcum powder, antioxidant are not added in material.Remaining technique is corresponding to be equal to embodiment 1-1~embodiment 1-7.Respectively by poly- third
Alkene/bamboo particle/ultra micro bamboo charcoal fraction scale is changed to as follows:
70/30/0,70/25/5,70/20/10,70/15/15,70/10/20,70/5/25,70/0/30.
Gained composite material is detected according to the method described above, tensile strength, stretch modulus and elongation at break such as Fig. 1
It is described.
Embodiment 2, a kind of polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method successively carry out following step
It is rapid:
1), by the step of step 1) 3. in, silane coupling agent: the weight ratio of bamboo particle is changed to 0.5% by 2%, remaining etc.
It is same as the step 1) of embodiment 1-1；
2), by the step of step 2) 3. in, silane coupling agent: the weight ratio of micro- bamboo charcoal particle is changed to 0.5% by 2%；Its
The remaining step 2) for being equal to embodiment 1-1；
3), raw material is changed to by as follows at being grouped as: weighing 68 parts of polypropylene, 15 parts of modified bamboo particles, 15 parts of modifications
Ultra micro bamboo charcoal, 1 part of talcum powder and 1 part of antioxidant 1010 afterwards；Remaining is equal to the step 3) of embodiment 1-1.
Referring to ASTM testing standard, every group is at least tested 3 samples for sample Mechanics Performance Testing, take sample tensile strength,
The average value of stretch modulus and elongation at break, respectively 20.58MPa, 336.99MPa and 4.90%, wherein tensile strength and
70.22% and 99.44% has been respectively increased compared with polypropylene in stretch modulus, is respectively increased compared with polypropylene/bamboo particulate composite
22.06%, 18.96%.The scanning electron microscope (SEM) photograph of its fracture behavior is as shown in Figure 5.
Sample bent intensity and bending modulus average value are respectively 40.09 and 2750.65MPa, are respectively increased compared with polypropylene
61.52% and 78.78%, compared with polypropylene/bamboo particulate composite 20.72% and 30.32% is respectively increased.
For the test of sample moisture blocking property referring to GB/T 1034-2008 testing standard, every group is at least tested 3 samples, takes sample
The average value of hydroscopicity is 0.20%, reduces 41.18% compared with polypropylene/bamboo particulate composite.
Silane coupling agent in embodiment 1-1 is changed to by 3 series of embodiment respectively by KH-590: A-151, KH-550,
KH-570, remaining is equal to embodiment 1-1.Properties testing result (average value) is as shown in table 1 below.
Remarks explanation: when silane coupling agent is KH-570 or KH-590, alcohol in the step 1) and step 2)/water-soluble
Liquid is methanol/water solution；
When silane coupling agent is A-151 or KH-550, alcohol/aqueous solution in the step 1) and step 2) be ethyl alcohol/
Aqueous solution.
Table 1
Comparative example 2,
99 parts of polypropylene, 0.5 part of talcum powder and 0.5 part of antioxidant are weighed, 10min, screw speed are kneaded in kneading machine
For 60r/min, there are three bringing-up section, temperature to be respectively as follows: I section 190 DEG C, II section 185 DEG C, III section 190 DEG C for kneading machine.Take out mixing
Body is placed in the mold on heat pressing forming machines, and molding temperature is 195 DEG C, preheats 15min, pressure 3MPa, hot pressing 5min, pressure maintaining
Polypropylene material is made after cooling.
For sample mechanical test referring to ASTM testing standard, every group is at least tested 3 samples, is taken sample tensile strength, is stretched
The average value of modulus and elongation at break, respectively 12.09MPa, 168.97MPa and 6.39%, the scanning of fracture behavior
Electron microscope is as shown in Figure 6.Sample bent intensity and bending modulus average value are 24.82MPa and 1538.53MPa.
Embodiment 4-1, by embodiment 1-1, silane coupling agent: the weight ratio of bamboo particle is changed to 0.3% by 2%, silane
Coupling agent: the weight ratio of micro- bamboo charcoal particle is changed to 0.3% by 2%；Remaining is the same as embodiment 1-1.
The average value of sample tensile strength, stretch modulus and elongation at break, respectively 28.02MPa, 460.52MPa and
6.68%；
Sample bent intensity and bending modulus average value are 50.23MPa and 2012.21MPa；
The average value of sample hydroscopicity is 0.05%.
Embodiment 4-2, by embodiment 1-1, silane coupling agent: the weight ratio of bamboo particle is changed to 4% by 2%, and silane is even
Join agent: the weight ratio of micro- bamboo charcoal particle is changed to 4% by 2%；Remaining is the same as embodiment 1-1.
The average value of sample tensile strength, stretch modulus and elongation at break, respectively 25.02MPa, 530.55MPa and
6.02%；
Sample bent intensity and bending modulus average value are 48.23MPa and 2320.24MPa；
The average value of sample hydroscopicity is 0.06%.
The above list is only a few specific embodiments of the present invention for finally, it should also be noted that.Obviously, this hair
Bright to be not limited to above embodiments, acceptable there are many deformations.Those skilled in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (8)
1. polypropylene/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that including the following steps:
1), bamboo is granule modified:
Bamboo particle is subjected to surface modification treatment using alkali process and silane coupling agent combination, comprising the following steps:
1., the bamboo particles of 40 mesh immersed in the aqueous slkali of 3~5wt%, bath raio is 1kg:20~30L, at 60~80 DEG C of water-baths
20~28h is managed, then washes, is dry, obtaining bamboo particle after alkali process；
2., silane coupling agent as surface modifier is added in alcohol/aqueous solution, adjusting pH to 4~5 is stirred in 40~60 DEG C
Mix hydrolysis 30-60min, silane coupler solution after must hydrolyzing；The silane coupling agent and alcohol/aqueous solution solid-liquid ratio are 1kg/
10-25L；In the alcohol/aqueous solution, alcohol/water is the volume ratio of 80:20；
3., according to silane coupling agent: bamboo particle be 0.5%-3% weight ratio, will after alkali process in bamboo particle be added to hydrolyze
Afterwards in silane coupler solution, continue 2~3h of stirring under the conditions of 40~60 DEG C, it is dry after washing, obtain modified bamboo particle；
2), ultra micro bamboo charcoal particle is modified:
Ultra micro bamboo charcoal particle silane coupling agent surface modification treatment, comprising the following steps:
1., by ultra micro bamboo charcoal particle benzene alcoholic solution 6~10h of soxhlet type, dry, ultra micro bamboo charcoal particle after must drying；It is described
In benzene alcoholic solution, benzene/alcohol: the volume ratio of 80:20；
The partial size of the ultra micro bamboo charcoal particle is 1000-5000 mesh；
2., silane coupling agent as surface modifier is added in alcohol/aqueous solution, adjusting pH to 4~5 is stirred in 40~60 DEG C
30~50min of hydrolysis is mixed, silane coupler solution after must hydrolyzing；The silane coupling agent is with alcohol/aqueous solution solid-liquid ratio
1kg/10-25L；In the alcohol/aqueous solution, alcohol/water is the volume ratio of 80:20；
3., according to silane coupling agent: ultra micro bamboo charcoal particle=0.5%-3% weight ratio, after hydrolyzing silane coupler solution
Ultra micro bamboo charcoal particle after middle addition is dry continues 2~3h of stirring under the conditions of 40~60 DEG C, dry after washing, obtains modified ultra micro
Bamboo charcoal particle；
3), raw material is composed of the following components in parts by weight: 65-70 parts of polypropylene, modified bamboo particle > 0-30 parts, modified super
Micro- bamboo charcoal particle > 0-30 parts, 0-2 parts of talcum powder, 0-2 parts of antioxidant；
Raw material is melted, is formed, polypropylene/bamboo particle/ultra micro bamboo charcoal composite material is obtained.
2. polypropylene according to claim 1/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that:
Silane coupling agent in the step 1) be it is following any one: A-151, KH-550, KH-570, KH-590；
When silane coupling agent be KH-570 or KH-590 when, the step 1) 2. in alcohol/aqueous solution be methanol/water solution；
When silane coupling agent be A-151 or KH-550 when, the step 1) 2. in alcohol/aqueous solution be ethanol/water solution.
3. polypropylene according to claim 2/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that:
In the step 1), step 2. use acetic acid adjust Ph, step 3. in drying be in 60~90 DEG C dry.
4. polypropylene according to claim 3/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterised in that:
Silane coupling agent in the step 2) be it is following any one: A-151, KH-550, KH-570, KH-590；
When silane coupling agent be KH-570 or KH-590 when, the step 2) 2. in alcohol/aqueous solution be methanol/water solution；
When silane coupling agent be A-151 or KH-550 when, the step 1) 2. in alcohol/aqueous solution be ethanol/water solution.
5. polypropylene according to claim 4/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterised in that:
In the step 2),
Step 1. in, the solid-liquid ratio of ultra micro bamboo charcoal particle and benzene alcoholic solution is 1kg/10-25L；
Step 2. in, using second acid for adjusting pH；
The step 1. in drying be in 100~110 DEG C of dryings；The step 3. in drying be in 70~80 DEG C dry.
6. polypropylene according to claim 1/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that:
Any one following mode is selected in melting, the molding of the step 3):
It is mode one, melting mixing, hot-forming:
By raw material in kneading machine after melting mixing it is hot-forming, obtain composite material；
Mode two, melting extrusion granulation, injection molding:
By raw material in high-speed mixer after mixing, add twin-screw extrude melting extrusion molding, tie rod is cooling,
It is granulated, then injection molding obtains composite material in injection molding machine.
7. polypropylene according to claim 6/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that:
In mode one, 6-12min, screw speed 40-60r/min are kneaded in kneading machine after raw material mixing, kneading machine has three
A heating section, temperature range are 170-195 DEG C；Hot-forming temperature is 175-200 DEG C, pressure 2-4MPa, hot pressing 4-6min
Polypropylene/bamboo particle/ultra micro bamboo charcoal composite material is obtained after pressure maintaining is cooling afterwards；
In mode two, raw material is uniformly mixed in high-speed mixer, and adding twin-screw extrude heating temperature is 170-195
DEG C, rear extrusion molding, tie rod is cooling, is granulated, injection molding in composite particles injection molding machine, injection temperature 175-200
℃。
8. polypropylene according to claim 1/bamboo particle/ultra micro bamboo charcoal composite material preparation method, it is characterized in that:
The antioxidant is antioxidant 1010.
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| CN106977787B (en) * | 2017-03-08 | 2020-01-21 | 天津科技大学 | HDPE/FF composite material added with carbonized FF and preparation method thereof |
| CN109735070B (en) * | 2018-12-12 | 2021-07-27 | 宁波大学 | Preparation method of polylactic acid/bamboo particle/bamboo charcoal composite material |
| CN111117069A (en) * | 2019-12-31 | 2020-05-08 | 广东顺威赛特工程塑料开发有限公司 | Enhanced polypropylene composite material and preparation method thereof |
| CN112692947A (en) * | 2020-12-11 | 2021-04-23 | 宣城宏宇竹业有限公司 | Waterproof light bamboo material for biomass traffic guardrail and preparation method thereof |
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