CN107892799A - A kind of antifatigue degradation material and preparation method thereof - Google Patents
A kind of antifatigue degradation material and preparation method thereof Download PDFInfo
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- CN107892799A CN107892799A CN201711239064.7A CN201711239064A CN107892799A CN 107892799 A CN107892799 A CN 107892799A CN 201711239064 A CN201711239064 A CN 201711239064A CN 107892799 A CN107892799 A CN 107892799A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of antifatigue degradation material and preparation method thereof, including following parts by weight raw material to be prepared：8 12 parts of nanometer basalt fibre, 25 parts of modifying agent, 25 40 parts of polyethylene, 55 75 parts of PLA, 0.3 0.8 parts of coupling agent, the polyacrylic acid of 35 parts of 5 10 parts of crosslinking agent；The present invention carries out the nanometer basalt fibre Jing Guo specific aim modification with PLA compound, and a nanometer basalt fibre is set to be dispersed in PLA system, obtained degradation material anti-fatigue performance is excellent, is advantageous to application of the PLA in more areas.
Description
Technical field
The present invention relates to material modified field, and in particular to a kind of antifatigue degradation material and preparation method thereof.
Background technology
PLA（PLA）It is a kind of new biodegradation material, uses reproducible plant resources（Such as corn）Carried
The starch material gone out is made.Lactic acid is made via fermentation process in starch material, then is converted into PLA by chemical synthesis.It has
There is good biodegradability, can be degradable by microorganism in nature after use, carbon dioxide and water are ultimately generated, no
Environment is polluted, this is highly beneficial to environmental protection, is generally acknowledged environment-friendly material.The mechanical performance and physics of poly-lactic acid material
Functional, compatibility is good, and many advantages, such as breathing freely, the every field in life and production has extensive application.
With the continuous improvement that people are required material anti-fatigue performance, the PLA without antifatigue modification has been difficult to full
Sufficient demand, thus, antifatigue modification is carried out to PLA and necessitated.Now to the antifatigue modification processing method kind of PLA
Class is various, and modified effect is also fine, especially with the appearance and application of nano material, the fatigue resistance increase effect of PLA
Significantly, PLA is enable largely to be used in more areas, but there is also deficiency.Although nano material has antifatigue enhancing effect
It is good, the advantages of addition is small, but there is also difficulties in dispersion, the defects of cost is high.In antifatigue modifying process is carried out, nanometer material
The scattered inequality of material can influence its antifatigue effect, and obtained material modified fatigue resistance is poor, to material modified production and answer
With adversely affecting.
The content of the invention
The defects of it is an object of the invention to overcome existing polylactic acid degradable material fatigue resistance poor, there is provided Yi Zhongkang
Tired degradation material and preparation method thereof；The present invention is by the nanometer basalt fibre and PLA Jing Guo specific aim modification
Carry out compound, and a nanometer basalt fibre is dispersed in PLA system, obtained degradation material anti-fatigue performance
It is excellent, be advantageous to application of the PLA in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of antifatigue degradation material, including following parts by weight
Raw material are prepared：The nanometer basalt fibre of 8-12 parts, the modifying agent of 2-5 parts, the polyethylene of 25-40 parts, 55-75 parts
PLA, the coupling agent of 0.3-0.8 parts, the crosslinking agent of 3-5 parts, the polyacrylic acid of 5-10 parts.
A kind of above-mentioned antifatigue degradation material, it is antifatigue that resin material can be increased according to nanometer basalt fibre and crosslinking
The general principle of property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve a nanometer basalt
Compatibility between fiber and PLA, and make nanometer basalt fibre disperse evenly, to make a nanometer basalt in PLA
Fiber is more preferable to the fatigue resistance humidification of PLA, is also made by controlling the degree of polymerization of PLA modified degradable
Material reaches optimum balance relation between fatigue resistance and processability, so as to which the degradation material that makes to obtain is with excellent
Under conditions of fatigue resistance, it may have excellent processability, it is applied in more areas.
A kind of above-mentioned antifatigue degradation material, wherein, the described a diameter of 1-10nm of nanometer basalt fibre, draw ratio
For 2-10 ︰ 1；Nanometer basalt fibre draw ratio is bigger, and dispersiveness is poorer, and nanometer basalt fibre draw ratio is smaller, to poly- breast
The tensile strength humidification of acid is poorer；Preferably, the described a diameter of 3-5nm of nanometer basalt fibre, draw ratio are 3-6 ︰
1。
A kind of above-mentioned antifatigue degradation material, wherein, described modifying agent is acrylic acid hydroxyl ester and polyadipate fourth two
The mixture of alcohol ester composition；Described modifying agent can improve the compatibility of nanometer basalt fibre and PLA, and and can is being received
Rice basalt fibre surface forms polar group, beneficial to scattered；Preferably, in described modifying agent acrylic acid hydroxyl ester with gather oneself two
The ratio between amount of material of sour butanediol ester is 1 ︰ 1.
A kind of above-mentioned antifatigue degradation material, wherein, the degree of polymerization of polyethylene is bigger, then degradation material after being crosslinked
Fatigue resistance is poorer, and processability is better, and the polymer of polyethylene is smaller, then the fatigue resistance of degradation material is better after being crosslinked,
Processability is poorer, therefore, selects rational polyethylene polymerization degree, is the important means for balancing fatigue resistance and processability.It is described
The degree of polymerization of polyethylene be 200-300；Preferably, the degree of polymerization of described polyethylene is 230-280；Optimal, it is described
The degree of polymerization of polyethylene is 250；By preferred, obtained degradation material both has excellent fatigue resistance, it may have preferably
Processability, be adapted to the application in more areas.
Wherein, described polymerisation degree of poly-lactic acid is 800-1200；Preferably, the degree of polymerization of the PLA is 900-
1100；Most preferably, the degree of polymerization of described PLA is 1000；By preferred, obtained degradation material had both had excellent
Fatigue resistance, it may have preferable processability.
A kind of above-mentioned antifatigue degradation material, wherein, described coupling agent is methacryloxypropyl silane coupling agent；
Methacryloxypropyl silane can increase the compatibility nanometer between basalt fibre and PLA and modifying agent, and raising can drop
Solve the performance of material.
Wherein, described crosslinking agent is methacrylic acid, and the crosslinking agent can be by the polymer former material of two kinds of different polymerization degrees
The appropriate crosslinking of material, improve the fatigue resistance of degradation material.
A kind of above-mentioned antifatigue degradation material, wherein, its raw material also includes dispersant, plasticizer, antistatic additive, dye
One or more auxiliary agents in toner, brightener；Above-mentioned auxiliary agent can improve the processability of degradation material, increase its feature
Deng effect, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of system of antifatigue degradation material
Preparation Method, comprise the following steps：
（1）Nanometer basalt fibre is handled with coupling agent；
（2）Nanometer basalt fibre Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out in the electric field after nanometer basalt fibre after cladding is well mixed with PLA, is mixed
Close material；
（4）After compound is well mixed with polyethylene, crosslinking agent, polyacrylic acid carry out Combined Processing, obtain it is antifatigue can
Degradable material.
A kind of preparation method of antifatigue degradation material, is first carried out at coupling with coupling agent to nanometer basalt fibre
Reason, increase nanometer basalt fibre and modifying agent, the compatibility of PLA；Nanometer basalt fibre is changed with modifying agent again
Property processing, and its surface formed polar group；Finally made using external electric field in nanometer basalt fibre surface and polylactic acid chain
Polar group polarization, it is powered, by repelling each other between electric charge or attracting principle, make dispersed same of nanometer basalt fibre
When, also can be bonded with the polar group in polylactic acid chain, so that the antifatigue enhancing effect of nanometer basalt fibre obtains most
The embodiment of big degree, so as to get polydactyl acid fatigue resistance significantly improve；The preparation method is simple and reliable, is suitable for resisting
Extensive, the industrialized production of tired degradation material.
A kind of preparation method of above-mentioned antifatigue degradation material, wherein, it is preferred that step 1 carries out coupling processing process
In can use ultrasonic assistant；Shaken by the high speed of ultrasonic wave, make nanometer basalt fibre dispersiveness more preferable, and to coupling at
Reason has facilitation.
A kind of preparation method of above-mentioned antifatigue degradation material, wherein, the electric field energy described in step 3 produces to group
Polarization, make group powered, so as to promote the scattered and bonded effect of nanometer basalt fibre, improve polydactyl acid
Fatigue resistance.
Preferably, described electric-field intensity is 0.5-2kv/m；Electric-field intensity is too small, and polarization effect is weak, to nanometer basalt
The dispersion effect of fiber is poor；Electric-field intensity is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces orientation and moved
It is dynamic, arrangement and the bonded performance for having an impact, degradation material may being reduced to strand；Most preferably, described electric field
Intensity is 0.8-1.5kv/m.
Wherein, it is preferred that described electric field is the constant parallel electric field of direction of an electric field；The constant parallel electric field of direction of an electric field
Best to the polarization effect of polar group, group intermolecular forces are stable, the scattered and bonded promotion to nanometer basalt fibre
Action effect is optimal.
Compared with prior art, beneficial effects of the present invention：
1st, degradation material of the present invention targetedly screens the species of modifying agent, coupling agent and crosslinking agent, makes a nanometer basalt fibre
Compatibility between dimension and PLA is more preferable, and the dispersiveness in PLA is more preferable, and nanometer basalt fibre resists to PLA
Fatigability humidification is more preferable.
2nd, degradation material of the present invention makes modified degradable material by controlling the degree of polymerization of PLA and polyethylene
Material reaches optimum balance relation between fatigue resistance and processability, so as to get degradation material with excellent antifatigue
Under conditions of property, it may have excellent processability.
3rd, the preparation method of degradation material of the present invention, using the polarization of external electric field, nanometer basalt can be promoted fine
Dimension is scattered and bonded in PLA system, and the antifatigue enhancing effect of nanometer basalt fibre is more preferable, and what is obtained is degradable
The fatigue resistance of material is higher.
4th, the preparation method of degradation material of the present invention is simple, reliable, is adapted to extensive, the work of antifatigue degradation material
Industry metaplasia is produced.
Embodiment
With reference to test example and embodiment, the present invention is described in further detail.But this should not be understood
Following embodiment is only limitted to for the scope of the above-mentioned theme of the present invention, it is all that this is belonged to based on the technology that present invention is realized
The scope of invention.
Embodiment 1
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of polyadipate fourth
Diol ester carries out cladding processing；
（3）In electric-field strength after nanometer basalt fibre after cladding is well mixed with the PLA that 65 parts of the degree of polymerization is 1000
Spend to be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, obtain compound；
（4）The compound that step 3 is obtained and 35 parts of the degree of polymerization are 250 polyethylene, 4 parts of methacrylic acids, poly- the third of 8 parts
Extruded after olefin(e) acid is well mixed, obtain antifatigue degradation material.
Embodiment 2
（1）8 parts of nanometer basalt fibre is handled with 0.3 part of methacryloxypropyl silane；
（2）By nanometer basalt fibre 1 part of the acrylic acid hydroxyl ester and 1 part of polybutyleneadipate Jing Guo coupling agent treatment
Ester carries out cladding processing；
（3）In electric field after nanometer basalt fibre after cladding is well mixed with the PLA that 55 parts of the degree of polymerization is 800
Intensity is to be extruded in 2.0kv/m electric field, obtains compound；
（4）The compound that step 3 is obtained and 25 parts of the degree of polymerization are 200 polyethylene, 3 parts of methacrylic acids, poly- the third of 5 parts
Extruded after olefin(e) acid is well mixed, obtain antifatigue degradation material.
Embodiment 3
（1）12 parts of nanometer basalt fibre is handled with 0.6 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 2.5 parts of acrylic acid hydroxyl ester and 2.5 parts of polyadipate fourth
Diol ester carries out cladding processing；
（3）In electric field after nanometer basalt fibre after cladding is well mixed with the PLA that 75 parts of the degree of polymerization is 1200
Intensity is to be extruded in the constant parallel electric field of 0.5kv/m direction of an electric field, obtains compound；
（4）Polyethylene that the compound that step 3 is obtained and 40 parts of the degree of polymerization are 300,5 parts of methacrylic acids, 10 parts poly-
Extruded after acrylic acid is well mixed, obtain antifatigue degradation material.
Comparative example 1
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment and 3 parts of dispersant, the poly- breast that 65 parts of the degree of polymerization is 1000
Extruded after acid is well mixed in the constant parallel electric field of the direction of an electric field that electric-field intensity is 1.2kv/m, obtain compound；
（3）The compound that step 2 is obtained and 12 parts of the degree of polymerization are 250 polyethylene, 4 parts of methacrylic acids, poly- the third of 8 parts
Extruded after olefin(e) acid is well mixed, obtain degradation material.
Comparative example 2
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of polyadipate fourth
Diol ester carries out cladding processing；
（3）It is 250 by PLA that the nanometer basalt fibre after cladding and 65 parts of the degree of polymerization are 1000,35 parts of the degree of polymerization
Polyethylene, 4 parts of methacrylic acids, 8 parts of polyacrylic acid it is well mixed after extruded, obtain degradation material.
Comparative example 3
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of polystyrene and 1.5 parts of polyadipate fourth two
Alcohol ester carries out cladding processing；
（3）In electric-field strength after nanometer basalt fibre after cladding is well mixed with the PLA that 65 parts of the degree of polymerization is 1000
Spend to be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, obtain compound；
（4）The compound that step 3 is obtained and 35 parts of the degree of polymerization are 250 polyethylene, 4 parts of methacrylic acids, poly- the third of 8 parts
Extruded after olefin(e) acid is well mixed, obtain degradation material.
Comparative example 4
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of polyadipate fourth
Diol ester carries out cladding processing；
（3）By polyethylene that the nanometer basalt fibre after cladding and 35 parts of the degree of polymerization are 250,4 parts of methacrylic acids, 8 parts
Polyacrylic acid, 65 parts of the degree of polymerization be 1000 PLA it is well mixed after be 1.2kv/m in electric-field intensity direction of an electric field
Extruded in constant parallel electric field, obtain degradation material.
Comparative example 5
（1）10 parts of nanometer basalt fibre is handled with 0.5 part of methacryloxypropyl silane；
（2）By the nanometer basalt fibre Jing Guo coupling agent treatment 1.5 parts of acrylic acid hydroxyl ester and 1.5 parts of polyadipate fourth
Diol ester carries out cladding processing；
（3）In electric-field strength after nanometer basalt fibre after cladding is well mixed with the PLA that 65 parts of the degree of polymerization is 1300
Spend to be extruded in the constant parallel electric field of 1.2kv/m direction of an electric field, obtain compound；
（4）The polyethylene, 8 parts of polyacrylic acid, 4 parts of methyl-props that the compound that step 3 is obtained and 35 parts of the degree of polymerization are 180
Extruded after olefin(e) acid is well mixed, obtain degradation material.
By the degradation material in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data is as follows：
| Performance | Fatigue resistance | Processability |
| Embodiment 1 | ++++++ | ++++ |
| Embodiment 2 | ++++++ | ++++ |
| Embodiment 3 | ++++++ | ++++ |
| Comparative example 1 | ++++ | ++++ |
| Comparative example 2 | ++++ | ++++ |
| Comparative example 3 | +++++ | ++++ |
| Comparative example 4 | +++++ | ++++ |
| Comparative example 5 | +++++ | ++ |
Note："+" is more, illustrates that performance is better.
Above-mentioned analysis of experimental data is understood, the antifatigue degradation material of the invention being prepared in embodiment 1-3, received
Rice basalt fibre is uniformly dispersed, and good with the compatibility of PLA, degradation material fatigue resistance is good, and processability is good；And contrast
In example 1, modifying agent is not used processing is modified to nanometer basalt fibre, although adding dispersant, nanometer basalt
Fiber dispersion effect is poor, and the poor compatibility with PLA, the fatigue resistance of degradation material significantly reduces；Do not exist in comparative example 2
Combined Processing is carried out in electric field, nanometer basalt fibre dispersion effect is poor, and the fatigue resistance of degradation material significantly reduces；Contrast
Modifying agent is not the application defined in example 3, and nanometer basalt fibre dispersion effect is poor, and the fatigue resistance of degradation material shows
Writing reduces；Cross-linking reaction is equally carried out in the electric field in comparative example 4, and electric field has a negative impact to cross-linking reaction, so as to get
The fatigue resistance of BS resin materials reduces；The PLA and polyethylene polymerization used in comparative example 5 spend it is small, it is compound after it is antifatigue
Property is preferable, but processability significantly reduces, and is unfavorable for the application of degradation material.
Claims (10)
1. a kind of antifatigue degradation material, it is characterised in that be prepared including following parts by weight raw material：8-12 parts are received
Rice basalt fibre, the modifying agent of 2-5 parts, the polyethylene of 25-40 parts, the PLA of 55-75 parts, 0.3-0.8 parts coupling agent,
The crosslinking agent, the polyacrylic acid of 5-10 parts of 3-5 parts；The modifying agent is acrylic acid hydroxyl ester and poly adipate succinic acid ester composition
Mixture；The coupling agent is methacryloxypropyl silane coupling agent, and the crosslinking agent is methacrylic acid；The polyethylene
The degree of polymerization be 200-300；The polymerisation degree of poly-lactic acid is 800-1200.
2. degradation material according to claim 1, it is characterised in that in the modifying agent acrylic acid hydroxyl ester with gather oneself two
The ratio between amount of material of sour butanediol ester is 1 ︰ 1.
3. degradation material according to claim 1, it is characterised in that the degree of polymerization of the polyethylene is 900-1100.
4. degradation material according to claim 3, it is characterised in that the degree of polymerization of the polyethylene is 1000.
5. degradation material according to claim 1, it is characterised in that the polymerisation degree of poly-lactic acid is 230-280.
6. degradation material according to claim 5, it is characterised in that the polymerisation degree of poly-lactic acid is 250.
7. a kind of preparation method of the degradation material as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nanometer basalt fibre is handled with coupling agent；
（2）Nanometer basalt fibre Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out in the electric field after nanometer basalt fibre after cladding is well mixed with PLA, is mixed
Close material；（4）After compound is well mixed with polyethylene, crosslinking agent, polyacrylic acid carry out Combined Processing, obtain it is antifatigue can
Degradable material.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric-field intensity is 0.5-2kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric-field intensity is 0.8-1.5kv/m.
10. preparation method according to claim 7, it is characterised in that step（3）Middle electric field, which is that direction of an electric field is constant, puts down
Row electric field.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711239064.7A CN107892799A (en) | 2017-11-30 | 2017-11-30 | A kind of antifatigue degradation material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711239064.7A CN107892799A (en) | 2017-11-30 | 2017-11-30 | A kind of antifatigue degradation material and preparation method thereof |
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