CN107892800A - A kind of PLA creep resistant is material modified and preparation method thereof - Google Patents
A kind of PLA creep resistant is material modified and preparation method thereof Download PDFInfo
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- CN107892800A CN107892800A CN201711244370.XA CN201711244370A CN107892800A CN 107892800 A CN107892800 A CN 107892800A CN 201711244370 A CN201711244370 A CN 201711244370A CN 107892800 A CN107892800 A CN 107892800A
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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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- 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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- 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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- C—CHEMISTRY; METALLURGY
- 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
It is material modified and preparation method thereof the invention discloses a kind of PLA creep resistant, including following parts by weight raw material are prepared：10 15 parts of nano-bentonite, 35 parts of modifying agent, 15 25 parts of chlorinated polyether, 50 60 parts of PLA, 0.3 0.6 parts of coupling agent, 35 parts of crosslinking agent, 20 30 parts of polyurethane rubber；The present invention is compound by the nano-bentonite Jing Guo specific aim modification and PLA progress, and nano-bentonite is dispersed in PLA system, and obtained material modified creep-resistant property is excellent, is advantageous to application of the PLA in more areas.
Description
Technical field
The present invention relates to modified polylactic acid material field, and in particular to a kind of PLA creep resistant is material modified and its prepares
Method.
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 creep-resistant property, the PLA being modified without creep resistant has been difficult to full
Sufficient demand, thus, creep resistant modification is carried out to PLA and is necessitated.Now to the creep resistant 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 creep 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 creep resistant 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 creep resistant modifying process is carried out, nanometer material
The scattered inequality of material can influence its creep resistant effect, and obtained material modified creep resistance is relatively low, 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 modified polylactic acid material creep resistance poor, there is provided the poly- breast of one kind
Sour creep resistant is material modified and preparation method thereof；The present invention enters the nano-bentonite Jing Guo specific aim modification with PLA
Row is compound, and nano-bentonite is dispersed in PLA system, and obtained material modified creep-resistant property is excellent, favorably
In application of the PLA in more areas.
In order to realize foregoing invention purpose, the invention provides a kind of PLA creep resistant is material modified, including it is following heavy
Amount part raw material are prepared：The nano-bentonite of 10-15 parts, the modifying agent of 3-5 parts, the chlorinated polyether, 50-60 of 15-25 parts
The PLA, the coupling agent of 0.3-0.6 parts, the crosslinking agent of 3-5 parts, the polyurethane rubber of 20-30 parts of part.
A kind of above-mentioned PLA creep resistant is material modified, can increase resin material creep resistant according to nano-bentonite and crosslinking
The general principle of property, not only by targetedly screening modifying agent, coupling agent and the species of crosslinking agent, to improve nano-bentonite
Compatibility between PLA, and make nano-bentonite disperse evenly, to make nano-bentonite to PLA in PLA
Creep resistance humidification it is more preferable, also made by controlling the degree of polymerization of PLA modified material modified in creep resistance
Reach optimum balance relation between processability, it is material modified in the condition with excellent creep resistance so as to make to obtain
Under, it may have excellent processability, it is applied in more areas.
A kind of above-mentioned PLA creep resistant is material modified, wherein, described nano-bentonite particle diameter is 10-80nm；Nanometer
Bentonite particle diameter is smaller, and dispersiveness is poorer, and nano-bentonite particle diameter is bigger, poorer to the creep resistant humidification of PLA；It is excellent
Choosing, described nano-bentonite particle diameter is 30-50nm；Most preferably, described nano-bentonite particle diameter is 40nm.
A kind of above-mentioned PLA creep resistant is material modified, wherein, described modifying agent is triacetyl glycerine and six methylenes
The mixture of group diisocyanate composition；Described modifying agent can improve the compatibility of nano-bentonite and PLA, and can
Polar group is formed on nano-bentonite surface, beneficial to scattered；Preferably, triacetyl glycerine and six Asias in described modifying agent
The ratio between amount of material of methyl diisocyanate is 1 ︰ 1.
A kind of above-mentioned PLA creep resistant is material modified, wherein, the degree of polymerization of chlorinated polyether is bigger, then is crosslinked post-modification material
The creep resistance of material is poorer, and processability is better, and the polymer of chlorinated polyether is smaller, then the creep resistance for being crosslinked post-modification material is got over
Good, processability is poorer, therefore, selects the rational chlorinated polyether degree of polymerization, is the important means for balancing creep resistance and processability.
The degree of polymerization of described chlorinated polyether is 120-200；Preferably, the degree of polymerization of described chlorinated polyether is 140-180；It is optimal
, the degree of polymerization of described chlorinated polyether is 160；By preferred, obtain it is material modified both there is excellent creep resistance,
With preferable processability, it is adapted to the application in more areas.
Wherein, described polymerisation degree of poly-lactic acid is 1200-1800；Preferably, the degree of polymerization of the PLA is 1400-
1600；Most preferably, the degree of polymerization of described PLA is 1500；By preferred, what is obtained is material modified both with excellent
Creep resistance, it may have preferable processability.
A kind of above-mentioned PLA creep resistant is material modified, wherein, described coupling agent is aluminate coupling agent；Aluminate energy
Increase the compatibility between nano-bentonite and PLA and modifying agent, improve material modified performance.
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, improves material modified creep resistance.
A kind of above-mentioned PLA creep resistant is material modified, wherein, its raw material also includes dispersant, plasticizer, antistatic
One or more auxiliary agents in agent, coloring agent, brightener；Above-mentioned auxiliary agent can improve material modified processability, increase its work(
The effects such as energy property, so as to increase its applicability.
In order to realize foregoing invention purpose, further, present invention also offers a kind of PLA creep resistant is material modified
Preparation method, comprise the following steps：
（1）Nano-bentonite is handled with coupling agent；
（2）Nano-bentonite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano-bentonite after cladding is well mixed with PLA in the electric field, obtains compound；
（4）Combined Processing is being carried out after compound is well mixed with chlorinated polyether, crosslinking agent, polyurethane rubber, is obtaining poly- breast
Sour creep resistant is material modified.
A kind of material modified preparation method of PLA creep resistant, is first carried out at coupling with coupling agent to nano-bentonite
Reason, increase nano-bentonite and modifying agent, the compatibility of PLA；Processing is modified to nano-bentonite with modifying agent again,
And form polar group on its surface；Finally make the polar group pole in nano-bentonite surface and polylactic acid chain using external electric field
Change, it is powered,, also can be with PLA while making nano-bentonite dispersed by repelling each other between electric charge or attracting principle
Polar group on chain is bonded, so that the creep resistant enhancing effect of nano-bentonite is farthest embodied, so as to get
Polydactyl acid creep resistance significantly improve；The preparation method is simple and reliable, and it is material modified to be suitable for PLA creep resistant
Extensive, industrialized production.
A kind of material modified preparation method of above-mentioned PLA creep resistant, wherein, it is preferred that step 1 carries out coupling processing
During can use ultrasonic assistant；Shaken by the high speed of ultrasonic wave, make nano-bentonite dispersiveness more preferable, and to coupling at
Reason has facilitation.
A kind of material modified preparation method of above-mentioned PLA creep resistant, wherein, the electric field energy described in step 3 is to group
Polarization is produced, makes group powered, so as to promote the scattered and bonded effect of nano-bentonite, improves polydactyl acid
Creep resistance.
Preferably, described electric-field intensity is 1.5-2.5kv/m；Electric-field intensity is too small, and polarization effect is weak, to nanometer swelling
The dispersion effect of soil is poor；Electric-field intensity is excessive, and polarization effect is too strong, and intermolecular force is too big, and strand produces displacement,
Arrangement to strand and it is bonded have an impact, material modified performance may be reduced；Most preferably, described electric-field intensity is
1.8-2.0kv/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, to the scattered and bonded facilitation of nano-bentonite
Best results.
Compared with prior art, beneficial effects of the present invention：
1st, the material modified species for targetedly screening modifying agent, coupling agent and crosslinking agent of the present invention, nano-bentonite is made with gathering
Compatibility between lactic acid is more preferable, and the dispersiveness in PLA is more preferable, creep resistance enhancing of the nano-bentonite to PLA
Effect is more preferable.
2nd, the present invention it is material modified made by controlling the degree of polymerization of PLA and chlorinated polyether it is modified material modified
Reach optimum balance relation between creep resistance and processability, so as to get it is material modified with excellent creep resistance
Under the conditions of, it may have excellent processability.
3rd, the material modified preparation method of the present invention, using the polarization of external electric field, nano-bentonite can be promoted poly-
Scattered and bonded in lactic acid system, the creep resistant enhancing effect of nano-bentonite is more preferable, obtained material modified creep resistant
Property is higher.
4th, the material modified preparation method of the present invention is simple, reliable, be adapted to PLA creep resistant it is material modified it is extensive,
Industrialized production.
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）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）By the nano-bentonite Jing Guo coupling agent treatment 2 parts of triacetyl glycerine and 2 parts of the isocyanic acid of hexa-methylene two
Ester carries out cladding processing；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the PLA that 55 parts of the degree of polymerization is 1500
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Chlorinated polyether that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,4 parts of methacrylic acids, 25 parts
Extruded after polyurethane rubber is well mixed, it is material modified to obtain PLA creep resistant.
Embodiment 2
（1）10 parts of nano-bentonite is handled with 0.3 part of Aluminate；
（2）Nano-bentonite Jing Guo coupling agent treatment is different with 1.5 parts of triacetyl glycerine and 1.5 parts of hexa-methylene two
Cyanate carries out cladding processing；
（3）In electric-field intensity after nano-bentonite after cladding is well mixed with the PLA that 50 parts of the degree of polymerization is 1200
To be extruded in 1.5kv/m electric field, compound is obtained；
（4）Chlorinated polyether that the compound that step 3 is obtained and 15 parts of the degree of polymerization are 120,3 parts of methacrylic acids, 20 parts
Extruded after polyurethane rubber is well mixed, it is material modified to obtain PLA creep resistant.
Embodiment 3
（1）15 parts of nano-bentonite is handled with 0.6 part of Aluminate；
（2）Nano-bentonite Jing Guo coupling agent treatment is different with 2.5 parts of triacetyl glycerine and 2.5 parts of hexa-methylene two
Cyanate carries out cladding processing；
（3）In electric-field intensity after nano-bentonite after cladding is well mixed with the PLA that 60 parts of the degree of polymerization is 1800
To be extruded in the constant parallel electric field of 2.5kv/m direction of an electric field, compound is obtained；
（4）Chlorinated polyether that the compound that step 3 is obtained and 25 parts of the degree of polymerization are 200,5 parts of methacrylic acids, 30 parts
Extruded after polyurethane rubber is well mixed, it is material modified to obtain PLA creep resistant.
Comparative example 1
（1）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）Nano-bentonite Jing Guo coupling agent treatment and 5 parts of dispersant, the PLA that 55 parts of the degree of polymerization is 1500 are mixed
Extruded after closing uniformly in the constant parallel electric field of the direction of an electric field that electric-field intensity is 2.0kv/m, obtain compound；
（3）Chlorinated polyether that the compound that step 2 is obtained and 20 parts of the degree of polymerization are 160,4 parts of methacrylic acids, 25 parts
Extruded, obtained material modified after polyurethane rubber is well mixed.
Comparative example 2
（1）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）By the nano-bentonite Jing Guo coupling agent treatment 2 parts of triacetyl glycerine and 2 parts of the isocyanic acid of hexa-methylene two
Ester carries out cladding processing；
（3）The chlorine for being 160 by PLA that the nano-bentonite after cladding and 55 parts of the degree of polymerization are 1500,20 parts of the degree of polymerization
Change polyethers, 4 parts of methacrylic acids, 25 parts of polyurethane rubber to be extruded after being well mixed, obtain material modified.
Comparative example 3
（1）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）Nano-bentonite Jing Guo coupling agent treatment is entered with 2 parts of polystyrene and 2 parts of hexamethylene diisocyanate
The processing of row cladding；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the PLA that 55 parts of the degree of polymerization is 1500
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Chlorinated polyether that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 160,4 parts of methacrylic acids, 25 parts
Extruded, obtained material modified after polyurethane rubber is well mixed.
Comparative example 4
（1）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）By the nano-bentonite Jing Guo coupling agent treatment 2 parts of triacetyl glycerine and 2 parts of the isocyanic acid of hexa-methylene two
Ester carries out cladding processing；
（3）By chlorinated polyether that the nano-bentonite after cladding and 20 parts of the degree of polymerization are 160,4 parts of methacrylic acids, 25 parts
The direction of an electric field for being 2.0kv/m in electric-field intensity after PLA that polyurethane rubber, 55 parts of the degree of polymerization are 1500 is well mixed
Extruded, obtained material modified in constant parallel electric field.
Comparative example 5
（1）12 parts of nano-bentonite is handled with 0.5 part of Aluminate；
（2）By the nano-bentonite Jing Guo coupling agent treatment 2 parts of triacetyl glycerine and 2 parts of the isocyanic acid of hexa-methylene two
Ester carries out cladding processing；
（3）It is in electric-field intensity after nano-bentonite after cladding is well mixed with the PLA that 55 parts of the degree of polymerization is 1000
Extruded in the constant parallel electric field of 2.0kv/m direction of an electric field, obtain compound；
（4）Chlorinated polyether that the compound that step 3 is obtained and 20 parts of the degree of polymerization are 100,25 parts of polyurethane rubber, 4 parts
Extruded, obtained material modified after methacrylic acid is well mixed.
Will be material modified in above-described embodiment 1-3 and comparative example 1-5, performance detection is carried out, record data is as follows：
| Performance | Creep 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 PLA creep resistant of the present invention being prepared in embodiment 1-3 is modified material
Material, nano-bentonite are uniformly dispersed, and good with the compatibility of PLA, material modified creep resistance is good, and processability is good；And comparative example
In 1, modifying agent is not used processing is modified to nano-bentonite, although adding dispersant, the scattered effect of nano-bentonite
Fruit is poor, and the poor compatibility with PLA, material modified creep resistance significantly reduces；Do not answered in the electric field in comparative example 2
Conjunction is handled, and nano-bentonite dispersion effect is poor, and material modified creep resistance significantly reduces；Modifying agent is not this in comparative example 3
Apply for defined, nano-bentonite dispersion effect is poor, and material modified creep resistance significantly reduces；It is crosslinked in comparative example 4 anti-
Equally should carry out in the electric field, electric field has a negative impact to cross-linking reaction, so as to get material modified creep resistance reduce；
The PLA and the chlorinated polyether degree of polymerization used in comparative example 5 is too small, although creep resistance increased after compound, it is processed
Property significantly reduces, and is unfavorable for material modified application.
Claims (10)
1. a kind of PLA creep resistant is material modified, it is characterised in that is prepared including following parts by weight raw material：10-15
The nano-bentonite of part, the modifying agent of 3-5 parts, the chlorinated polyether of 15-25 parts, the PLA of 50-60 parts, the idol of 0.3-0.6 parts
Join agent, the crosslinking agent of 3-5 parts, the polyurethane rubber of 20-30 parts；The modifying agent is that triacetyl glycerine and hexa-methylene two are different
The mixture of cyanate composition；The coupling agent is aluminate coupling agent, and the crosslinking agent is methacrylic acid；The chlorination gathers
The degree of polymerization of ether is 120-200；The polymerisation degree of poly-lactic acid is 1200-1800.
It is 2. according to claim 1 material modified, it is characterised in that triacetyl glycerine and six methylenes in the modifying agent
The ratio between amount of material of group diisocyanate is 1 ︰ 1.
It is 3. according to claim 1 material modified, it is characterised in that the degree of polymerization of the chlorinated polyether is 140-180.
It is 4. according to claim 3 material modified, it is characterised in that the degree of polymerization of the chlorinated polyether is 160.
It is 5. according to claim 1 material modified, it is characterised in that the polymerisation degree of poly-lactic acid is 1400-1600.
It is 6. according to claim 5 material modified, it is characterised in that the polymerisation degree of poly-lactic acid is 1500.
7. a kind of material modified preparation method as described in claim 1-6, it is characterised in that comprise the following steps：
（1）Nano-bentonite is handled with coupling agent；
（2）Nano-bentonite Jing Guo coupling agent treatment is subjected to cladding processing with modifying agent；
（3）Combined Processing is carried out after nano-bentonite after cladding is well mixed with PLA in the electric field, obtains compound；
（4）By compound and chlorinated polyether, crosslinking agent, polyurethane rubber, be well mixed after carrying out Combined Processing, obtain poly- breast
Sour creep resistant is material modified.
8. preparation method according to claim 7, it is characterised in that step（3）Middle electric-field intensity is 1.5-2.5kv/m.
9. preparation method according to claim 8, it is characterised in that step（3）Middle electric-field intensity is 1.8-2.0kv/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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| CN201711244370.XA CN107892800A (en) | 2017-11-30 | 2017-11-30 | A kind of PLA creep resistant is material modified and preparation method thereof |
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| CN201711244370.XA CN107892800A (en) | 2017-11-30 | 2017-11-30 | A kind of PLA creep resistant is material modified and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456415A (en) * | 2018-04-16 | 2018-08-28 | 合肥欧克斯新型建材有限公司 | A kind of compound floor tile of insulation antiseptic and preparation method thereof |
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2017
- 2017-11-30 CN CN201711244370.XA patent/CN107892800A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456415A (en) * | 2018-04-16 | 2018-08-28 | 合肥欧克斯新型建材有限公司 | A kind of compound floor tile of insulation antiseptic and preparation method thereof |
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Application publication date: 20180410 |