CN107022181A - A kind of toughness reinforcing enhancing PLA and its preparation method and application - Google Patents
A kind of toughness reinforcing enhancing PLA and its preparation method and application Download PDFInfo
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- CN107022181A CN107022181A CN201710293942.7A CN201710293942A CN107022181A CN 107022181 A CN107022181 A CN 107022181A CN 201710293942 A CN201710293942 A CN 201710293942A CN 107022181 A CN107022181 A CN 107022181A
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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Abstract
Strengthen PLA the invention provides a kind of toughness reinforcing, the toughness reinforcing strengthens PLA, obtained by the raw materials melt blending including following weight fraction：75~95 parts of PLA, 3~20 parts of epoxy natural rubber, 2~5 parts of lactic acid nano titanium oxide graft.The preparation method of the toughness reinforcing enhancing PLA includes：By dry polylactic acid raw material, epoxy natural rubber and lactic acid nano titanium oxide graft melt blending, the temperature of melt blending is 150~170 DEG C, and the melt blending time is 5~15min.The toughness reinforcing enhancing PLA that the application is provided can improve the toughness and intensity of PLA simultaneously.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of toughness reinforcing enhancing PLA and preparation method thereof and
Using.
Background technology
PLA (PLA) be using living resources as raw material, by chemical synthesis come Biodegradable high-molecular, have
Excellent physical and mechanical properties and good biocompatibility, be widely used in packaging material, agricultural mulching, textile and
The fields such as medical material.However, the glass transition temperature of PLA is higher, glassy state is under normal temperature, elongation at break is low
In 10%, impact strength and tensile toughness are all relatively low, are a kind of fragile materials, are not suitable for requirement material energy under higher stress
The occasion being plastically deformed.Attempt to improve the toughness of PLA therefore, prior art takes various means.Wherein, by PLA
It is the most and most efficient method of research with other plasticizer or the polymer blended toughness to improve PLA.However, adopting
While with plasticizer or the polymer blended toughness reinforcing to PLA, its modulus, intensity and heat resistance are often reduced.How in toughness reinforcing
While improve intensity, be one of the problem in polymer material science research.
Natural rubber (NR) derives from the latex extracted in rubber tree, with excellent toughness, biocompatibility and life
Thing degradability, and because its resource is renewable and the characteristic of biomass source, it is considered to be toughness reinforcing PLA preferable macromolecule material
Material.In the prior art, it can be effectively improved using graft modification natural rubber in Chinese invention patent ZL201110173286.X
PLA toughness, but the intensity of PLA can be also reduced simultaneously.(the Journal ofApplied Polymer such as Desa
Science,2016,133(48)：44344) PLA/NR/ CNTs (CNT) ternary blends are prepared for.The fracture of blend
Elongation is increased compared to pure PLA, but tensile strength and Young's modulus are substantially reduced, and still there is toughness reinforcing not enhanced
Problem.
Therefore, natural rubber disclosed in prior art, which is modified PLA, can not realize that toughness reinforcing strengthens PLA simultaneously, obtain simultaneous
High-strength, high-ductility high comprehensive performance the PLA material of tool.
The content of the invention
In order to solve the above mentioned problem of this area presence, PLA is strengthened it is an object of the invention to provide a kind of toughness reinforcing,
And the method for preparing toughness reinforcing enhancing PLA.
Strengthen PLA the invention provides a kind of toughness reinforcing, the toughness reinforcing strengthens PLA, by including following weight fraction
Raw materials melt blending obtain：
75~95 parts of PLA
3~20 parts of epoxy natural rubber
Lactic acid -2~5 parts of nano titanium oxide graft.
It is preferred that, the toughness reinforcing strengthens PLA, is obtained by the raw materials melt blending including following parts by weight：
80~90 parts of PLA
5~18 parts of epoxy natural rubber
Lactic acid -3~4 parts of nano titanium oxide graft.
It is preferred that, the epoxy content of the epoxy natural rubber is 10%~50%.
The lactic acid grafting amount of the lactic acid-nano titanium oxide graft is 30%~65%.
It is preferred that, the preparation method of the epoxy natural rubber comprises the following steps：Under conditions of formic acid presence, adopt
Heveatex is aoxidized with aqueous hydrogen peroxide solution, epoxidized natural latex is obtained；The epoxidized natural latex is dried, obtained
To epoxy natural rubber；The solid content of the Heveatex is 60%；The mass concentration of the formic acid is preferably 88%, described
The mass concentration of aqueous hydrogen peroxide solution is preferably 30%；The Heveatex, hydrogen peroxide, the mass ratio of formic acid are 1:
0.3~0.4:0.15~0.2；The temperature of the oxidation is 30~55 DEG C, and the time of oxidation is 8~24 hours.
It is preferred that, the preparation method of the lactic acid-nano titanium oxide graft comprises the following steps：By nanometer titanium dioxide
Titanium is scattered in polar organic solvent, obtains nano titanium oxide dispersion；By the nano titanium oxide dispersion and lactic acid
Monomer is mixed, and obtains material liquid；Under vacuum, the material liquid is catalyzed using stannous octoate and carries out graft reaction, it is described
The temperature of graft reaction is 150 DEG C~170 DEG C, and the time of graft reaction is 8~12 hours, obtains lactic acid-titanium dioxide grafting
Thing；The quality of the nano titanium oxide, the volume of organic solvent, the mass ratio of the quality of lactic acid monomer and stannous octoate are
1g:10~25mL:2~5g:0.01~0.05g；The polar organic solvent is chloroform, tetrahydrofuran, dichloromethane or N, N-
Dimethylformamide；The particle diameter of the nano titanium oxide is 25~100nm, preferably 50~75nm.
It is preferred that, the toughness reinforcing strengthens the preparation method of PLA, comprises the following steps：By dry polylactic acid raw material,
Epoxy natural rubber and lactic acid-nano titanium oxide graft melt blending, obtain toughness reinforcing enhancing PLA.
It is preferred that, in the preparation method that toughness reinforcing strengthens PLA, dry polylactic acid raw material, epoxy natural rubber and
The mass ratio of lactic acid-nano titanium oxide graft is 75~95:3~20:2~5.
It is preferred that, in the preparation method that toughness reinforcing strengthens PLA, dry polylactic acid raw material, epoxy natural rubber and
The mass ratio of lactic acid-nano titanium oxide graft is 80~90:5~18:3~4.
It is preferred that, in the preparation method that toughness reinforcing strengthens PLA, the temperature of melt blending is 150~170 DEG C, and melting is altogether
The mixed time is 5~15min.
It is preferred that, in the preparation method that toughness reinforcing strengthens PLA, the temperature of melt blending is 155~165 DEG C, and melting is altogether
Do time as 8~12min.
It is preferred that, the number-average molecular weight of polylactic acid raw material is 12~180,000.
It is preferred that, in the preparation method that toughness reinforcing strengthens PLA, it is total to using banbury formula torque rheology instrument apparatus
Mixed, the rotating speed of torque rheometer is 60rpm.
Beneficial effect：
Strengthen PLA the invention provides a kind of toughness reinforcing, strengthen poly- using elastomer and rigid nano-particle coordination plasticizing
Lactic acid, elastomer is made with epoxy natural rubber, improves the compatibility of epoxy natural rubber and PLA；With lactic acid-two
Titanium oxide graft makees rigid nano-particle, improves the compatibility of rigid nano-particle and PLA；So that epoxidation is natural
Rubber and lactic acid-dispersive property of the titanium dioxide graft in PLA matrix are preferable, and PLA/epoxy natural rubber/
The compatibility of lactic acid-titanium dioxide graft ternary blend systems is preferable, with excellent mechanical property.
The stretching for PLA/epoxy natural rubber/lactic acid-titanium dioxide graft ternary blends that the application is provided
The purer PLA of performance and notched impact properties is significantly improved, and shows epoxy natural rubber and lactic acid-titanium dioxide
Coordination plasticizing humidification of the graft to PLA.In addition, the present invention provide PLA/epoxy natural rubber/lactic acid-
Titanium dioxide graft ternary blends also have certain antibiotic property and UV Aging Resistance.It can be applied to engineering plastics neck
Domain, breaking through it is used for bio-medical field and the limitation of the general chemical product manufacture relatively low to material performance requirement.
Embodiment
Strengthen PLA the invention provides a kind of toughness reinforcing, obtained by the raw materials melt blending including following parts by weight：
75~95 parts of PLA, 3~20 parts of epoxy natural rubber, lactic acid -2~5 parts of nano titanium oxide graft.
In the present invention, preparing the raw material of toughness reinforcing enhancing PLA includes 75~95 parts of PLA, preferably 80~90
Part, more preferably 83~87 parts.
In the present invention, the number-average molecular weight of PLA is preferably 12~180,000, more preferably 13~170,000.
In the present invention, preparing the raw material of toughness reinforcing enhancing PLA includes 3~20 parts of epoxy natural rubber, is preferably
5~18 parts, more preferably more preferably 8~15 parts, 10~13 parts.In the present invention, the epoxy natural rubber
Epoxy content is preferably 10%~50%, preferably 20%~45%, more preferably 25%~40%.In the present invention, epoxy content is excellent
Infra-red sepectrometry was gated to obtain.
In the present invention, the preparation method of the epoxy natural rubber preferably includes following steps：
Under conditions of formic acid presence, Heveatex is aoxidized using aqueous hydrogen peroxide solution, epoxidation natural gum is obtained
Breast；The epoxidized natural latex is dried, epoxy natural rubber is obtained.
In the present invention, the solid content of the Heveatex is 60%；The Heveatex is commercially available Heveatex.
In the present invention, the Heveatex, aqueous hydrogen peroxide solution, the mass ratio of formic acid are 1:0.3~0.4:0.15
~0.2；Preferably 1:0.33~0.37:0.16~0.19.
In the present invention, the mass concentration of formic acid is preferably 88%, and the concentration of aqueous hydrogen peroxide solution is preferably 30%.
In the present invention, the addition sequence of Heveatex, aqueous hydrogen peroxide solution and formic acid is not particularly limited, and preferably first adds
Enter Heveatex, then sequentially add aqueous hydrogen peroxide solution and formic acid.
In the present invention, the temperature of the oxidation is preferably 30~55 DEG C, preferably 35~50 DEG C, more preferably 40~45
℃；The time of oxidation is 8~24 hours, more preferably preferably 10~22 hours, 13~20 hours.
In the present invention, the method for drying epoxidized natural latex is preferred to use vacuum drying, the vacuum drying temperature
Preferably 40~45 DEG C, the vacuum drying time is preferably 48~50 hours, and the vacuum drying vacuum is preferably-
0.02MPa~-0.03MPa.The present invention is preferably by the epoxidized natural latex drying to weight.
In the present invention, preparing the raw material of toughness reinforcing enhancing PLA includes 2~5 parts of lactic acid-nano titanium oxide grafting
Thing, preferably 3~4 parts.
The lactic acid grafting amount of heretofore described lactic acid-nano titanium oxide graft is 30%~65% by mass,
Preferably 35%~60%, more preferably 40%~55%.
In the present invention, the grafting amount is preferably obtained by weight method.
In the present invention, the preparation method of the lactic acid-nano titanium oxide graft preferably includes following steps：
Nano titanium oxide is scattered in polar organic solvent, nano titanium oxide dispersion is obtained；
The nano titanium oxide dispersion is mixed with lactic acid monomer, material liquid is obtained；
Under vacuum, the material liquid is catalyzed using stannous octoate and carries out graft reaction, obtain lactic acid-titanium dioxide
Graft.
In the present invention, the particle diameter of the nano titanium oxide is preferably 25~100nm, preferably 50~75nm.
In the present invention, the polar organic solvent is preferably chloroform, tetrahydrofuran, dichloromethane or N, N- dimethyl formyl
Amine.
In the present invention, nano titanium oxide is scattered in polar organic solvent, the process for dispersing used is not limited especially
It is fixed, as long as titanium dioxide can be scattered in polar organic solvent, ultrasonic dispersion is preferably used, what ultrasonic wave disperseed
Time is preferably 10~30min.
In the present invention, obtain after nano titanium oxide dispersion, by the nano titanium oxide dispersion and lactic acid monomer
Mixing, obtains material liquid.
In the present invention, the hybrid mode of nano titanium oxide dispersion and lactic acid monomer is not particularly limited, preferably by breast
Acid monomers are added in nano titanium oxide dispersion.
In the present invention, the quality of the nano titanium oxide and the volume ratio of organic solvent are preferably 1g:10~25mL.
In the present invention, obtain after material liquid, being catalyzed the material liquid using stannous octoate carries out graft reaction, obtains breast
Acid-titanium dioxide graft.
In the present invention, the hybrid mode of stannous octoate and material liquid is not particularly limited, and preferably adds stannous octoate former
In feed liquid.
In the present invention, the mass ratio of the stannous octoate and nano titanium oxide is 0.01~0.05g:1g.
In the present invention, the mass ratio of the lactic acid monomer and nano titanium oxide is 2~5g:1g.
In the present invention, the graft reaction is carried out under vacuum, and vacuum is preferably -0.02~0.03MPa.
In the present invention, the temperature of the graft reaction is preferably 150~170 DEG C, more preferably 155~165 DEG C.This
In invention, the time of the graft reaction is preferably 8~12 hours, more preferably 9~11 hours.
In the present invention, preferably the product of the graft reaction is centrifuged, the solid phase components that centrifugation is obtained are washed successively
Wash and be dried in vacuo, obtain lactic acid-titanium dioxide graft.
The parameter centrifuged in the present invention, such as rotating speed, time are not particularly limited, as long as can separate precipitation.
In the present invention, in the washing step after centrifugation, the solvent preferably ethanol used is washed.
In the present invention, the temperature that graft reaction product vacuum is dried is preferably：80~85 DEG C.
In the present invention, the time that graft reaction product vacuum is dried is preferably：8~10 hours.
In the present invention, the method for preparing toughness reinforcing enhancing PLA comprises the following steps：By dry polylactic acid raw material, epoxy
Change natural rubber and lactic acid-nano titanium oxide graft melt blending, obtain toughness reinforcing enhancing PLA.
In the present invention, the method for drying polylactic acid raw material is preferred to use vacuum drying, and the vacuum drying temperature is preferred
For 75~80 DEG C, the vacuum drying time is preferably 4~5 hours, and the vacuum drying vacuum is preferably-
0.02MPa~-0.03MPa.Preferably by polylactic acid raw material drying to constant weight in the present invention.
In the present invention, the temperature of melt blending is 150~170 DEG C, preferably 155~165 DEG C, more preferably 158~162
℃.In the present invention, the time of melt blending is 5~15min, more preferably preferably 7~13min, 8~12min.
Made present invention also offers toughness reinforcing enhancing PLA described in above-mentioned technical proposal or according to described in above-mentioned technical proposal
The application of toughness reinforcing enhancing PLA prepared by Preparation Method in polymeric material field.In the present invention, the toughness reinforcing enhancing is poly-
Lactic acid is preferred for preparing the shell of textile, biological medicine material and electronic and electrical equipment.
The present invention has no particular limits to the species of the textile, and in the present invention, the textile is preferably fiber
Product.
The present invention has no particular limits to the biological medicine material category, in the present invention, the biological medicine material
Preferably disposable infusion instrument, exempt to tear open type operation suture thread, medicine and alleviate packaging agent, artificial bone fracture internal fixation material and tissue
Repair materials.
The present invention to the species of the electronic and electrical equipment without special standby limitation, it is of the invention in, the electronic equipment is excellent
Elect notebook computer, tablet personal computer, mobile phone, word processor or mobile data holder as.
In order to further illustrate the present invention, PLA and its system are strengthened to the toughness reinforcing that the present invention is provided with reference to embodiment
Preparation Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1
The aqueous hydrogen peroxide solution and mass concentration that the Heveatex for being 60% by solid content, mass concentration are 30% be
88% formic acid is with mass ratio 1:0.38:0.18 ratio mixing, under conditions of 45 DEG C, aoxidizes 18 hours, obtains epoxy content
For 36% epoxy natural rubber.
It is that 50nm nano titanium oxides are scattered in 200mL chloroforms by 10g particle diameters, then is mixed with 40g lactic acid monomers, is obtained
Material liquid；Under vacuum, 0.3g stannous octoates are added and are catalyzed the material liquid, graft reaction is carried out under the conditions of 160 DEG C,
Reaction time is 10 hours；The product of the graft reaction is centrifuged, the solid phase components that the centrifugation is obtained are washed successively
Wash and be dried in vacuo, obtain lactic acid-titanium dioxide graft.The lactic acid grafting amount of the lactic acid-nano titanium oxide graft
For 46%.
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft in mass ratio 87:
10:3 melt blendings, melt blending temperature is 165 DEG C, melt blending time 8min, obtains toughness reinforcing enhancing PLA.
Embodiment 2
The aqueous hydrogen peroxide solution and mass concentration that the Heveatex for being 60% by solid content, mass concentration are 30% be
88% formic acid is with mass ratio 1:0.4:0.2 ratio mixing, under conditions of 30 DEG C, is aoxidized 24 hours, obtaining epoxy content is
40% epoxy natural rubber.
It is that 75nm nano titanium oxides are scattered in 250mL dichloromethane by 10g particle diameters, then is mixed with 50g lactic acid monomers,
Obtain material liquid；Under vacuum, 0.5g stannous octoates are added and is catalyzed the material liquid, be grafted under the conditions of 170 DEG C
Reaction, the reaction time is 12 hours；The product of the graft reaction is centrifuged, by it is described centrifuge obtained solid phase components according to
Secondary washing and vacuum drying, obtain lactic acid-titanium dioxide graft.The lactic acid of the lactic acid-nano titanium oxide graft connects
Branch amount is 61%.
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft in mass ratio 84:
12.2:3.8 melt blendings, melt blending temperature is 160 DEG C, melt blending time 10min, obtains toughness reinforcing enhancing PLA.
Embodiment 3
The aqueous hydrogen peroxide solution and mass concentration that the Heveatex for being 60% by solid content, mass concentration are 30% be
88% formic acid is with mass ratio 1:0.4:0.2 ratio mixing, under conditions of 40 DEG C, is aoxidized 20 hours, obtaining epoxy content is
42% epoxy natural rubber.
By 10g particle diameters be 100nm nano titanium oxides be scattered in 250mLN, dinethylformamide, then with 40g lactic acid
Monomer is mixed, and obtains material liquid；Under vacuum, 0.4g stannous octoates are added and is catalyzed the material liquid, under the conditions of 160 DEG C
Graft reaction is carried out, the reaction time is 12 hours；The product of the graft reaction is centrifuged, by consolidating that the centrifugation is obtained
Phase component is washed and is dried in vacuo successively, obtains lactic acid-titanium dioxide graft.The lactic acid-nano titanium oxide graft
Lactic acid grafting amount be 60%.
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft in mass ratio 75:
20:5 melt blendings, melt blending temperature is 155 DEG C, melt blending time 15min, obtains toughness reinforcing enhancing PLA.
Embodiment 4
The aqueous hydrogen peroxide solution and mass concentration that the Heveatex for being 60% by solid content, mass concentration are 30% be
88% formic acid is with mass ratio 1:0.37:0.18 ratio mixing, under conditions of 45 DEG C, aoxidizes 18 hours, obtains epoxy content
For 39% epoxy natural rubber.
It is that 50nm nano titanium oxides are scattered in 200mL tetrahydrofurans by 10g particle diameters, then is mixed with 40g lactic acid monomers,
Obtain material liquid；Under vacuum, 0.4g stannous octoates are added and is catalyzed the material liquid, be grafted under the conditions of 165 DEG C
Reaction, the reaction time is 10 hours；The product of the graft reaction is centrifuged, by it is described centrifuge obtained solid phase components according to
Secondary washing and vacuum drying, obtain lactic acid-titanium dioxide graft.The lactic acid of the lactic acid-nano titanium oxide graft connects
Branch amount is 62%.
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft in mass ratio 86:
10.5:3.5 melt blendings, melt blending temperature is 160 DEG C, melt blending time 10min, obtains toughness reinforcing enhancing PLA.
Comparative example 1
After testing, the tensile strength of pure PLA is 76.8MPa, and the row elongation that breaks is 8%, and impact strength is 3.6KJ/
m2。
Comparative example 2
The aqueous hydrogen peroxide solution and mass concentration that the Heveatex for being 60% by solid content, mass concentration are 30% be
88% formic acid is with mass ratio 1:0.37:0.18 ratio mixing, under conditions of 45 DEG C, aoxidizes 18 hours, obtains epoxy content
For 39% epoxy natural rubber.
By dry polylactic acid raw material and epoxy natural rubber in mass ratio 86:14 melt blendings, melt blending temperature
For 160 DEG C, melt blending time 10min obtains polylactic acid composition.
After testing, the tensile strength of the polylactic acid composition is 72.6MPa, and the row elongation that breaks is 56%, impact strength
For 6.5KJ/m2。
Comparative example 3
It is that 50nm nano titanium oxides are scattered in 200mL tetrahydrofurans by 10g particle diameters, then is mixed with 40g lactic acid monomers,
Obtain material liquid；Under vacuum, 0.4g stannous octoates are added and is catalyzed the material liquid, be grafted under the conditions of 165 DEG C
Reaction, the reaction time is 10 hours；The product of the graft reaction is centrifuged, by it is described centrifuge obtained solid phase components according to
Secondary washing and vacuum drying, obtain lactic acid-titanium dioxide graft.The lactic acid of the lactic acid-nano titanium oxide graft connects
Branch amount is 62%.
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft in mass ratio
96.5:3.5 melt blendings, melt blending temperature is 160 DEG C, melt blending time 10min, obtains toughness reinforcing enhancing PLA.
After testing, the tensile strength of the polylactic acid composition is 78.9MPa, and the row elongation that breaks is 13%, impact strength
For 5.2KJ/m2。
The polyamide material that embodiment 1~4 and comparative example 1~3 are obtained is tested, test event and method mark
It is accurate as follows, as a result as shown in table 1：
Tensile strength and elongation at break：GB/T 1040.2-2006；
Impact strength：GB/T 1043.1-2008.
The test result for the polydactyl acid that the embodiment of the present invention of table 1 and comparative example are obtained
As can be seen from the above embodiments, the tensile strength of pure PLA is 76.8MPa, and elongation at break is 8%, impact
Intensity is 3.6KJ/m2.Using only epoxy natural rubber to it is polylactic acid modified when, the tensile strength of polydactyl acid is
72.6MPa, elongation at break is 56%, and impact strength is 6.5KJ/m2, improving PLA elongation at break and impact strength
In the case of, reduce the tensile strength of polydactyl acid.Using only nanometer-titanium dioxide graft to it is polylactic acid modified when,
The tensile strength of polydactyl acid is 78.9MPa, and elongation at break is 13%, and impact strength is 5.2KJ/m2。
And the toughness reinforcing enhancing PLA that the present invention is provided can be while improve the tensile property and strength character of PLA.When
The tensile strength of toughness reinforcing enhancing PLA reaches 80.8MPa, and elongation at break is reached in the case of 82%, toughness reinforcing enhancing PLA
Impact strength up to 8.6KJ/m2；When the tensile strength that toughness reinforcing strengthens PLA reaches 78.3MPa, elongation at break reaches
In the case of 86%, the impact strength of toughness reinforcing enhancing PLA is up to 10.4KJ/m2；When toughness reinforcing strengthens the tensile strength of PLA
81.6MPa is reached, elongation at break is reached in the case of 78%, the impact strength of toughness reinforcing enhancing PLA is up to 10.2KJ/m2。
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of toughness reinforcing strengthens PLA, obtained by the raw materials melt blending including following parts by weight：
75~95 parts of PLA
3~20 parts of epoxy natural rubber
Lactic acid -2~5 parts of nano titanium oxide graft.
2. toughness reinforcing according to claim 1 strengthens PLA, it is characterised in that melted by the raw material including following parts by weight
Melt blending to obtain：
80~90 parts of PLA
5~18 parts of epoxy natural rubber
Lactic acid -3~4 parts of nano titanium oxide graft.
3. toughness reinforcing according to claim 1 strengthens PLA, it is characterised in that the epoxy content of the epoxy natural rubber
For 10%~50%.
4. toughness reinforcing according to claim 1 strengthens PLA, it is characterised in that the lactic acid-nano titanium oxide grafting
The lactic acid grafting amount of thing is 30%~65%.
5. the toughness reinforcing enhancing PLA according to claim 1 or 3, it is characterised in that the system of the epoxy natural rubber
Preparation Method comprises the following steps：Under conditions of formic acid presence, Heveatex is aoxidized using aqueous hydrogen peroxide solution, ring is obtained
Aoxidize Heveatex；The epoxidized natural latex is dried, epoxy natural rubber is obtained；
The solid content of the Heveatex is 60%；
The Heveatex, hydrogen peroxide, the mass ratio of formic acid are 1:0.3~0.4:0.15~0.2；
The temperature of the oxidation is 30~55 DEG C, and the time of oxidation is 8~24 hours.
6. the toughness reinforcing enhancing PLA according to claim 1 or 4, it is characterised in that the lactic acid-nano titanium oxide connects
The preparation method of branch thing comprises the following steps：
Nano titanium oxide is scattered in polar organic solvent, nano titanium oxide dispersion is obtained；
The nano titanium oxide dispersion is mixed with lactic acid monomer, material liquid is obtained；
Under vacuum, the material liquid is catalyzed using stannous octoate and carries out graft reaction, the temperature of the graft reaction is
150 DEG C~170 DEG C, the time of graft reaction is 8~12 hours, obtains lactic acid-titanium dioxide graft；
The quality of the nano titanium oxide, the volume of organic solvent, the mass ratio of the quality of lactic acid monomer and stannous octoate are
1g:10~25mL:2~5g:0.01~0.05g；
The polar organic solvent is chloroform, tetrahydrofuran, dichloromethane or N,N-dimethylformamide；
The particle diameter of the nano titanium oxide is 25~100nm.
7. toughness reinforcing described in claim 1~6 any one strengthens the preparation method of PLA, comprise the following steps：
By dry polylactic acid raw material, epoxy natural rubber and lactic acid-nano titanium oxide graft melt blending, increased
Tough enhancing PLA.
8. toughness reinforcing according to claim 7 strengthens the preparation method of PLA, it is characterised in that dry PLA is former
The mass ratio of material, epoxy natural rubber and lactic acid-nano titanium oxide graft is 75~95:3~20:2~5.
9. toughness reinforcing according to claim 8 strengthens the preparation method of PLA, it is characterised in that the temperature of melt blending is
150~170 DEG C, the time of melt blending is 5~15min.
10. toughness reinforcing described in any one strengthens preparation method described in PLA or claim 7~9 and prepared in claim 1~6
Application of the toughness reinforcing enhancing PLA in polymeric material field.
Priority Applications (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574679A (en) * | 2020-06-09 | 2020-08-25 | 张中明 | Degradable TiO2Polylactic acid grafted polyurethane antibacterial material and preparation method thereof |
| CN114957938A (en) * | 2022-02-28 | 2022-08-30 | 上海理工大学 | Preparation method of bio-based fully-degradable nut shell fiber modified polylactic acid material |
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| CN102453319A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Polylactic resin composition film and preparation method thereof |
| CN105176027A (en) * | 2015-09-23 | 2015-12-23 | 芜湖环瑞汽车内饰件有限公司 | Low-VOC environmentally-friendly high-quality automobile interior trim part material and preparation method thereof |
| CN106317816A (en) * | 2016-09-07 | 2017-01-11 | 清华大学深圳研究生院 | Low-cost toughening polylactic-acid composite material and preparation method thereof |
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| CN102453319A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Polylactic resin composition film and preparation method thereof |
| CN105176027A (en) * | 2015-09-23 | 2015-12-23 | 芜湖环瑞汽车内饰件有限公司 | Low-VOC environmentally-friendly high-quality automobile interior trim part material and preparation method thereof |
| CN106317816A (en) * | 2016-09-07 | 2017-01-11 | 清华大学深圳研究生院 | Low-cost toughening polylactic-acid composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111574679A (en) * | 2020-06-09 | 2020-08-25 | 张中明 | Degradable TiO2Polylactic acid grafted polyurethane antibacterial material and preparation method thereof |
| CN114957938A (en) * | 2022-02-28 | 2022-08-30 | 上海理工大学 | Preparation method of bio-based fully-degradable nut shell fiber modified polylactic acid material |
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