CN110003629A - A kind of biology base high-ductility poly (lactic acid) composition and preparation method thereof - Google Patents
A kind of biology base high-ductility poly (lactic acid) composition and preparation method thereof Download PDFInfo
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- CN110003629A CN110003629A CN201910342095.8A CN201910342095A CN110003629A CN 110003629 A CN110003629 A CN 110003629A CN 201910342095 A CN201910342095 A CN 201910342095A CN 110003629 A CN110003629 A CN 110003629A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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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
- 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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Abstract
The invention belongs to technical field of polymer materials, and in particular to a kind of biology base high-ductility poly (lactic acid) composition and preparation method thereof.The raw material of the poly (lactic acid) composition includes: polylactic acid and the toughener not higher than 10wt%；Toughener is a kind of biological poly amide polymer, structural formula are as follows:5≤n≤5000；Wherein, the R1And R3For aliphatic backbone structure；R2For the side-chain structure with ester functional groups, R4For the backbone structure with thioether.The poly (lactic acid) composition can greatly improve elongation at break, the toughness of polylactic acid in the case where a small amount of toughener is added, and be able to maintain the higher rigidity of polylactic acid and intensity；With great industrial prospect and commercial value.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of biology base high-ductility poly (lactic acid) composition and its system
Preparation Method.
Background technique
Polylactic acid (PLA) is a series of a kind of high score being prepared by the renewable substance such as starch and carbohydrate by processes
Sub- material has good biocompatibility and biodegradability；And the power such as mechanical strength for the polystyrene that is enough to match in excellence or beauty
Learn performance；This has obtained relatively broad application it all preferentially in fields such as packaging material, bio-medical materials.
The comprehensive performance of poly-lactic acid material is superior, but the performance deficiency poor there are toughness.In the prior art, polylactic acid
Toughening modifying is mainly two methods.One is modification by copolymerization, for this method since step is complex, yield is very low, is difficult reality
Border application.Another kind is blending and modifying, and this method is to improve the most economical effective method of toughness.Traditional polylactic acid blend changes
Property used in plasticizer have polyethylene glycol, glycerol, glyceride citrate etc., but these plasticizer molecule amounts are smaller, are easy
Cause polylactic acid blend glass transition temperature to decline, is not easy to poly-lactic acid material processing, and with using the time to increase
The problems such as long, plasticizer is easy migration and precipitation, eventually leads to material embrittlement.
Polyamide (PA) is used as a kind of thermoplastic resin, and the toughening modifying for being also once used for polylactic acid is studied, but toughening
It is ineffective.Such as when carrying out tensile property test to PLA/PA11 blend, test result shows PLA/PA11 blend
Tension fracture elongation rate and tensile strength are not significantly improved compared with pure PLA, and PLA/PA11 blend is still brittleness material
Expect (Polymer, 2011,52,1417-1425).Researcher also found, using PA resin as basis material and PLA resin into
Row is blended, and only when the content of polyamide increases to 15%, the tension fracture elongation rate of PLA/PA blend could be from 8%
Rise to 70% (Journal of Macromolecular Science, Part B:Physics, 2010,49,1117-
1127).Although polylactic acid toughness can be improved to a certain extent, the dosage of polyamide is generally large, generally up to
Polylactic acid toughness could be improved to 15% or so, and toughening effect is not significant.Simultaneously as polyamide and polylactic acid
The interface interaction of resin is poor, and the dispersibility and compatibility between matrix do not protrude, and a large amount of additions of polyamide can also to gather
The performances such as the intensity and rigidity of lactate material are a greater impact.In addition, a large amount of additions of conventional polyamide, to altogether
The biodegradability of mixing composition can also have an impact, so that the environmental-protecting performance of poly-lactic acid material substantially reduces.
Summary of the invention
A kind of biology is provided the purpose of the present invention is designing a new technical solution for the problems of the prior art
Base high-ductility poly (lactic acid) composition and preparation method thereof, solves foregoing problems.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
A kind of biology base high-ductility poly (lactic acid) composition, according to mass fraction, the raw material of poly (lactic acid) composition includes: polylactic acid
90-100 parts, 0-10 parts of toughener；
Polylactic acid is one of Poly-L-lactide, poly- D-ALPHA-Hydroxypropionic acid, poly-DL-lactic acid or a variety of；
Toughener is a kind of biological poly amide polymer, and structural formula is as follows:
5≤n≤5000；
Wherein, the R in biological poly amide polymer1And R3For aliphatic backbone structure；R2For with ester functional groups
Side-chain structure, R4For the backbone structure with thioether.
Preferably, the R in biology base polyamide polymer backbone1And R3For with any one of flowering structure, including but not
It is confined to as shown below:
Preferably, the side group R in biology base polyamide polymer backbone2For with any one of flowering structure, including but not
It is confined to as shown below:
Preferably, the R in biology base polyamide polymer backbone4For with any one of flowering structure, including but do not limit to
In as shown below:
A method of preparing biology base high-ductility poly (lactic acid) composition, which comprises the steps of:
(1) according to mass fraction, polylactic acid and toughener are located in vacuum drying oven with 40-100 DEG C of temperature in advance respectively
Reason 4-12 hours, it is spare after the completion of dry materials；
(2) it is added in mixer after mixing the pretreatment material of upper step, with 160-220 DEG C of temperature, 40-500r/
The revolving speed of min is kneaded 3-20min；
(3) mixture of upper step is sent in tablet press machine, with 160-220 DEG C of temperature compression moulding, needed for obtaining
Poly (lactic acid) composition.
The present invention using a kind of biological poly amide polymer synthesized by substances such as vegetable oil as the toughener of polylactic acid,
High-ductility poly-lactic acid material is prepared by Blending Processes.Good hydrogen bond action, biology base can be formed between polylactic acid and toughener
Hydrogen in polyamide polymer backbone on amino and the oxygen on polylactic acid carbonyl form hydrogen bond, in biological poly amide polymer
R2Oxygen on side-chain ester group can form hydrogen bond with hydrogen on hydroxyl in polylactic acid.Hydrogen bond content is than traditional polylactic acid and polyamide
Hydrogen bond content is much higher in blend material, these hydrogen bonds cause polyamide toughener and polylactic acid to form good interface work
With, and the formation of hydrogen bond has the dispersion conducive to toughener in polylactic acid.Meanwhile the polyamide polymer is a kind of elasticity
Body, polyamide elastomer are dispersed in polylactic acid matrix with micro-nano-scale, can be played the role of absorbing energy, be mentioned
Rise the mechanical performance of composition.Good interface interaction and dispersion effect are the key reasons for improving polylactic acid material toughness.
The present invention have it is following the utility model has the advantages that
Used using biological poly amide polymer as toughener, can on the basis of significantly reducing toughener dosage,
Significantly promote the mechanical performances such as toughness, elongation at break and the impact strength of poly (lactic acid) composition；And to the rigid of material
The influence of property and intensity is smaller.
Toughener in the present invention is the bio-based materials synthesized by vegetable oil, and raw material sources are extensive, the biology drop of product
Better performances are solved, it is more friendly to ecological environment.
Toughener in the present invention itself has better biodegradability, and in poly (lactic acid) composition matrix
Additive amount is relatively small, therefore smaller on the influence of the biodegradability of poly-lactic acid material, has better environmentally protective effect
Benefit.
The polyamide toughener that the present invention adds is a kind of elastomeric phase, is easy to and polylactic acid melt blending, preparation work
It is lower to equipment investment in skill, easy to operate, great economic value and market potential.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the stress-strain curve of high-ductility poly (lactic acid) composition in embodiment 1,2,3,4,5；
Fig. 2 is the scanning electron microscope cross-section photographs of high-ductility poly (lactic acid) composition in embodiment 4.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below with reference to embodiment to the present invention
Technical solution makes more specific detail, and following embodiment is only section Example of the invention, rather than all implements
Example.
The preparation of biological poly amide polymer:
(1) methyl undecylenate 100g, 1,3- diamino-propyl alcohol 1g is taken to be added in 4ml tetrahydrofuran；It is passed through argon gas half
It after hour, is placed in 40 DEG C of oil bath pans, after 10ml sodium methoxide is added, 40 DEG C are reacted 20 hours, white using being recrystallized to give
Color pulverulent solids, as required function monomer of polyamide 1；
(2) it takes 54g function monomer of polyamide A, 12g butyric anhydride, 40mg dimethylamino naphthyridine to set in a round bottom flask, adds
Enter the mixing of 3ml tetrahydrofuran, is reacted 10 hours at 50 DEG C, obtain clear solution, purified obtained function monomer of polyamide 2；
(3) by the function monomer of polyamide 2 of 1350mg, 150mg function monomer of polyamide 1, two mercaptan of 200mg oxa-, with
And 10mg azodiisobutyronitrile catalyst and 10ml tetrahydrofuran are added in reaction vessel；It is passed through argon gas 15 minutes, will mix later
It closes object and is placed in 36 hours of reaction in 100 DEG C of oil bath pans；Reaction product is purified, required complete biology base polyamides is obtained
Amine polymer.
In preparation process, solvent must be evaporated under reduced pressure after anhydrous magnesium sulfate is dry before the use, and azodiisobutyronitrile needs
By recrystallization purifying.
(above content be disclosed in detail in earlier application CN107501554A " a kind of superhigh intensity thermoplastic elastomer (TPE) and its
Preparation method " disclosure in)
It is used biological poly amide polymer as the toughener in subsequent embodiment.
Embodiment 1
1) 1000g Poly-L-lactide is placed on drying 4 hours under 40 DEG C of vacuum drying ovens, in case subsequent experimental uses；
2) the obtained pretreatment material 1000g polylactic acid of step 1) is added in mixer, at a temperature of 160 DEG C,
Under the revolving speed of 40r/min, being blended is uniformly mixed various materials；
3) the obtained poly (lactic acid) composition of step 2) is pressed at 160 DEG C to the shape of defined respectively with tablet press machine
It is tested.
Test is tested for the property to the high-ductility poly-lactic acid material that embodiment 1 obtains, performance is as shown in Figure 1；Specific value
As shown in table 1.
Embodiment 2
1) the poly- D-ALPHA-Hydroxypropionic acid of 990g and 10g toughener are placed on drying 12 hours under 100 DEG C of vacuum drying ovens, in case subsequent reality
Test use；
2) it is added in mixer after mixing the obtained pretreatment material 990g polylactic acid of step 1) and 10g toughener,
220 DEG C at a temperature of, under 500 revs/min of revolving speed, being blended is uniformly mixed various materials；
3) the obtained poly (lactic acid) composition of step 2) is pressed at 220 DEG C to the shape of defined respectively with tablet press machine
It is tested.
Test is tested for the property to the high-ductility poly-lactic acid material that embodiment 2 obtains, performance is as shown in Figure 1；Specific value
As shown in table 1.
Embodiment 3
1) 980g Poly-L-lactide and 20g toughener are placed on drying 10 hours under 80 DEG C of vacuum drying ovens, in case subsequent reality
Test use；
2) it is added in mixer after mixing the obtained pretreatment material 980g polylactic acid of step 1) and 20g toughener,
190 DEG C at a temperature of, under 200 revs/min of revolving speed, being blended is uniformly mixed various materials；
3) the obtained poly (lactic acid) composition of step 2) is pressed at 180 DEG C to the shape of defined respectively with tablet press machine
It is tested.
Test is tested for the property to the high-ductility poly-lactic acid material that embodiment 3 obtains, performance is as shown in Figure 1；Specific value
As shown in table 1.
Embodiment 4
1) 950g poly-DL-lactic acid and 50g toughener are placed on drying 10 hours under 80 DEG C of vacuum drying ovens, in case subsequent reality
Test use；
2) it is added in mixer after mixing the obtained pretreatment material 950g polylactic acid of step 1) and 50g toughener,
190 DEG C at a temperature of, under 80 revs/min of revolving speed, being blended is uniformly mixed various materials；
3) the obtained poly (lactic acid) composition of step 2) is pressed at 200 DEG C to the shape of defined respectively with tablet press machine
It is tested.
Test is tested for the property to the high-ductility poly-lactic acid material that embodiment 4 obtains, performance is as shown in Figure 1；Specific value
As shown in table 1；Scanning electron microscope cross-section photographs are as shown in Figure 2.
Embodiment 5
1) the poly- D-ALPHA-Hydroxypropionic acid of 900g and 100g toughener are placed on drying 6 hours under 100 DEG C of vacuum drying ovens, in case subsequent reality
Test use；
2) mixer is added to after mixing the obtained pretreatment material 900g polylactic acid of step 1) and 100g toughener
In, 190 DEG C at a temperature of, under 80 revs/min of revolving speed, being blended is uniformly mixed various materials；
3) the obtained poly (lactic acid) composition of step 2) is pressed at 220 DEG C to the shape of defined respectively with tablet press machine
It is tested.
Test is tested for the property to the high-ductility poly-lactic acid material that embodiment 5 obtains, performance is as shown in Figure 1；Specific value
As shown in table 1.
Test data and analysis
1, according to relevant test method, the mechanical property of poly-lactic acid material in embodiment 1-5 is tested, is obtained
Such as the performance test results of following table:
Table 1: the performance test data statistical form of poly (lactic acid) composition in the present embodiment
2, in conjunction with the load-deformation curve of the test data in table 1 and poly (lactic acid) composition in Fig. 1；It can be concluded that as follows
Conclusion:
After only adding 1% toughener in polylactic acid, the elongation at break of the biology base high-ductility poly-lactic acid material can be mentioned
Height is to 195.2%, and yield strength still has 59MPa, and tensile toughness can achieve 73.7MJ/m3, it is pure PLA tensile toughness
19 times or so.After adding 5% toughener in polylactic acid, the elongation at break of the biology base high-ductility poly-lactic acid material can be mentioned
Height is to 272.7%, and yield strength still has 54.3MPa, and tensile toughness can achieve 92MJ/m3, it is pure PLA tensile toughness
24 times or so.In conclusion the poly (lactic acid) composition can greatly improve poly- in the case where a small amount of toughener is added
The elongation at break and toughness of lactic acid, and it is able to maintain the higher rigidity of polylactic acid and intensity；With great industrial prospect
And commercial value.
3, the scanning electron microscope cross-section photographs of Fig. 2 are observed, it will thus be seen that the toughener is uniformly dispersed in polylactic acid matrix
In, and form the toughener phase of micro-nano-scale.The toughener is mutually dispersed in polylactic acid matrix with micro-nano-scale,
It can play the role of absorbing energy, promote the mechanical performance of composition.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although referring to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution documented by example is modified.All within the spirits and principles of the present invention, it is made it is any modification, equally replace
It changes, improve, should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of biology base high-ductility poly (lactic acid) composition, which is characterized in that according to mass fraction, the raw material packet of the composition
It includes: 90-100 parts of polylactic acid, 0-10 parts of toughener；
The toughener is a kind of biological poly amide polymer, and structural formula is as follows:
5≤n≤5000；
Wherein, the R1And R3For aliphatic backbone structure；R2For the side-chain structure with ester functional groups, R4For with thioether
Backbone structure.
2. a kind of biology base high-ductility poly (lactic acid) composition according to claim 1, it is characterised in that: the R on the main chain1
And R3It is including but not limited to as shown below for any one of flowering structure:
3. a kind of biology base high-ductility poly (lactic acid) composition according to claim 1, it is characterised in that: the side group R2For with
Any one of flowering structure, including but not limited to as shown below:
4. a kind of biology base high-ductility poly (lactic acid) composition according to claim 1, it is characterised in that: the R on the main chain4
It is including but not limited to as shown below for any one of flowering structure:
5. a kind of method for preparing biology base high-ductility poly (lactic acid) composition described in claim 1-4 any one, which is characterized in that
Include the following steps:
(1) according to mass fraction, by polylactic acid and toughener respectively in vacuum drying oven with 40-100 DEG C of Temperature pre-treatment 4-
It is 12 hours, spare after the completion of dry materials；
(2) will upper step pretreatment material mix after be added in mixer, with 160-220 DEG C of temperature, 40-500r/min's
Revolving speed is kneaded 3-20min；
(3) mixture of upper step is sent in tablet press machine, with 160-220 DEG C of temperature compression moulding, poly- cream needed for obtaining
Acid composition.
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| CN112226050A (en) * | 2020-10-13 | 2021-01-15 | 安徽农业大学 | Biodegradable heat shrinkable film with high transparency, and preparation method and application thereof |
| CN112760747A (en) * | 2020-12-29 | 2021-05-07 | 安徽农业大学 | High-strength elastic fiber material based on bio-based nylon and preparation method thereof |
| CN112853533A (en) * | 2021-01-07 | 2021-05-28 | 安徽农业大学 | Castor oil-based functional polyamide fiber with ultralow-temperature toughness and preparation method thereof |
| CN113105584A (en) * | 2021-04-29 | 2021-07-13 | 安徽农业大学 | Castor oil-based reprocessable thermosetting elastomer and preparation method thereof |
| CN114230992A (en) * | 2022-01-20 | 2022-03-25 | 江南大学 | Preparation method and application of high-strength high-toughness biodegradable plastic |
| CN114350129A (en) * | 2022-01-11 | 2022-04-15 | 励塑新材料科技(嘉兴)有限公司 | Full-bio-based high-degradation composite material and preparation method thereof |
| CN114479068A (en) * | 2022-03-02 | 2022-05-13 | 安徽农业大学 | Preparation method and application of castor oil-based polyamide capable of being crosslinked by ultraviolet light |
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| CN113105584A (en) * | 2021-04-29 | 2021-07-13 | 安徽农业大学 | Castor oil-based reprocessable thermosetting elastomer and preparation method thereof |
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Application publication date: 20190712 |