CN107227007A - A kind of bio-based toughening flame-proof PLA and preparation method thereof - Google Patents
A kind of bio-based toughening flame-proof PLA and preparation method thereof Download PDFInfo
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- CN107227007A CN107227007A CN201710614569.0A CN201710614569A CN107227007A CN 107227007 A CN107227007 A CN 107227007A CN 201710614569 A CN201710614569 A CN 201710614569A CN 107227007 A CN107227007 A CN 107227007A
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- lactic acid
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention relates to technical field of polymer materials, more particularly to a kind of bio-based toughening flame-proof poly (lactic acid) composition and preparation method thereof.The toughening flame-proof PLA includes each component with following mass fractions：60 100 parts of PLA, 0 20 parts of fire retardant, 0 20 parts of vegetable oil toughener.The present invention is using vegetable oil toughener come toughening flame-proof PLA so that PLA has again also keeps good toughness during good fire resistance, and obtained bio-based toughening flame-proof poly (lactic acid) composition has higher elongation at break and notch impact strength.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of bio-based toughening flame-proof PLA and its preparation
Method.
Technical background
PLA (PLA) has good as a kind of bio-based recyclable materials extracted from cornstarch and carbohydrate
Good biological compatibility, biodegradability, workability and mechanical performance.Because these performances cause PLA in medicine, change
There is very big prospect in the field such as fibre weaving, environmentally friendly packing material and agricultural production and electronic apparatus.But PLA has disconnected again
Split low elongation, poor toughness, it is inflammable the shortcomings of, PLA elongation at break only has 2%-10%, and its limited oxygen index also only has
19%, it significantly limit its application.Therefore, in order to which therefore the performance advantage for giving full play to PLA needs to increase PLA
It is tough flame-retardant modified.At present, for PLA it is flame-retardant modified most easily method be exactly additive flame retardant, example are added into PLA matrixes
Such as ammonium phosphate, melamine phosphate, Cu (NO3)2、Al(OH)3Etc..But PLA mechanics can be caused by adding additive flame retardant
Performance, especially toughness have very big decline.
Method on PLA toughening modifyings is broadly divided into two classes：One class method is common by chemical modification, that is, utilization
Gather the molecular chain structure that other monomers change PLA is introduced into PLA strands or change molecule with chemical modification or cross-linking method
Chain structure to it so as to be modified, but this method has complex process, the shortcomings of cost is higher.One class is using blending, again
The method closed or be plasticized, that is, some small molecule auxiliary agents or other high polymer materials are added to PLA to reach the effect of toughness reinforcing,
This method is simple, and the time that both saved relative to chemical modification method has saved economy.
Wherein, the toughener that traditional PLA physical blending method is used has polyethylene glycol, glycerine, lactic acid, butyric acid sweet
Grease and citric acid glyceride etc..As can be seen that most of product used is all oil resource from these toughener
Product, therefore can not be biodegradable, so as to produce very big pollution and the wasting of resources.Although traditional toughener energy as can be seen here
The enough toughness for improving PLA to a certain degree, but all there is non-biodegradable shortcoming, therefore waste can be produced, environment is made
Into certain pollution.
The content of the invention
For defect in the prior art mentioned above, the present invention provides one kind using vegetable oil come toughening flame-proof PLA
And preparation method thereof, replace petroleum using organism-based raw material, it is low without economic cost, and to the pollution of environment also compared with
It is small.Described composition not only causes PLA to have good flame-retarding characteristic, and can increase substantially the fracture of flame-proof polylactic acid
Elongation and notch impact strength, so as to substantially improve the toughness of PLA.
The present invention is achieved through the following technical solutions：
A kind of toughening flame-proof PLA, it includes each component with following mass fractions：
60-100 parts of PLA,
0-20 parts of fire retardant,
0-20 parts of vegetable oil toughener
Described toughening flame-proof poly-lactic acid material, it is characterised in that the PLA be Poly-L-lactide, poly- D-ALPHA-Hydroxypropionic acid,
One or more in poly-DL-lactic acid, the vegetable oil is the one or more of epoxidized soybean oil, castor oil and sunflower oil,
Fire retardant is APP, melamine polyphosphate, the one or more of hypo-aluminum orthophosphate.
Described toughening flame-proof poly-lactic acid material, it is characterised in that the vegetable oil can form a kind of crosslinking knot with PLA
Structure
A kind of described toughening flame-proof poly-lactic acid material, it is characterised in that described toughening flame-proof poly (lactic acid) composition, its
It is characterised by being prepared by the following method and obtains：
1) 60-100 parts of PLAs and 0-20 parts of fire retardants have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequently
Experiment is used；
2) by step 1) obtained by 60-100 parts of PLAs of pretreatment material, 0-20 parts of vegetable oil toughener and 0-20 parts resistance
Combustion agent is added in banbury according to certain order, under 180 DEG C of temperature conditionss, under 25-35r/min speed conditions,
Blending causes various materials to be well mixed in 20 minutes.
3) shape that the above-mentioned material 2) obtained is processed into defined respectively at 190 DEG C with tablet press machine and injection machine is entered
Row test.
The present invention plasticized modifier is used as by vegetable oil, by using with fire retardant compounding come reach can simultaneously toughness reinforcing
Flame-proof polylactic acid is so as to prepare the poly (lactic acid) composition with high tenacity and anti-flammability.Vegetable oil can not only increase to PLA
It is tough, and vegetable oil belongs to bio-based materials and PLA good compatibility and degradability, while also being deposited in vegetable oil
It can be compounded to improve the anti-flammability and final carbon left of material with fire retardant as carbon forming agent in a certain amount of hydroxyl.
And the price of vegetable oil, than less expensive, can reduce the cost of manufacture of material relative to traditional toughener on the market, improve
The mobility of material, solves the shortcoming of poor in processability.
A kind of toughening flame-proof poly (lactic acid) composition, relative to traditional toughening flame-proof PLA, outstanding feature of the invention exists
In：
1st, the present invention is by vegetable oil, using the processing mode of banbury by vegetable oil is full and uniform and flame-proof polylactic acid
Mix, so as to increase the toughness of PLA.
2nd, there is this feature of polyhydroxy using vegetable oil, it is compounded with fire retardant, so that the resistance of PLA
Combustion performance is also improved.
3rd, the present invention can also improve other of poly-lactic acid material outside the toughness and fire resistance that improve poly-lactic acid material
Mechanical property.
4th, the present invention is low to equipment investment, simple to operate, belongs to environmentally friendly, great market potential.
Specific embodiment
Embodiment 1
1) 80 PLAs and 10 parts of APPs have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequent experimental makes
With.
2) by step 1) obtained by pretreatment 80 parts of PLAs of material and 100 parts of APPs added according to certain order
Into banbury, under 180 DEG C of temperature conditionss, under 30r/min speed conditions, blending causes various material mixing for 20 minutes
Uniformly.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 1 is obtained is tested, as shown in table 1 with regard to performance.
Embodiment 2
1) 75 PLAs and 5 parts of APPs have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequent experimental makes
With.
2) by step 1) obtained by 75 parts of PLAs of pretreatment material, 20 parts of ring castor oil plasticizing agent and 5 parts of APPs
It is added to according to certain order in banbury, under 180 DEG C of temperature conditionss, under 35r/min speed conditions, is blended 20 points
Clock causes various materials to be well mixed.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 2 is obtained is tested, as shown in table 1 with regard to performance.
Embodiment 3
1) 90 PLAs and 5 parts of melamine polyphosphates have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case after
Continuous experiment is used.
2) by step 1) obtained by 90 parts of PLAs of pretreatment material, 5 parts of sunflower oil toughener and 5 parts of APPs according to
Certain order is added in banbury, under 180 DEG C of temperature conditionss, under 30r/min speed conditions, and blending makes for 20 minutes
Various materials are obtained to be well mixed.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 3 is obtained is tested, as shown in table 1 with regard to performance.
Embodiment 4
1) 90 PLAs and 5 parts of melamine polyphosphates have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case after
Continuous experiment is used.
2) by step 1) obtained by 85 parts of PLAs of pretreatment material, 10 parts of sunflower oil toughener and 5 parts of melamines gather
Phosphate is added in banbury according to certain order, under 180 DEG C of temperature conditionss, under 30r/min speed conditions, altogether
Various materials were well mixed in mixed 20 minutes.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 4 is obtained is tested, as shown in table 1 with regard to performance.
Embodiment 5
1) 90 PLAs and 5 parts of hypo-aluminum orthophosphates have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequent experimental makes
With.
2) by step 1) obtained by 90 parts of PLAs of pretreatment material, 5 parts of castor oil plasticizing agent and 5 parts of hypo-aluminum orthophosphates according to
Certain order is added in banbury, under 180 DEG C of temperature conditionss, under 30r/min speed conditions, and blending makes for 20 minutes
Various materials are obtained to be well mixed.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 5 is obtained is tested, as shown in table 1 with regard to performance.
Embodiment 6
1) 80 PLAs and 10 parts of hypo-aluminum orthophosphates have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequent experimental makes
With.
2) by step 1) obtained by 80 parts of PLAs of pretreatment material, 5 parts of castor oil plasticizing agent and 10 parts of hypo-aluminum orthophosphates are pressed
It is added in banbury, under 180 DEG C of temperature conditionss, under 30r/min speed conditions, is blended 20 minutes according to certain order
So that various materials are well mixed.
3) the above-mentioned material 2) obtained is processed into the shape of defined respectively with tablet press machine and injection machine at 190 DEG C.
The toughening flame-proof PLA that embodiment 6 is obtained is tested, as shown in table 1 with regard to performance.
As seen from the above table, applied to technical solution of the present invention embodiment batten test performance relative to unmodified batten
There is very big improvement in elongation at break, impact strength, limited oxygen index and UL-94 grades, and in the drawing of material
Stretch the mechanical property for also being met in intensity and being normally applied requirement.That is, composition of the present invention is in the fire-retardant of toughness
While performance is improved, tensile strength also meets the normal value applied usually, with high innovative value.
Claims (4)
1. a kind of toughening flame-proof poly-lactic acid material, it is characterised in that each component with following mass fractions：
60-100 parts of PLA,
0-20 parts of vegetable oil toughener,
0-20 parts of fire retardant.
2. toughening flame-proof poly-lactic acid material according to claim 1, it is characterised in that the PLA be Poly-L-lactide,
One or more in poly- D-ALPHA-Hydroxypropionic acid, poly-DL-lactic acid, the vegetable oil is epoxidized soybean oil, castor oil and sunflower oil
One or more, fire retardant is APP, melamine polyphosphate, the one or more of hypo-aluminum orthophosphate.
3. the toughening flame-proof poly-lactic acid material according to claim 1 and 2, it is characterised in that the vegetable oil energy and PLA
Form a kind of cross-linked structure.
4. toughening flame-proof poly-lactic acid material according to claim 1, it is characterised in that be prepared by the following method and obtain：
1) 60-100 parts of PLAs and 0-20 parts of fire retardants have been placed in vacuum drying oven at 70 DEG C and have dried 7h, in case subsequent experimental
Use；
2) by step 1) obtained by 60-100 parts of PLAs of pretreatment material, 0-20 parts of vegetable oil toughener and 0-20 parts of fire retardants
It is added to according to certain order in banbury, under 180 DEG C of temperature conditionss, under 25-35r/min speed conditions, blending
Various materials were well mixed in 20 minutes.
3) shape that the above-mentioned material 2) obtained is processed into defined respectively at 190 DEG C with tablet press machine and injection machine is surveyed
Examination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710614569.0A CN107227007A (en) | 2017-07-25 | 2017-07-25 | A kind of bio-based toughening flame-proof PLA and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710614569.0A CN107227007A (en) | 2017-07-25 | 2017-07-25 | A kind of bio-based toughening flame-proof PLA and preparation method thereof |
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| CN107227007A true CN107227007A (en) | 2017-10-03 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109667045A (en) * | 2018-12-19 | 2019-04-23 | 吉林中天生物科技有限公司 | A kind of polylactic acid Car-use Fabric and preparation method thereof |
| CN110003629A (en) * | 2019-04-26 | 2019-07-12 | 安徽农业大学 | A kind of biology base high-ductility poly (lactic acid) composition and preparation method thereof |
| CN110423447A (en) * | 2019-08-19 | 2019-11-08 | 浙江衡昶科技有限公司 | A kind of preparation method by modified natural plant fiber, bio-based materials strengthening and toughening unsaturated polyester resin |
| CN111171539A (en) * | 2020-02-27 | 2020-05-19 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant biodegradable polylactic acid/starch composite material and preparation method thereof |
| CN114981358A (en) * | 2020-01-16 | 2022-08-30 | 弗洛里昂转换包装有限公司 | Polylactic acid flame retardant blend |
-
2017
- 2017-07-25 CN CN201710614569.0A patent/CN107227007A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109667045A (en) * | 2018-12-19 | 2019-04-23 | 吉林中天生物科技有限公司 | A kind of polylactic acid Car-use Fabric and preparation method thereof |
| CN110003629A (en) * | 2019-04-26 | 2019-07-12 | 安徽农业大学 | A kind of biology base high-ductility poly (lactic acid) composition and preparation method thereof |
| CN110423447A (en) * | 2019-08-19 | 2019-11-08 | 浙江衡昶科技有限公司 | A kind of preparation method by modified natural plant fiber, bio-based materials strengthening and toughening unsaturated polyester resin |
| CN114981358A (en) * | 2020-01-16 | 2022-08-30 | 弗洛里昂转换包装有限公司 | Polylactic acid flame retardant blend |
| CN111171539A (en) * | 2020-02-27 | 2020-05-19 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant biodegradable polylactic acid/starch composite material and preparation method thereof |
| CN111171539B (en) * | 2020-02-27 | 2022-05-31 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant biodegradable polylactic acid/starch composite material and preparation method thereof |
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20171003 |
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| WD01 | Invention patent application deemed withdrawn after publication |