CN115028976B - Polylactic acid blending material with stereo composite interface compatibilization and preparation method thereof - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 15
- 239000002952 polymeric resin Substances 0.000 claims abstract description 8
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 8
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 15
- 239000011165 3D composite Substances 0.000 claims description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 6
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- 238000001816 cooling Methods 0.000 claims description 5
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- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 4
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- 239000011347 resin Substances 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 2
- -1 polypropylene carbonate Polymers 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- OPZZWWFHZYZBRU-UHFFFAOYSA-N butanedioic acid;butane-1,1-diol Chemical compound CCCC(O)O.OC(=O)CCC(O)=O OPZZWWFHZYZBRU-UHFFFAOYSA-N 0.000 claims 1
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Abstract
The invention discloses a polylactic acid blending material with a stereo composite interface for compatibilization and a preparation method thereof. The blending material comprises the following components in percentage by mass: 50% -90% of matrix polylactic acid; 10% -50% of a second component polymer resin; 2% -15% of polylactic acid which is opposite to the polylactic acid of the matrix; 0.01% -5% of chain extender. The preparation method comprises the steps of firstly carrying out melt blending on the second component of high polymer resin, polylactic acid with opposite stereochemistry with the matrix polylactic acid and a chain extender to obtain master batch, then carrying out melt blending on the master batch and the matrix polylactic acid, and forming stereocomplex crystals between the polylactic acid with opposite stereochemistry through intermolecular hydrogen bonding, thereby enhancing the interfacial effect of the polylactic acid blending material and improving the comprehensive performance of the material. The method is simple and efficient, is easy to apply industrially, and the prepared polylactic acid blending material has excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a polylactic acid blending material with a stereo composite interface for compatibilization and a preparation method thereof.
Background
Polylactic acid (PLA) is the most mature biodegradable material in the current industrialization, has rich and renewable sources, good biocompatibility, biodegradability, mechanical property, optical property and thermoplasticity, has huge application prospect in the fields of film packaging, disposable products, fiber spinning and the like, but has the defects of poor toughness, low elongation at break, slow crystallization rate, poor thermal stability and the like, so that the practical application degree of the polylactic acid is far lower than that of the traditional petroleum-based polymer material.
In order to overcome the deficiency in PLA performance, researchers have made a great deal of work in modifying polylactic acid in recent years. At present, the modification method of polylactic acid mainly comprises chemical modification and physical modification, wherein other components are introduced into PLA (polylactic acid) in a chemical copolymerization mode to achieve the modification purpose, and the physical modification mainly comprises blending the PLA with other components to achieve the material performance compounding. Numerous studies have shown that blending PLA with flexible/elastic polymers such as poly (adipic acid)/poly (butylene terephthalate) (PBAT), poly (propylene carbonate) (PPC), poly (epsilon-caprolactone) (PCL), poly (butylene carbonate) (PBC), polyolefin elastomer (POE), thermoplastic Polyurethane (TPU), butylene succinate (PBS), polyhydroxyalkanoate (PHA), etc., can effectively improve the toughness of PLA. However, due to the difference of molecular structures, PLA and most flexible/elastic polymers have the problem of poor compatibility, and obvious phase separation can occur when the PLA and the most flexible/elastic polymers are directly blended, so that the mechanical property of the material is reduced, and the modification effect is limited. Therefore, it is often desirable to incorporate compatibilizers to enhance the two-phase interface effect in order to achieve good dispersion of the flexible/elastomeric polymer in the PLA matrix, thereby achieving the modifying effect.
The current methods for compatibilizing PLA blend materials are mainly reactive compatibilization and non-reactive compatibilization. The reactive compatibilization is to add a proper chain extender, such as a multifunctional epoxy chain extender (ADR), an epoxy chain extender (REC), cage Polysilsesquioxane (POSS) and the like, in the material blending process, and the chain extender can chemically react with PLA and the second component under certain processing conditions, so that a bridge effect is built between two phases to realize the compatibilization. The non-reactive compatibilization is to add a block or graft copolymer containing two or more components into the PLA blending material, wherein different components of the copolymer have better compatibility with PLA and the second component respectively, so that an indirect bridge effect can be constructed between the PLA and the second component, and the two-phase compatibility is improved.
In recent years, with the intensive research on polylactic acid Stereocomplex Crystals (SC), the SC crystals also show great potential in the aspect of modified PLA, the SC crystals are special crystals formed by the L-polylactic acid (PLLA) and the D-polylactic acid (PDLA) through hydrogen bonding, and related research shows that the interfacial effect can be obviously enhanced by introducing the SC crystals at the two-phase interface of the PLA blending material, and the two-phase compatibility is promoted. The polylactic acid chain segments which are opposite to the polylactic acid of the matrix are adopted in Chinese patent (CN 112812348A) and (CN 104725801A) to respectively carry out grafting modification on the inorganic fiber, the nano cellulose and the polyurethane elastomer, the interface effect between the inorganic fiber, the nano cellulose and the polylactic acid of the matrix after modification is obviously enhanced, and the efficient modification effect on PLA is shown. In addition, chinese patent (CN 111849139A) and (CN 110079065A) respectively disclose two compatilizers containing PBAT and dextrorotation polylactic acid (PDLA) chain segments, and the compatilizers can effectively compatibilize PLA/PBAT blending materials, and the prepared PLA/PBAT blending materials have better strength and toughness. Although related works have been carried out to apply SC crystals to research of polylactic acid blending materials, in the reported works, introducing SC crystals into polylactic acid blending materials generally requires complex chemical reactions of the second component, or separately preparing a compatibilizer through molecular structure design, and the process is relatively complex, has no universality and is unfavorable for industrial production.
Disclosure of Invention
The invention aims to provide a method which is universal and can simply and efficiently introduce a Stereocomplex Crystal (SC) compatibilized polylactic acid blending material at a two-phase interface so as to prepare the polylactic acid blending material with excellent comprehensive performance.
The aim of the invention is realized by the following technical scheme:
The polylactic acid blending material with the compatibilized stereocomplex interface comprises the following components in percentage by mass:
50% -90% of matrix polylactic acid;
10% -50% of a second component polymer resin;
2% -15% of polylactic acid which is opposite to the polylactic acid of the matrix;
0.01% -5% of chain extender.
Preferably, the matrix polylactic acid is l-polylactic acid (PLLA), and the polylactic acid which is stereospecifically opposite to the matrix polylactic acid is d-polylactic acid (PDLA); or the matrix polylactic acid is dextrorotatory polylactic acid (PDLA), and polylactic acid which is in stereo contrast to the matrix polylactic acid is levorotatory polylactic acid (PLLA).
Preferably, the second component polymer resin includes poly (adipic acid)/butylene terephthalate (PBAT), poly (propylene carbonate) (PPC), poly (epsilon-caprolactone) (PCL), poly (butylene carbonate) (PBC), polyolefin elastomer (POE), thermoplastic Polyurethane (TPU), poly (butylene succinate) (PBS), or poly (hydroxy fatty acid ester) (PHA).
Preferably, the chain extender comprises a multifunctional epoxy chain extender, an isocyanate chain extender, a hydrogen peroxide chain extender, an anhydride chain extender or cage polysilsesquioxane.
The invention also provides a preparation method of the polylactic acid blending material with the stereo composite interface compatibilization, which comprises the following steps:
Respectively carrying out vacuum drying on the matrix polylactic acid, the second component high molecular resin and polylactic acid with the opposite stereochemistry to the matrix polylactic acid;
step two, adding the dried second component high polymer resin, polylactic acid with opposite stereochemistry to the matrix polylactic acid and a chain extender into melting and mixing equipment for melting and mixing to obtain master batch;
And thirdly, discharging the master batch from the melt mixing equipment, cooling to normal temperature, mixing with the matrix polylactic acid, and adding into the melt mixing equipment for melt blending to obtain the polylactic acid blending material with the compatibilized three-dimensional composite interface.
Preferably, in the second step, the melt blending time is 2-10min, the temperature is 160-220 ℃, and the rotor rotating speed is 50-100rpm/min.
Preferably, in the third step, the melt blending time is 2-10min, the temperature is 160-220 ℃, and the rotor rotating speed is 50-100rpm/min.
Preferably, the melt mixing device is an internal mixer, a haak torque rheometer, a single screw extruder or a double screw extruder.
The beneficial effects of the invention are as follows:
(1) The polylactic acid blending material with the compatibilized stereocomplex interface has the advantages of easily available raw materials, being commercially available materials, simple and efficient method and easy industrial production.
(2) The polylactic acid blending material with the compatibilized stereocomplex interface can achieve excellent compatibilization effect under the addition of a small amount of chain extender, and has high toughness and high strength. In addition, the SC crystal introduced by the invention can also effectively improve the crystallization performance of the polylactic acid blending material and improve the melt strength.
(3) When the second component high molecular resin is biodegradable resin, the polylactic acid blending material with the compatibilized stereocomplex interface can be completely biodegraded, has the advantage of environmental protection, and has great application potential in the fields of disposable products, film packaging and the like.
Detailed Description
In order to make the technical scheme and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the following examples, PLLA was used as matrix polylactic acid, PDLA was a polylactic acid having a stereocomplex opposite to that of matrix polylactic acid, and ADR-4468 was used as a chain extender. The melt mixing equipment is a Hark rheometer.
Example 1
The components of the three-dimensional composite interface compatibilized polylactic acid blending material are as follows:
PLLA mass fraction: 65%
PBAT mass fraction: 31%
PDLA mass fraction: 3.55%
Chain extender mass fraction: 0.45%
The preparation process is as follows:
Step 1: PLLA, PBAT, PDLA was vacuum dried at 60 ℃ for 24h, respectively;
Step 2: adding the dried PBAT, PDLA and chain extender into a Hark torque rheometer, setting the mixing temperature to 180 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the master batch.
Step 3: discharging the master batch from the Hark torque rheometer, cooling to normal temperature, adding the master batch and a matrix PLLA into the Hark torque rheometer, setting the mixing temperature to 200 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLLA/PBAT blending material with the compatibilization of the three-dimensional composite interface.
Example 2
The components of the three-dimensional composite interface compatibilized polylactic acid blending material are as follows:
PLLA mass fraction: 65%
PPC mass fraction: 31%
PDLA mass fraction: 3.55%
Chain extender mass fraction: 0.45%
The preparation process is as follows:
step 1: PLLA, PPC, PDLA was vacuum dried at 60 ℃ for 24h, respectively;
step 2: PPC, PDLA and a chain extender are added into a Hark torque rheometer, the mixing temperature is set to 180 ℃, the rotating speed of a rotor is set to 100rpm/min, and the mixture is melt-blended for 10min, so as to obtain a master batch.
Step 3: discharging the master batch from the Hark torque rheometer, cooling to normal temperature, adding the master batch and a matrix PLLA into the Hark torque rheometer, setting the mixing temperature to 200 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLA/PPC blending material with the compatibilization of the three-dimensional composite interface.
Example 3
The components of the three-dimensional composite interface compatibilized polylactic acid blending material are as follows:
PLLA mass fraction: 65%
PBS mass fraction: 31%
PDLA mass fraction: 3.55%
Chain extender mass fraction: 0.45%
The preparation process is as follows:
step 1: PLLA, PBS, PDLA was vacuum dried at 60 ℃ for 24h, respectively;
Step 2: adding PBS, PDLA and a chain extender into a Hark torque rheometer, setting the mixing temperature to 180 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain a master batch.
Step 3: discharging the master batch from the Hark torque rheometer, cooling to normal temperature, adding the master batch and a matrix PLLA into the Hark torque rheometer, setting the mixing temperature to 200 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLA/PBS blend material with the compatibilization of the three-dimensional composite interface.
Comparative example 1
The PLA/PBAT blend material comprises the following components in percentage by weight:
PLLA mass fraction: 65%
PBAT mass fraction: 35%
The preparation process is as follows:
Step 1: vacuum drying PLLA and PBAT at 60deg.C for 24 hr;
step 2: adding PLLA and PBAT into a Hark torque rheometer, setting the mixing temperature to 180 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLA/PBA blending material.
Comparative example 2
The PLA/PPC blending material comprises the following components in percentage by weight:
PLLA mass fraction: 65%
PPC mass fraction: 35%
The preparation process is as follows:
step 1: vacuum drying PLLA and PPC at 60deg.C for 24 hr;
Step 2: adding PLLA and PPC into a Hark torque rheometer, setting the mixing temperature to 180 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLA/PPC blending material.
Comparative example 3
The PLA/PBS blend material comprises the following components in percentage by weight:
PLLA mass fraction: 65%
PBS mass fraction: 35%
The preparation process is as follows:
Step 1: vacuum drying PLLA and PBS at 60deg.C for 24 hr;
Step 2: adding PLLA and PBS into a Hark torque rheometer, setting the mixing temperature to 180 ℃, setting the rotating speed of a rotor to 100rpm/min, and carrying out melt blending for 10min to obtain the PLA/PBS blend material.
TABLE 1 Performance results of polylactic acid blend materials prepared in examples 1-3 and comparative examples 1-3
| Sample name | Tensile Strength (MPa) | Elongation at break (%) |
| Example 1 | 39 | 374 |
| Example 2 | 45 | 156 |
| Example 3 | 45 | 175 |
| Comparative example 1 | 30 | 182 |
| Comparative example 2 | 34 | 72 |
| Comparative example 3 | 35 | 89 |
As can be seen from table 1, the stereocomplex interface-compatibilized polylactic acid blend material of the present invention has higher tensile strength and elongation at break than the comparative example. The performance of the polylactic acid blending material can be greatly improved by introducing the chain extender and the stereocomplex crystal structure.
The above-described embodiment is only a preferred embodiment of the present invention, and is not limited in any way, and other variations and modifications may be made without departing from the technical aspects set forth in the claims.
Claims (1)
1. The preparation method of the polylactic acid blending material with the stereo composite interface for compatibilization is characterized by comprising the following steps:
Respectively carrying out vacuum drying on 50% -90% of matrix polylactic acid, 10% -50% of second component polymer resin and 2% -15% of polylactic acid which is opposite to the matrix polylactic acid in stereospecificity according to mass fraction; the matrix polylactic acid is L-polylactic acid (PLLA), and polylactic acid which is opposite to the matrix polylactic acid in a stereochemistry mode is D-polylactic acid (PDLA); or the matrix polylactic acid is dextrorotatory polylactic acid (PDLA), and polylactic acid which is opposite to the matrix polylactic acid in a stereochemistry way is levorotatory polylactic acid (PLLA); the second component high molecular resin is polypropylene carbonate (PPC), poly epsilon-caprolactone (PCL), polycarbonate Butanediol (PBC), polyolefin elastomer (POE), thermoplastic Polyurethane (TPU), butanediol succinate (PBS) or Polyhydroxyalkanoate (PHA);
Step two, adding the dried second component high polymer resin, polylactic acid with the opposite structure to the matrix polylactic acid and 0.01% -5% of chain extender into a Hark torque rheometer for melt blending for 10min at 180 ℃ to obtain master batch; the chain extender comprises isocyanate chain extender, hydrogen peroxide chain extender, anhydride chain extender or cage polysilsesquioxane;
Discharging the master batch from the Hark torque rheometer, cooling to normal temperature, mixing with the matrix polylactic acid, adding into the Hark torque rheometer, and carrying out melt blending for 10min at 200 ℃ to obtain the polylactic acid blending material with the compatibilization of the three-dimensional composite interface; the mass fraction of the sum of the matrix polylactic acid, the second component polymer resin, the polylactic acid with the opposite stereochemistry to the matrix polylactic acid and the chain extender is 100 percent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN106467657A (en) * | 2016-10-20 | 2017-03-01 | 上海弘睿化工产品有限公司 | High heat-resisting PLA/PHA composite and preparation method thereof |
| CN106916424A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof |
| CN109666272A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | 3D printing modified polylactic acid material, printing silk thread and preparation method thereof |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467950A (en) * | 2013-09-29 | 2013-12-25 | 成都新柯力化工科技有限公司 | 3D printing modified polylactic acid material and preparation method thereof |
| CN106467657A (en) * | 2016-10-20 | 2017-03-01 | 上海弘睿化工产品有限公司 | High heat-resisting PLA/PHA composite and preparation method thereof |
| CN106916424A (en) * | 2017-04-07 | 2017-07-04 | 常州大学 | A kind of high-tenacity heat-resistant type full-biodegradable polylactic acid material and preparation method thereof |
| CN109666272A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | 3D printing modified polylactic acid material, printing silk thread and preparation method thereof |
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