CN112852133B - Anti-droplet PLA/PVA composite material and preparation method thereof - Google Patents
Anti-droplet PLA/PVA composite material and preparation method thereof Download PDFInfo
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- CN112852133B CN112852133B CN202110301038.2A CN202110301038A CN112852133B CN 112852133 B CN112852133 B CN 112852133B CN 202110301038 A CN202110301038 A CN 202110301038A CN 112852133 B CN112852133 B CN 112852133B
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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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention discloses an anti-dripping PLA/PVA composite material and a preparation method thereof, wherein the anti-dripping PLA/PVA composite material comprises the following raw materials in parts by mass: 50-80 parts of polylactic acid, 1-30 parts of polyvinyl alcohol, 0.1-10 parts of cross-linking agent, 0.1-10 parts of plasticizer, 1-10 parts of interfacial compatilizer, 0.1-5 parts of diethyl aluminum hypophosphite and 0.1-10 parts of bisphenol A-bis (diphenyl) phosphate. According to the invention, the cross-linking agent epoxy group POSS and bismaleimide respectively form a hyperbranched structure with polylactic acid and polyvinyl alcohol to improve the molecular weight and the melt strength, and the hyperbranched structure is extruded under the action of the interfacial compatilizer to prepare the anti-dripping PLA/PVA composite material containing a cross-linked network structure. The melt strength of the composite material is effectively enhanced, the anti-dripping performance is obviously improved, and the tensile strength and the impact strength are improved.
Description
Technical Field
The invention belongs to the technical field of anti-droplet high polymer materials, and particularly relates to an anti-droplet PLA/PVA composite material and a preparation method thereof.
Background
With the application of petrochemicals, social progress is promoted to a great extent, but environmental pollution is increased, and nowadays, green environmental protection becomes the main melody of the times, so that there is an increasing need to develop new materials which can be regenerated and can be completely degraded into harmless substances after the use is finished. PLA (polylactic acid) has been widely spotlighted because it is fully biodegradable, widely available, and excellent in mechanical properties, but its application is limited by its flammability and severe dripping characteristics. Therefore, it is necessary to modify it to be resistant to dripping.
The characteristic of easy molten drop of PLA is caused by the molecular structure of the PLA, and the effective means for endowing the PLA composite material with the characteristic of molten drop resistance is to improve the melt strength of the PLA composite material and promote the PLA composite material to form a compact carbon layer during combustion. The polylactic acid and the high molecular polymer are directly blended and are easy to cause the reduction of mechanical property due to poor compatibility, and a cross-linked network structure is formed under the action of a cross-linking agent and an interface compatilizer, so that the melt strength of the composite material is fully improved, and the defect of poor compatibility is overcome. In addition, the flame retardant property of the material has positive influence on the anti-dripping property of the composite material, the phosphorus flame retardant applied to the polylactic acid flame retardant modification can perform flame retardant modification on PLA through two flame retardant mechanisms of gas phase and condensed phase, and the phosphorus flame retardant is widely concerned and rapidly developed due to the halogen-free environment-friendly property and high flame retardant efficiency.
Disclosure of Invention
The invention aims to provide an anti-dripping PLA/PVA composite material and a preparation method thereof, which overcome the defects of the prior art, endow the material with anti-dripping performance and improve the mechanical property of the material. The anti-dripping system adopted by the invention is halogen-free and non-toxic, and has low pollution degree and harm degree to the environment and human body.
The invention relates to an anti-dripping PLA/PVA composite material, which comprises the following raw materials in parts by mass:
50-80 parts of polylactic acid (PLA), 1-30 parts of polyvinyl alcohol (PVA), 0.1-10 parts of cross-linking agent, 0.1-10 parts of plasticizer, 1-10 parts of interfacial compatilizer, 0.1-5 parts of diethyl aluminum hypophosphite and 0.1-10 parts of bisphenol A-bis (diphenyl) phosphate.
The polylactic acid is common commercial polylactic acid.
The polyvinyl alcohol is polyvinyl alcohol 1788.
The cross-linking agent is epoxy POSS and bismaleimide, and the addition mass ratio is 1.
The plasticizer is a compound plasticizer consisting of one of ethylene glycol, triethylene glycol or polyethylene glycol 200 and glycerol, and the compound mass ratio is 1.
The interfacial compatilizer is at least one of Toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) and isophorone diisocyanate (IPDI).
The preparation method of the anti-dripping PLA/PVA composite material comprises the following steps:
step 1: weighing the required raw materials according to the proportion;
step 2: pretreating polylactic acid, polyvinyl alcohol, a cross-linking agent and a plasticizer;
and 3, step 3: and fully and uniformly mixing the pretreated product, the interfacial compatilizer, the diethyl aluminum hypophosphite and the bisphenol A-bis (diphenyl) phosphate, and performing reaction extrusion to obtain the anti-dripping PLA/PVA composite material.
In step 2, the pretreatment process comprises: extruding and blending polylactic acid and epoxy group POSS to obtain a component 1; the polyvinyl alcohol, plasticizer and bismaleimide were extrusion blended to give component 2.
Further, in the step 2, the extrusion temperature of the extruder is 160-180 ℃, and the screw rotation speed is 50-80rpm.
In the step 3, the component 1, the component 2, the interfacial compatilizer, the diethyl aluminum hypophosphite and the bisphenol A-bis (diphenyl) phosphate are uniformly blended through a high-speed mixer, then a double-screw extruder is used for melt blending and extrusion granulation to prepare the PLA/PVA composite material, and then a flat-plate vulcanizer is used for pressing the PLA/PVA composite material into a standard sample.
Further, in the step 3, the melt blending temperature of the high-speed mixer is 80-100 ℃, and the mixing time is 10-25min; the extrusion temperature of the extruder is 160-180 ℃, and the rotating speed of the screw is 50-80rpm; the hot pressing temperature of the vulcanizing press is 160-185 ℃, the hot pressing time is 5-10min, and the pressure is 10-20MPa.
In the invention, cross-linking agents of epoxy group POSS and bismaleimide respectively form hyperbranched structures with polylactic acid and polyvinyl alcohol to improve the molecular weight and the melt strength, and the hyperbranched structures are extruded under the action of an interfacial compatilizer to prepare the anti-dripping PLA/PVA composite material containing a cross-linked network structure. The promotion of molecular weight and the formation of a cross-linked structure provide certain melt strength, and a compact carbon layer is formed after combustion, so that the composite material has excellent anti-dripping property. Meanwhile, the high-temperature dehydration characteristic of the PVA molecular chain and the epoxy POSS containing silicon elements are used as potential silicon flame retardants to act synergistically with phosphorus flame retardants, so that the flame retardant property of the composite material is improved, and the anti-dripping property of the PLA/PVA composite material is further enhanced.
Compared with the prior art, the invention has the beneficial effects that:
the components of the invention are simple, and the proportion is reasonable and effective; the preparation process is simple, safe, environment-friendly, efficient and convenient for industrial production; the melt strength of the composite material is effectively enhanced, and the anti-dripping performance is obviously improved; the mechanical properties of the composite material are unaffected and enhanced.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Example 1:
this example prepares an anti-dripping PLA/PVA composite as follows:
1. firstly, 50 percent (500 g) of PLA and 2 percent (20 g) of epoxy POSS are extruded and blended in an extruder to obtain a component 1 for standby;
2. extruding and blending 30 percent (300 g) of PVA powder, 3 percent (30 g) of glycerin, 3 percent (30 g) of ethylene glycol and 2 percent (20 g) of bismaleimide in an extruder to obtain a component 2 for later use;
3. placing component 1, component 2 and 5% (50 g) of diethyl aluminum hypophosphite, 5% (50 g) of bisphenol A-bis (diphenyl) phosphate in a high speed mixer, and mixing at 80 deg.C for 15min;
4. putting the mixture into a double-screw extruder, and performing melt blending extrusion granulation; the extrusion temperature of the extruder is 170 ℃, and the rotating speed of the screw is 60rpm;
5. pressing the pellet PLA blend into a standard sample strip in a mould by using a flat vulcanizing instrument, wherein the hot pressing temperature is 170 ℃, and the hot pressing time is 5min, so as to prepare the anti-dripping PLA/PVA composite material.
Example 2:
this example prepared an anti-drip PLA/PVA composite in the same manner as in example 1, except that: the "50% (500 g) of PLA" in step 1 was changed to "60% (600 g) of PLA", and the "30% (300 g) of PVA powder" in step 2 was changed to "20% (200 g) of PVA powder".
Example 3:
this example prepared an anti-drip PLA/PVA composite in the same manner as in example 1, except that: the "50% (500 g) of PLA" in step 1 was changed to "70% (700 g) of PLA", and the "30% (300 g) of PVA powder" in step 2 was changed to "10% (100 g) of PVA powder".
Example 4:
this example prepared an anti-drip PLA/PVA composite in the same manner as in example 1, except that: the "extrusion temperature of the extruder" in step 4 was changed to "extrusion temperature of the extruder" was 180 ℃, and the "hot pressing temperature of 170 ℃ in step 5" was changed to "hot pressing temperature of 180 ℃.
Example 5:
this example prepared an anti-drip PLA/PVA composite in the same manner as in example 1, except that: the "extruder extrusion temperature 170 ℃ in step 4" was changed to "extruder extrusion temperature 160 ℃, and the" hot pressing temperature 170 ℃ in step 5 "was changed to" hot pressing temperature 160 ℃.
Comparative example:
600g of PLA, 300g of PVA powder, 30g of glycerol, 30g of ethylene glycol, 20g of bismaleimide, 50g of aluminum diethylphosphinate, and 50g of bisphenol A-bis (diphenyl) phosphate were placed in a high-speed mixer and mixed at 80 ℃ for 15 minutes at high speed. And (3) placing the mixture into a double-screw extruder, carrying out melt blending, extruding and granulating, wherein the extrusion temperature of the extruder is 170 ℃, and the rotating speed of the screw is 60rpm. And pressing the manufactured granules in a flat vulcanizing machine to prepare a standard sample strip, wherein the hot pressing temperature is 170 ℃, and the hot pressing time is 5min, so as to prepare the PLA/PVA composite material of the reference sample.
In order to characterize the anti-dripping performance and the mechanical property of the obtained product, the anti-dripping performance and the comprehensive mechanical property of the products obtained in the above examples and comparative examples are tested according to the ASTM standard, and the test results are shown in the following table 1:
TABLE 1 test results
As can be seen from the test results in the table above, the method can effectively improve the anti-dripping performance of the polylactic acid. The molecular weight of the polylactic acid is improved through the action of the cross-linking agent, a cross-linked network structure is formed, the melt strength of the PLA composite material is enhanced, the PLA composite material is endowed with excellent anti-dripping performance through the cooperation of the PLA composite material and the phosphorus-containing flame retardant, all the embodiments 1-4 reach the V-0 grade in the UL-94 test, and no dripping phenomenon exists in the combustion process. The comparative example further illustrates that simply directly mixing polylactic acid and polyvinyl alcohol does not effectively improve the melt strength of the composite due to poor compatibility, resulting in the generation of a droplet phenomenon in a combustion experiment.
The results of examples 1-3 show that the tensile strength, impact strength and other mechanical properties of the PLA composite material are obviously enhanced under the action of the cross-linked network structure formed by the PLA and the PVA.
In addition, in example 5, the crosslinking reaction did not proceed completely due to the low processing temperature, resulting in a composite material that could not effectively suppress the dripping phenomenon and significantly reduced the mechanical properties compared to example 1. In example 4, the higher processing temperature resulted in a small amount of decomposition of PVA, which resulted in a small decrease in the mechanical properties of the composite material compared to example 1.
Claims (4)
1. The anti-dripping PLA/PVA composite material is characterized by comprising the following raw materials in parts by mass:
50-80 parts of polylactic acid, 1-30 parts of polyvinyl alcohol, 0.1-10 parts of cross-linking agent, 0.1-10 parts of plasticizer, 1-10 parts of interfacial compatilizer, 0.1-5 parts of diethyl aluminum hypophosphite and 0.1-10 parts of bisphenol A-bis (diphenyl) phosphate;
the cross-linking agent is epoxy group POSS and bismaleimide;
the anti-dripping PLA/PVA composite material is prepared by a method comprising the following steps:
step 1: weighing the required raw materials according to the proportion;
and 2, step: pretreating polylactic acid, polyvinyl alcohol, a cross-linking agent and a plasticizer; the pretreatment process comprises the following steps: extruding and blending polylactic acid and epoxy group POSS to obtain a component 1; extruding and blending polyvinyl alcohol, plasticizer and bismaleimide to obtain a component 2;
and 3, step 3: uniformly blending the component 1, the component 2, the interfacial compatilizer, diethyl aluminum hypophosphite and bisphenol A-bis (diphenyl) phosphate by a high-speed mixer, then carrying out melt blending by a double-screw extruder, extruding and granulating to prepare a PLA/PVA composite material, and pressing the PLA/PVA composite material into a standard sample by a flat-plate vulcanizing machine;
in the step 3, the melt blending temperature of the high-speed mixer is 80-100 ℃, and the mixing time is 10-25min; the extrusion temperature of the extruder is 160-180 ℃, and the rotating speed of the screw is 50-80rpm; the hot pressing temperature of the vulcanizing press is 160-185 ℃, the hot pressing time is 5-10min, and the pressure is 10-20MPa.
2. The drip resistant PLA/PVA composite of claim 1, wherein:
the polyvinyl alcohol is polyvinyl alcohol 1788.
3. The drip resistant PLA/PVA composite of claim 1, wherein:
the plasticizer is a compound plasticizer consisting of glycerol and one of ethylene glycol, triethylene glycol or polyethylene glycol 200.
4. The drip resistant PLA/PVA composite of claim 1, wherein:
the interfacial compatilizer is at least one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
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| CN114875574B (en) * | 2022-05-23 | 2024-01-19 | 江南大学 | High-strength high-modulus polyvinyl alcohol fiber reinforced polylactic acid composite material and preparation method thereof |
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| JP5046079B2 (en) * | 2006-05-22 | 2012-10-10 | 名古屋市 | Flame retardant polylactic acid resin composition |
| EP2330148A4 (en) * | 2008-09-29 | 2015-03-18 | Teijin Ltd | Polylactic acid film |
| CN101831156B (en) * | 2010-05-07 | 2012-11-07 | 四川大学 | Toughened halogen-free flame-retardant polylactic acid blending material |
| CN102268144B (en) * | 2011-06-14 | 2013-05-15 | 武汉华丽环保科技有限公司 | Biodegradable polylactic acid-starch thermal-resistance composite material and preparation method thereof |
| US9534116B2 (en) * | 2012-10-17 | 2017-01-03 | Polyone Corporation | Flame retardant polylactic acid compounds |
| CN105131543B (en) * | 2015-09-23 | 2017-01-18 | 南京理工大学 | Halogen-free expansive-type flame-retardant system flame-retardant polylactic acid material and preparation method thereof |
| CN105694405A (en) * | 2016-04-28 | 2016-06-22 | 青岛科技大学 | Halogen-free flame retardant polylactic acid toughening modification composite material and preparing method thereof |
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