CN115819940B - Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof - Google Patents
Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof Download PDFInfo
- Publication number
- CN115819940B CN115819940B CN202211512473.0A CN202211512473A CN115819940B CN 115819940 B CN115819940 B CN 115819940B CN 202211512473 A CN202211512473 A CN 202211512473A CN 115819940 B CN115819940 B CN 115819940B
- Authority
- CN
- China
- Prior art keywords
- polylactic acid
- modified polylactic
- modifier
- parts
- transparency
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 78
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 24
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims abstract description 16
- 235000012209 glucono delta-lactone Nutrition 0.000 claims abstract description 16
- 229960003681 gluconolactone Drugs 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 13
- -1 cyclic polyol Chemical class 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 239000005022 packaging material Substances 0.000 claims abstract description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 6
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims abstract description 4
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims abstract description 4
- 229960000367 inositol Drugs 0.000 claims abstract description 4
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims abstract description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 3
- 229960001553 phloroglucinol Drugs 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a high-transparency high-toughness modified polylactic acid material, which comprises the following steps: s1: uniformly blending polylactic acid and cyclic polyol, and extruding and granulating to obtain modified polylactic acid master batch; the cyclic polyol is selected from one or more of gluconolactone, inositol, and ribonucleotide-1, 4-lactone; s2: adding the mixture obtained after the modified polylactic acid master batch and the composite modifier are uniformly mixed into an extruder through a main feeding port, adding a catalyst and a processing aid which can be selectively added into the extruder through a side feeding port, and extruding and granulating the mixture to obtain the high-transparency high-toughness modified polylactic acid material; the composite modifier comprises a phenol modifier and an anhydride modifier. The modified polylactic acid material prepared by the method has high transparency and high toughness, can be completely biodegraded, and is particularly suitable for preparing film packaging materials.
Description
Technical Field
The invention relates to the technical field of full-biodegradable materials, in particular to a preparation method of a high-transparency high-toughness modified polylactic acid material and application of a product thereof in a film packaging material.
Background
Because the technological level is continuously improved, the living standard of people is continuously increased, the consumption of plastic products is increased, but waste products generated by treating the plastic products are quite troublesome, a large amount of carbon dioxide and toxic gas are generated by burning, and land resources are seriously wasted by landfill, so that the degradable material is used to form an ideal scheme.
Along with the promotion of plastic inhibition, common film packaging materials are gradually replaced by degradable materials such as food packages, shopping bags, garbage bags and the like, other functional requirements such as transparency are met for users besides normal use requirements, polylactic acid (PLA) is a high-transparency material with good degradability, has two characteristics of 100% biomass sources and 100% biodegradability, has extremely obvious environmental protection advantages, has very wide application prospect, has higher brittleness, has no application value when being independently blown into films, is generally modified by adding a toughening agent or a plasticizer, but has influence on transparency, and cannot have high transparency and high toughness.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of a high-transparency high-toughness modified polylactic acid material, and the prepared product has high transparency and high toughness, can be completely biodegraded, and is particularly suitable for preparing film packaging materials.
The specific technical scheme is as follows:
a preparation method of a high-transparency high-toughness modified polylactic acid material comprises the following steps:
s1: uniformly blending polylactic acid and cyclic polyol, and extruding and granulating to obtain modified polylactic acid master batch;
the cyclic polyol is selected from one or more of gluconolactone, inositol, and ribonucleotide-1, 4-lactone;
s2: adding the mixture obtained after the modified polylactic acid master batch and the composite modifier are uniformly mixed into an extruder through a main feeding port, adding a catalyst and a processing aid which can be selectively added into the extruder through a side feeding port, and extruding and granulating to obtain the high-transparency high-toughness modified polylactic acid material;
the composite modifier comprises a phenol modifier and an anhydride modifier.
The preparation method disclosed by the invention comprises the steps of firstly modifying polylactic acid by using cyclic polyol, then blending the obtained modified PLA master batch with a special composite modifier, and finally extruding and granulating. Experiments show that the modification treatment is particularly critical in the invention, in the step S1, the cyclic polyol with a special cyclic structure is adopted as the modifier, and if the modifier is replaced by the conventional selection in the field, such as linear triol glycerol, the improvement on the toughening performance of PLA is extremely limited; in the step S2, two modifiers with different functional groups are uniformly dispersed in the annular three-dimensional space structure obtained after modification in the step S1 in a premixing mode, and then the catalyst is used for preparing the polylactic acid material with high toughness and high transparency; tests show that compared with the composite modifier, if a single modifier is adopted, the mechanical property and the transparency are obviously reduced.
In step S1:
preferably, the optical purity of the polylactic acid is 90-96%; experiments show that the transparency of the modified polylactic acid material prepared from the raw materials is higher.
Preferably, the mass ratio of polylactic acid to cyclic polyol is 3-9: 1, a step of; more preferably 4 to 7:1, a step of; more preferably 4:1.
further preferably, the cyclic polyol is selected from gluconolactone.
In the step S1, the extrusion granulation is carried out, the extrusion temperature is 150-180 ℃, the screw speed is 300-500 rpm, and the length-diameter ratio is 50-64.
The melt index of the modified polylactic acid master batch obtained after extrusion granulation is not higher than 1g/10min. Experiments show that if the processing technology is not proper, the mechanical properties of the finally prepared product can be obviously affected.
In step S2:
the phenolic modifier is selected from resorcinol and/or phloroglucinol;
the anhydride modifier is selected from phthalic anhydride;
preferably, the mass ratio of the phenol modifier to the anhydride modifier is 1-3: 1, a step of; further preferably 1:1.
preferably, the mass ratio of the modified polylactic acid master batch to the composite modifier is 7-9: 1, a step of; further preferably 7.3:1.
in step S2:
the catalyst is selected from titanate and/or zirconate;
the processing aid includes a lubricant selected from the common classes in the art, such as erucamide, oleamide, and the like.
In the step S2, the extrusion granulation is carried out, the extrusion temperature is 180-200 ℃, the screw speed is 300-500 rpm, and the length-diameter ratio is 50-64.
Experiments show that the mixture in the step S2 is subjected to melt blending from a main feeding port to a side feeding port of the extruder, so that the mixture is uniformly mixed; the modifier in the molten mixture is subjected to esterification and acetylation reaction from a side feeding port to a die under the action of a catalyst to generate aromatic polyester, and the polyester generated by the reaction further weakens acting force among PLA molecular chains due to the increase of molecular weight, simultaneously hinders the crystallization of PLA and increases the toughness and the transparency of the PLA. It has been found that the addition of the composite modifier with the mixture from the main feed port results in reduced product performance. This is probably because macromolecules generated by the esterification and blending of the two modifiers are more difficult to enter between the molecular chains of PLA, and plasticization cannot be exerted.
Preferably, in step S2, the raw materials include, in parts by weight:
the invention also discloses a modified polylactic acid material prepared by the method, which has high toughness and high transparency and low haze, and is particularly suitable for application in film packaging materials.
Compared with the prior art, the invention has the following beneficial effects:
the modified polylactic acid material with high toughness and high transparency is prepared by taking polylactic acid as a base material through a two-step extrusion process and adding a special auxiliary agent during each step of extrusion granulation; the light transmittance is more than 92%, and the haze is less than 5.0%; and the product has high elongation at break and high impact strength, and is especially suitable for preparing film packaging materials.
Detailed Description
In order to better understand the above technical scheme, the present invention will be described in further detail with reference to examples and comparative examples, but embodiments of the present invention are not limited thereto. All raw material amounts are in parts by mass unless otherwise specified below.
Example 1
S1, uniformly mixing 70 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 18 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
s2, adding the modified polylactic acid master batch, 6 parts of resorcinol and 6 parts of phthalic anhydride into a stirrer, and uniformly stirring to obtain a mixture;
s3, adding the mixture obtained in the step S2 into a double-screw extruder through a main feed, adding 2 parts of titanate and 1 part of erucic acid amide into the double-screw extruder through a side feed, wherein the temperature of a first region to a fifteen region of the extruder is 180-200 ℃, the temperature of a die head is 190 ℃, the length-diameter ratio is 60, and extruding and granulating to obtain the modified polylactic acid material.
The substrate FY804 employed in this example had an elongation at break of 14% and an impact strength of 2.5kJ/m 2 The light transmittance was 92% and the haze was 3%.
Example 2
S1, 77 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 11 parts of gluconolactone are added into a double-screw extruder from a main feeding port after being uniformly mixed by a stirrer, the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 1.
Example 3
S1, evenly mixing 79 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 9 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 1.
Examples 4 to 5
The preparation process was substantially the same as in example 1, except that 18 parts of gluconolactone added in step S1 was replaced with equal parts by mass of inositol, ribonucleotide-1, 4-lactone, respectively.
Example 6
S1, uniformly mixing 71 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 18 parts of gluconolactone by a stirrer, and adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
s2, adding 5.5 parts of modified polylactic acid master batch, 5.5 parts of resorcinol and 5.5 parts of phthalic anhydride into a stirrer, and uniformly stirring to obtain a mixture;
s3, adding the mixture obtained in the step S2 into a double-screw extruder through a main feed, adding 2 parts of titanate and 1 part of erucamide into the double-screw extruder through a side feed, wherein the temperature of a first region to a fifteen region of the extruder is 180-200 ℃, the die head temperature is 190 ℃, and the length-diameter ratio is 60; and extruding and granulating to obtain the modified polylactic acid material.
Example 7
S1, uniformly mixing 78 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 11 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 6.
Example 8
S1, uniformly mixing 80 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 9 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 6.
Example 9
S1, evenly mixing 72 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 18 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
s2, adding 5 parts of modified polylactic acid master batches, 5 parts of phloroglucinol and 5 parts of phthalic anhydride into a stirrer, and uniformly stirring to obtain a mixture;
s3, adding the mixture obtained in the step S2 into a double-screw extruder through a main feed, adding 2 parts of titanate and 1 part of erucamide into the double-screw extruder through a side feed, wherein the temperature of a first region to a fifteen region of the extruder is 180-200 ℃, and the temperature of a die head is 190 ℃ and the length-diameter ratio is 60; and extruding and granulating to obtain the modified polylactic acid material.
Example 10
S1, evenly mixing 79 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 11 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first area to a tenth area of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 9.
Example 11
S1, mixing 81 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 9 parts of gluconolactone uniformly by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
steps S2 to S3 are exactly the same as in example 9.
Comparative example 1
S1, uniformly mixing 65 parts of polylactic acid (Fengyuan group, low-light pure FY 804) and 21 parts of gluconolactone by a stirrer, and then adding the mixture into a double-screw extruder from a main feeding port, wherein the temperature of a first region to a tenth region of the extruder is 150-180 ℃, the temperature of a die head is 160 ℃, the rotating speed of a screw is 350rpm, and the length-diameter ratio is 40; extruding and granulating to obtain modified polylactic acid master batch;
s2, adding 7 parts of modified polylactic acid master batch, 7 parts of resorcinol and 7 parts of phthalic anhydride into a stirrer, and uniformly stirring to obtain a mixture.
S3, adding the mixture obtained in the step S2 into a double-screw extruder through a main feed, adding 2 parts of titanate and 1 part of erucamide into the double-screw extruder through a side feed, wherein the temperature of a first region to a fifteen region of the extruder is 180-200 ℃, the die head temperature is 190 ℃, and the length-diameter ratio is 60; and extruding and granulating to obtain the modified polylactic acid material.
Comparative example 2
The preparation process was substantially the same as in example 1, except that 70 parts of polylactic acid added in step S1 was replaced with equal parts by mass of high-gloss pure FY801.
Comparative example 3
The preparation process was substantially the same as in example 1, except that 18 parts of gluconolactone added in step S1 was replaced with equal parts by mass of glycerol.
Comparative example 4
The preparation process was substantially the same as in example 1, except that 12 parts by mass of the complex modifier added in step S2 was replaced with 10 parts by resorcinol and 2 parts by phthalic anhydride.
Comparative example 5
The preparation process was substantially the same as in example 1, except that 12 parts of the composite modifier added in step S2 was replaced with 12 parts of resorcinol.
Comparative example 6
The preparation process was substantially the same as in example 1, except that 12 parts of the complex modifier added in step S2 was replaced with 12 parts of phthalic anhydride.
Comparative example 7
The preparation process was essentially the same as in example 1 except that in step S3, the mixture obtained in S2 was fed to a twin screw extruder via the main feed with 2 parts of titanate and 1 part of erucamide, and the extrusion process was exactly the same as in example 1.
The various performance data of the modified high-transparency high-toughness polylactic acid materials prepared in each of the examples and comparative examples are shown in the following table 1.
Wherein, the test reference standard of the elongation at break is ISO 527-2:2012;
the test reference standard of the impact strength is GB/T1043.1;
light transmittance test reference standard GB/T2410-2008;
haze test reference standard GB/T2410-2008.
TABLE 1
The above examples are intended to aid in understanding the method and key points of the invention. The description is not to be taken as limiting the invention.
Claims (7)
1. The preparation method of the high-transparency high-toughness modified polylactic acid material is characterized by comprising the following steps of:
s1: uniformly blending polylactic acid and cyclic polyol, and extruding and granulating to obtain modified polylactic acid master batch;
the cyclic polyol is selected from one or more of gluconolactone, inositol, and ribonucleotide-1, 4-lactone;
the polylactic acid is selected from low-light pure FY804 of Fengyuan group;
the optical purity of the polylactic acid is 90-96%;
the mass ratio of the polylactic acid to the cyclic polyol is 3-9: 1, a step of;
s2: adding the mixture obtained after the modified polylactic acid master batch and the composite modifier are uniformly mixed into an extruder through a main feeding port, adding a catalyst and a processing aid which can be selectively added into the extruder through a side feeding port, and extruding and granulating to obtain the high-transparency high-toughness modified polylactic acid material;
the composite modifier comprises a phenol modifier and an anhydride modifier;
the phenolic modifier is selected from resorcinol and/or phloroglucinol;
the anhydride modifier is selected from phthalic anhydride;
the mass ratio of the phenol modifier to the anhydride modifier is 1-3: 1, a step of;
the mass ratio of the modified polylactic acid master batch to the composite modifier is 7-9: 1, a step of;
the raw materials comprise the following components in parts by weight:
88-90 parts of modified polylactic acid master batch;
10-12 parts of a composite modifier;
0.5-3 parts of a catalyst;
0-3 parts of a processing aid.
2. The method for preparing the high-transparency high-toughness modified polylactic acid material according to claim 1, wherein the mass ratio of polylactic acid to cyclic polyol is 4-7: 1.
3. the method for preparing a high-transparency high-toughness modified polylactic acid material according to claim 1, wherein in the step S1, the extrusion granulation is performed at a temperature of 150-180 ℃, the screw rotation speed is 300-500 rpm, and the length-diameter ratio is 50-64.
4. The method for preparing a high-transparency high-toughness modified polylactic acid material according to claim 1, wherein in step S2:
the catalyst is selected from titanate and/or zirconate;
the processing aid includes a lubricant.
5. The method for preparing a high-transparency high-toughness modified polylactic acid material according to claim 1, wherein in step S2:
and the extrusion granulation is carried out, the extrusion temperature is 180-200 ℃, the screw speed is 300-500 rpm, and the length-diameter ratio is 50-64.
6. A highly transparent high toughness modified polylactic acid material prepared according to the method of any one of claims 1 to 5.
7. Use of the high-transparency high-toughness modified polylactic acid material according to claim 6 in a film packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211512473.0A CN115819940B (en) | 2022-11-28 | 2022-11-28 | Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211512473.0A CN115819940B (en) | 2022-11-28 | 2022-11-28 | Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115819940A CN115819940A (en) | 2023-03-21 |
| CN115819940B true CN115819940B (en) | 2024-02-20 |
Family
ID=85532665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211512473.0A Active CN115819940B (en) | 2022-11-28 | 2022-11-28 | Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115819940B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622310A (en) * | 2007-02-23 | 2010-01-06 | 帝人株式会社 | Polylactic acid composition |
| CN102675577A (en) * | 2012-03-20 | 2012-09-19 | 中国科学院长春应用化学研究所 | Long-chain branched polylactic resin and preparation method and application thereof |
| CN104312121A (en) * | 2014-11-19 | 2015-01-28 | 威海共达塑胶化工制品有限公司 | High-toughness transparent polylactic acid film and preparing method thereof |
| FR3098443A1 (en) * | 2019-07-12 | 2021-01-15 | Qingdao Zhoushi Plastic Packaging Co., Ltd | A fully high mechanical strength biodegradable composite film, its processing technology and application |
-
2022
- 2022-11-28 CN CN202211512473.0A patent/CN115819940B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622310A (en) * | 2007-02-23 | 2010-01-06 | 帝人株式会社 | Polylactic acid composition |
| CN102675577A (en) * | 2012-03-20 | 2012-09-19 | 中国科学院长春应用化学研究所 | Long-chain branched polylactic resin and preparation method and application thereof |
| CN104312121A (en) * | 2014-11-19 | 2015-01-28 | 威海共达塑胶化工制品有限公司 | High-toughness transparent polylactic acid film and preparing method thereof |
| FR3098443A1 (en) * | 2019-07-12 | 2021-01-15 | Qingdao Zhoushi Plastic Packaging Co., Ltd | A fully high mechanical strength biodegradable composite film, its processing technology and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115819940A (en) | 2023-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3404067B1 (en) | Plasticised biodegradable polyester film and preparation method therefor | |
| JPH04505031A (en) | Continuous production method for high molecular weight polyester resin | |
| CN110628185B (en) | Poly (butylene terephthalate) -adipate/poly (methyl ethylene carbonate) full-biodegradable film and preparation method thereof | |
| CN112552654B (en) | PBAT/PHA/wood flour composition suitable for preparing film and preparation and application thereof | |
| CA2641922A1 (en) | Environmentally degradable polymeric blend and process for obtaining an environmentally degradable polymeric blend | |
| CN113956640B (en) | Biodegradable PLA film and preparation method thereof | |
| CN101775199B (en) | High-rigidity PHAs/PLA blending alloy and preparation method thereof | |
| EP4442760A1 (en) | Biodegradable material, and film product and application thereof | |
| CN114181506A (en) | Preparation method and application of toughened ultrahigh-fluidity polylactic acid | |
| CN115819940B (en) | Preparation method of high-transparency high-toughness modified polylactic acid material, and product and application thereof | |
| CN113831702B (en) | Degradable plastic cutlery box composition and preparation method thereof | |
| JP3266264B2 (en) | Polyester resin composition for producing high modulus fiber and film | |
| US6403728B1 (en) | Formed articles from polyester resins | |
| JP2002012674A (en) | Aliphatic polyester composition for master batch and method for producing aliphatic polyester film using the composition | |
| JP2000239508A (en) | Biodegradable molding compound and its molding | |
| CN115926406A (en) | Full-degradable high-barrier polyester composite film material and preparation method and application thereof | |
| CN114702799A (en) | Biodegradable polylactic acid plastic uptake sheet | |
| CN116426099B (en) | Seawater degradation film and preparation method thereof | |
| CN113150520A (en) | Biodegradable plastic for disposable spoon | |
| JP3623053B2 (en) | Biodegradable resin molding | |
| CN118027630B (en) | Transparent toughened polylactic acid composite material and preparation method and application thereof | |
| CN115785595B (en) | Polyvinyl alcohol melt blown film based on anhydrous plasticization and preparation method thereof | |
| JP7158790B1 (en) | Biodegradable composite composition | |
| EP4438670A1 (en) | Method for preparing thermoplastic cellulose acetate composition | |
| CN118725529A (en) | Toughening master batch for high-transparency biodegradable material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |