CN112480617A - Polylactic resin prepared from various plant materials and preparation method thereof - Google Patents
Polylactic resin prepared from various plant materials and preparation method thereof Download PDFInfo
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- CN112480617A CN112480617A CN202011291828.9A CN202011291828A CN112480617A CN 112480617 A CN112480617 A CN 112480617A CN 202011291828 A CN202011291828 A CN 202011291828A CN 112480617 A CN112480617 A CN 112480617A
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- polylactic acid
- polylactic
- corn
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- potato starch
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- 239000011347 resin Substances 0.000 title claims abstract description 92
- 229920005989 resin Polymers 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 79
- 239000004626 polylactic acid Substances 0.000 claims abstract description 79
- 240000008042 Zea mays Species 0.000 claims abstract description 58
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 58
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 58
- 235000005822 corn Nutrition 0.000 claims abstract description 58
- 244000061456 Solanum tuberosum Species 0.000 claims abstract description 52
- 235000002595 Solanum tuberosum Nutrition 0.000 claims abstract description 52
- 241000196324 Embryophyta Species 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229920001592 potato starch Polymers 0.000 claims description 71
- 229920002261 Corn starch Polymers 0.000 claims description 48
- 239000008120 corn starch Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 39
- 235000013339 cereals Nutrition 0.000 claims description 38
- 238000004140 cleaning Methods 0.000 claims description 30
- 235000012015 potatoes Nutrition 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- -1 polybutylene terephthalate Polymers 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000004310 lactic acid Substances 0.000 claims description 13
- 235000014655 lactic acid Nutrition 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 235000013336 milk Nutrition 0.000 claims description 10
- 239000008267 milk Substances 0.000 claims description 10
- 210000004080 milk Anatomy 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 230000001376 precipitating effect Effects 0.000 claims description 10
- 102000004169 proteins and genes Human genes 0.000 claims description 10
- 108090000623 proteins and genes Proteins 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004631 polybutylene succinate Substances 0.000 claims description 3
- 229920002961 polybutylene succinate Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 150000003951 lactams Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229920002472 Starch Polymers 0.000 abstract description 5
- 239000008107 starch Substances 0.000 abstract description 5
- 235000019698 starch Nutrition 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 20
- 238000002156 mixing Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/81—Preparation processes using solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of polylactic resin, in particular to polylactic resin prepared from various plant materials and a preparation method thereof. The feed comprises the following raw materials: polylactic acid, chain extender, heat-resistant agent, blend, polylactic acid resin prepared from various plant materials prepared by the invention, corn and potato can produce a large amount of starch, the cost for preparing the polylactic acid is reduced, meanwhile, the polylactic acid resin has high stretchability and good transparency, and is more suitable for preparing the polylactic acid resin.
Description
Technical Field
The invention relates to the technical field of polylactic resin, in particular to polylactic resin prepared from various plant materials and a preparation method thereof.
Background
Polylactic acid is a novel biodegradable material, is prepared by using starch raw materials provided by renewable plant resources, the starch raw materials are saccharified to obtain glucose, then the glucose and certain strains are fermented to prepare high-purity lactic acid, and the polylactic acid with a certain molecular weight is synthesized by a chemical synthesis method. The common plastic treatment method still comprises the steps of burning and cremating to cause a large amount of greenhouse gases to be discharged into the air, the polylactic acid plastic is buried in soil to be degraded, the generated carbon dioxide directly enters soil organic matters or is absorbed by plants, the carbon dioxide is not discharged into the air and does not cause greenhouse effect, and the preservative film prepared from the polylactic acid resin has good air permeability, oxygen permeability and carbon dioxide permeability and also has the characteristic of odor isolation;
the existing products prepared by polylactic resin have high preparation cost, the application range is limited due to poor mechanical property and low relative molecular mass, and the use duration is greatly shortened due to poor heat resistance, so that the defects are corrected, and a novel polylactic resin needs to be prepared.
Disclosure of Invention
The present invention aims to provide a polylactic acid resin prepared from various plant materials and a preparation method thereof, so as to solve the problems in the background art.
In order to achieve the above objects, in one aspect, the present invention provides a polylactic acid resin prepared from a plurality of plant materials, comprising the following raw materials: 60-80% of polylactic acid, 1-5% of chain extender, 5-10% of heat-resistant agent and 10-20% of blend.
As a further improvement of the technical scheme, the polylactic acid is prepared by a solution direct polymerization method and comprises the following raw materials:
lactic acid, wherein the lactic acid is prepared by fermenting potato starch and corn starch;
a catalyst, wherein the catalyst is tin powder;
a solution that is diphenyl ether;
the preparation method of the polylactic acid comprises the following steps: adding the emulsion, the catalyst and the solution into a reactor, performing azeotropic reflux at 135 ℃ under the condition of 4500Pa, and directly polymerizing the solution to obtain the polylactic acid.
As a further improvement of the technical scheme, the extraction steps of the potato starch are as follows:
s2.1, cleaning the potatoes to remove impurities on the surfaces of the potatoes;
s2.2, grinding the cleaned potatoes to obtain potato paste;
s2.3, screening and washing the potato paste, wherein the screened substances are potato starch milk;
s2.4, adding potato starch into the launder, separating protein and other substances, and cleaning to obtain wet potato starch;
s2.5, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain potato starch;
compared with starch of other crops, the potato starch has good transparency and high stretchability.
As a further improvement of the technical scheme, the extraction steps of the corn starch are as follows:
s3.1, cleaning corn grains, and adding sodium sulfite to soak for softening;
s3.2, crushing the cleaned grains, and grinding the crushed grains into corn steep liquor;
s3.3, precipitating the corn steep liquor for 4 hours to prepare wet corn starch;
and S3.4, adding the wet corn flour into a dryer, and drying for 4 hours to obtain the corn starch.
In a further improvement of the present invention, the chain extender is at least one selected from lauric peroxide, styrene/epoxypropyl/acrylate copolymer, 2-bis (2-oxazoline) and 1, 6-hexamethylene diisocyanate, and the low polymer of polylactic acid obtained by direct polycondensation is treated with the chain extender to obtain polylactic acid with high relative molecular mass.
As a further improvement of the technical scheme, the heat-resistant agent is selected from at least one of polymethyl methacrylate, polybutylene terephthalate and polyethylene terephthalate, and the heat resistance of the polylactic acid resin can be improved by compounding the heat-resistant agent and polylactic acid, and meanwhile, the mechanical properties of the polylactic acid resin are greatly improved;
polymethyl methacrylate is preferable, and since polymethyl methacrylate has high Tg and high transparency, PMMA blended with polylactic acid has good heat resistance, transparency, moldability and durability.
As a further improvement of the technical solution, the blend is at least one selected from the group consisting of polylactam, polybutylene succinate, polyethylene glycol, and polybutylene oxalate/terephthalate, and the polylactic acid and the biodegradable polymer are blended and modified on the premise that the biodegradability of the polylactic acid is not damaged, so that the rigidity and toughness of the modified PLA material can be adjusted.
In another aspect, the present invention provides a method for preparing a polylactic acid resin from a plurality of plant materials, comprising the steps of:
s4.1, heating and melting the heat-resistant agent and the blend, and taking out for later use;
s4.2, adding the polylactic resin into a stirring kettle, and heating and melting;
s4.3, heating, adding the chain extender into the stirring kettle, and uniformly stirring;
s4.4, adding the melted heat-resistant agent and the blend, and uniformly stirring to obtain a mixed solution;
and S4.5, adding the mixed solution into a double-screw extruder for extrusion to obtain the polylactic resin.
Preferably, in the S4.3-S4.4, the temperature of the reaction kettle is 160-.
Preferably, in S4.5, the extrusion temperature of the twin-screw extruder is 180-220 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. in the polylactic resin prepared from the various plant materials and the preparation method thereof, corn and potato can be processed to produce a large amount of starch, so that the cost for preparing polylactic acid is reduced, and the polylactic resin has high stretchability and good transparency and is more suitable for preparing the polylactic resin.
2. In the polylactic acid resin prepared from various plant materials and the preparation method thereof, the low polymer of polylactic acid obtained by direct polycondensation is treated by using a chain extender to obtain the polylactic acid with high relative molecular mass.
3. In the polylactic resin prepared from various plant materials and the preparation method thereof, the heat resistance of the polylactic resin can be improved by compounding the heat-resistant agent and the polylactic acid, and the mechanical properties are greatly improved.
4. In the polylactic resin prepared from various plant materials and the preparation method thereof, the added blend is used for blending and modifying the polylactic acid and the biodegradable high polymer on the premise of not damaging the biodegradability of the polylactic acid, so that the rigidity and the toughness of the modified PLA material can be adjusted.
Drawings
Fig. 1 is a schematic view of the entire structure of embodiment 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 5% of heat-resistant agent and 10% of blend, taking out for later use, adding 60% of polylactic resin into a stirring kettle, heating and melting, heating, adding 1% of chain extender into the stirring kettle, uniformly stirring, adding the melted heat-resistant agent and blend, and uniformly stirring to obtain mixed solution, wherein the temperature of the reaction kettle is 160-plus-180 ℃, and the stirring speed is 110-plus-120 r/min;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Example 2 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 7% of heat-resistant agent and 12.5% of blend, taking out for later use, adding 65% of polylactic resin into a stirring kettle, heating and melting, heating, adding 2% of chain extender into the stirring kettle, uniformly stirring, adding the melted heat-resistant agent and blend, and uniformly stirring to obtain mixed solution, wherein the temperature of the reaction kettle is 160-180 ℃, and the stirring speed is 110-120 r/min;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Example 3 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 8% of heat-resistant agent and 15% of blend, taking out for later use, adding 70% of polylactic resin into a stirring kettle, heating and melting, heating, adding 3% of chain extender into the stirring kettle, uniformly stirring, adding the melted heat-resistant agent and blend, and uniformly stirring to obtain a mixed solution, wherein the temperature of the reaction kettle is 160-plus-180 ℃, and the stirring speed is 110-plus-120 r/min;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Example 4 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 9% of heat-resistant agent and 17.5% of blend, taking out for later use, adding 75% of polylactic resin into a stirring kettle, heating and melting, heating, adding 4% of chain extender into the stirring kettle, uniformly stirring, adding the melted heat-resistant agent and blend, and uniformly stirring to obtain mixed solution, wherein the temperature of the reaction kettle is 160-180 ℃, and the stirring speed is 110-120 r/min;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Example 5 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 10% of heat-resistant agent and 20% of blend, taking out for later use, adding 80% of polylactic resin into a stirring kettle, heating and melting, heating, adding 5% of chain extender into the stirring kettle, uniformly stirring, adding the melted heat-resistant agent and blend, and uniformly stirring to obtain mixed solution, wherein the temperature of the reaction kettle is 160-;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
The chain extender is at least one selected from lauric acid peroxide, styrene/epoxypropyl/acrylate copolymer, 2-bis (2-oxazoline) and 1, 6-hexamethylene diisocyanate, and the low polymer of the polylactic acid obtained by direct polycondensation is treated by the chain extender to obtain the polylactic acid with high relative molecular mass;
the heat-resistant agent is selected from at least one of polymethyl methacrylate, polybutylene terephthalate and polyethylene terephthalate, and the heat resistance of the polylactic resin can be improved by compounding the heat-resistant agent and polylactic acid, and the mechanical properties are greatly improved;
polymethyl methacrylate is preferred, and because polymethyl methacrylate has high Tg and high transparency, PMMA is mixed with polylactic acid to have good heat resistance, transparency, moldability and durability;
the blend is at least one selected from polyethylene lactam, polybutylene succinate, polyethylene glycol and polybutylene terephthalate, and the polylactic acid and the biodegradable polymer are blended and modified on the premise of not damaging the biodegradability of the polylactic acid, so that the rigidity and the toughness of the modified PLA material can be adjusted.
In the polylactic resin prepared from various plant materials, the relative molecular mass is high, the strength of the generated polylactic resin is good, and the heat resistance is strong, and the detection indexes of the polylactic resin prepared from various plant materials are shown in table 1:
TABLE 1
As shown in table 1, in the polylactic acid resins prepared from various plant materials prepared by the present invention, in examples 1 to 5, when 70% of polylactic acid, 3% of chain extender, 8% of heat resistant agent and 15% of blend, the polylactic acid resin has the best tensile strength, flexural modulus, elongation at break and impact strength, the strongest heat resistance and the highest relative molecular mass, and thus, the polylactic acid blended from the chain extender, the heat resistant agent and the blend has better mechanical properties.
Comparative example 1 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 15% of the blend, taking out for later use, adding 70% of polylactic resin into a stirring kettle, heating and melting, heating, wherein the temperature of the reaction kettle is 160-180 ℃, the stirring speed is 110-120r/min, adding 3% of chain extender into the stirring kettle, stirring uniformly, adding the melted blend, and stirring uniformly to obtain a mixed solution;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Comparative example 2 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: adding 70% of polylactic resin into a stirring kettle, heating for melting, heating, wherein the temperature of the reaction kettle is 160-;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
Comparative example 3 a polylactic acid resin prepared from a plurality of plant materials, comprising:
firstly, preparation of polymer
(1) Preparing potato starch: cleaning the potatoes to remove impurities on the surfaces of the potatoes; grinding the cleaned potatoes to obtain potato paste, screening and washing the potato paste to obtain potato starch milk as undersize, adding the potato starch into a trough, separating substances such as protein and the like, cleaning to obtain wet potato starch, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch;
(2) preparing corn starch: cleaning corn grains, adding sodium sulfite for soaking to soften the corn grains, crushing the cleaned corn grains, grinding the corn grains into corn steep liquor, precipitating the corn steep liquor for 4 hours to obtain wet corn starch, adding the wet corn starch into a dryer, and drying for 4 hours to obtain the corn starch;
(3) preparation of polymer: fermenting potato starch and corn starch to obtain lactic acid, adding the emulsion, catalyst and solution into a reactor, performing azeotropic reflux at 135 deg.C and 4500Pa, and directly polymerizing the solution to obtain polylactic acid.
Preparation of polylactic resin
(1) Blending modification: heating and melting 8% of heat-resistant agent and 15% of blend, taking out for later use, adding 70% of polylactic resin into a stirring kettle, heating and melting, heating, wherein the temperature of the reaction kettle is 160-;
(2) extruding resin: adding the mixed solution into a double-screw extruder for extrusion, wherein the extrusion temperature is 180-220 ℃ to prepare the polylactic resin.
The polylactic resin prepared from various plant materials has high relative molecular weight and high strength and heat resistance, has a great relationship with a chain extender, a heat-resistant agent and a blend added into the polylactic resin, and in order to verify the related technical scheme, the applicant performs the following tests:
comparative examples 1 to 3: by adopting the method of example 3, the relevant indexes of the polylactic acid resin prepared from various prepared plant materials are detected under the condition of removing the chain extender, the heat-resistant agent and the blend, and the concrete indexes are shown in table 2:
TABLE 2
As shown in table 2, in comparative examples 1-2, tensile strength, elongation at break and impact strength of the polylactic acid resin were all decreased and heat resistance was greatly decreased in the case of removing the heat-resistant agent alone, and in the case of removing the heat-resistant agent and the blending agent at the same time, tensile strength of the polylactic acid resin was less than 40MPa, elongation at break was less than 100%, impact strength was less than 200J/m, and heat-resistant temperature was 120 ℃, so it can be seen that the heat-resistant agent and the blending agent are important factors affecting mechanical properties of the polylactic acid;
in comparative examples 1 to 3, comparative example 3, when the chain extender was removed, the relative molecular mass was remarkably decreased, not more than 150000Mr, and when the relative molecular mass was too low, the application range of the polylactic acid resin was limited, and thus it can be seen that the addition of the chain extender to the polylactic acid was a large factor affecting the relative molecular mass of the polylactic acid resin.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A polylactic resin prepared from various plant materials comprises the following raw materials: 60-80% of polylactic acid, 1-5% of chain extender, 5-10% of heat-resistant agent and 10-20% of blend.
2. The polylactic acid resin prepared from a plurality of plant materials according to claim 1, wherein: the polylactic acid is prepared by a solution direct polymerization method and comprises the following raw materials:
lactic acid, wherein the lactic acid is prepared by fermenting potato starch and corn starch;
a catalyst, wherein the catalyst is tin powder;
a solution that is diphenyl ether;
the preparation method of the polylactic acid comprises the following steps: adding the emulsion, the catalyst and the solution into a reactor, performing azeotropic reflux at 135 ℃ under the condition of 4500Pa, and directly polymerizing the solution to obtain the polylactic acid.
3. The polylactic acid resin prepared from a plurality of plant materials according to claim 2, wherein: the extraction steps of the potato starch are as follows:
s2.1, cleaning the potatoes to remove impurities on the surfaces of the potatoes;
s2.2, grinding the cleaned potatoes to obtain potato paste;
s2.3, screening and washing the potato paste, wherein the screened substances are potato starch milk;
s2.4, adding potato starch into the launder, separating protein and other substances, and cleaning to obtain wet potato starch;
s2.5, dehydrating the wet potato starch, and drying for 4 hours by using a dryer to obtain the potato starch.
4. The polylactic acid resin prepared from a plurality of plant materials according to claim 2, wherein: the extraction steps of the corn starch are as follows:
s3.1, cleaning corn grains, and adding sodium sulfite to soak for softening;
s3.2, crushing the cleaned grains, and grinding the crushed grains into corn steep liquor;
s3.3, precipitating the corn steep liquor for 4 hours to prepare wet corn starch;
and S3.4, adding the wet corn flour into a dryer, and drying for 4 hours to obtain the corn starch.
5. The polylactic acid resin prepared from a plurality of plant materials according to claim 1, wherein: the chain extender is at least one selected from lauric peroxide, styrene/epoxypropyl/acrylate copolymer, 2-bis (2-oxazoline) and 1, 6-hexamethylene diisocyanate.
6. The polylactic acid resin prepared from a plurality of plant materials according to claim 1, wherein: the heat-resistant agent is at least one selected from polymethyl methacrylate, polybutylene terephthalate and polyethylene terephthalate;
preferably polymethyl methacrylate.
7. The polylactic acid resin prepared from a plurality of plant materials according to claim 1, wherein: the blend is selected from at least one of polyethylene lactam, polybutylene succinate, polyethylene glycol and polybutylene oxalate/terephthalate.
8. A method for preparing polylactic resin prepared from a plurality of plant materials, which comprises the polylactic resin prepared from a plurality of plants in any one of claims 1 to 7, and comprises the following operation steps:
s4.1, heating and melting the heat-resistant agent and the blend, and taking out for later use;
s4.2, adding the polylactic resin into a stirring kettle, and heating and melting;
s4.3, heating, adding the chain extender into the stirring kettle, and uniformly stirring;
s4.4, adding the melted heat-resistant agent and the blend, and uniformly stirring to obtain a mixed solution;
and S4.5, adding the mixed solution into a double-screw extruder for extrusion to obtain the polylactic resin.
9. The method for producing a polylactic acid resin from a plurality of plant materials according to claim 8, wherein: in the S4.3-S4.4, the temperature of the reaction kettle is 160-.
10. The method for producing a polylactic acid resin from a plurality of plant materials according to claim 8, wherein: in the S4.5, the extrusion temperature of the double-screw extruder is 180-220 ℃.
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