CN110016133B - Macromolecular nucleating agent for rapid crystallization of polylactic acid and use method thereof - Google Patents
Macromolecular nucleating agent for rapid crystallization of polylactic acid and use method thereof Download PDFInfo
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- CN110016133B CN110016133B CN201910342079.9A CN201910342079A CN110016133B CN 110016133 B CN110016133 B CN 110016133B CN 201910342079 A CN201910342079 A CN 201910342079A CN 110016133 B CN110016133 B CN 110016133B
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- 230000008025 crystallization Effects 0.000 title claims abstract description 97
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 30
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229920006021 bio-based polyamide Polymers 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- MRHPRDYMSACWSG-UHFFFAOYSA-N 1,3-diaminopropan-1-ol Chemical compound NCCC(N)O MRHPRDYMSACWSG-UHFFFAOYSA-N 0.000 claims description 2
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 claims description 2
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 2
- JBPWRHDFVVEDTJ-UHFFFAOYSA-N oxadithiole Chemical compound O1SSC=C1 JBPWRHDFVVEDTJ-UHFFFAOYSA-N 0.000 claims description 2
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- -1 hydrazino-oxy group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a macromolecular nucleating agent for rapid crystallization of polylactic acid and a use method thereof. The structural formula of the macromolecular nucleating agent is as follows:
n is more than or equal to 5 and less than or equal to 5000; wherein, R is1And R3Is an aliphatic main chain structure; r2Is a side chain structure with an ester functional group, R4Is a main chain structure with thioether. The macromolecular nucleating agent can be added into a polylactic acid matrix, the addition amount is 0-2 wt%, and the polylactic acid is rapidly crystallized by a melt blending or solution blending method to prepare the polylactic acid resin. The macromolecular nucleating agent can greatly improve the crystallization rate of the polylactic acid on the basis of adding a small amount of the macromolecular nucleating agent. The addition amount of the nucleating agent in the polylactic acid matrix is small, and the compatibility and the dispersibility between the nucleating agent and the polylactic acid matrix are good, so that the influence of the use of the nucleating agent on the mechanical property and the processing characteristic of the polylactic acid material is small.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a macromolecular nucleating agent for rapid crystallization of polylactic acid and a use method thereof.
Background
With the increasing problem of environmental pollution and exhaustion of petrochemical resources, the research and development of biobased materials using natural biomass as raw material become the research hot spots in the material field in the world today. Polylactic acid has advantages of good processability, biodegradability and environmental friendliness, and thus is considered to be a polymer material that can effectively reduce waste pollution on the earth. However, polylactic acid is not perfect, and has the disadvantages of slow crystallization speed, low heat distortion temperature and the like, which greatly limit the step of replacing traditional plastics with polylactic acid.
In the polylactic acid synthesis process, the crystallization speed is low, and the low crystallinity can cause the problems of low thermal deformation temperature, long molding period, low transparency and the like of the polylactic acid material, so that the acceleration of the nucleation capability of the polylactic acid has important significance for improving the application of the polylactic acid material. The nucleating agent is added to accelerate the nucleation density of the polylactic acid, which is a main method for accelerating the crystallization of the polylactic acid at the present stage, and the polylactic acid nucleating agent is mainly divided into an inorganic nucleating agent and an organic nucleating agent. The inorganic nucleating agent comprises mica, talcum powder, kaolin and the like. The inorganic nucleating agent is low in price and high in practicability, but the inorganic nucleating agent has the biggest problems of poor compatibility with polylactic acid, and finally, the mechanical property of a polylactic acid product is reduced, the surface glossiness is poor, the transparency is reduced and the like. The organic nucleating agent used in the polylactic acid product mainly comprises an amide nucleating agent, an organic phosphate nucleating agent, a supermolecule chemical nucleating agent, a hydrazide nucleating agent and the like. The organic nucleating agent overcomes the problem of poor transparency and glossiness of the inorganic nucleating agent, and can remarkably improve the processing performance of products, so the development of the organic nucleating agent becomes the key point of the research and development of the polylactic acid nucleating agent in recent years.
The organic compound containing amide groups is the most applied organic nucleating agent in the field of polylactic acid. The hyperbranched polyesteramide and polylactic acid are subjected to melt blending, and the hyperbranched polyesteramide can be used as a heterogeneous nucleating agent to improve the crystallinity of the polylactic acid and accelerate the crystallization rate of the polylactic acid. However, the nucleation effect is not good, and only when the content of the hyperbranched polyester amide is more than 10%, the obvious nucleation effect can be observed from an optical microscope (Macromolecules 2007,40, 6257-6267).
The Chinese invention patent publication No. CN103102661B discloses a rapid nucleating agent for polylactic acid resin, which is a small molecular substance containing two amido bonds, a hydrazino-oxy group and a plurality of benzene ring structures, and the nucleating agent has the effects of promoting the nucleation of the polylactic acid and reducing the crystallization time, but the nucleating performance of the polylactic acid resin needs to be improved by increasing the dosage, the dosage of the nucleating agent with the optimal effect is up to 10 percent, and the crystallinity of the polylactic acid is lower when the nucleating agent is used at low dosage; the economic benefit of the product is poor. Moreover, the nucleating agent can influence the performance of the polylactic acid, so that the degradability and partial mechanical properties of the polylactic acid resin are obviously reduced after the nucleating agent is added in a large amount.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design a new technical scheme, provide a macromolecular nucleating agent for rapid crystallization of polylactic acid and a using method thereof, and solve the problems.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a macromolecular nucleating agent for quick crystallization of polylactic acid is a bio-based polyamide polymer, and the structural formula of the macromolecular nucleating agent is as follows:
wherein, R is1And R3Is an aliphatic main chain structure; r2Is a side chain structure with an ester functional group, R4Is a main chain structure with thioether.
Preferably, R in the main chain1And R3Is any one of the following structures, including the following:
preferably, the side group R2Is any one of the following structures, including the following:
preferably, R in the main chain4Is any one of the following structures, including the following:
the use method of the macromolecular nucleating agent in the rapid polylactic acid crystallization process comprises the steps of adding the macromolecular nucleating agent into a polylactic acid matrix, wherein the adding amount is 0.5-2 wt%, and rapidly crystallizing the polylactic acid by a melt blending or solution blending method to prepare the polylactic acid resin.
Preferably, the process flow of the melt blending method is as follows:
1) drying the polylactic acid and the macromolecular nucleating agent in a vacuum oven at 40-100 ℃ for 4-12 hours according to the mass fraction ratio for later use;
2) adding the polylactic acid and macromolecular nucleating agent pretreatment material into an internal mixer, and blending for 3-20 minutes at the temperature of 160-200 ℃ and at the rotating speed of 40-500 r/min to uniformly mix various materials to obtain the rapidly crystallized polylactic resin.
Preferably, the process flow of the solution blending method is as follows:
1) drying the polylactic acid and the macromolecular nucleating agent for 4-12 hours in a vacuum oven at 40-100 ℃ according to the mass fraction ratio for later use;
2) mixing and dissolving the polylactic acid and the macromolecular nucleating agent pretreatment material in the previous step in a good solvent to form a clear solution;
3) and (3) adding the clarified solution obtained in the previous step into a poor solvent, and rapidly stirring to obtain the rapidly crystallized polylactic resin.
Wherein, the good solvent in the step 2) is any one of dichloromethane and trichloromethane or a mixture in any proportion.
The poor solvent in the step 3) is any one of methanol and ethanol or a mixture of any proportion.
The invention takes a bio-based polyamide polymer synthesized by castor oil and the like as a polylactic acid macromolecular nucleating agent, and prepares the rapid crystallization polylactic acid resin by melt blending or solution blending. The polylactic acid and the macromolecular nucleating agent can form good hydrogen bond action, hydrogen on amino in the main chain of the polyamide polymer and oxygen on the carbonyl group of the polylactic acid form hydrogen bond, and oxygen on the ester group of the R2 side chain in the polyamide polymer and hydrogen on the hydroxyl group of the polylactic acid form hydrogen bond. The formation of hydrogen bonds is beneficial to the dispersion of the macromolecular nucleating agent in the polylactic acid, and the compatibility between the macromolecular nucleating agent and the polylactic acid is improved.
The invention has the following beneficial effects:
the nucleating agent used in the invention is a macromolecular bio-based polyamide polymer, and can greatly improve the crystallization rate of polylactic acid and the crystallization rate on the basis of adding a small amount of the nucleating agent. The addition amount of the nucleating agent in the polylactic acid matrix is small, and the compatibility and the dispersibility between the nucleating agent and the polylactic acid matrix are good, so that the influence of the use of the nucleating agent on the properties of the polylactic acid material, such as strength, rigidity and the like, is small. The nucleating agent is white powder, is easy to add in the polylactic acid processing and forming process, and does not influence the transparency of the polylactic acid product.
The nucleating agent is synthesized by castor oil and other materials, and has wide raw material source and reasonable cost control; has better economic value and commercial prospect; and the polylactic acid material has good biodegradability, has low influence on the degradability of the polylactic acid material after being added, and is very green and environment-friendly.
The macromolecular nucleating agent provided by the invention can achieve the purpose of rapid crystallization and nucleation by adding a small amount of nucleating agent, plays a role in enhancing and toughening polylactic acid, and is beneficial to improving the performance of the polylactic acid.
The macromolecular nucleating agent is in a solid state, is easy to blend with polylactic acid, has low investment on processing equipment, has relatively simple process and has great market potential.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph showing heat flow and crystallization time of 115 ℃ isothermal crystallization of polylactic acid resin of examples 1,2 and 3;
FIG. 2 is a graph showing the relationship between heat flow and crystallization time of 120 ℃ isothermal crystallization of the rapidly crystallized polylactic acid resin of examples 1,2 and 3;
FIG. 3 is a graph showing the relationship between the degree of crystallization and the crystallization time of 120 ℃ isothermal crystallization of the rapidly crystallized polylactic acid resin according to examples 1,2 and 3;
FIG. 4 is a graph showing heat flow of 115 ℃ isothermal crystallization versus crystallization time for the rapidly crystallized polylactic acid resin of examples 4,5, 6;
FIG. 5 is a graph showing the relationship between the degree of crystallization and the crystallization time of isothermal crystallization at 115 ℃ for the rapidly crystallized polylactic acid resin of examples 4,5, 6;
FIG. 6 is a graph showing the relationship between heat flow and crystallization time of 120 ℃ isothermal crystallization of the rapidly crystallized polylactic acid resin of examples 4,5, 6;
FIG. 7 is a graph showing the relationship between the degree of crystallization and the crystallization time in the 120 ℃ isothermal crystallization of the rapidly crystallized polylactic acid resin of examples 4,5, 6;
FIG. 8 is a graph of the crystallization temperature versus the crystallization half-crystallization time for the rapidly crystallizing polylactic acid resins of examples 4,5, 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention are described in more detail below with reference to the embodiments, and the following embodiments are only some embodiments, but not all embodiments, of the present invention.
Preparation of bio-based polyamide polymer:
(1) adding 100g of methyl undecylenate and 1g of 1, 3-diamino-propanol into 4ml of tetrahydrofuran; introducing argon for half an hour, placing the mixture in an oil bath kettle at 40 ℃, adding 10ml of sodium methoxide, reacting for 20 hours at 40 ℃, and recrystallizing to obtain a white powdery solid, namely the required functional polyamide monomer 1;
(2) putting 54g of functional polyamide monomer A, 12g of butyric anhydride and 40mg of dimethylaminopyridine into a round-bottom flask, adding 3ml of tetrahydrofuran, mixing, reacting at 50 ℃ for 10 hours to obtain a clear solution, and purifying to obtain a functional polyamide monomer 2;
(3) 1350mg of the functional polyamide monomer 2, 150mg of the functional polyamide monomer 1, 200mg of oxadithiol, 10mg of azobisisobutyronitrile catalyst and 10ml of tetrahydrofuran were added to a reaction vessel; introducing argon for 15 minutes, and then placing the mixture in an oil bath kettle at the temperature of 100 ℃ for reacting for 36 hours; purifying the reaction product to obtain the required bio-based polyamide polymer.
In the preparation process, the solvent is dried by anhydrous magnesium sulfate and then distilled under reduced pressure before use, and the azobisisobutyronitrile is purified by recrystallization.
(the above is disclosed in detail in the disclosure of the prior application CN107501554A "an ultra high strength thermoplastic elastomer and a method for its preparation")
The bio-based polyamide polymer was used as a toughening agent in the subsequent examples.
Example 1
1) Drying 100 parts of polylactic acid in a vacuum oven at 40 ℃ for 12 hours for subsequent experiments;
2) adding 100 parts of polylactic acid of the pretreatment material obtained in the step 1) into an internal mixer, and blending for 3 minutes at the temperature of 160 ℃ and the rotating speed of 40 r/min to uniformly mix various materials to obtain the polylactic resin.
The polylactic acid resin obtained in example 1 was subjected to an isothermal crystallization test, and the relationship between the heat flow and the crystallization time of the isothermal crystallization at 115 ℃ in example 1 is shown in FIG. 1, the relationship between the heat flow and the crystallization time of the isothermal crystallization at 120 ℃ in example 1 is shown in FIG. 2, and the relationship between the crystallinity and the crystallization time of the isothermal crystallization at 120 ℃ in example 1 is shown in FIG. 3.
Example 2
1) 99.5 parts of polylactic acid and 0.5 part of macromolecular nucleating agent are put in a vacuum oven at 100 ℃ to be dried for 4 hours for subsequent experiments;
2) mixing 99.5 parts of polylactic acid and 0.5 part of macromolecular nucleating agent obtained in the step 1), adding the mixture into an internal mixer, and blending for 20 minutes at the temperature of 200 ℃ and the rotating speed of 500 rpm to uniformly mix various materials to obtain the rapidly crystallized polylactic resin.
The rapid crystallization polylactic acid resin obtained in example 2 was subjected to isothermal crystallization test, and the relationship between heat flow and crystallization time of isothermal crystallization at 115 ℃ in example 2 is shown in FIG. 1, the relationship between heat flow and crystallization time of isothermal crystallization at 120 ℃ in example 2 is shown in FIG. 2, and the relationship between crystallinity and crystallization time of isothermal crystallization at 120 ℃ in example 2 is shown in FIG. 3.
Example 3
1) Drying 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent in a vacuum oven at 80 ℃ for 10 hours for subsequent experiments;
2) mixing 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent obtained in the step 1), adding the mixture into an internal mixer, and blending for 10 minutes at the temperature of 180 ℃ and the rotating speed of 200 r/min to uniformly mix various materials to obtain the rapidly crystallized polylactic resin.
The rapid crystallization polylactic acid resin obtained in example 3 was subjected to an isothermal crystallization test, and the relationship between the heat flow and the crystallization time of isothermal crystallization at 115 ℃ in example 3 is shown in FIG. 1, the relationship between the heat flow and the crystallization time of isothermal crystallization at 120 ℃ in example 3 is shown in FIG. 2, and the relationship between the crystallinity and the crystallization time of isothermal crystallization at 120 ℃ in example 3 is shown in FIG. 3.
Example 4
1) Drying 100 parts of polylactic acid in a vacuum oven at 40 ℃ for 12 hours for subsequent experiments;
2) mixing 100 parts of polylactic acid of the pretreatment material obtained in the step 1), and dissolving the mixture in a dichloromethane solvent to obtain a clear solution.
3) Pouring the clear solution obtained in the step 2) into a methanol solution, and quickly stirring to obtain the quickly crystallized polylactic resin.
The rapidly crystallized polylactic acid resin obtained in example 4 was subjected to isothermal crystallization test, wherein the relationship between heat flow and crystallization time of isothermal crystallization at 115 ℃ in example 4 is shown in FIG. 4, the relationship between crystallinity and crystallization time of isothermal crystallization at 115 ℃ in example 4 is shown in FIG. 5, the relationship between heat flow and crystallization time of isothermal crystallization at 120 ℃ in example 4 is shown in FIG. 6, the relationship between crystallinity and crystallization time of isothermal crystallization at 120 ℃ in example 4 is shown in FIG. 7, and the relationship between half-crystallization time and crystallization temperature of isothermal crystallization in example 4 is shown in FIG. 8.
Example 5
1) 99.5 parts of polylactic acid and 0.5 part of macromolecular nucleating agent are put in a vacuum oven at 100 ℃ to be dried for 4 hours for subsequent experiments;
2) mixing 99.5 parts of polylactic acid and 0.5 part of macromolecular nucleating agent obtained in the step 1) and dissolving in a trichloromethane solvent to obtain a clear solution.
3) Pouring the clear solution obtained in the step 2) into an ethanol solution, and quickly stirring to obtain the quickly crystallized polylactic resin.
The rapidly crystallized polylactic acid resin obtained in example 5 was subjected to isothermal crystallization test, wherein the relationship between heat flow and crystallization time of isothermal crystallization at 115 ℃ in example 5 is shown in FIG. 4, the relationship between crystallinity and crystallization time of isothermal crystallization at 115 ℃ in example 5 is shown in FIG. 5, the relationship between heat flow and crystallization time of isothermal crystallization at 120 ℃ in example 5 is shown in FIG. 6, the relationship between crystallinity and crystallization time of isothermal crystallization at 120 ℃ in example 5 is shown in FIG. 7, and the relationship between half-crystallization time and crystallization temperature of isothermal crystallization in example 5 is shown in FIG. 8.
Example 6
1) Drying 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent in a vacuum oven at 80 ℃ for 8 hours for subsequent experiments;
2) mixing 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent obtained in the step 1) and dissolving the mixture in a dichloromethane solvent to obtain a clear solution.
3) Pouring the clear solution obtained in the step 2) into a methanol solution, and quickly stirring to obtain the quickly crystallized polylactic resin.
Isothermal crystallization test was performed on the rapidly crystallizing polylactic acid resin obtained in example 6, and the relationship between heat flow and crystallization time of isothermal crystallization at 115 ℃ in example 6 is shown in FIG. 4, the relationship between crystallinity and crystallization time of isothermal crystallization at 115 ℃ in example 6 is shown in FIG. 5, the relationship between heat flow and crystallization time of isothermal crystallization at 120 ℃ in example 6 is shown in FIG. 6, the relationship between crystallinity and crystallization time of isothermal crystallization at 120 ℃ in example 6 is shown in FIG. 7, and the relationship between half-crystallization time and crystallization temperature of isothermal crystallization in example 6 is shown in FIG. 8.
Test data and analysis
It can be found from the data in fig. 1-8 that: no matter the method of melt blending or solution blending is adopted, the macromolecular nucleating agent can improve the crystallization rate of the polylactic acid, the nucleating effect is obvious, and the crystallinity of the finished product is high. In the embodiment, the crystallization rate of the polylactic acid is in a positive correlation with the addition amount of the macromolecular nucleating agent; and when only 0.5 percent of macromolecular nucleating agent is added, the semi-crystallization time of the polylactic acid can be shortened to half of the original semi-crystallization time, and when the addition amount reaches 2 percent by weight, the improvement effect of the crystallization rate is extremely remarkable. The dosage of the macromolecular nucleating agent is greatly reduced compared with the dosage of the conventional organic nucleating agent.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. A use method of a macromolecular nucleating agent for rapid crystallization of polylactic acid, wherein the macromolecular nucleating agent is a bio-based polyamide polymer, and the preparation method comprises the following steps:
(1) adding 100g of methyl undecylenate and 1g of 1, 3-diamino-propanol into 4ml of tetrahydrofuran; introducing argon for half an hour, placing the mixture in an oil bath kettle at 40 ℃, adding 10ml of sodium methoxide, reacting for 20 hours at 40 ℃, and recrystallizing to obtain a white powdery solid, namely the required functional polyamide monomer 1;
(2) putting 54g of functional polyamide monomer 1, 12g of butyric anhydride and 40mg of dimethylaminopyridine into a round-bottom flask, adding 3ml of tetrahydrofuran, mixing, reacting at 50 ℃ for 10 hours to obtain a clear solution, and purifying to obtain a functional polyamide monomer 2;
(3) 1350mg of the functional polyamide monomer 2, 150mg of the functional polyamide monomer 1, 200mg of oxadithiol, 10mg of azobisisobutyronitrile catalyst and 10ml of tetrahydrofuran were added to a reaction vessel; introducing argon for 15 minutes, and then placing the mixture in an oil bath kettle at the temperature of 100 ℃ for reacting for 36 hours; purifying the reaction product to obtain the macromolecular nucleating agent;
the method is characterized in that: the polylactic acid is obtained by rapid crystallization through a melt blending or solution blending method;
the melt blending process comprises the steps of: putting 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent into a vacuum oven at 80 ℃ for drying for 10 hours for pretreatment; mixing 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent, adding the mixture into an internal mixer, and blending for 10 minutes at the temperature of 180 ℃ and the rotating speed of 200 revolutions per minute to obtain polylactic resin;
the solution blending process comprises the steps of: putting 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent into a vacuum oven at 80 ℃ for drying for 8 hours for pretreatment; mixing 98 parts of polylactic acid and 2 parts of macromolecular nucleating agent of the pretreatment material, and dissolving the mixture in a dichloromethane solvent to obtain a clear solution; and pouring the clear solution into a methanol solution, and quickly stirring to obtain the quickly crystallized polylactic resin.
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