CN113563700A - Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof - Google Patents
Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof Download PDFInfo
- Publication number
- CN113563700A CN113563700A CN202110807940.1A CN202110807940A CN113563700A CN 113563700 A CN113563700 A CN 113563700A CN 202110807940 A CN202110807940 A CN 202110807940A CN 113563700 A CN113563700 A CN 113563700A
- Authority
- CN
- China
- Prior art keywords
- hydrazide
- polylactic acid
- nucleating agent
- type nucleating
- acid composition
- 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.)
- Pending
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 63
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 63
- 239000002667 nucleating agent Substances 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002808 molecular sieve Substances 0.000 claims abstract description 10
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 16
- 230000008025 crystallization Effects 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/04—Preparation of hydrazides
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- 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
Abstract
The invention relates to a polylactic acid composition containing a hydrazide type nucleating agent and a preparation method thereof, belonging to the technical field of polylactic resin, wherein the raw materials comprise a hydrazide type nucleating agent, an antioxidant, a hydrolysis resistant agent and L-polylactic acid, and the polylactic acid composition is prepared by mixing the raw materials in a high-speed mixer and extruding and granulating the mixture by a double screw; in the preparation process, pyromellitic acid and hydrazine hydrate are used as raw materials, and hydrazide type nucleating agent with four hydrazide groups at the end group is generated by hydrazide reaction under the condition of using mordenite molecular sieve as a catalyst; the hydrazide-type nucleating agent has good compatibility with L-polylactic acid, and can improve the tensile strength of the composition; after the hydrazide-type nucleating agent and the L-polylactic acid are melted and blended, four hydrazide groups contained in the molecules of the hydrazide-type nucleating agent can form hydrogen bonds with ester bonds in the polylactic acid molecules, and can quickly form crystal nuclei in the polylactic acid, so that the aim of improving the crystallization rate and the crystallinity of the polylactic acid composition is fulfilled.
Description
Technical Field
The invention belongs to the technical field of polylactic acid resin, and particularly relates to a polylactic acid composition containing a hydrazide type nucleating agent and a preparation method thereof.
Background
Polylactic acid is a polyester, and lactic acid is a biomonomer that occurs in nature. The polylactic acid is thermoplastic, can be processed by the production process of common plastics, such as films, sheets and fibers, and is a bio-based degradable material with wide application prospect.
However, polylactic acid has a disadvantage of poor heat resistance, and the glass transition temperature of polylactic acid products obtained by various molding methods is only 55 to 65 ℃ and is difficult to satisfy practical use. After crystallization, the heat distortion temperature can be increased to more than 100 ℃, but although polylactic acid is a crystalline polymer, the polylactic acid is difficult to be fully crystallized in the actual molding process because the crystallization rate is slow.
The nucleating agent is an additive capable of promoting matrix crystallization through a nucleating effect, and can improve the nucleation density by reducing the surface free energy barrier required during the nucleation of the polylactic acid, thereby playing roles in refining the grain size, accelerating the crystallization rate, and improving the mechanical properties of the product, such as transparency, heat-resistant stability, tensile strength, flexural modulus and the like.
The hydrazide compound is mainly applied to the fields of polyolefin copper-resistant agents and polylactic acid nucleating agents at present. The dihydrazide nucleating agent which is mainstream in the market at present comprises phenyl substituted dihydrazide and aliphatic chain dihydrazide, the crystallization capacity of the dihydrazide nucleating agent is relatively weak, and in order to improve the crystallization rate of the polylactic acid resin, the invention provides a polylactic acid composition containing the hydrazide nucleating agent and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a polylactic acid composition containing a hydrazine type nucleating agent and a preparation method thereof, and solves the technical problem of how to improve the crystallization rate of a polylactic acid material.
The purpose of the invention can be realized by the following technical scheme:
a polylactic acid composition containing a hydrazide type nucleating agent comprises the following raw materials in percentage by weight: 2-5% of hydrazide nucleating agent, 0.2-1.5% of antioxidant, 0.1-1.5% of hydrolysis-resistant agent and the balance of L-polylactic acid which is supplemented to 100%;
the structural formula of the hydrazide-type nucleating agent is shown as follows:
further, the hydrazide-type nucleating agent is prepared by the following steps:
adding pyromellitic acid, excessive hydrazine hydrate and a mordenite molecular sieve into a reaction kettle, heating to 99-104 ℃ while stirring, performing hydrazide reaction, continuously separating water generated by the reaction from the reaction system until no condensed water flows out, terminating the reaction, performing reduced pressure distillation to recover excessive hydrazine hydrate, adding distilled water to dissolve a reaction product after recovery, filtering and recovering the mordenite molecular sieve, evaporating and concentrating filtrate to obtain a crude nucleating agent, and washing and drying the crude nucleating agent by absolute ethyl alcohol to obtain the hydrazide-type nucleating agent.
The reaction process is as follows:
further, the molar ratio of the pyromellitic acid to the hydrazine hydrate is 1: 4.2-4.5.
Further, the dosage of the mordenite molecular sieve is 20-40% of the mass of the pyromellitic acid.
Further, the antioxidant is any one of antioxidant 168 or antioxidant 1010.
Further, the hydrolysis-resistant agent is any one of monomer carbodiimide or polymeric carbodiimide.
Further, the L-polylactic acid is commercially available L-polylactic acid, and the L-lactic acid content is more than 90%.
A preparation method of a polylactic acid composition containing a hydrazide type nucleating agent specifically comprises the following steps:
step S1, adding all the formula raw materials into a high-speed mixer, and stirring for 10min to obtain a mixture;
and step S2, adding the mixture into a double-screw extruder for granulation, wherein the melting temperature is 180-230 ℃, the length-diameter ratio of the screw is more than 30, extruding and granulating after melting and plasticizing, and drying to obtain the polylactic acid composition.
The invention has the beneficial effects that:
in the invention, pyromellitic acid and hydrazine hydrate are used as raw materials, and the hydrazide nucleating agent with four hydrazide groups at the end group is generated by hydrazide reaction under the condition of taking a mordenite molecular sieve as a catalyst;
the hydrazide-type nucleating agent is an organic micromolecule, has good compatibility with L-polylactic acid, is beneficial to the uniform distribution of the components of the polylactic acid composition, and can improve the tensile strength of the composition; after the hydrazide-type nucleating agent and the L-polylactic acid are melted and blended, four hydrazide groups contained in the molecules of the hydrazide-type nucleating agent can form hydrogen bonds with ester bonds in the polylactic acid molecules, and can quickly form crystal nuclei in the polylactic acid, so that the aim of improving the crystallization rate and the crystallinity of the polylactic acid composition is fulfilled.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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
The hydrazide-type nucleating agent is prepared by the following steps:
adding pyromellitic acid and hydrazine hydrate into a reaction kettle according to a molar ratio of 1:4.4, simultaneously adding a mordenite molecular sieve with the mass of 30% of the pyromellitic acid, heating to 103 ℃ at the rotation speed of 300r/min while stirring, performing hydrazide reaction, continuously separating water generated by the reaction from the reaction system when steam enters a rectification column and the column top temperature is 99 ℃, stopping the reaction until no condensed water flows out, recovering excessive hydrazine hydrate by reduced pressure distillation, adding distilled water to dissolve a reaction product after recovery, filtering and recovering the mordenite molecular sieve, evaporating and concentrating filtrate to obtain a crude nucleating agent, washing and drying the crude nucleating agent by absolute ethyl alcohol to obtain the hydrazide-type nucleating agent.
Examples 2 to 7
A polylactic acid composition is prepared by the following steps:
step S1, respectively weighing L-polylactic acid, hydrazide type nucleating agent, antioxidant 1010 and polycarbodiimide according to the formula data in the following table 1, adding all the raw materials into a high-speed mixer, and stirring for 10min to obtain a mixture;
and step S2, adding the mixture into a double-screw extruder for granulation, wherein the melting temperature is 200 ℃, the length-diameter ratio of a screw is 35, extruding and granulating after melting and plasticizing, and drying to obtain the polylactic acid composition.
Comparative examples 1 to 2
A polylactic acid composition is prepared by the following steps:
step S1, respectively weighing L-polylactic acid, an antioxidant 1010 and polycarbodiimide according to the formula data shown in the following table 1, adding all the raw materials into a high-speed mixer, and stirring for 10min to obtain a mixture;
and step S2, adding the mixture into a double-screw extruder for granulation, wherein the melting temperature is 210 ℃, the length-diameter ratio of a screw is 35, extruding and granulating after melting and plasticizing, and drying to obtain the polylactic acid composition.
TABLE 1
In table 1, L-polylactic acid 175 was produced by Total Corbion, and its D body/L body mass was 1/99; l-polylactic acid 175 produced by Total Corbion, having a D body/L body mass of 4/96; antioxidant 1010 is manufactured by basf corporation; the polycarbodiimide is a polycarbodiimide hydrolysis resistant agent Stabaxol P produced by Rhine company; the hydrazide-type nucleating agent was the product prepared in example 1.
The polylactic acid compositions prepared in examples 2 to 7 and comparative examples 1 to 2 were respectively charged into molds having a nozzle temperature of 220 ℃ and a temperature of 90 ℃ and were kept for 20 seconds to prepare standard sample bars. And then testing the crystallization enthalpy, the heat distortion temperature and the tensile strength of the standard sample strip, wherein the specific testing method comprises the following steps:
and (3) determination of crystallization enthalpy: adopting a German Netzsch differential scanning calorimeter DSC 3500, operating according to GB/T19466.3-2004 'Plastic differential scanning calorimetry' standard, setting the cooling speed at 5 ℃/min, obtaining a crystallization enthalpy value through integral calculation, wherein the larger the crystallization enthalpy value is, the more effective the nucleating agent is, and the larger the crystallization rate and the crystallinity of the prepared polylactic acid are;
measurement of Heat distortion temperature: testing is carried out according to GB/T1634-1979 test method of plastic bending load thermal deformation temperature (thermal deformation temperature for short);
and (3) measuring the tensile strength: testing is carried out according to GB/T1040 + 1992 test method for tensile properties of plastics;
the specific test data are shown in table 2 below.
TABLE 2
As can be seen from the test data in Table 2, the crystallization enthalpy values of the polylactic acid compositions prepared in examples 2 to 7 are much higher than those of the polylactic acid compositions prepared in comparative examples 1 to 2, which shows that the addition of the hydrazide-type nucleating agent prepared by the invention can effectively improve the crystallization rate and the crystallinity of the polylactic acid; and the polylactic acid compositions prepared in examples 2 to 7 can endure higher heat distortion temperature and have more excellent tensile strength than the polylactic acid compositions prepared in comparative examples 1 to 2.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. A polylactic acid composition containing a hydrazide-type nucleating agent is characterized in that: comprises the following raw materials in percentage by weight: 2-5% of hydrazide nucleating agent, 0.2-1.5% of antioxidant, 0.1-1.5% of hydrolysis-resistant agent and the balance of L-polylactic acid;
the structural formula of the hydrazide-type nucleating agent is shown as follows:
2. the polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 1, wherein: the hydrazide-type nucleating agent is prepared by the following steps:
adding pyromellitic acid, hydrazine hydrate and a mordenite molecular sieve into a reaction kettle, heating to 99-104 ℃ while stirring, performing hydrazide reaction, continuously separating water generated by the reaction out of the reaction system until no condensed water flows out, terminating the reaction, performing reduced pressure distillation to recover excessive hydrazine hydrate, adding distilled water to dissolve a reaction product after recovery, filtering and recovering the mordenite molecular sieve, evaporating and concentrating filtrate to obtain a crude nucleating agent, and washing and drying the crude nucleating agent by absolute ethyl alcohol to obtain the hydrazide-type nucleating agent.
3. The polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 2, wherein: the molar ratio of the pyromellitic acid to the hydrazine hydrate is 1: 4.2-4.5.
4. The polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 2, wherein: the dosage of the mordenite molecular sieve is 20-40% of the mass of pyromellitic acid.
5. The polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 1, wherein: the antioxidant is one of antioxidant 168 or antioxidant 1010.
6. The polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 1, wherein: the hydrolysis-resistant agent is any one of monomer carbodiimide or polymeric carbodiimide.
7. The polylactic acid composition containing the hydrazide-type nucleating agent as claimed in claim 1, wherein: the L-polylactic acid has an L-lactic acid content of more than 90%.
8. The method for preparing a polylactic acid composition containing a hydrazide-type nucleating agent as claimed in claim 1, which comprises the following steps:
step S1, adding all the formula raw materials into a high-speed mixer, and stirring for 10min to obtain a mixture;
and step S2, adding the mixture into a double-screw extruder, extruding and granulating after melting and plasticizing, and drying to obtain the polylactic acid composition.
9. The method for preparing a polylactic acid composition containing a hydrazide-type nucleating agent as claimed in claim 8, wherein the melting temperature is 180 ℃ and 230 ℃, and the length-diameter ratio of the screw of the twin-screw extruder is greater than 30.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110807940.1A CN113563700A (en) | 2021-07-16 | 2021-07-16 | Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110807940.1A CN113563700A (en) | 2021-07-16 | 2021-07-16 | Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113563700A true CN113563700A (en) | 2021-10-29 |
Family
ID=78165235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110807940.1A Pending CN113563700A (en) | 2021-07-16 | 2021-07-16 | Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113563700A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115477834A (en) * | 2022-09-26 | 2022-12-16 | 广东祥利科技有限公司 | Inorganic nucleating agent capable of being rapidly crystallized and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102190813A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院宁波材料技术与工程研究所 | Nucleating agent, its preparation method and application |
CN107810228A (en) * | 2015-06-22 | 2018-03-16 | 3M创新有限公司 | Hydrazide compound suitable for being nucleated polylactic acid polymer |
CN108191704A (en) * | 2018-01-26 | 2018-06-22 | 重庆晶萃化工科技有限公司 | A kind of method for synthesizing acethydrazide |
-
2021
- 2021-07-16 CN CN202110807940.1A patent/CN113563700A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102190813A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院宁波材料技术与工程研究所 | Nucleating agent, its preparation method and application |
CN107810228A (en) * | 2015-06-22 | 2018-03-16 | 3M创新有限公司 | Hydrazide compound suitable for being nucleated polylactic acid polymer |
CN108191704A (en) * | 2018-01-26 | 2018-06-22 | 重庆晶萃化工科技有限公司 | A kind of method for synthesizing acethydrazide |
Non-Patent Citations (1)
Title |
---|
LI-SHA ZHAO ET AL.: ""Physical properties of Poly(L-lactic acid) fabricated using salicylic hydrazide derivative with tetraamide structure"", 《POLYMER-PLASTICS TECHNOLOGY AND MATERIALS》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115477834A (en) * | 2022-09-26 | 2022-12-16 | 广东祥利科技有限公司 | Inorganic nucleating agent capable of being rapidly crystallized and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN85100465A (en) | Beta-crystalline polyacrylic, production method and application | |
EP3037460B1 (en) | Shaped polylactide article and method of preparation | |
CN113429768B (en) | Polylactic acid composition containing amide nucleating agent and preparation method thereof | |
WO2024045338A1 (en) | Granulation processing method for degradable material and formed body prepared thereby | |
CN102558679A (en) | Novel bamboo fiber/polypropylene composite material and method for preparing same | |
CN113583407B (en) | Polylactic acid composition containing carboxylate nucleating agent and preparation method thereof | |
CN115232456B (en) | Polyhydroxyalkanoate composition containing hydroxy acid nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof | |
CN112143103A (en) | Cage-type silsesquioxane modified polypropylene composite material and preparation method thereof | |
CN114230986A (en) | Stereo composite crystal reinforced biodegradable material | |
WO2024007494A1 (en) | Polyhydroxyalkanoate molded body and preparation method therefor | |
WO2023231732A1 (en) | Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method therefor | |
CN113563700A (en) | Polylactic acid composition containing hydrazide type nucleating agent and preparation method thereof | |
CN111534064A (en) | Polylactic acid with high stereospecific composite content and preparation method thereof | |
CN107974025B (en) | Non-filling low-shrinkage polypropylene composite material and preparation method thereof | |
CN113429767B (en) | Polylactic acid composition containing imidazole type nucleating agent and preparation method thereof | |
CN117464947A (en) | High-temperature-resistant polylactic acid biaxially oriented film and preparation method thereof | |
WO2024060636A1 (en) | Polyhydroxyalkanoate composition containing ester nucleating agent, polyhydroxyalkanoate molded body, and preparation method therefor | |
CN107474495B (en) | Modified PBAT resin composition and preparation method thereof | |
CN114058123B (en) | Masterbatch for polyolefin film, preparation method, polyolefin film and BOPP film | |
CN113502041A (en) | Polylactic acid composition containing phosphate nucleating agent and preparation method thereof | |
CN111087726B (en) | High-viscosity polyvinyl alcohol composition, and preparation method and application thereof | |
CN108219291B (en) | Polypropylene resin suitable for preparing hollow product by blow molding process and preparation method thereof | |
CN113429762A (en) | Starch/polylactic acid/PBAT nano composite material and preparation method thereof | |
CN111454571A (en) | Preparation method of glass fiber reinforced PA56/PP alloy material | |
CN111269568A (en) | Complex type nylon nucleating agent, compound containing complex type nylon nucleating agent and preparation method of complex |
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 | ||
TA01 | Transfer of patent application right |
Effective date of registration: 20220714 Address after: 412000 room 01, building C2, phase 3-1, power Valley Independent Innovation Park, No. 899, Xianyue Ring Road, Tianyuan District, Zhuzhou City, Hunan Province Applicant after: Hunan yueshengjie Technology Co.,Ltd. Address before: 412000 No. 88 Taishan West Road, Zhuzhou City, Hunan Province Applicant before: HUNAN University OF TECHNOLOGY |
|
TA01 | Transfer of patent application right | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211029 |
|
RJ01 | Rejection of invention patent application after publication |