CN112759905B - Halogen-free flame-retardant polylactic acid mixture - Google Patents
Halogen-free flame-retardant polylactic acid mixture Download PDFInfo
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- CN112759905B CN112759905B CN201911057414.7A CN201911057414A CN112759905B CN 112759905 B CN112759905 B CN 112759905B CN 201911057414 A CN201911057414 A CN 201911057414A CN 112759905 B CN112759905 B CN 112759905B
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- antioxidant
- polylactic acid
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- retardant
- pla
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free flame-retardant polylactic acid PLA mixture, which comprises (A) at least one PLA polylactic acid resin as a component A (B) and at least one flame retardant as a component B, wherein the flame retardant is selected from the group consisting of: organic phosphinate compounds, hypophosphites, phosphate compounds, phosphazenes, melamine compounds, and mixtures thereof. (C) At least one flame retardant synergist as component C, said flame retardant synergist being selected from the group consisting of: montmorillonite, zinc oxide, calcium oxide, mica powder, polysiloxane, and mixtures thereof. (D) An anti-drip agent as component D, said anti-drip agent being: polytetrafluoroethylene micropowder. (E) At least one antioxidant as component E, said antioxidant being selected from the group consisting of: antioxidant 1010, antioxidant 168, antioxidant 264, and mixtures thereof.
Description
Technical Field
The invention relates to the technical field of PLA (polylactic acid) resins, in particular to a halogen-free flame-retardant polylactic acid PLA resin.
Background
Polylactic acid resin PLA is a biodegradable polymer material derived from renewable crops, has the advantages of excellent mechanical property, good biocompatibility, easy processing and forming and the like, and is a material which is recognized as being capable of replacing petroleum-based polymers to a certain extent. However, PLA is easy to burn and has serious dripping phenomenon during burning, which limits its application in the fields of electronic products, automotive upholstery, sanitary articles, and the like, so that flame retardant modification is required. Traditional halogen flame-retardant PLA can release a large amount of black smoke when burning, even generates extremely toxic dioxin substances, and is contrary to the original purpose of green and environment-friendly PLA. The traditional halogen-free flame-retardant PLA material generally adopts ammonium polyphosphate APP as an acid source, melamine and derivatives as an air source, and PLA or lignin as a carbon source to form the composite intumescent flame-retardant material, so that a good flame-retardant effect is achieved. However, APP is very hygroscopic, while PLA is easily degraded in a humid environment, so the PLA market has a need for a solution for non-hygroscopic halogen-free flame retardant PLA material.
The invention overcomes the defects of the traditional flame-retardant PLA material and adopts the combination of a plurality of non-hygroscopic flame retardants to prepare the non-hygroscopic halogen-free flame-retardant PLA material.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a halogen-free flame-retardant polylactic acid material which has the advantages of good flame retardant effect, low moisture absorption rate and the like, and solves the problem of contradiction between flame retardance and moisture absorption.
Technical proposal
In order to achieve the above purpose, the present invention provides the following technical solutions: a halogen-free flame retardant polylactic acid, PLA, material comprising at least one PLA resin; at least one flame retardant; at least one flame retardant synergist; an anti-drip agent; at least one antioxidant.
Comprising wherein the polylactic acid is selected from the group consisting of: PDLA, PLLA, PDLLA.
Wherein the flame retardant is selected from: the organic phosphinate compound is preferably aluminum diethylphosphinate, the hypophosphite salt is preferably aluminum hypophosphite, the phosphate compound is preferably a cyclic phosphate, the phosphazene is preferably a phenoxy polyphosphazene, the melamine compound is preferably melamine cyanurate MCA, and mixtures thereof.
The flame retardant synergist is selected from the group consisting of: montmorillonite, zinc oxide, calcium oxide, mica powder, polysiloxane, white carbon black, and a mixture thereof.
The anti-dripping agent is as follows: polytetrafluoroethylene micropowder.
The antioxidant is selected from the group consisting of: antioxidant 1010, antioxidant 168, antioxidant 264 and mixtures thereof.
(III) beneficial effects
Compared with the prior art, the invention provides a halogen-free flame-retardant polylactic acid PLA material, which has the following beneficial effects:
the raw materials of the various components of the material are all materials with extremely low moisture absorption rate, the hydrolysis of the polylactic acid PLA material caused by the moisture absorption of the flame retardant is avoided, and the mechanical properties of the polylactic acid PLA are ensured and meanwhile, the material has good flame retardance and non-hygroscopicity through the synergistic effect of the components. The decomposition temperature of each component raw material of the material is far higher than the processing and using temperature of the PLA material, and after the components are matched, chemical reaction is not generated at the processing and using temperature, so that the material has good thermal stability, and the quality stability of the prepared polylactic acid PLA material is ensured.
Detailed Description
The invention is further illustrated below in connection with specific embodiments.
Example 1: the invention provides a halogen-free flame-retardant polylactic acid PLA material, which comprises the following raw materials in parts by weight:
| PLLA | 75 |
| diethyl phosphinic acid aluminum | 5 |
| Melamine cyanurate | 10 |
| Organic nano montmorillonite | 5 |
| Polysiloxane | 5 |
| Antioxidant 1010 | 0.1 |
| Antioxidant 168 | 0.1 |
| Antioxidant 264 | 0.05 |
| PTFE micropowder | 0.2 |
Example 2: the invention provides a halogen-free flame-retardant polylactic acid PLA material, which comprises the following raw materials in parts by weight:
| PDLA | 70 |
| phenoxy polyphosphazenes | 15 |
| Melamine cyanurate | 10 |
| Organic nano montmorillonite | 5 |
| Antioxidant 1010 | 0.12 |
| Antioxidant 168 | 0.12 |
| Antioxidant 264 | 0.06 |
| PTFE micropowder | 0.2 |
Example 3: the invention provides a halogen-free flame-retardant polylactic acid PLA material, which comprises the following raw materials in parts by weight:
| PDLLA | 70 |
| cyclic phosphate esters | 10 |
| Aluminum hypophosphite | 5 |
| Melamine cyanurate | 10 |
| Nanometer mica powder | 4 |
| White carbon black | 1 |
| Antioxidant 1010 | 0.12 |
| Antioxidant 168 | 0.12 |
| Antioxidant 264 | 0.06 |
| PTFE micropowder | 0.2 |
Experimental example 4: the invention provides a halogen-free flame-retardant polylactic acid PLA material, which comprises the following raw materials in parts by weight:
| PLLA | 70 |
| phenoxy polyphosphazenes | 5 |
| Diethyl phosphinic acid aluminum | 10 |
| Melamine cyanurate | 10 |
| Organic nano montmorillonite | 5 |
| Antioxidant 1010 | 0.1 |
| Antioxidant 168 | 0.1 |
| Antioxidant 264 | 0.05 |
| PTFE micropowder | 0.2 |
Experimental example 5: the invention provides a halogen-free flame-retardant polylactic acid PLA material, which comprises the following raw materials in parts by weight:
| PLLA | 70 |
| diethyl phosphinic acid aluminum | 5 |
| Phenoxy polyphosphazenes | 5 |
| Cyclic phosphate esters | 5 |
| Melamine cyanurate | 5 |
| Organic nano montmorillonite | 3 |
| Zinc oxide | 2 |
| Polysiloxane | 5 |
| Antioxidant 1010 | 0.12 |
| Antioxidant 168 | 0.12 |
| Antioxidant 264 | 0.06 |
| PTFE micropowder | 0.2 |
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (1)
1. The halogen-free flame-retardant polylactic acid PLA material is characterized by comprising the following raw materials in parts by weight:
PLLA 70；
aluminum diethylphosphinate 5;
phenoxy polyphosphazene 5;
cyclic phosphate 5;
melamine cyanurate 5;
organic nano montmorillonite 3;
zinc oxide 2;
a polysiloxane 5;
antioxidant 1010.12;
antioxidant 168.12;
antioxidant 264.06;
PTFE micropowder 0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911057414.7A CN112759905B (en) | 2019-11-01 | 2019-11-01 | Halogen-free flame-retardant polylactic acid mixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911057414.7A CN112759905B (en) | 2019-11-01 | 2019-11-01 | Halogen-free flame-retardant polylactic acid mixture |
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| Publication Number | Publication Date |
|---|---|
| CN112759905A CN112759905A (en) | 2021-05-07 |
| CN112759905B true CN112759905B (en) | 2023-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201911057414.7A Active CN112759905B (en) | 2019-11-01 | 2019-11-01 | Halogen-free flame-retardant polylactic acid mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115637032B (en) * | 2021-07-20 | 2024-06-11 | 北京服装学院 | Heat-resistant flame-retardant polylactic acid material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176032A (en) * | 2015-08-08 | 2015-12-23 | 同济大学 | Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof |
| CN105694405A (en) * | 2016-04-28 | 2016-06-22 | 青岛科技大学 | Halogen-free flame retardant polylactic acid toughening modification composite material and preparing method thereof |
| CN105968753A (en) * | 2016-05-04 | 2016-09-28 | 北京工商大学 | Phosphonitrile/triazine double-group molecular synergistic flame retardation polylactic acid composite material and preparation method thereof |
| CN109401254A (en) * | 2018-11-30 | 2019-03-01 | 广东顺德优线三维科技有限公司 | A kind of halogen-free flame-proof polylactic acid material and preparation method thereof for 3D printing |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007035417A1 (en) * | 2007-07-28 | 2009-01-29 | Chemische Fabrik Budenheim Kg | Halogen-free flame retardant |
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- 2019-11-01 CN CN201911057414.7A patent/CN112759905B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176032A (en) * | 2015-08-08 | 2015-12-23 | 同济大学 | Halogen-free flame retardant polylactic acid nanocomposite and preparation method thereof |
| CN105694405A (en) * | 2016-04-28 | 2016-06-22 | 青岛科技大学 | Halogen-free flame retardant polylactic acid toughening modification composite material and preparing method thereof |
| CN105968753A (en) * | 2016-05-04 | 2016-09-28 | 北京工商大学 | Phosphonitrile/triazine double-group molecular synergistic flame retardation polylactic acid composite material and preparation method thereof |
| CN109401254A (en) * | 2018-11-30 | 2019-03-01 | 广东顺德优线三维科技有限公司 | A kind of halogen-free flame-proof polylactic acid material and preparation method thereof for 3D printing |
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