CN112745587B - Flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer composition, elastomer, and preparation method and application thereof - Google Patents
Flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer composition, elastomer, and preparation method and application thereof Download PDFInfo
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- CN112745587B CN112745587B CN201911050442.6A CN201911050442A CN112745587B CN 112745587 B CN112745587 B CN 112745587B CN 201911050442 A CN201911050442 A CN 201911050442A CN 112745587 B CN112745587 B CN 112745587B
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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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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Abstract
The invention relates to the flame retardant field of ethylene propylene diene monomer/polylactic acid thermoplastic elastomer materials. Discloses a composition for preparing a flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, the elastomer, a preparation method and application thereof. The composition comprises the following components in parts by weight: 100 parts of ethylene propylene diene monomer, 30-100 parts of polylactic acid, 0.5-10 parts of vulcanizing agent, 40-100 parts of flame retardant system, 1-15 parts of compatibilizer, 0.5-5 parts of anti-aging agent and 0.1-10 parts of antioxidant; wherein the flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant. The ethylene propylene diene monomer/polylactic acid thermoplastic vulcanizate prepared by the composition has good flame retardance and impact resistance.
Description
Technical Field
The invention relates to the flame retardant field of ethylene propylene diene monomer/polylactic acid thermoplastic elastomer materials, in particular to a flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer composition, a method for preparing the flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer by adopting a dynamic vulcanization method through the composition, the flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer prepared by the method, and application of the elastomer in automobile materials.
Background
Polylactic acid (PLA) is a high polymer material which is prepared by using crops rich in starch, such as corn, wheat, cassava and the like as raw materials, fermenting the starch to generate lactic acid, and performing a polymerization reaction process, and belongs to thermoplastic straight-chain aliphatic polyester. Compared with the traditional plastics, the polylactic acid has the following advantages: the raw materials are rich in source, and the composite material has good biocompatibility and biodegradability, transparency and processability. However, polylactic acid also has the defects of poor toughness and impact resistance.
The ethylene propylene diene monomer/polylactic acid thermoplastic elastomer is prepared by using a dynamic vulcanization method, the impact resistance of polylactic acid is improved, and the method is a feasible method. The dynamic vulcanization refers to that under the conditions of high temperature and high shear, rubber is vulcanized under the action of a crosslinking agent and is crushed and dispersed into a plastic continuous phase, and finally a micron-sized vulcanized rubber phase is formed in the plastic continuous phase. TPVs successfully combine the properties of vulcanized rubber, such as heat resistance and low compression set, with the easy processability of thermoplastics, and are environmentally friendly, recyclable and widely applicable.
The ethylene propylene diene monomer/polylactic acid thermoplastic elastomer material prepared by the dynamic vulcanization method has good impact resistance and processability, and can be applied to the fields of automobile interior and exterior trim, rail transit and the like.
However, both Ethylene Propylene Diene Monomer (EPDM) and polylactic acid are easily burned in air, and generate a large amount of smoke and toxic gases when burned. The automotive industry therefore places stringent flame retardant requirements on the plastics and rubber materials used.
Disclosure of Invention
The invention aims to solve the flame retardant problem of an ethylene propylene diene monomer/polylactic acid thermoplastic elastomer material, and provides a composition for preparing a flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, the flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, and a preparation method and application thereof. The provided composition is dynamically vulcanized to prepare particles of the flame-retardant thermoplastic elastomer, and has good flame retardance and impact resistance.
In order to achieve the purpose of the invention, the first aspect of the invention provides a composition for preparing a flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, which is characterized by comprising the following components in parts by weight:
wherein the flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant.
Preferably, the phosphorus-nitrogen halogen-free intumescent flame retardant is one or more of ammonium polyphosphate, pentaerythritol, dipentaerythritol, polypentaerythritol, zinc borate, zinc acetate and melamine.
In a second aspect, the present invention provides a method for preparing flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer from the composition of the present invention, comprising:
(1) sequentially adding polylactic acid, an anti-aging agent and an antioxidant into blending equipment at 160-; extruding and granulating the mixed material through a single-screw extruder to obtain mixed material particles;
(2) and respectively adding the mixed material particles, the vulcanizing agent and the flame-retardant system into a double-screw extruder for dynamic vulcanization and granulation to obtain the particles of the thermoplastic elastomer obtained through dynamic vulcanization.
The third aspect of the invention provides a flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer prepared by the method.
The invention provides the application of the flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer in automobile materials.
Through the technical scheme, the composition for preparing the flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer can be suitable for preparing the flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer by adopting a dynamic vulcanization method. The elastomer has good flame retardance, good tensile strength, wear resistance and excellent solvent resistance, also has the performances of high elasticity, easy processing, repeated processing and the like, and can be used for oil pipelines and sealing parts of automobiles.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a composition for preparing a flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer, which is characterized by comprising the following components in parts by weight:
wherein the flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant.
In the present invention, the composition described above is added with other components with respect to 100 parts by weight of ethylene propylene diene monomer.
According to the present invention, preferably, the phosphorus-nitrogen halogen-free intumescent flame retardant is one or more of ammonium polyphosphate, pentaerythritol, dipentaerythritol, polypentaerythritol, zinc borate, zinc acetate and melamine. The flame retardant is selected to provide the flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer with good mechanical property, impact resistance and flame retardance.
In the invention, the total weight of the ethylene propylene diene monomer is taken as a reference, wherein the content of ethylene is 50-75 wt%, and the content of ethylidene norbornene or ethylene norbornene is 2-10 wt%. The ethylene-propylene-diene monomer rubber is commercially available, for example, EPT 3092PM (ethylene content 65 wt%, ethylidene norbornene content 4.6 wt%) from Mitsui corporation, Japan.
According to the invention, preferably, the vulcanizing agent is an organic peroxide selected from dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 2, 5-bis (t-butylperoxy) -2, 5-dimethyl-3-hexyne, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, dibenzoyl peroxide, t-butyl peroxybenzoate or di-t-butyl peroxide.
According to the present invention, preferably, the polylactic acid selected is one or more of levorotatory polylactic acid, dextrorotatory polylactic acid and racemic polylactic acid.
According to the invention, the compatibilizer is preferably an aromatic diisocyanate and/or an aliphatic diisocyanate.
According to the invention, the anti-aging agent is preferably one or more of 2,2, 4-trimethyl-1, 2-dihydrooumarin, and the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol, 2-methylenebis (4-methyl-6-tert-butylphenol) and 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
In a second aspect, the present invention provides a method for preparing flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer from the composition of the present invention, comprising:
(1) sequentially adding polylactic acid, an anti-aging agent and an antioxidant into blending equipment at 160-; extruding and granulating the mixed material through a single-screw extruder to obtain mixed material particles;
(2) and respectively adding the mixing material particles, the vulcanizing agent and the flame-retardant system into a double-screw extruder for dynamic vulcanization and granulation to obtain the thermoplastic elastomer particles (TPV particles) obtained through dynamic vulcanization.
According to the present invention, preferably, the blending apparatus is an internal mixer; the rotor speed of the internal mixer is 60-90 rpm.
According to the invention, preferably, in the single-screw extruder, the length-diameter ratio of the screw is 10-20, the rotation speed of the screw is 50-200rpm, and the extrusion granulation temperature is 160-220 ℃.
According to the invention, preferably, the double-screw extruder is a co-rotating meshed double-screw extruder, the length-diameter ratio of the double screws is 32-40, the rotating speed of the double screws is 50-200rpm, the main feeding speed is 30-50rpm, the head temperature is 170-.
According to the invention, the preparation equipment and the preparation method can be used for preparing the flame-retardant EPDM/polylactic acid thermoplastic elastomer composition, and the thermoplastic elastomer obtained through dynamic vulcanization is prepared.
The third aspect of the invention provides a flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer prepared by the method. Wherein the elastomer is flame retardant and the measured oxygen index of the elastomer is higher than 32%.
The invention provides the application of the flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer in automobile materials.
The present invention will be described in detail below by way of examples.
The polylactic acid in the following examples and comparative examples is 4032D from Natureworks, usa;
ethylene propylene diene monomer is EPT 3092PM (ethylene content 65 wt%, ethylidene norbornene content 4.6 wt%) available from Mitsui, Japan;
the vulcanizing agent is dicumyl peroxide;
the flame retardant is ammonium polyphosphate;
the anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydrojavanine;
the compatibilizer is diphenylmethane diisocyanate;
the antioxidant is prepared from the following components in percentage by weight: 1 antioxidant 1010 and antioxidant 168.
Examples 1 to 8
Flame retardant EPDM/polylactic acid thermoplastic elastomers P1-P8 were obtained according to the formulation given in Table 1 and the following procedure.
(1) Sequentially adding 4032D, an anti-aging agent (2,2, 4-trimethyl-1, 2-dihydrojalin) and an antioxidant (an antioxidant 1010 and an antioxidant 168 in a weight ratio of 1: 1) into an internal mixer at the temperature of 200 ℃, adding ethylene propylene diene monomer (EPT 3092PM) and a compatibilizer (diphenylmethane diisocyanate) after the polylactic acid is molten, carrying out melt blending to obtain a mixed material, and carrying out extrusion granulation on the mixed material through a single-screw extruder to obtain mixed material particles.
(2) Adopting a co-rotating meshed double-screw extruder, wherein the rotating speed of a screw is 100rpm, the main feeding speed is 40rpm, the temperature of a machine head is 180 ℃, the temperature of a screw feeding section is 150 ℃, the temperature of a melting and mixing section is 180 ℃, adding mixing material particles, a vulcanizing agent (dicumyl peroxide) and a flame retardant (ammonium polyphosphate), dynamically vulcanizing and extruding, and granulating to obtain the TPV particles.
Comparative example 1
The procedure of example 1 and the formulation of elastomer P1 were followed except that the compatibilizer was used in an amount of 0 parts by weight. TPV particles DP1 were obtained.
Comparative example 2
The process of example 1 and the formulation of elastomer P1 were followed except that the vulcanizing agent was used in an amount of 0 parts by weight. TPV particles DP2 were obtained.
Comparative example 3
The procedure of example 1 and the formulation of elastomer P1 were followed except that the flame retardant was used in an amount of 0 parts by weight. TPV particles DP3 were obtained.
Comparative example 4
The procedure of example 1 and the formulation of elastomer P1 were followed except that 45 parts by weight of antimony oxide was used as the flame retardant. TPV particles DP4 were obtained.
TABLE 1
Note: the amounts of the components in the table are parts by weight.
Test example
The tensile strength, elongation at break, compression set and percent volume swell of the elastomers P1-P8 and DP1-DP7, respectively, were measured and are shown in Table 2, wherein:
tensile strength, elongation at break were tested according to the method in GB/T528-2009.
Notched impact strength was tested according to the method in GB/T1843-2008.
The oxygen index is measured according to the method in ASTM 2863. Refers to the minimum oxygen concentration required for the material to undergo flaming combustion in a flow of oxygen-nitrogen mixture under specified conditions. Expressed as a volume percentage of oxygen. A high oxygen index indicates that the material is not readily combustible, and a low oxygen index indicates that the material is readily combustible.
TABLE 2
| Elastic body | Tensile strength MPa | Elongation at break％ | Notched impact strength kJ/m 2 | Oxygen index/% |
| P1 | 21.3 | 253 | 8.6 | 34 |
| P2 | 19.5 | 203 | 8.3 | 32 |
| P3 | 23.2 | 215 | 9.2 | 35 |
| P4 | 18.9 | 246 | 7.9 | 36 |
| P5 | 20.8 | 273 | 8.1 | 33 |
| P6 | 10.4 | 211 | 9.6 | 38 |
| P7 | 22.3 | 232 | 7.6 | 32 |
| P8 | 23.5 | 267 | 10.3 | 34 |
| DP1 | 10.8 | 125 | 4.1 | 26 |
| DP2 | 9.7 | 81 | 3.9 | 28 |
| DP3 | 18.5 | 178 | 4.8 | 22 |
| DP4 | 15.5 | 135 | 5.2 | 25 |
As can be seen from Table 2, the elastomer obtained by using the composition of the present invention can obtain suitable tensile strength, elongation at break hardness and notched impact strength, thereby showing that the elastomer obtained by using the composition of the present invention can simultaneously have excellent mechanical properties, impact resistance and flame retardant properties.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. The flame-retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer composition is characterized by comprising the following components in parts by weight:
ethylene propylene diene monomer 100 parts
30-100 parts of polylactic acid
0.5 to 10 portions of vulcanizing agent
40-100 parts of flame-retardant system
1-15 parts of compatibilizer
0.5 to 5 portions of anti-aging agent
0.1-10 parts of antioxidant;
wherein the flame retardant system is a phosphorus-nitrogen halogen-free intumescent flame retardant;
the phosphorus-nitrogen halogen-free expansion flame retardant is ammonium polyphosphate;
the compatibilizer is aromatic diisocyanate and/or aliphatic diisocyanate.
2. The composition according to claim 1, wherein the vulcanizing agent is an organic peroxide selected from dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, 2, 5-bis (t-butylperoxy) -2, 5-dimethyl-3-hexyne, 2, 5-bis (t-butylperoxy) -2, 5-dimethylhexane, dibenzoyl peroxide, t-butyl peroxybenzoate or di-t-butyl peroxide.
3. The composition of claim 1, wherein the selected polylactic acid is one or more of levorotatory polylactic acid, dextrorotatory polylactic acid, and racemic polylactic acid;
the anti-aging agent is 2,2, 4-trimethyl-1, 2-dihydrojalin, and the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol, 2-methylenebis (4-methyl-6-tert-butylphenol) and 1,1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
4. A method of preparing a flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer from the composition of any one of claims 1 to 3, comprising:
(1) sequentially adding polylactic acid, an anti-aging agent and an antioxidant into blending equipment at 160-; extruding and granulating the mixed material through a single-screw extruder to obtain mixed material particles;
(2) and respectively adding the mixed material particles, the vulcanizing agent and the flame-retardant system into a double-screw extruder for dynamic vulcanization and granulation to obtain the particles of the thermoplastic elastomer obtained through dynamic vulcanization.
5. The method of claim 4, wherein the blending apparatus is an internal mixer; the rotor speed of the internal mixer is 60-90 rpm.
6. The method as claimed in claim 4, wherein in the single-screw extruder, the length-diameter ratio of the screw is 10-20, the rotation speed of the screw is 50-200rpm, and the extrusion granulation temperature is 160-220 ℃.
7. The method as claimed in claim 4, wherein the twin-screw extruder is a co-rotating intermeshing twin-screw extruder, the length-diameter ratio of twin-screws is 32-40, the rotation speed of twin-screws is 50-200rpm, the main feeding speed is 30-50rpm, the head temperature is 170-200 ℃, the temperature of the feeding section of the twin-screw extruder is 120-170 ℃, and the temperature of the melting and mixing section is 180-200 ℃.
8. A flame retardant EPDM/PLA thermoplastic elastomer made by the process of any one of claims 5-7.
9. Use of the flame retardant ethylene propylene diene monomer/polylactic acid thermoplastic elastomer according to claim 8 in automotive materials.
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| CN102675754A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Halogen-free flame-retardant ethylene-propylene-diene monomer rubber material and preparation method thereof |
| CN103709720A (en) * | 2013-11-28 | 2014-04-09 | 青岛科技大学 | Polyurethane/polylactic acid thermoplastic vulcanized rubber and preparation method thereof |
| CN104130490A (en) * | 2014-07-04 | 2014-11-05 | 江南大学 | Thermoplastic vulcanized rubber based on polylactic acid, 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675754A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Halogen-free flame-retardant ethylene-propylene-diene monomer rubber material and preparation method thereof |
| CN103709720A (en) * | 2013-11-28 | 2014-04-09 | 青岛科技大学 | Polyurethane/polylactic acid thermoplastic vulcanized rubber and preparation method thereof |
| CN104130490A (en) * | 2014-07-04 | 2014-11-05 | 江南大学 | Thermoplastic vulcanized rubber based on polylactic acid, 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 |
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