CN112679863A - Flame-retardant polypropylene composite material and preparation method and application thereof - Google Patents
Flame-retardant polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN112679863A CN112679863A CN202011536780.3A CN202011536780A CN112679863A CN 112679863 A CN112679863 A CN 112679863A CN 202011536780 A CN202011536780 A CN 202011536780A CN 112679863 A CN112679863 A CN 112679863A
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Abstract
The invention discloses a flame-retardant polypropylene composite material which comprises the following components in parts by weight: 100 parts of polypropylene resin; 20-50 parts of ammonium polyphosphate; 4-10 parts of triazine charring agent; 3-10 parts of low-melting-point ester polymer; the melting point of the low-melting-point ester polymer is lower than that of the polypropylene resin. According to the invention, the ester polymer with the melting point lower than that of polypropylene is adopted, and is melted before the polypropylene in the melt extrusion process, and the flame retardant is wrapped, so that the flame retardant is uniformly distributed in the resin matrix of the flame-retardant polypropylene composition, is not easy to migrate and separate out after being baked at high temperature for a long time, and has the advantage of good flame retardant property.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant polypropylene composite material and a preparation method and application thereof.
Background
Polypropylene is one of the most widely used general plastics due to its excellent comprehensive properties, good cost performance and wider processing and forming conditions. The polypropylene is a typical flammable material, the limiting oxygen index of the polypropylene is 17-18%, the polypropylene is extremely easy to burn and cannot be self-extinguished after being ignited, and the polypropylene material must be subjected to flame retardant modification along with the gradual increase of the safety requirement of the material.
The flame retardant for polypropylene is mainly divided into a brominated flame retardant and a halogen-free flame retardant, the brominated flame retardant is a main flame retardant of polypropylene resin, and the brominated flame retardant has the advantages of high flame retardant efficiency, excellent heat resistance, small influence on physical properties and the like, but the brominated flame retardant generally needs to be used together with an antimony compound (mainly antimony trioxide), and has the defects of high smoke density, high toxicity and the like during combustion. In addition, antimony brings some risks of environmental protection and carcinogenesis, and causes environmental pollution and harm to the safety of workers in the production and processing processes, so that the application limit is more limited.
In the existing flame-retardant modified polypropylene material, in order to meet the requirements of low smoke density and no halogenation, a flame retardant containing phosphorus and nitrogen or a compound system of the phosphorus and nitrogen is required to be added, ammonium polyphosphate is mainly used, and a char forming agent and a synergist are used as auxiliary materials, so that the ammonium polyphosphate halogen-free flame-retardant system has the defects of large addition amount, low flame-retardant efficiency, poor physical properties and easiness in precipitation, and particularly oily and powdery precipitates are easily generated on the surface of a product under the high-temperature and high-humidity environment condition, so that the wide application of the ammonium polyphosphate halogen-free flame-retardant system is greatly limited. In recent years, with the increasing application demand of downstream industries on materials, the materials are expected to have good flame retardant efficiency, lower smoke density and excellent appearance performance, and particularly, no obvious foreign matters can be separated out from the surfaces of products in a long-term process, so that although a halogen-free ammonium polyphosphate flame retardant system has lower smoke emission, the migration-resistant separation performance is difficult to meet the downstream requirements.
Disclosure of Invention
The invention aims to provide a flame-retardant polypropylene composite material which has the advantages of good flame-retardant property and difficult precipitation of a flame retardant.
The invention also aims to provide a preparation method of the flame-retardant polypropylene composite material.
The invention is realized by the following technical scheme:
the flame-retardant polypropylene composite material comprises the following components in parts by weight:
100 parts of polypropylene resin;
20-50 parts of ammonium polyphosphate;
4-10 parts of triazine charring agent;
3-10 parts of low-melting-point ester polymer;
the melting point of the low-melting-point ester polymer is lower than that of the polypropylene resin.
Preferably, the composition comprises the following components in parts by weight:
100 parts of polypropylene resin;
20-50 parts of ammonium polyphosphate;
6-8 parts of triazine charring agent;
5-8 parts of low-melting-point ester polymer.
The low-melting-point ester polymer is at least one selected from polybutylene succinate, polybutylene succinate-adipate, polybutylene adipate/terephthalate and polycaprolactone.
Preferably, the melting point of the low-melting-point ester polymer is lower than 140 ℃; the low-melting-point ester polymer with the melting point lower than 140 ℃ is PBS (floating at about 114 ℃), PBSA (floating at about 100 ℃), PBAT (floating at about 115 ℃) and PCL (floating at about 60 ℃).
More preferably, the melting point of the low-melting ester polymer is less than 100 ℃. The low-melting-point ester polymer with the melting point lower than 100 ℃ is PCL.
Due to poor compatibility with polypropylene, if the addition amount is too high, the low melting point ester polymer will reduce flame retardancy and precipitation resistance of the flame retardant.
The viscosity average molecular weight of the low-melting-point ester polymer is 10000-200000.
The flame retardant mechanism of triazine char-forming agents is the formation of a foamy char layer during high temperature combustion. Based on this mechanism, the triazine char-forming agent of the present invention is not particularly limited as long as it is an organic substance having a triazine ring in its molecular structure. The triazine charring agent can be 2, 4-diamino-6-hydroxyethylamino-1, 3, 5-triazine, triazine ring-containing compounds, tris (phosphaphenanthrene- (hydroxymethyl) -phenoxy) -1,3, 5-triazine, 2-chloro-4, 6-bis (3-triethoxysilyl-1-aminopropyl) -1,3, 5-triazine, 2,4, 6-tris (ethoxy-phenylphosphinoyl) -1,3, 5-triazine, tris { 2-chloro-3- [ tris (dichloropropoxy) siloxy-xy-1, 3, 5-triazine]Propyl isocyanurate, poly (4, 6-dichloro-N-butyl-1, 3, 5-triazine-2-amino-ethylenediamine), 3- (ethyl methacrylate) -9- (4, 6-diamino-1, 3, 5-triazine) amino) -3, 9-dioxo-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5 ]]Undecane phosphate, poly (4, 6-dichloro-N-butyl-1, 3, 5-triazine-2-amino-ethylenediamine), poly [ N4-bis- (ethylenediamine) -phenylphosphine-N2,N6Bis- (ethylenediamine) -1,3, 5-triazine-N-phenylphosphine]And at least one of aminobenzenesulfonic acid melamine salt and ammonium polyphosphate.
Commercially available triazine compounds, as well as triazine char-forming agents blended with high hydroxyl compounds (pentaerythritol, starch) and the like, may also be used.
The polypropylene resin is at least one of homopolymerized polypropylene and copolymerized polypropylene; the melting point of the polypropylene resin is more than or equal to 140 ℃.
Whether the antioxidant and the processing aid are added can be determined according to actual conditions. The antioxidant can be one or a mixture of phenol, phosphite ester, bivalent sulfur or sterically hindered amine antioxidants. The processing aid can be low molecular lipid, metal soap, stearic acid composite ester, and amide; wherein the low molecular lipid is solid paraffin, liquid paraffin or low molecular polyolefin wax, the metal soap is calcium stearate, magnesium stearate, zinc stearate or barium stearate, the stearic acid composite ester is ethylene glycol stearate, glyceryl stearate or pentaerythritol stearate, and the amide is erucyl amide, methylene bis stearamide or N, N-ethylene bis stearamide.
The preparation method of the flame-retardant polypropylene composite material comprises the following steps: the components are uniformly mixed, and then are melted, extruded and granulated by a double-screw extruder at the temperature of 180-200 ℃, and dried to obtain the flame-retardant polypropylene composite material.
The flame-retardant polypropylene composite material is applied to preparing automotive upholsteries and toy shells.
The invention has the following beneficial effects
According to the invention, a certain amount of ester polymer with a melting point lower than that of the polypropylene resin is added into the flame-retardant polypropylene composition, so that the polypropylene is melted before the polypropylene is melted in the melt extrusion process, and the polypropylene is gradually melted after the flame retardant is wrapped, so that the flame retardant is wrapped by the low-melting-point ester polymer and dispersed in the polypropylene resin matrix. Through analysis, the ester polymer can form a strong polarity microenvironment in a polypropylene matrix under the high-temperature high-humidity condition, so that the ammonium polyphosphate flame retardant is strongly inclined to migrate to the strong polarity microenvironment under the high-temperature high-humidity condition and is not inclined to migrate to the surface of a product. Thereby effectively inhibiting the surface migration of the ammonium polyphosphate fire retardant under the conditions of high temperature and high humidity and obviously improving the weather resistance of the product.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples are as follows:
homo-polypropylene: PP N-Z30S, China petrochemical;
copolymerized polypropylene: PP K9017, taiwan chemical fiber gmbh;
ammonium polyphosphate: chemical engineering of shou guang wei dong;
triazine charring agent a: 2, 4-diamino-6-hydroxyethylamino-1, 3, 5-triazine, commercially available;
triazine charring agent B: tris (phosphaphenanthrene- (hydroxymethyl) -phenoxy) -1,3, 5-triazine, commercially available;
triazine charring agent C: tris { 2-chloro-3- [ tris (dichloropropoxy) siloxy ] propyl } isocyanurate, commercially available.
PBS: 114 ℃, viscosity average molecular weight of 8 ten thousand, golden hair technology;
PBSA: viscosity average molecular weight of 6.5 ten thousand at 100 ℃, chemical of Mitsubishi Japan;
PBAT: the viscosity average molecular weight is 6.4 ten thousand at the temperature of 115 ℃, and the technology of golden hair is adopted;
PCL: viscosity average molecular weight is 9 ten thousand at 60 ℃, boston, sweden;
examples and comparative examples preparation methods of flame retardant polypropylene composites: the components are uniformly mixed, and then are melted, extruded and granulated by a double-screw extruder at the temperature of 180-200 ℃, and dried to obtain the flame-retardant polypropylene composite material.
The test methods are as follows:
(1) UL-94, 3.2 mm: according to the UL-94 standard, the thickness of the test sample strip is 3.2 mm;
(2) UL-94, 1.6 mm: according to the UL-94 standard, the thickness of the test sample strip is 1.6 mm;
(3) migration precipitation resistance test method 1: placing a 2.0mm square plate (10 cm x 10 cm) in an oven with 85 ℃ and 85% humidity for baking for 30 days, cleaning the surface of the square plate, placing the square plate in an oven with 100 ℃ for baking for 4 hours, recording the mass change before and after the experiment, and evaluating the migration and precipitation resistant effect through the mass retention rate after high-temperature and high-humidity treatment
(4) Migration precipitation resistance test method 2: the 1.6mm and 2.0mm standard fire-retardant sample strips are placed in an oven with 85 ℃ and 85% humidity for baking for 30 days, then the surfaces of the sample strips are cleaned and placed in an oven with 100 ℃ for drying for 4 hours, and then the vertical burning grade after high-temperature and high-humidity treatment is tested according to the UL94 standard.
Table 1: EXAMPLES 1-7 flame-retardant Polypropylene composite Material content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Homo-polypropylene | 100 | 100 | 100 | 100 | 100 | 100 | |
| Polypropylene copolymer | 100 | ||||||
| Ammonium polyphosphate | 30 | 30 | 30 | 30 | 30 | 20 | 50 |
| Triazine charring agent A | 6 | 4 | 6 | 8 | 10 | 10 | 6 |
| PBS | 4 | 3 | 5 | 8 | 9 | 5 | 8 |
| UL-94，3.2mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| UL-94，1.6mm | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Quality retention (%), after baking treatment at 80 ℃/85% humidity | 98.5 | 96.5 | 98.5 | 98.7 | 97.1 | 98.7 | 98.3 |
| Baking at 80 deg.C/85% humidityDirect combustion (UL-94, 1.6 mm) | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Vertical burning (UL-94, 3.2 mm) after baking treatment at 80 ℃/85% humidity | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
From example 2/3/4/5, it is preferable that the triazine charring agent is 6 to 8 parts and the low melting point ester polymer is 5 to 8 parts.
Table 2: EXAMPLES 8-13 flame-retardant Polypropylene composite Material content (parts by weight) and test results
From example 3/8/9/10, PCL is preferred.
Table 3: comparative example flame-retardant polypropylene composite material component content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Homo-polypropylene | 100 | 100 | 100 |
| Ammonium polyphosphate | 30 | 30 | 30 |
| Triazine charring agent A | 6 | 6 | 6 |
| PBS | 1 | ||
| PBSA | 13 | ||
| PBAT | |||
| PCL | |||
| UL-94，3.2mm | V-0 | V-0 | V-2 |
| UL-94，1.6mm | V-0 | V-0 | V-1 |
| Quality retention (%), after baking treatment at 80 ℃/85% humidity | 92.3 | 95.2 | 99.1 |
| Vertical burning (UL-94, 1.6 mm) after 80 ℃/85% humidity baking treatment | NR | V-1 | V-2 |
| Vertical burning (UL-94, 3.2 mm) after baking treatment at 80 ℃/85% humidity | V-2 | V-0 | V-1 |
As can be seen from comparative examples 1-2, the addition of the low-melting-point ester polymer in too low or no amount results in poor precipitation resistance and poor flame retardancy of the flame retardant.
From comparative example 3, it is understood that the addition amount of the low melting point ester polymer is too high, and the flame retardancy is rather lowered due to poor compatibility between the low melting point ester polymer and polypropylene although the precipitation resistance of the flame retardant is good.
Claims (9)
1. The flame-retardant polypropylene composite material is characterized by comprising the following components in parts by weight:
100 parts of polypropylene resin;
20-50 parts of ammonium polyphosphate;
4-10 parts of triazine charring agent;
3-10 parts of low-melting-point ester polymer;
the melting point of the low-melting-point ester polymer is lower than that of the polypropylene resin.
2. The flame retardant polypropylene composite according to claim 1, comprising the following components in parts by weight:
100 parts of polypropylene resin;
20-50 parts of ammonium polyphosphate;
6-8 parts of triazine charring agent;
5-8 parts of low-melting-point ester polymer.
3. The flame retardant polypropylene composite according to claim 1 or 2, wherein the low melting point ester polymer is at least one selected from polybutylene succinate, polybutylene succinate-adipate, polybutylene adipate/terephthalate, and polycaprolactone.
4. The flame retardant polypropylene composite according to claim 3, wherein the low melting point ester polymer has a melting point of less than 140 ℃; preferably, the melting point of the low-melting ester polymer is lower than 100 ℃.
5. The flame retardant polypropylene composite material as defined in claim 4, wherein the viscosity average molecular weight of the low melting point ester polymer is 10000-200000.
6. The flame retardant polypropylene composite according to claim 1 or 2, wherein the triazine char-forming agent is selected from the group consisting of 2, 4-diamino-6-hydroxyethylamino-1, 3, 5-triazine, triazine ring-containing compounds, tris (phosphaphenanthrene- (hydroxymethyl) -phenoxy) -1,3, 5-triazine, 2-chloro-4, 6-bis (3-triethoxysilyl-1-aminopropyl) -1,3, 5-triazine, 2,4, 6-tris (ethoxy-phenylphosphinyl) -1,3, 5-triazine, tris { 2-chloro-3- [ tris (dichloropropoxy) siloxy-loxy-l-y-l-1, 3, 5-triazine]Propyl isocyanurate, poly (4, 6-dichloro-N-butyl-1, 3, 5-triazine-2-amino-ethylenediamine), 3- (ethyl methacrylate) -9- (4, 6-diamino-1, 3, 5-triazine) amino) -3, 9-dioxo-2, 4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5 ]]Undecane phosphate, poly (4, 6-dichloro-N-butyl-1, 3, 5-triazine-2-amino-ethylenediamine), poly [ N4-bis- (ethylenediamine) -phenylphosphine-N2,N6Bis- (ethylenediamine) -1,3, 5-triazine-N-phenylphosphine]And at least one of aminobenzenesulfonic acid melamine salt and ammonium polyphosphate.
7. The flame retardant polypropylene composite according to claim 1 or 2, wherein the polypropylene resin is at least one selected from the group consisting of homo polypropylene and co polypropylene; the melting point of the polypropylene resin is more than or equal to 140 ℃.
8. A method for preparing a flame retardant polypropylene composite according to any one of claims 1 to 7, comprising the steps of: the components are uniformly mixed, and then are melted, extruded and granulated by a double-screw extruder at the temperature of 180-200 ℃, and dried to obtain the flame-retardant polypropylene composite material.
9. Use of the flame retardant polypropylene composite according to any one of claims 1 to 7 for the preparation of automotive upholstery, toy housings.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154282A (en) * | 1998-11-20 | 2000-06-06 | Daicel Chem Ind Ltd | Flame-retardant polyolefin resin composition and its molding |
| JP2000265072A (en) * | 1999-03-12 | 2000-09-26 | Suzuhiro Kagaku:Kk | Flame-retarded resin composition and molded article thereof |
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- 2020-12-23 CN CN202011536780.3A patent/CN112679863A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000154282A (en) * | 1998-11-20 | 2000-06-06 | Daicel Chem Ind Ltd | Flame-retardant polyolefin resin composition and its molding |
| JP2000265072A (en) * | 1999-03-12 | 2000-09-26 | Suzuhiro Kagaku:Kk | Flame-retarded resin composition and molded article thereof |
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Application publication date: 20210420 |