CN118085412B - Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition - Google Patents
Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition Download PDFInfo
- Publication number
- CN118085412B CN118085412B CN202410291571.9A CN202410291571A CN118085412B CN 118085412 B CN118085412 B CN 118085412B CN 202410291571 A CN202410291571 A CN 202410291571A CN 118085412 B CN118085412 B CN 118085412B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- component
- composition
- mass
- cost
- 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.)
- Active
Links
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K3/38—Boron-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-cost intumescent flame retardant composition and a flame retardant polyolefin resin composition, and belongs to the field of flame retardants. The composition comprises (A) piperazine pyrophosphate, (B) melamine pyrophosphate and (C) calcium phosphate, wherein the mass ratio of the sum of the (A) component and the (B) component to the (C) component [ (A) component ]: [ (B) component + the (C) component ] is 70:30-30:70, and the mass ratio of the (B) component to the (C) component [ (B) component ] to the (C) component ] is 60:40-95:5. The composition also contains (D) a flame retardant synergist and (E) a coupling agent. The invention introduces the low-cost calcium phosphate into the combination of the piperazine pyrophosphate and the melamine pyrophosphate, which can obviously improve the flame retardant efficiency of the flame retardant composition, and simultaneously the mass proportion of the piperazine pyrophosphate in the flame retardant composition can be lower than the proportion published in the prior published literature, thereby reducing the cost of the flame retardant composition.
Description
Technical Field
The invention relates to the field of flame retardants, in particular to a low-cost intumescent flame retardant composition and a flame retardant polyolefin resin composition containing the flame retardant composition.
Background
The polyolefin intumescent flame retardant is considered to be a green flame retardant with great development potential because of the advantages of no halogen, high flame retardant efficiency, low smoke, low toxicity, no molten drops and the like during combustion. Intumescent flame retardants are generally composed of three components, an acid source (dehydrating agent), a char source (char former) and a gas source (blowing agent). The principle of action is that when the material burns, the phosphorus-containing flame retardant burns simultaneously to generate a combustion product with dehydration function, the combustion product is dehydrated in the system to form carbon, and at the same time, the air source generates inert gas to become a foaming agent, so that a compact porous carbon layer is formed on the surface of the material. The carbon layer has the functions of heat insulation and oxygen isolation, can prevent further degradation of the inner layer high polymer and release of combustible matters to the surface, and can prevent heat sources from transmitting to the high polymer and isolating oxygen sources, so that flame spreading and spreading are effectively prevented, and the aim of flame retardance is fulfilled.
The currently used intumescent flame retardant is mainly prepared by compounding melamine and a char forming agent by taking ammonium polyphosphate as an acid source. The flame retardant has the problems of unsatisfactory effect, poor compatibility with base materials, great influence on the electrical property, insulating property, mechanical property and the like of polymers, easy migration, poor hydrolytic stability and thermal stability and the like. The piperazine pyrophosphate-based intumescent flame retardant is a novel flame retardant composition, has better flame retardant effect, heat-resistant stability and water precipitation resistance compared with an ammonium polyphosphate-based flame retardant composition, and can be widely applied to materials such as polypropylene, polyethylene, acrylonitrile-butadiene-styrene, epoxy resin, polyurethane and the like. The patent number CN201880042218.X discloses a flame retardant composition which is mainly formed by combining piperazine pyrophosphate, melamine pyrophosphate and silicone oil, wherein the mass part range of the piperazine pyrophosphate and the melamine pyrophosphate is 90:10-50:50, namely the mass part of the piperazine pyrophosphate cannot be lower than 50 parts. "Du Yuying research on the flame retardant action of piperazine pyrophosphate based intumescent flame retardant on polyolefin. Qingdao university of science and technology. Academic paper, 2019". The flame retardant system is preferably used for polyethylene and polypropylene, and the mass part ratio of piperazine pyrophosphate to melamine pyrophosphate salt is 2.5:1. "CHEN CHENG et al .Synergistic flame retardancy of ZnO with piperazine pyrophosphate/melamine polyphosphate in PP.Polymer Testing,2023,117:107878" also show that even if piperazine pyrophosphate and melamine pyrophosphate are synergistic with ZnO, the ratio of the parts by mass of piperazine pyrophosphate to melamine pyrophosphate is still approximately 2:1.
The piperazine pyrophosphate is synthesized by neutralization reaction of phosphoric acid and piperazine and condensation dehydration according to a known method, such as ' Zhao Zhen and the like, synthesis of piperazine pyrophosphate, chemical technology, 2022,30 (5): 18-21 ', zhang Lingling and the like, synthesis of melamine polyphosphate, journal of chemical engineering, 2013,27 (11): 14-17 '. Similarly, melamine pyrophosphate is synthesized from phosphoric acid and melamine by neutralization and dehydration. Since the price of piperazine, which is a main raw material for synthesizing both, is significantly higher than that of melamine, in a practically applied flame retardant composition, if the proportion of piperazine pyrophosphate is high, this means that the application cost is high, such as that the mass part of piperazine pyrophosphate described in the foregoing patent and paper cannot be less than 50 parts. This suggests that the presently disclosed flame retardant formulation is costly to use due to the higher mass parts of piperazine pyrophosphate.
Disclosure of Invention
Based on the technical problems, the invention provides a low-cost intumescent flame retardant composition which can provide good flame retardance, can reduce the mass fraction of piperazine pyrophosphate in a system and has lower application cost.
The technical scheme adopted by the invention is as follows:
A low cost intumescent flame retardant composition comprising (a) piperazine pyrophosphate, (B) melamine pyrophosphate, and (C) calcium phosphate;
The mass ratio of the sum of the component (A) and the component (B) to the component (C) [ (A) to the component [ (B) plus the component (C) ] is 70:30 to 30:70.
In the flame retardant composition, the mass ratio of the sum of the component (A) and the component (B) to the component (C) [ (A) to the component [ (B) plus the component (C) ] is preferably 65:70 to 30:70, more preferably 50:70 to 40:70.
In the flame retardant composition, the mass ratio of the component (B) to the component (C) is 60:40 to 95:5. The mass ratio of the component (B) to the component (C) [ (B) to the component [ (C) ] is preferably 36:19 to 35:5, more preferably 30:10 to 40:10.
The flame retardant composition further comprises (D) a flame retardant synergist and (E) a coupling agent;
The composition comprises 0.01 to 20 parts by mass of the component (D) and 0.001 to 0.5 part by mass of the component (E) relative to 100 parts by mass of the total of the components (A), (B) and (C).
Further preferably, the component (A) contains 5 to 15 parts by mass of the component (D) and 0.2 to 0.3 part by mass of the component (E) based on 100 parts by mass of the total of the components (A), (B) and (C).
In the flame retardant composition, the component (D) is one or more of titanium oxide, aluminum oxide, magnesium oxide, zinc oxide, talcum, zeolite, montmorillonite, antimony trioxide, zinc borate, hydrotalcite, nano montmorillonite, aluminum hydroxide and magnesium hydroxide.
In the flame retardant composition, the component (E) is one or a combination of more of titanate, methyl silicone oil and methyl hydrogen-containing silicone oil.
In the above-mentioned flame retardant composition, the component (C) may be added in a designed ratio at the time of synthesizing the component (B), or may be added at the time of mixing and pulverizing the component (A) and the component (B).
The above-mentioned flame retardant composition can be prepared in a conventional manner on the basis of the specific components and amounts.
The invention also provides a flame-retardant polyolefin resin composition which adopts the low-cost intumescent flame retardant composition, and comprises 10-60 parts by mass of the flame retardant composition relative to 100 parts by mass of the flame-retardant polyolefin resin composition.
More preferably, the flame retardant composition is contained in an amount of 15 to 45 parts by mass in the flame retardant polyolefin resin composition.
Further, an antioxidant, a lubricant, a neutralizing agent, and the like are added to the flame retardant polyolefin resin composition.
The beneficial technical effects of the invention are as follows:
(1) The invention introduces the low-cost calcium phosphate into the combination of the piperazine pyrophosphate and the melamine pyrophosphate, which can obviously improve the flame retardant efficiency of the flame retardant composition, and simultaneously the mass proportion of the piperazine pyrophosphate in the flame retardant composition can be lower than the proportion published in the prior published literature, thereby reducing the cost of the flame retardant composition.
(2) The flame retardant efficiency of the flame retardant composition can be further improved by combining the flame retardant composition with other flame retardant synergists, and the compatibility of the flame retardant composition and a high polymer material is improved by modifying the coupling agent, so that the use amount is further reduced, and the purpose of reducing the application cost is achieved.
Detailed Description
The present invention relates to a low-cost intumescent flame retardant composition and a flame retardant resin composition, such as a flame retardant polyolefin resin composition. Hereinafter, the present invention will be described based on preferred embodiments thereof.
1. Flame retardant composition
The flame retardant composition of the invention consists of (A) piperazine pyrophosphate, (B) melamine pyrophosphate, (C) calcium phosphate, (D) flame retardant synergist and (E) coupling agent.
Wherein, the component (A) piperazine pyrophosphate can be synthesized by neutralizing phosphoric acid and piperazine to generate piperazine phosphate and then dehydrating the piperazine phosphate at high temperature, and the molar ratio of phosphoric acid to piperazine is preferably 1:1.5-1:2.5 when synthesizing the piperazine phosphate.
(B) The component melamine pyrophosphate can be prepared by firstly carrying out neutralization reaction on phosphoric acid and melamine to generate melamine phosphate, and then carrying out high-temperature dehydration, wherein the molar ratio of phosphoric acid to melamine is preferably 1:5-1:2.5 when the melamine phosphate is synthesized.
(C) The component calcium phosphate is commercially available calcium phosphate with the content higher than 99.0%, and can be added according to the designed proportion during the synthesis of the component (B) or can be added during the mixing and crushing of the component (A) and the component (B).
Through intensive researches, researchers of the invention find that the flame retardant efficiency of the composition can be obviously improved by introducing low-cost calcium phosphate into the combination of piperazine pyrophosphate and melamine pyrophosphate. Particularly, the invention can reduce the mass part of the piperazine pyrophosphate in the flame retardant composition on the basis of ensuring the flame retardant effect, namely the mass part of the piperazine pyrophosphate in the composition can be lower than 50 parts, thereby reducing the use cost of the flame retardant.
The flame retardant efficiency of the flame retardant composition can be further improved by combining the flame retardant composition with other synergists, and the compatibility of the flame retardant composition and a high polymer material is improved by modifying the flame retardant composition with a coupling agent, so that the use amount is further reduced, and the purpose of reducing the application cost is achieved.
The flame retardant synergist of the component (D) in the flame retardant composition is one or more of titanium oxide, aluminum oxide, magnesium oxide, zinc oxide, talcum, zeolite, montmorillonite, antimony trioxide, zinc borate, hydrotalcite, nano montmorillonite, aluminum hydroxide and magnesium hydroxide, preferably zinc oxide and zinc borate.
The component (E) in the flame retardant composition is one or more of titanate, methyl silicone oil and methyl hydrogen silicone oil, preferably methyl hydrogen silicone oil.
The flame retardant composition of the present invention has a mass ratio of the sum of the component (A) and the component (B) to the component (C), i.e., the ratio of the component [ (A) to the component [ (B) plus the component [ (C) ] of 70:30 to 30:70, preferably 65:70 to 30:70, more preferably 50:70 to 40:70, in terms of flame retardance and reduction in application cost.
The mass ratio of the component (B) to the component (C) [ (B) is 60:40 to 95:5, preferably 36:19 to 35:5, more preferably 30:10 to 40:10, from the viewpoints of flame retardance and reduction in application cost.
The particle size of the solid component of the flame retardant composition is controlled to be 0.1 μm or less and D90 or less and 80. Mu.m, preferably 1 μm or less and D90 or less and 50. Mu.m.
2. Flame retardant polyolefin resin composition
A flame retardant polyolefin resin composition comprising 10 to 60 parts by mass of the above flame retardant composition per 100 parts by mass of the resin. Preferably, the flame retardant composition contains 15 to 45 parts by mass of the above-mentioned flame retardant composition.
The polyolefin resin used in the flame retardant polyolefin resin composition may be polyethylene resins such as polyethylene, low density polyethylene, linear low density polyethylene and high density polyethylene, polypropylene resins such as polypropylene, homo-polypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, high impact copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene and stereoblock polypropylene, alpha-olefin polymers such as polybutene, cycloolefin polymer, poly-3-methyl-1-butene, poly-3-methyl-1-pentene and poly-4-methyl-1-pentene, homopolymers or copolymers of styrene monomers (styrene, vinyl toluene and the like), copolymers of styrene monomers and vinyl monomers, styrene graft copolymers, styrene block copolymers and the like.
The flame retardant polyolefin resin composition can be added with common plastic additives such as an antioxidant, a plasticizer, a lubricant, an ultraviolet absorber, a filler, a nucleating agent and the like according to practical processing and use requirements, and the flame retardant does not produce antagonism with the plastic additives.
The above-mentioned flame retardant polyolefin resin composition may be produced by a known method for mixing and processing plastics, such as a method for mixing by a mixer, a stirrer, a method for melt kneading by an internal mixer, an extruder, or the like, a method for solution casting by mixing with a solvent, or the like, or a method for processing by extrusion molding, injection molding, calender molding, blow molding, compression molding, lamination molding, or the like.
The invention will be further illustrated with reference to specific examples.
Examples 1-16 formulation of flame retardant compositions.
The basic raw materials comprise piperazine pyrophosphate as a commercial product, wherein the initial decomposition temperature is greater than 280 ℃, the volatile component is less than or equal to 0.5%, the grain diameter is less than or equal to 1 mu m D90 and less than or equal to 50 mu m, the whiteness (YI) is less than or equal to 8, melamine pyrophosphate as a commercial product, the initial decomposition temperature is greater than 280 ℃, the volatile component is less than or equal to 0.5%, the grain diameter is less than or equal to 1 mu m D90 and less than or equal to 50 mu m, the whiteness (YI) is less than or equal to 6, the calcium phosphate as a commercial product has the main content of more than or equal to 99.5%, the grain diameter is less than or equal to 1 mu m D90 and less than or equal to 50 mu m, the flame retardant synergist is a commercial product, the main content is more than or equal to 99.5%, the grain diameter is less than or equal to 1 mu m D90 and the purity of the coupling agent is more than or equal to 99.0%.
The flame retardant compositions of examples 1 to 16, labeled as flame retardant compositions No.1 to No.16, respectively, were obtained by mixing (A) piperazine pyrophosphate, (B) melamine pyrophosphate, (C) calcium phosphate, (D) flame retardant synergist, and (E) coupling agent in a high-speed mixer for 15 minutes according to the formulation ratios shown in Table 1.
TABLE 1
Examples 17-32 flame retardant polyolefin resin compositions were prepared.
The basic raw materials comprise, in the formula, polyolefin (PP-h) [ MFR=8dg/min ], commercial polypropylene copolymer (PP-b) [ MFR=8dg/min ], commercial Low Density Polyethylene (LDPE) [ MFR=8dg/min ], 100 parts by mass of polyolefin, 0.1 part by mass of calcium stearate as a neutralizer, 0.05 parts by mass of antioxidant 1010 and antioxidant 168 as primary antioxidant and secondary antioxidant, 0.4 part by mass of glycerol monostearate as a lubricant, and the flame retardant is the flame retardant composition in examples 1-16, wherein the amounts are shown in Table 3.
Mixing the flame retardant composition, the polyolefin, the antioxidant, the lubricant and the acid neutralizer calcium stearate in a high-speed mixer for 30 minutes, adding the mixture into a double-screw extruder, extruding and granulating at 190-210 ℃, then placing the particles into a tablet press for molding, taking out the mold after 20 minutes at the molding pressure of 5MPa and the molding temperature of 190-220 ℃, cooling, and cutting a sample plate into standard sample bars for vertical combustion performance test.
The vertical burning test was carried out in accordance with GB/T2408-2008, and the flame retardant polypropylene composition sample had dimensions of 100mm by 13mm by 1.6mm and the flame retardant polyethylene composition sample had dimensions of 100mm by 13mm by 0.8mm. Placing flame (blue flame with the height of 20 mm) at the lower end of a vertically placed sample bar, igniting for 10s, removing the flame, igniting the flame for 10s after the flame is extinguished, recording the flame burning time and the flameless burning time of the sample bar after the flame is removed, and recording the flame burning time of the first ignition and the second ignition as t1 and t2 respectively. Table 2 shows the criteria for the vertical burn test, requiring that each set of five samples meet each index.
TABLE 2
Table 3 shows the formulation compositions and flame retardant property test results of the flame retardant polyolefin resin compositions of examples 17 to 46.
TABLE 3 Table 3
In Table 3, the amounts of polyolefin and flame retardant are shown, and other additives and the like are added in the preparation of the flame retardant polyolefin resin composition, specifically, 0.1 part of calcium stearate is used as a neutralizing agent, 0.05 parts of antioxidant 1010 and 168 are used as primary antioxidant and secondary antioxidant, respectively, and 0.4 parts of glycerol monostearate is used as a lubricant.
As can be seen from tables 1 and 3, the present invention introduces inexpensive calcium phosphate into the combination of piperazine pyrophosphate and melamine pyrophosphate, which can significantly improve the flame retardant efficiency of the flame retardant composition while reducing the amount of piperazine pyrophosphate used in the flame retardant composition.
To further demonstrate the effect of calcium phosphate incorporation, the present invention also adds a set of comparative examples, i.e., the amounts of ingredients used are the same as in example 13, except that the inorganic flame retardant silicon carbide is used in place of calcium phosphate. And the prepared flame retardant was applied to the polypropylene copolymer (PP-b) in the same amount as in example 35. Through experimental tests, the flame retardant grade of the finally obtained flame retardant polyolefin composition is V-2, and the flame retardant property is obviously reduced.
Claims (3)
1. A low-cost intumescent flame retardant composition, characterized in that it contains (A) piperazine pyrophosphate, (B) melamine pyrophosphate and (C) calcium phosphate;
the mass ratio of the component (A) to the sum of the component (B) and the component (C) [ (A) to the component [ (B) plus the component (C) ] is 65:70-30:70;
(B) The mass ratio of the component (B) to the component (C) is 60:40-95:5;
the composition also contains (D) a flame retardant synergist and (E) a coupling agent;
the composition comprises 0.01 to 20 parts by mass of a component (D) and 0.001 to 0.5 part by mass of a component (E) based on 100 parts by mass of the total of the components (A), (B) and (C);
(D) The components are one or a combination of more of zinc oxide, zinc borate and nano montmorillonite;
(E) The components are one or a combination of more of titanate, methyl silicone oil and methyl hydrogen silicone oil.
2. A low-cost intumescent flame retardant composition as claimed in claim 1, wherein component (C) is added in a designed proportion during the synthesis of component (B) or is added during the mixing and crushing of component (A) and component (B).
3. A flame retardant polyolefin resin composition comprising 10 to 60 parts by mass of the flame retardant composition per 100 parts by mass of the flame retardant polyolefin resin composition, wherein the flame retardant composition is a low-cost intumescent flame retardant composition as defined in any one of claims 1 and 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410291571.9A CN118085412B (en) | 2024-03-14 | 2024-03-14 | Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410291571.9A CN118085412B (en) | 2024-03-14 | 2024-03-14 | Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118085412A CN118085412A (en) | 2024-05-28 |
| CN118085412B true CN118085412B (en) | 2025-02-18 |
Family
ID=91163102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410291571.9A Active CN118085412B (en) | 2024-03-14 | 2024-03-14 | Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118085412B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021054913A (en) * | 2019-09-27 | 2021-04-08 | 積水化学工業株式会社 | Polyolefin resin foam sheet |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015189785A (en) * | 2014-03-27 | 2015-11-02 | 出光ライオンコンポジット株式会社 | Flame retardant soft resin composition |
| CN107286563B (en) * | 2017-07-06 | 2020-01-03 | 上海化工研究院有限公司 | Intumescent flame retardant for ABS electrical switch outer cover and preparation and application thereof |
| CN108912676A (en) * | 2018-08-09 | 2018-11-30 | 江苏利思德新材料有限公司 | Melamine derivative based flame retardant high-temperature thermal stability method and products thereof and application are improved using inorganic phosphorous acid metal salt |
| KR20210144771A (en) * | 2019-03-29 | 2021-11-30 | 가부시키가이샤 아데카 | Flame retardant composition and flame retardant synthetic resin composition |
| CN110591152A (en) * | 2019-09-02 | 2019-12-20 | 上海化工研究院有限公司 | A kind of flame retardant stabilizer, halogen-free flame retardant glass fiber reinforced polypropylene and its preparation method |
| CN117534897A (en) * | 2023-11-17 | 2024-02-09 | 北京理工大学 | A high-toughness, low-smoke, halogen-free, flame-retardant wire and cable sheathing material |
-
2024
- 2024-03-14 CN CN202410291571.9A patent/CN118085412B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021054913A (en) * | 2019-09-27 | 2021-04-08 | 積水化学工業株式会社 | Polyolefin resin foam sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118085412A (en) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101293983B (en) | Expansion flame-proof polypropelene composition and preparation method thereof | |
| CN101735514B (en) | Flame-retardant polypropylene material and preparation method | |
| US5137937A (en) | Flame retardant thermoplastic resin composition with intumescent flame retardant | |
| CN101293984B (en) | Expanded carbon flame-proof polypropelene composition and preparation method thereof | |
| CN102558659B (en) | Halogen-free flame retardant olefin foam body and preparation method thereof | |
| CN106496759A (en) | A kind of low smoke and zero halogen nano fire-retarding composite material for the ethylene vinyl acetate copolymer for promoting into charcoal and preparation method thereof | |
| CN102964667B (en) | Halogen-free flame-retardant polyethylene composite material and preparation method thereof | |
| CN101875745A (en) | Flame-retardant styrene polymer compound containing smoke inhibitor and preparation method thereof | |
| CN102367306A (en) | High efficiency halogen-free flame retardant polypropylene composite material and its preparation method | |
| WO2021164353A1 (en) | Antimony-free flame-retardant polypropylene composition and preparation method therefor | |
| CN102863691A (en) | Polypropylene composite material and preparation method thereof | |
| CN108676248A (en) | A kind of high fire-retardance polypropylene material and the preparation method and application thereof | |
| CN116218031A (en) | Halogen-free flame retardant composition and preparation method of polyolefin-based master batch thereof | |
| CN115505172B (en) | Halogen-free flame retardant, and preparation method and application thereof | |
| KR20070091037A (en) | Fire retardant composition | |
| CN118085412B (en) | Low-cost intumescent flame retardant composition and flame-retardant polyolefin resin composition | |
| CN108467547A (en) | A kind of converter environment-protection flame-proof electrostatic resistance polypropylene composition and preparation method thereof | |
| CN102153811B (en) | Polypropylene composite material with fire retardance and toughening performance | |
| CN110372956B (en) | Halogen-free flame-retardant polypropylene composite with high glow wire | |
| CN111748156A (en) | A halogen-free flame retardant mineral powder reinforced polypropylene composition | |
| US4253972A (en) | Flame retardant polyolefins | |
| CN115160692B (en) | Halogen-free flame-retardant plastic-sucking polypropylene alloy material and preparation method and application thereof | |
| CN115216089B (en) | Halogen-free flame-retardant master batch, thin-wall halogen-free flame-retardant polypropylene and preparation methods thereof | |
| CN116023744A (en) | Halogen-free flame-retardant polyolefin composition and preparation method thereof | |
| EP0691374A1 (en) | Reinforced, flame-resistant thermoplastic composition |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |