CN113583299A - High-expansion fireproof low-smoke halogen-free flame retardant composition and thermoplastic resin composition - Google Patents
High-expansion fireproof low-smoke halogen-free flame retardant composition and thermoplastic resin composition Download PDFInfo
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- 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
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- 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
- C08K5/34922—Melamine; Derivatives thereof
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- 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
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- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08K2003/323—Ammonium polyphosphate
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Abstract
The invention relates to a high-expansion fireproof low-smoke halogen-free flame retardant composition and a thermoplastic resin composition. The high-expansion fireproof low-smoke halogen-free flame retardant composition comprises: (A) 20 to 70 parts by mass of component (B), 10 to 50 parts by mass of component (B), and 15 to 60 parts by mass of component (C), wherein the total amount of components (A), (B), and (C) is 100 parts by mass; (A) the component is selected from one or more than two of polyphosphoric acid piperazine, pyrophosphoric acid piperazine, orthophosphoric acid piperazine or diphosphoric acid piperazine; (B) the components are selected from one or more than two of ammonium polyphosphate, melamine polyphosphate, melamine ditrimexophosphate or melamine cyanuric acid; (C) the component is expanded graphite. The high-expansion fireproof low-smoke halogen-free flame retardant composition has the double characteristics of flame retardance and fire resistance, can quickly expand after being ignited at high temperature to form a compact expanded carbon layer, and realizes the effects of blocking, flame retardance, fire resistance, heat insulation, oxygen isolation and smoke suppression.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a high-expansion fireproof low-smoke halogen-free flame retardant composition and a thermoplastic resin composition.
Background
The fire safety of materials used in crowded places plays a crucial role in fire protection. In the partitions between different areas in the building and the ship cabin, such as the space division areas of walls, bulkheads, ceilings, floors and the like, through holes and devices such as cables, pipes and the like are needed to realize the transmission of water, electricity, gas, signals and the like between different areas. However, through-penetrations can damage the original fire protection system of a building, and fire and smoke can quickly spread between different areas through the pipe penetration device, causing significant losses. In particular in ships, through-going holes are subjected not only to high temperatures and to erosion by flames, but also to mechanical loads due to collapse of the pipeline and to the flow of fire-fighting water. Therefore, the through-penetration needs to be blocked, and the through-penetration device needs to have a good blocking and fireproof function, so that fire and smoke can be quickly and effectively blocked in a fire area, and the spread of fire can be inhibited, thereby ensuring the safety of life and property of people.
At present, the traditional fireproof materials such as organic fireproof blocking materials, inorganic fireproof blocking materials, fireproof bags, inorganic fireproof partition plates and the like are generally used for combined construction in domestic fireproof treatment measures for cables, pipeline through holes, empty openings and gaps. These fire-resistant materials present a certain safety risk: (1) the halogen flame retardant is added to obtain good fireproof and flame-retardant effects. The halogen flame retardant emits toxic hydrogen halide gas in fire, so that the halogen flame retardant is harmful to the life of personnel, and the hydrogen halide gas is attached to electrical equipment and can corrode and damage the equipment; (2) the fire-proof materials have poor expansibility in fire, cannot fully fill gaps of through holes, particularly dense cable through holes, cannot fully meet the size of the holes, and cause flame, dense smoke and toxic gas diffusion; (3) the smoke quantity of the fireproof material is large, and dense smoke is released in fire; (4) the construction process is backward, stirring needs to be allocated and stirred on the construction site, the environment is polluted, and short circuit of electrified equipment can be caused in the construction process.
The intumescent flame retardant has the advantages of low smoke generation during combustion, no toxicity, no generation of corrosive gases, expansion in fire, excellent resistance to long-term or repeated exposure to flame and the like, and is considered to be one of the most promising approaches for realizing non-halogenation. The expansion flame-retardant technology is applied to the research of the plugging material, and a novel organic fireproof plugging product with high flame-retardant effect, good low-temperature flexibility and less halogen acid gas and smoke can be prepared. The expansion flame-retardant system of the halogen-free expansion organic putty is expanded rapidly when being heated, and the resin system is matched, the filler forms a layer of hard and porous carbon layer barrier, the volume after expansion exceeds 3 times to 10 times of the original volume, the space part around the through hole is enough to be completely blocked, and various threading pipes, cable insulating layers and pipeline heat-insulating layers can be sealed, the space and the hole caused by burning are sealed, the unique effects of fire prevention and smoke prevention are achieved in a fire scene, the different partition areas are not influenced mutually, the fire behavior is controlled in the fire-proof partition area of a fire source, and the loss of the fire disaster is reduced to the lowest. Therefore, the development and application of the novel halogen-free fireproof plugging product which has high-efficiency flame retardance, plugging and fire prevention, is more convenient to construct and meets the environmental protection requirement have important significance.
Disclosure of Invention
In view of the above problems, the present invention provides a high-expansion fireproof low-smoke halogen-free flame retardant composition and a thermoplastic resin composition. The high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition has the double characteristics of flame retardance and fire prevention, can quickly expand after catching fire at high temperature to form a compact expanded carbon layer, realizes the effects of plugging, flame retardance, fire prevention, heat insulation, oxygen isolation and smoke suppression, suppresses flame spread and reduces the harm caused by fire.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a high-expansion fireproof low-smoke halogen-free flame retardant composition, which comprises the following components in percentage by weight: (A) 20 to 70 parts by mass of component (A), 10 to 50 parts by mass of component (B), and 15 to 60 parts by mass of component (C), wherein the total amount of components (A), (B), and (C) is 100 parts by mass;
(A) the component (B) is one or more than two of polyphosphoric acid piperazine, pyrophosphoric acid piperazine, orthophosphoric acid piperazine or diphosphoric acid piperazine (phosphoric acid piperazine salt);
(B) the components are selected from one or more than two of ammonium polyphosphate, melamine polyphosphate, melamine ditrimexophosphate or melamine cyanuric acid;
(C) the component is expanded graphite;
the pH value of the high-expansion fireproof low-smoke halogen-free flame retardant composition is 4.5-6.5.
In one embodiment of the present invention, in the piperazine phosphate salt as the component (a), the piperazine orthophosphate or piperazine diphosphate is piperazine orthophosphate or piperazine diphosphate prepared by an acid-base reaction from phosphoric acid or piperazine as a raw material; the polyphosphoric acid piperazine or the pyrophosphoric acid piperazine is prepared by taking phosphoric acid and piperazine as raw materials and carrying out high-temperature polymerization.
In one embodiment of the present invention, the component (a) is preferably piperazine polyphosphate or piperazine pyrophosphate from the viewpoints of thermal stability, flame retardancy, and compatibility with a resin matrix, and when used as a mixture, the higher the content of piperazine polyphosphate or piperazine pyrophosphate is, the more preferable it is.
In one embodiment of the present invention, the piperazine polyphosphate or piperazine pyrophosphate in the component (a) is preferably piperazine diphosphate prepared by using water as an intermediate raw material and polymerizing and dehydrating the piperazine polyphosphate or piperazine pyrophosphate at a high temperature of 200 to 270 ℃, and the polymerization degree is not less than 15.
In one embodiment of the present invention, the reaction apparatus for dehydration condensation of piperazine polyphosphate or piperazine pyrophosphate in the component (a) is not particularly limited as long as it is required to satisfy high-temperature heating, mixing and dehydration, and a batch high-speed mixer may be used, or a vacuum kneader, a pressure type kneader, an extruder or the like may be used. From the viewpoint of production efficiency and cost of piperazine polyphosphate or piperazine pyrophosphate, an extruder and a high-speed mixer are preferable.
In one embodiment of the present invention, the piperazine polyphosphate or piperazine pyrophosphate in the component (a) may contain unreacted phosphoric acid, piperazine diphosphate, or other by-products.
In one embodiment of the present invention, an excess of phosphoric acid is required during the synthesis of the piperazine phosphate in the component (a), and the prepared piperazine phosphate has a certain acidity and slightly different phosphorus content. From the viewpoint of improving the flame-retardant efficiency and reducing the risk of corrosion of processing equipment, the phosphorus content of the component (A) is controlled to be 22 to 25%, and the pH value is 3.0 to 5.0.
In one embodiment of the present invention, the particle size of the component (A) is not critical, and D is50Less than or equal to 25 mu m, and can be mechanically pulverized or air-jet pulverized. From the viewpoint of extrusion processing and dispersibility in resins, jet milling is preferred, and the particle diameter of the component (A) is 5 μm. ltoreq. D50≤15μm。
In one embodiment of the present invention, the piperazine phosphate salt in the component (a) is a condensed phase intumescent flame retardant with three sources in one (phosphorus source, nitrogen source, carbon source), and has good heat resistance and char formation. But condensed phase flame retardance needs moderate proportion of phosphorus, nitrogen and carbon flame retardant elements to play a flame retardant role well, the phosphorus content in the piperazine phosphate is 22% -25%, the acid source is sufficient, the nitrogen content is low, and a certain gas source needs to be supplemented.
In one embodiment of the invention, because piperazine phosphate is an acidic flame retardant system, an acidic or weakly alkaline compound is needed for a supplementary gas source, so that the problems of acid-base dehydration reaction and degradation foaming of the high-expansion fireproof low-smoke halogen-free flame retardant composition in the extrusion processing process are solved.
In one embodiment of the present invention, the component (B) is used as a supplementary gas source, and ammonium polyphosphate, melamine polyphosphate, melamine ditrimer phosphate, melamine pyrophosphate, melamine orthophosphate, melamine cyanuric acid, which can be used alone or as a mixture.
In one embodiment of the present invention, the ammonium polyphosphate in the component (B) is ammonium polyphosphate II with a polymerization degree of more than 1000, a nitrogen content of 14 to 15%, and a particle diameter D50Less than or equal to 20 mu m and the pH value is 5.5-7.5.
In one embodiment of the present invention, the ammonium polyphosphate in the component (B) may be used without surface treatment or may be used after surface treatment. From the viewpoint of water resistance and compatibility, surface-treated ammonium polyphosphate is preferable.
In one embodiment of the present invention, the surface-treated ammonium polyphosphate may be selected from silane coupling agents, melamine resins, melamine-formaldehyde, and epoxy resin surface-coated ammonium polyphosphates, but is not limited to the above-listed coated ammonium polyphosphate types, and modified ammonium polyphosphates having improved water resistance, moisture migration resistance, and resin compatibility through dry or wet processes may be used in the present invention.
In one embodiment of the present invention, the melamine polyphosphate, the melamine ditrimexophosphate, the melamine pyrophosphate, and the melamine orthophosphate in the component (B) are obtained by reacting phosphoric acid or a phosphoric acid salt with melamine, and one of them may be used, or a mixture thereof may be used.
In one embodiment of the present invention, melamine pyrophosphate is preferable from the viewpoint of nitrogen element content, thermal stability, and flame retardancy synergy.The nitrogen content of the melamine pyrophosphate is 42.5-43.5%, and the particle diameter D is50Less than or equal to 10 mu m and the pH value is 4.5-6.0.
In one embodiment of the present invention, the melamine cyanuric acid in the component (B) is prepared from melamine and cyanuric acid as raw materials by various processes.
In one embodiment of the invention, the melamine cyanurate products obtained from different processes have different microscopic morphologies, which can be divided into rods, flakes, blocks or mixtures of different morphologies. From the viewpoint of flame retardant efficiency, the flake melamine cyanurate is preferable, and when the morphology is a mixed state, the higher the proportion of the flake melamine cyanurate is, the better the proportion is.
In one embodiment of the present invention, the component (B) has a melamine cyanurate nitrogen content of 27% or more and a particle diameter D50Less than or equal to 5 mu m and the pH value is 5.0-7.5.
In one embodiment of the present invention, the expanded graphite of the component (C) has a mesh size of 100 to 400 mesh and a pH of 4.0 to 7.0.
In one embodiment of the present invention, the expanded graphite of the component (C) needs to use concentrated sulfuric acid in the preparation process of the chemical oxidation method, and the surface of the expanded graphite obtained by the method is still residual acid after being washed with water, and shows a certain acidity. The pH of the expanded graphite is preferably 5.0 to 7.0 from the viewpoint of reducing the corrosivity of processing equipment.
In the invention, the pH value of the high-expansion fireproof low-smoke halogen-free flame retardant composition is 4.5-6.5, the influence of the acidity and alkalinity among the components is fully considered, and the problems of acid-base dehydration reaction and degradation foaming of the flame retardant in the extrusion processing process are avoided.
The invention also provides a high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition which is formed by combining the thermoplastic resin and the high-expansion fireproof low-smoke halogen-free flame retardant composition, wherein the weight ratio of the thermoplastic resin to the high-expansion fireproof low-smoke halogen-free flame retardant composition is 100 (40-120).
In one embodiment of the present invention, the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin is one of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, styrene thermoplastic elastomer, olefin thermoplastic elastomer and polyurethane thermoplastic elastomer.
In one embodiment of the present invention, the thermoplastic resin is preferably an ethylene-vinyl acetate copolymer from the viewpoint of convenience in use and post-maintenance when the molded article of the thermoplastic resin composition has a certain elasticity.
In one embodiment of the invention, the compounded high-expansion fireproof low-smoke halogen-free flame retardant composition is used for endowing the thermoplastic resin with flame retardance, high expansion and fireproof performance, and further preferably added with functional additives such as an antioxidant, a light stabilizer, an anti-aging agent, a compatilizer and a lubricant from the viewpoint of taking mechanical performance, processability and weather resistance of the flame-retardant thermoplastic resin composition into consideration.
In one embodiment of the present invention, the functional auxiliary is a conventional commercially available component and an amount, and is not otherwise particularly limited.
The invention also provides a preparation method of the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition, which adopts a double-screw extrusion granulation and one-time injection molding preparation process, and the preparation method comprises the following specific steps:
(1) mixing the component (A), the component (B) and the component (C) in a high-speed mixer for 5-10 minutes according to the proportion to obtain a high-expansion fireproof low-smoke halogen-free flame retardant composition;
(2) adding thermoplastic resin in a corresponding weight proportion into the high-expansion fireproof low-smoke halogen-free flame retardant composition, and premixing for 5-10 minutes by using a high-speed mixer to obtain the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition;
(3) and adding the mixed high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition through a main feeding port of a double-screw extruder, carrying out melt blending to uniformly mix the components, extruding, granulating and drying to obtain the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin modified particles.
(4) The high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin modified particles are subjected to one-time injection molding by an injection molding machine to obtain a product forming body.
A flame retardant system with quick carbonization and high expansion ratio is required to be used in the fireproof plugging material, and the flame retardant effect of the flame retardant is closely related to the thickness and the tightness of the expanded carbon layer. The expansion char formation can be divided into physical char formation that does not participate in the reaction and chemical char formation that participates in the reaction. (A) The component (A) and the component (B) are compounded into the halogen-free intumescent flame retardant, P, N, C is used as a main flame retardant element, halogen is not contained, and toxic and harmful gases harmful to the environment and human bodies are not generated. When the material catches fire at high temperature, firstly, phosphoric acid, metaphosphoric acid and the like are generated by dehydrating an acid source mainly containing P element, the generated acid is combined with a carbon source to generate esterification reaction, the ester is dehydrated and crosslinked to generate carbon on the surface of the material, and a large amount of inert gas is released from the gas source to promote the expansion of a carbon layer. The intumescent flame retardant forms a compact and continuous intumescent carbon layer on the surface of the material through continuous chemical reaction, so that oxygen and heat transfer are isolated, melting and dripping are prevented, and combustion is interrupted. The intumescent flame retardant has better flame retardance, but the expansion ratio of the intumescent flame retardant used alone is lower, and the sealing fire resistance is slightly poor.
Expanded Graphite (EG) is a physical intumescent flame retardant which is applied more at present, has proper initial expansion temperature (150-250 ℃), rapidly expands to form a worm-shaped fluffy graphite carbon layer at the initial stage of combustion, absorbs a large amount of heat and effectively reduces the surface temperature of a base material; the maximum expansion volume is reached before 500 ℃, the thickness of the carbon layer is greatly improved through the sharp expansion of the volume of the carbon layer, the flame is choked, the direct contact between the flame and the internal base material is prevented or delayed, and the secondary combustion caused by the combustion and molten drop of the high polymer base material is retarded; and the expanded graphite carbon layer has good heat resistance and lower heat conductivity coefficient, and can effectively protect the resin matrix. However, the expanded graphite is physically expanded only by the volume of the expanded graphite, no chemical action is generated between the expanded graphite and the flame-retardant resin, the adhesion force between the expanded graphite formed after expansion is weak, a firm carbon layer cannot be formed due to light weight, and the expanded carbon layer with a fluffy surface is easily damaged under the action of flame pressure or heat convection to form 'fly ash', so that the heat-insulating expanded carbon layer fails, the flame retardance is reduced, and the long-time fire resistance cannot be realized. The expansion multiplying power and the particle size of the expanded graphite have a certain relationship, generally, the expansion multiplying power of the graphite sheet with large particle size is high, the flame retardant effect is better than that of the graphite sheet with small particle size, but the expanded graphite with large particle size can cause the mechanical strength of the material to be obviously reduced, and the blanking is not uniform easily in the processing process. The particle size is too small, the expansion ratio of the expanded graphite is low, and the formation of a carbon layer is influenced.
In the invention, the chemical charring intumescent flame retardant and the physical charring intumescent graphite are combined for use, and the two fully play a synergistic flame retardant role in different combustion stages, thereby effectively solving the problems existing when the two are used independently. At the initial stage of material combustion, the expanded graphite quickly forms a worm-shaped carbon layer with high expansion ratio at about 200 ℃, so that the combustion temperature rise of the material is effectively slowed down; (A) the chemical intumescent flame retardant compounded by the components (B) is decomposed to generate phosphoric acid at 350 ℃, on one hand, the resin matrix is promoted to dehydrate to form carbon, on the other hand, the phosphoric acid reacts with piperazine rings in piperazine phosphate molecules, and is condensed to form a cross-linked inorganic polymer with strong stability through dehydration and deamination, so that a worm-shaped carbon layer is adhered and reinforced, and holes in the carbon layer are reduced; the expanded graphite is inserted into the substances to form a mutually-penetrated condensed phase embedded carbon layer structure, the reinforcing effect similar to a fiber material is achieved, a firm and compact high-rate expanded carbon layer is finally formed on the surface layer of the resin matrix, the phenomenon of fly ash is greatly reduced or eliminated, and the expanded graphite has good expansion, flame retardant, plugging, fire prevention and smoke suppression functions.
The high-expansion fireproof low-smoke halogen-free flame retardant composition, the thermoplastic resin composition and the formed body thereof prepared by the invention can be used for hole plugging parts and have better expansion flame-retardant and plugging fireproof functions. More specifically, the plugging agent can be injection-molded into a junction box, a bottom box, a fireproof protection pipe, a lamp fireproof cap and the like, and is used for plugging through holes of cables and pipelines in various environments such as building rooms, ship cabins and the like, so that fire and smoke in fire can be prevented from rapidly diffusing among different areas through a pipeline penetration device, and serious loss is caused.
Compared with the prior art, the invention has the following advantages:
(1) the high-expansion fireproof low-smoke halogen-free flame retardant composition takes 'three-source-in-one' piperazine phosphate as a main component, ammonium polyphosphate or melamine salt is added as a supplementary gas source in a compounding manner, expanded graphite is used as a supplementary carbon source, chemical char formation and physical char formation are combined, a compact and continuous carbon layer with high expansion ratio (more than 60mL/g) is quickly formed on the surface of thermoplastic resin during combustion, the problems that the piperazine phosphate expansion ratio is low, the plugging property is poor, and the expanded graphite carbon layer is loose and easy to generate fly ash are effectively solved, multiple functions of expansion, flame retardance, plugging, fire resistance, heat insulation, oxygen isolation and smoke suppression are realized, and the composition does not contain halogen and is environment-friendly.
(2) The piperazine phosphate is an acidic system, and the acidic or weakly alkaline synergistic components are selected, so that the problems of degradation and foaming of the components in the processing process and reduction of the flame retardant efficiency in the use process due to acid-base reaction are effectively solved, and the processing stability and the weather resistance are good.
(3) The high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition are used for plugging and fire prevention of holes, rapidly expand in volume after being heated, fill gaps, rapidly plug flame, smoke and heat in a closed range on fire, and inhibit fire spreading.
(4) The high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition are used for preparing a molded part by adopting an extrusion and injection molding process, and compared with a fireproof daub blocking material prepared by a traditional coating process, the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition have the advantages of simple preparation process and convenience in field construction and later maintenance.
Detailed Description
The purpose of the invention can be realized by the following technical scheme:
the invention provides a high-expansion fireproof low-smoke halogen-free flame retardant composition, which comprises the following components in percentage by weight: (A) 20 to 70 parts by mass of component (A), 10 to 50 parts by mass of component (B), and 15 to 60 parts by mass of component (C), wherein the total amount of components (A), (B), and (C) is 100 parts by mass;
(A) the components: one or more selected from piperazine polyphosphate, piperazine pyrophosphate, piperazine orthophosphate or piperazine diphosphate (piperazine phosphate);
(B) the components: one or more than two of ammonium polyphosphate, melamine polyphosphate, melamine ditrimexophosphate or melamine cyanuric acid;
(C) the component is expanded graphite.
In one embodiment of the present invention, in the piperazine phosphate salt in the component (a), the piperazine orthophosphate or piperazine diphosphate is piperazine orthophosphate or piperazine diphosphate prepared by an acid-base reaction from phosphoric acid or piperazine as a raw material; the polyphosphoric acid piperazine or the pyrophosphoric acid piperazine is prepared by taking phosphoric acid and piperazine as raw materials and carrying out high-temperature polymerization.
In one embodiment of the present invention, the component (a) is preferably piperazine polyphosphate or piperazine pyrophosphate from the viewpoints of thermal stability, flame retardancy, and compatibility with a resin matrix, and when used as a mixture, the higher the content of piperazine polyphosphate or piperazine pyrophosphate is, the more preferable it is.
In one embodiment of the present invention, the piperazine polyphosphate or piperazine pyrophosphate in the component (a) is preferably piperazine diphosphate prepared by using water as an intermediate raw material and polymerizing and dehydrating the piperazine polyphosphate or piperazine pyrophosphate at a high temperature of 200 to 270 ℃, and the polymerization degree is not less than 15.
In one embodiment of the present invention, the reaction apparatus for dehydration condensation of piperazine polyphosphate or piperazine pyrophosphate in the component (a) is not particularly limited as long as it is required to satisfy high-temperature heating, mixing and dehydration, and a batch high-speed mixer may be used, or a vacuum kneader, a pressure type kneader, an extruder or the like may be used. From the viewpoint of production efficiency and cost of piperazine polyphosphate or piperazine pyrophosphate, an extruder and a high-speed mixer are preferable.
In one embodiment of the present invention, the piperazine polyphosphate or piperazine pyrophosphate in the component (a) may contain unreacted phosphoric acid, piperazine diphosphate, or other by-products.
In one embodiment of the present invention, an excess of phosphoric acid is required during the synthesis of the piperazine phosphate in the component (a), and the prepared piperazine phosphate has a certain acidity and slightly different phosphorus content. From the viewpoint of improving the flame-retardant efficiency and reducing the risk of corrosion of processing equipment, the phosphorus content of the component (A) is controlled to be 22 to 25%, and the pH value is 3.0 to 5.0.
In one embodiment of the present invention, the particle size of the component (A) is not critical, and D is50Less than or equal to 25 mu m, and can be mechanically pulverized or air-jet pulverized. From the viewpoint of extrusion processing and dispersibility in resins, jet milling is preferred, and the particle diameter of the component (A) is 5 μm. ltoreq. D50≤15μm。
In one embodiment of the present invention, the piperazine phosphate salt in the component (a) is a condensed phase intumescent flame retardant with three sources in one (phosphorus source, nitrogen source, carbon source), and has good heat resistance and char formation. But condensed phase flame retardance needs moderate proportion of phosphorus, nitrogen and carbon flame retardant elements to play a flame retardant role well, the phosphorus content in the piperazine phosphate is 22% -25%, the acid source is sufficient, the nitrogen content is low, and a certain gas source needs to be supplemented.
In one embodiment of the invention, because piperazine phosphate is an acidic flame retardant system, an acidic or weakly alkaline compound is needed for a supplementary gas source, so that the problems of acid-base dehydration reaction and degradation foaming of the high-expansion fireproof low-smoke halogen-free flame retardant composition in the extrusion processing process are solved.
In one embodiment of the present invention, the component (B) is used as a supplementary gas source, and ammonium polyphosphate, melamine polyphosphate, melamine ditrimer phosphate, melamine pyrophosphate, melamine orthophosphate, melamine cyanuric acid, which can be used alone or as a mixture.
In one embodiment of the present invention, the ammonium polyphosphate in the component (B) is ammonium polyphosphate II with a polymerization degree of more than 1000, a nitrogen content of 14 to 15%, and a particle diameter D50Less than or equal to 20 mu m and the pH value is 5.5-7.5.
In one embodiment of the present invention, the ammonium polyphosphate in the component (B) may be used without surface treatment or may be used after surface treatment. From the viewpoint of water resistance and compatibility, surface-treated ammonium polyphosphate is preferable.
In one embodiment of the present invention, the surface-treated ammonium polyphosphate may be selected from silane coupling agents, melamine resins, melamine-formaldehyde, and epoxy resin surface-coated ammonium polyphosphates, but is not limited to the above-listed coated ammonium polyphosphate types, and modified ammonium polyphosphates having improved water resistance, moisture migration resistance, and resin compatibility through dry or wet processes may be used in the present invention.
In one embodiment of the present invention, the melamine polyphosphate, the melamine ditrimexophosphate, the melamine pyrophosphate, and the melamine orthophosphate in the component (B) are obtained by reacting phosphoric acid or a phosphoric acid salt with melamine, and one of them may be used, or a mixture thereof may be used.
In one embodiment of the present invention, melamine pyrophosphate is preferable from the viewpoint of nitrogen element content, thermal stability, and flame retardancy synergy. The nitrogen content of the melamine pyrophosphate is 42.5-43.5%, and the particle diameter D is50Less than or equal to 10 mu m and the pH value is 4.5-6.0.
In one embodiment of the present invention, the melamine cyanuric acid in the component (B) is prepared from melamine and cyanuric acid as raw materials by various processes.
In one embodiment of the invention, the melamine cyanurate products obtained from different processes have different microscopic morphologies, which can be divided into rods, flakes, blocks or mixtures of different morphologies. From the viewpoint of flame retardant efficiency, the flake melamine cyanurate is preferable, and when the morphology is a mixed state, the higher the proportion of the flake melamine cyanurate is, the better the proportion is.
In one embodiment of the present invention, the component (B) has a melamine cyanurate nitrogen content of 27% or more and a particle diameter D50Less than or equal to 5 mu m and the pH value is 5.0-7.5.
In one embodiment of the present invention, the expanded graphite of the component (C) has a mesh size of 100 to 400 mesh and a pH of 4.0 to 7.0.
In one embodiment of the present invention, the expanded graphite of the component (C) needs to use concentrated sulfuric acid in the preparation process of the chemical oxidation method, and the surface of the expanded graphite obtained by the method is still residual acid after being washed with water, and shows a certain acidity. The pH of the expanded graphite is preferably 5.0 to 7.0 from the viewpoint of reducing the corrosivity of processing equipment.
The invention also provides a high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition which is formed by combining the thermoplastic resin and the high-expansion fireproof low-smoke halogen-free flame retardant composition, wherein the weight ratio of the thermoplastic resin to the high-expansion fireproof low-smoke halogen-free flame retardant composition is 100 (40-120).
In one embodiment of the present invention, the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin is one of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, styrene thermoplastic elastomer, olefin thermoplastic elastomer and polyurethane thermoplastic elastomer.
In one embodiment of the present invention, the thermoplastic resin is preferably an ethylene-vinyl acetate copolymer from the viewpoint of convenience in use and post-maintenance when the molded article of the thermoplastic resin composition has a certain elasticity.
In one embodiment of the invention, the compounded high-expansion fireproof low-smoke halogen-free flame retardant composition is used for endowing the thermoplastic resin with flame retardance, high expansion and fireproof performance, and further preferably added with functional additives such as an antioxidant, a light stabilizer, an anti-aging agent, a compatilizer and a lubricant from the viewpoint of taking mechanical performance, processability and weather resistance of the flame-retardant thermoplastic resin composition into consideration.
In one embodiment of the present invention, the functional auxiliary is a conventional commercially available component and an amount, and is not otherwise particularly limited.
The invention also provides a preparation method of the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition, which adopts a double-screw extrusion granulation and one-time injection molding preparation process, and the preparation method comprises the following specific steps:
(1) mixing the component (A), the component (B) and the component (C) in a high-speed mixer for 5-10 minutes according to the proportion to obtain a high-expansion fireproof low-smoke halogen-free flame retardant composition;
(2) adding thermoplastic resin in a corresponding weight proportion into the high-expansion fireproof low-smoke halogen-free flame retardant composition, and premixing for 5-10 minutes by using a high-speed mixer to obtain the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition;
(3) and adding the mixed high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition through a main feeding port of a double-screw extruder, carrying out melt blending to uniformly mix the components, extruding, granulating and drying to obtain the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin modified particles.
(4) The high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin modified particles are subjected to one-time injection molding by an injection molding machine to obtain a product forming body.
The present invention will be described in detail with reference to specific examples.
Sample test methods and standards in the examples:
1) limiting Oxygen Index (LOI): testing according to GB/T2406.2 standard;
b15 fire rating: the test was carried out according to International maritime organization IMO Specification B15 fire rating.
2) Volume expansion ratio (VE): VE is V/m;
in the formula: m is the sample mass before firing, g;
v is the volume of the sample mL after burning for 30min at 600 ℃.
3) The phenomenon of fly ash: when the limiting oxygen index combustion test was performed, it was observed whether "fly ash" was produced.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products prepared by known methods.
Examples 1 to 11
The used piperazine pyrophosphate (PAPP) is self-made by Shanghai chemical research institute, Inc., or can be purchased commercially, or adopts the influence of the piperazine pyrophosphate of plastics ISSN1005-3360, CN21-1145/TQ on the combustion performance of polypropylene materialsAnd the flame retardant mechanism thereof, the polymerization degree of the PAPP is 26, the pH value is 4.8, and the particle size D of the powder is50And 12 μm.
The ammonium polyphosphate (APP) is II type ammonium polyphosphate produced by Zhejiang Asahson non-halogen smoke-eliminating flame retardant Limited company, the polymerization degree is more than 1000, and the particle size D5018 μm and pH 6.8.
The used melamine pyrophosphate (MPP) is produced by Sichuan institute of Fine chemical engineering design and has a particle size D508 μm, pH 5.2.
The Melamine Cyanuric Acid (MCA) is produced by Zhejiang Asahi non-halogen smoke-eliminating flame retardant, the polymerization degree is more than 1000, and the particle diameter D is50At 4 μm, pH 7.1.
The used Expanded Graphite (EG) is produced by Qingdao and Dagraphite Limited, the mesh number is 100 meshes, 200 meshes and 400 meshes respectively, the expansion multiplying power is 220mL/g, 170mL/g and 90mL/g respectively, and the pH value is 5.5-6.5.
The polypropylene (PP) used was a copolymer polypropylene K8003 produced by Shanghai petrochemical company, Ltd.
The ethylene-vinyl acetate copolymer (EVA) used was EVA 2318 produced by Korea group, and the Vinyl Acetate (VA) content was 18%.
In examples 1 to 11, the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition were prepared according to the following processing and preparation methods in parts by weight of the components in table 1.
(1) Mixing the component (A), the component (B) and the component (C) in parts by weight in a high-speed mixer for 8 minutes to obtain a high-expansion fireproof low-smoke halogen-free flame retardant composition;
(2) adding thermoplastic resin in a corresponding weight proportion into the halogen-free flame retardant, and premixing for 6 minutes by a high-speed mixer to obtain a high-expansion fireproof low-smoke halogen-free flame retardant composition and a thermoplastic resin composition;
(3) and adding the mixed high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin composition through a main feeding port of a double-screw extruder, carrying out melt blending to uniformly mix the components, extruding, granulating and drying to obtain the halogen-free flame-retardant thermoplastic resin modified particles. Wherein when processing PP resin, the temperature of the first section to the fifth section of the 20-twin-screw extruder is as follows in sequence: 180-190 ℃, 190-210 ℃ and 200-220 ℃; the main machine rotating speed of the double-screw extruder is 200-300 rpm; the feeding frequency is 12-15 Hz. Wherein, when processing EVA resin, 20 twin-screw extruder first section to fifth section temperature do in proper order: 130-140 ℃, 135-145 ℃ and 140-150 ℃; the main machine rotating speed of the double-screw extruder is 200-300 rpm; the feeding frequency is 15-18 Hz;
(4) the high-expansion fireproof low-smoke halogen-free flame retardant composition and the thermoplastic resin modified particles are subjected to one-time injection molding by using an injection molding machine to form standard sample strips according to different test requirements; wherein the injection molding temperature of the PP resin particles is 180-200 ℃, and the injection molding temperature of the EVA resin particles is 135-150 ℃.
The formulations of examples 1 to 11 and comparative examples 1 to 2 are shown in Table 1, and the results of the performance tests are shown in Table 2.
Examples 1-11 and comparative examples 1-2 were processed in the same manner.
TABLE 1 EXAMPLES 1 TO 8 AND COMPARATIVE EXAMPLES 1 TO 2 (in parts by weight)
TABLE 2 Performance test results of examples 1 to 11 and comparative examples 1 to 2
As can be seen from the test data in Table 2, in comparative example 1, only the component (A) and the component (B) compounded intumescent flame retardant are added into the EVA resin, the LOI of the material is increased from 18% of that of the pure EVA resin to 35.9%, a compact and continuous intumescent carbon layer is formed on the surface of the material during combustion, the material has better flame retardance, but the char formation speed in the initial heating stage is slightly slow, the expansion ratio is only 20mL/g, and the formed intumescent carbon layer cannot rapidly fill holes, so that flame and smoke can penetrate through the holes and can not reach the fire resistance grade of B15. Comparative example 2 only add expanded graphite and carry out fire-retardant treatment, form "worm form" expanded carbon layer fast at the initial stage of burning, the expansion ratio is great, and the charcoal layer can fill hole and hole fast, but along with burning flame pressure or the effect of heat convection, the fluffy expanded carbon layer in surface suffers destruction, forms serious "flying dust", leads to adiabatic expanded carbon layer to become invalid, can't pass 15 min' fire resistance test at last.
In examples 1 to 3, expanded graphite having different mesh numbers was used, and it can be seen from the test data in table 2 that as the mesh number of the expanded graphite increased, the particle size of the expanded graphite decreased, and the expansion ratio of the flame retardant material decreased significantly. However, the expanded graphite with the mesh number lower than 100 has an obvious large-particle lamellar structure, is not uniformly mixed with other components, is easy to bridge during extrusion processing, influences the processing efficiency, and simultaneously, the large lamellar can obviously reduce the mechanical property of the material, so that the practical application is not utilized. However, the expanded graphite with the mesh number larger than 400 is an ultrafine structure, the self expansion rate is low, the plugging and filling properties of holes and pores are affected, and the B15 fire-resistant grade cannot be passed.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A high-expansion fireproof low-smoke halogen-free flame retardant composition is characterized by comprising the following components in percentage by weight: (A) 20 to 70 parts by mass of component (A), 10 to 50 parts by mass of component (B), and 15 to 60 parts by mass of component (C), wherein the total amount of components (A), (B), and (C) is 100 parts by mass;
(A) the component is selected from one or more than two of polyphosphoric acid piperazine, pyrophosphoric acid piperazine, orthophosphoric acid piperazine or diphosphoric acid piperazine;
(B) the components are selected from one or more than two of ammonium polyphosphate, melamine polyphosphate, melamine ditrimexophosphate or melamine cyanuric acid;
(C) the component is expanded graphite;
the pH value of the high-expansion fireproof low-smoke halogen-free flame retardant composition is 4.5-6.5.
2. The high-expansion fireproof low-smoke halogen-free flame retardant composition according to claim 1, wherein piperazine orthophosphate or piperazine diphosphate is prepared by acid-base reaction of phosphoric acid and piperazine as raw materials;
the polyphosphoric acid piperazine or the pyrophosphoric acid piperazine is prepared by taking phosphoric acid and piperazine as raw materials and carrying out high-temperature polymerization.
3. The high-expansion fireproof low-smoke halogen-free flame retardant composition as claimed in claim 1, wherein the particle size D of the component (A) is50Less than or equal to 25 mu m, the phosphorus content is 22 to 25 percent, and the pH value is 3.0 to 5.0.
4. The high-expansion fireproof low-smoke halogen-free flame retardant composition as claimed in claim 1, wherein the particle size D of the component (B) is50≤20μm。
5. The high-expansion fireproof low-smoke halogen-free flame retardant composition according to claim 1, wherein the mesh number of the expanded graphite (C) is 100-400 meshes, and the pH is 4.0-7.0.
6. A high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition is characterized in that the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition is prepared by adding the high-expansion fireproof low-smoke halogen-free flame retardant composition in any one of claims 1 to 5 into thermoplastic resin.
7. The high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition as claimed in claim 6, wherein the weight ratio of the thermoplastic resin to the high-expansion fireproof low-smoke halogen-free flame retardant composition is 100 (40-120).
8. The high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition as claimed in claim 6, wherein the thermoplastic resin is one of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, styrene thermoplastic elastomer, olefin thermoplastic elastomer or polyurethane thermoplastic elastomer.
9. A preparation method of the high-expansion fireproof low-smoke halogen-free flame retardant composition as claimed in any one of claims 1 to 5, characterized in that the components (A), (B) and (C) are mixed in a high-speed mixer for 5 to 10 minutes according to the proportion to obtain the high-expansion fireproof low-smoke halogen-free flame retardant composition.
10. A preparation method of a high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition is characterized in that thermoplastic resin with a corresponding weight proportion is added into the high-expansion fireproof low-smoke halogen-free flame retardant composition in any one of claims 1 to 5, and the mixture is premixed for 5 to 10 minutes by a high-speed mixer to obtain the high-expansion fireproof low-smoke halogen-free flame-retardant thermoplastic resin composition.
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