CN113930012B - Flame-retardant polypropylene material and preparation method and application thereof - Google Patents
Flame-retardant polypropylene material and preparation method and application thereof Download PDFInfo
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a flame-retardant polypropylene material and a preparation method and application thereof. The flame-retardant polypropylene material disclosed by the invention is prepared from the following raw materials in parts by mass: 40 to 80 portions of polypropylene resin, 20 to 30 portions of compound flame retardant, 0 to 20 portions of filler, 0.3 to 1.2 portions of lubricant and 0.1 to 0.8 portion of antioxidant. The flame retardant has the advantages of UL94V-0 grade, short flame retardant time, no melt dripping, good extrusion moldability, environmental protection and no halogen. In the preparation method, a double-screw/single-screw double-stage mixing granulator set is preferably selected, the method is suitable for pipeline extrusion, the material can not be repeatedly thermally degraded, and the pipe with smooth surface and no obvious lines can be prepared.
Description
Technical Field
The invention belongs to the technical field of high polymer modified materials, and particularly relates to a flame-retardant polypropylene material, and a preparation method and application thereof.
Background
Polypropylene (PP) is one of five general-purpose resins, has the excellent characteristics of light weight, easiness in processing, chemical resistance and the like, and is widely applied to the industrial fields of chemical industry, electric appliances, packaging and the like. However, as the demand of polypropylene in the industries of construction, automobile, ship, and electrical and electronic insulation materials is increasing, the requirement of flame retardant property is also increasing. The polypropylene is a flammable material, the oxygen index of the polypropylene is only 17% -18%, the char forming rate of the polypropylene is low, molten drops are easily generated during combustion, surrounding combustibles can be ignited, and therefore the polypropylene is required to be modified in many application occasions.
At present, common flame-retardant polypropylene materials are generally halogen-antimony flame-retardant systems and have both gas-phase flame-retardant and solid-phase flame-retardant mechanisms. Adding bromine flame retardant and antimony flame retardant into polypropylene resin, when polypropylene is heated and cracked, firstly, the bromine flame retardant is heated and decomposed to release free radical inhibitor HBr, thereby interrupting combustion or delaying chain combustion reaction, HBr and Sb 2 O 3 The reaction produces fine particulate SbOBr which promotes free radical interactions to terminate the chain reaction, while also producing large quantities of inert gas or high density steam which dilutes the oxygen and gaseous combustible products and lowers the temperature of the combustible gas, resulting in termination of combustion. The conventional flame-retardant polypropylene is not efficient, part of flame retardant is easy to separate out, a plurality of flame retardants affect the weather resistance of polypropylene materials, and because the flame retardant contains halogen, toxic gas is released during combustion, so that the flame retardant seriously threatens human health and damages to the surrounding environment, and the flame retardant is forbidden to be used in many fields. Although the inorganic flame retardant meets the requirement of environmental protection, the flame retardant efficiency is not high, the addition amount is large, and the mechanical property of the polypropylene is seriously deteriorated and cannot be compensated.
The existing commonly used halogen-free flame retardant is an ammonium polyphosphate (APP) flame retardant system and a Jiao Pai flame retardant system, but the APP flame retardant system has poor water resistance and is easy to precipitate, the adverse conditions such as water marks, mold sticking and the like can easily occur, and the Jiao Pai flame retardant system has good water resistance and high flame retardant efficiency.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a flame-retardant polypropylene material in a first aspect, which has the advantages of UL94V-0 grade, short flame-retardant time, no melt dripping, good extrusion moldability, environmental protection and no halogen.
The second aspect of the invention provides a preparation method of the flame-retardant polypropylene material.
The third aspect of the invention provides an application of the flame-retardant polypropylene material.
According to a first aspect of the invention, a flame-retardant polypropylene material is provided, which is composed of the following raw materials in parts by mass: 40 to 80 portions of polypropylene resin, 20 to 30 portions of compound flame retardant, 0 to 20 portions of filler, 0.3 to 1.2 portions of lubricant and 0.1 to 0.8 portion of antioxidant; the lubricant comprises polyethylene wax and silicone master batches, and the antioxidant comprises antioxidant 168, antioxidant 1010 and antioxidant 1330.
In the invention, the polyethylene wax and the silicone master batch are mutually matched through the internal and external lubricating properties of the polyethylene wax and the silicone master batch, so that the flame retardant and the filler in the material formula are fully dispersed, the friction coefficient of the extruded surface is reduced, and the surface effect of the extruded pipe is smooth and flat; the antioxidants 168 and 1010 are common antioxidant addition combinations in the flame-retardant polypropylene, are easily decomposed in a long-term high-temperature process, so that the flame retardant property of the polypropylene material is reduced, the extrusion of the pipe is unstable, the hindered phenol antioxidant 1330 is added, the thermal degradation of the flame retardant can be better protected, and the antioxidants 168, 1010 and 1330 have a synergistic effect and high efficiency. Through the combination of the lubricant and the antioxidant, the polypropylene material has excellent flame retardant property and excellent extrusion property.
In some embodiments of the present invention, the flame retardant polypropylene material is composed of the following raw materials in parts by mass: 50-70 parts of polypropylene resin, 24-29 parts of compound flame retardant, 5-15 parts of filler, 0.8 part of lubricant and 0.6 part of antioxidant.
In some preferred embodiments of the present invention, the compounded flame retardant comprises piperazine pyrophosphate, melamine polyphosphate and nano zinc oxide; preferably, the compound flame retardant is piperazine pyrophosphate: melamine polyphosphoric acid: nanoscale zinc oxide = (20-80): (20 to 50): (0-5) compounding; further preferably, the compound flame retardant is piperazine pyrophosphate: melamine polyphosphoric acid: nanoscale zinc oxide = (40-60): (25-45): (1-3) are compounded. According to the invention, piperazine pyrophosphate is a 'three-in-one' flame retardant which is excellent in performance and integrates a carbon source, a gas source and an acid source into a whole, melamine polyphosphoric acid and nano zinc oxide are added, in the combustion process, piperazine pyrophosphate is heated and decomposed to generate a compact carbon layer, the melamine polyphosphoric acid releases phosphoric acid and metaphosphoric acid to promote the degradation of piperazine pyrophosphate and resin, esterification dehydration and cross-linking carbonization reactions occur, zinc oxide is used as a flame retardant synergist and has a certain catalytic action on the esterification reaction to advance the thermal oxidation degradation process of the material, and the compounded flame retardant forms an expanded carbon layer on the surface of the material after being heated and decomposed to isolate the transmission of oxygen and heat and effectively inhibit the further degradation of the material, so that good self-extinguishing performance is obtained, and the flame retardant performance is excellent.
In some more preferred embodiments of the invention, the lubricant is polyethylene wax: silicone master batch =1:1 is prepared by compounding.
In some more preferred embodiments of the invention, the antioxidant is an antioxidant 168: antioxidant 1010: antioxidant 1330=3:2:1 is prepared by compounding. Antioxidant 1330 has the chemical name 1,3,5-trimethyl-2,4,6- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene.
In some more preferred embodiments of the present invention, the polypropylene resin is a high impact polypropylene having a melt index of (2 to 5) g/10min at 2.16kg at 230 ℃ under test conditions and a notched Izod impact strength of > 500J/m.
In some more preferred embodiments of the invention, the filler is at least one of talc, calcium carbonate, barium sulfate, wollastonite, or mica; wollastonite is preferred. According to the invention, the filler can reduce the cost of the polypropylene material, and the filler is not easy to ignite, so that part of easily-combustible polypropylene resin is replaced in the polypropylene material, and the generation of a carbon layer can be promoted in the combustion process, and the transfer of oxygen and heat is isolated, thereby achieving the purpose of flame retardance.
In some more preferred embodiments of the invention, the filler is2500 meshes, loss on ignition lower than 2% (burning at 800 ℃ for 2 h), siO 2 Content > 52%, aspect ratio 20:1, wollastonite. Wollastonite with inferior performance is selected, the wollastonite has high purity, less impurities, high silicon content and certain length-diameter ratio, has small influence on flame retardant performance, is uniformly dispersed in a flame retardant polypropylene material, does not drip in the combustion process, and therefore, no anti-dripping agent is added, and because of the addition of the anti-dripping agent, the material is easy to expand and deform in the extrusion process, so that an ideal pipe cannot be obtained.
According to a second aspect of the present invention, there is provided a method for preparing the above flame retardant polypropylene material, comprising the following steps:
s1: preparing a compound flame retardant, a filler, an antioxidant and a lubricant into an auxiliary agent package according to a proportion;
s2: and mixing the polypropylene resin and the additive package according to a ratio, transferring the mixture into a double-screw/single-screw double-stage mixing granulator set, and extruding and granulating to obtain the flame-retardant polypropylene material.
According to the invention, a double-screw/single-screw double-stage mixing granulator set is selected for extrusion granulation, a first-stage double-screw extruder is used for fully and uniformly plasticizing the resin, the flame retardant and the filler, the materials can be better plasticized in double screws, the flame retardant and the filler are fully dispersed, and a second-stage single-screw extruder is suitable for pipeline extrusion, has weak single-screw shearing property and can not cause the materials to be repeatedly thermally degraded.
In some embodiments of the invention, the extrusion temperature of the twin screw/single screw dual stage compounding granulator set is from 190 ℃ to 225 ℃. The temperature is moderate, the flame retardant is not easy to degrade, the melt index of the polypropylene material can be better kept, and the polypropylene resin can be fully melted.
In some preferred embodiments of the invention, in the twin-screw/single-screw double-stage mixing granulator set, the screw diameter of the twin-screw extruder is 50-95 mm, and the length-diameter ratio is 24-48; preferably, the single-screw extruder has a screw diameter of 120 to 200mm and a length-diameter ratio of 7 to 20.
In some more preferred embodiments of the present invention, in the twin-screw/single-screw two-stage mixing granulator set, the twin-screw extruder has a screw diameter of 65mm and a length-to-diameter ratio of 44; preferably, the single screw extruder has a screw diameter of 150mm and a length to diameter ratio of 20.
According to a third aspect of the invention, a pipe is provided, wherein the pipe is prepared by melting, cooling and shaping the flame-retardant polypropylene material.
In some embodiments of the present invention, the setting is specifically performed by: and in a pipe neck mold, melting the flame-retardant polypropylene material, passing through a shaping device, vacuum forming, and cooling and shaping.
In some preferred embodiments of the present invention, the cooling is a water-cooling method; preferably, the cooling temperature is 50-70 ℃; more preferably 60 ℃. In the invention, the flame-retardant polypropylene material is subjected to vacuum forming and then is subjected to low-temperature cooling setting at the temperature of 50-70 ℃ through the mold wall, so that the flame-retardant polypropylene is prevented from being quenched to cause extrusion shrinkage deformation of the pipe.
The invention has the beneficial effects that:
1. the flame-retardant polypropylene material has excellent flame-retardant performance, the flame-retardant performance of sample strips (1.5 mm and 3.0 mm) can reach UL94V-0, the flame-retardant time is short, and the material has good self-extinguishment.
2. The polypropylene resin has a low melt index (the melt index is 2-5 g/10min, and the test conditions are 230 ℃/2.16 Kg), the flowability of the flame-retardant polypropylene material prepared by flame-retardant modification is reduced to about 1g/10min, the flame-retardant polypropylene material is suitable for extrusion molding, the impact strength of the base material is high, and a certain toughness can be maintained after modification.
3. In the flame-retardant polypropylene material, piperazine pyrophosphate: melamine polyphosphoric acid: nanoscale zinc oxide = (20-80): (20 to 50): (0-5) piperazine pyrophosphate is a flame retardant which has excellent performance and integrates a carbon source, a gas source and an acid source into a whole, melamine polyphosphoric acid and nano zinc oxide are added, the piperazine pyrophosphate is heated and decomposed to generate a compact carbon layer in the combustion process, the melamine polyphosphoric acid releases phosphoric acid and metaphosphoric acid to promote the degradation of the piperazine pyrophosphate and resin, esterification dehydration and crosslinking carbonization reactions are carried out, the zinc oxide is used as a flame-retardant synergist and has a certain catalytic action on the esterification reaction to advance the thermal oxidation degradation process of the material, an expanded carbon layer is formed on the surface of the material after the compounded flame retardant is heated and decomposed, the transmission of oxygen and heat is isolated, the further degradation of the material is effectively inhibited, and therefore, good self-extinguishing performance is obtained, and the flame-retardant performance is excellent.
4. The filler is preferably wollastonite, so that on one hand, the cost of the flame-retardant polypropylene material can be reduced, and the advantage of low cost is possible for the flame-retardant polypropylene material to become a PVC (polyvinyl chloride) substitute material; on the other hand, wollastonite with a certain length-diameter ratio is selected, so that the wollastonite has small influence on the flame retardant property of the flame retardant polypropylene material, can be uniformly dispersed in the flame retardant polypropylene material, does not need to be added with an anti-dripping agent, is easy to expand and deform the material in the extrusion process due to the addition of the anti-dripping agent, and cannot obtain an ideal pipe.
5. The invention selects the polyethylene wax and the silicone master batch as the lubricant, the polyethylene wax is a lubricant with excellent internal and external lubricating performance, has good compatibility with the base material polypropylene resin, can improve the dispersibility of the flame retardant and the filler, can improve the processing efficiency when extruding the pipe, overcomes the adhesion of the pipe, improves the smoothness and the glossiness of the finished product, and improves the appearance of the finished product; the silicone master batch serving as an excellent external lubricant can improve the extrusion processing performance of the material, reduce the scale deposition of an extrusion die, reduce the abrasion of equipment, improve the discharging speed and reduce the deformation of a product, has better lubricating and dispersing performance on the dispersibility of the filler and the toner, and the polyethylene wax and the silicone master batch fully disperse the flame retardant and the filler in the material formula through the internal and external lubricating performance, reduce the friction coefficient of the extruded surface and ensure that the surface effect of the extruded pipe is smooth and flat.
6. The invention selects the antioxidant as antioxidant 168: antioxidant 1010: the antioxidant 1330 is compounded, the antioxidant 168 and the antioxidant 1010 are common antioxidant addition combinations in the flame-retardant polypropylene, the antioxidant 168 can protect the thermal degradation of materials in the processing process, the antioxidant 1010 has excellent antioxidant performance on the polypropylene and can effectively prolong the service life of products, the extrusion speed of the pipe is low in the extrusion processing process, the residence time of the flame-retardant polypropylene in an extruder is long, and when the antioxidant 168 and the antioxidant 1010 are compounded to be used as a flame retardant, the flame retardant is easy to decompose in the long-term high-temperature process due to the high content of the flame retardant, the heat resistance of the flame retardant is low, the initial degradation temperature is about 280 ℃, the flame retardant performance is reduced, and the extrusion of the pipe is unstable. And the hindered phenol antioxidant 1330 is added in the flame retardant, so that the thermal degradation of the flame retardant can be better protected, and the antioxidant 168, the antioxidant 1010 and the antioxidant 1330 have a synergistic effect and high efficiency.
7. In the preparation method, a double-screw/single-screw double-stage mixing and granulating unit is preferably selected, a first-stage double-screw extruder is used for fully and uniformly plasticizing resin, a flame retardant and a filler, the length-diameter ratio is 24-48, the length of a screw is relatively long, materials can be better plasticized in the double screws, the flame retardant and the filler can be fully dispersed, the second-stage single-screw extruder is suitable for pipeline extrusion, the single screw is weak in shearing property and cannot be repeatedly degraded thermally, a pipe neck mold is connected to the tail end of the single-screw extruder, the pipe neck mold is formed by low temperature of 50-70 ℃ through a mold wall after vacuum plastic suction through a forming device, the situation that the flame retardant polypropylene is quenched to cause extrusion shrinkage deformation of a pipe is avoided, the pipe is conveyed through a conveying belt and cut by a fixed-length pipe cutting machine, the process from the raw materials to the finished product is realized in one step, the production efficiency is high, the extrusion temperature of the double-stage mixing and granulating unit is set to be 190-225 ℃, the temperature is moderate, the flame retardant is not easy to degrade, the melt index can be kept better, and the polypropylene resin can be fully melted.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can make a selection within suitable ranges through the description herein, and are not intended to be limited to the specific data of the following examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Polypropylene: 7032E3 (MI 4g/10 min), exxon; k8009 (MI is 8.5g/10 min), medium petrochemical
Flame retardant: piperazine pyrophosphate, marketed by pusilufos chemical ltd; melamine polyphosphoric acid, and Sichuan refining; nanoscale zinc oxide, commercially available
Filling materials: wollastonite, commercially available
Lubricant: polyethylene wax, commercially available
Lubricant: silicone masterbatches, daokoning
Antioxidant: antioxidants 168, 1010, 1330, basf
TABLE 1 raw Material compositions (parts by mass) of examples and comparative examples
The preparation method of the flame-retardant polypropylene material comprises the following steps of:
(1) Preparing a compound flame retardant, a filler, an antioxidant and a lubricant into an auxiliary agent package according to a proportion;
(2) Mixing polypropylene resin and an auxiliary agent bag in a high-speed stirring barrel for 60s according to a ratio, starting a discharging button, feeding the mixed material into a double-screw extruder, wherein the tail end of the double-screw extruder is linked with a double-stage mixing granulator set of a single-screw extruder, and the extrusion temperature of the double-stage mixing granulator set is set to 190-225 ℃;
(3) The tail end of the single-screw extruder is connected with a pipe neck mold, the pipe neck mold is formed through low-temperature cooling of the mold wall after vacuum plastic suction through a forming device, and the flame-retardant polypropylene pipe meeting UL94V-0 level is obtained after the pipe neck mold is conveyed through a conveying belt and cut through a fixed-length pipe cutting machine.
The double-screw extruder is characterized in that the diameter of a screw is 65mm, the length-diameter ratio of the screw is 44, the diameter of a single-screw extruder is 150mm, the length-diameter ratio of the single-screw extruder is 20, and the temperature of the die wall is controlled to be 60 ℃ by cooling the sizing device with water.
The step (2) of comparative example 3 was carried out in the same manner as in example 2 except that the extrusion temperature of the two-stage kneading and granulating unit was set to 230 to 255 ℃ and the screw aspect ratio of the twin-screw extruder section of the two-stage kneading and granulating machine was 36.
The extrusion temperature of the two-stage type mixing granulator set in step (2) of comparative example 4 was set to 230 to 255 ℃, and the other steps were the same as those of example 2.
The temperature of the mold wall was controlled to 35 ℃ by cooling with water in the molding apparatus of comparative example 5, and the other steps were the same as in example 1.
And (3) testing the material performance:
and (5) performing injection molding by using a CG110E horizontal injection machine to obtain a standard sample. The molding process conditions are as follows: injection temperature (feed inlet) 185/190/195/195 ℃ (nozzle); the injection pressure is 90MPa; the pressure maintaining time is 8s; the cooling time was 10s.
The performance test criteria were as follows:
melt index: testing was performed according to ASTM D-1238 (230 ℃/2.16 Kg), after cutting the extruded tubing into small particles with scissors;
and (3) flame retardant test: testing according to UL94 standard (1.5 mm and 3.0mm sample strips are obtained by crushing the extruded tube and then injection molding the tube into sample strips);
extrusion condition/appearance: and observing the discharge molding condition of the extruded pipe on site.
Table 1 the flame retardant polypropylene material pipe made of different formulations has various test properties and flame retardant properties as shown in table 2:
TABLE 2 results of various performance tests and flame retardant rating of polypropylene pipes prepared in examples and comparative examples
As can be seen from Table 2, according to the formula and the preparation method of the invention, the flame-retardant polypropylene material pipes can be prepared in the examples 1-3, the high MI polypropylene copolymer resin is used in the comparative example 1, the flowability is high, the moldability of the extruded pipe is poor, the extrusion is unstable and easy to deform, and the filler talcum powder is used in the comparative example 2, so that the flame-retardant performance of the prepared flame-retardant polypropylene is reduced, 1.5mm sample band cotton can be easily dropped to cause the flame-retardant performance, but the pipes can still be stably extruded and normally molded; comparative example 3 is not added with silicone master batch, so that scorched scale is easy to generate at an extrusion die after long-term production, thereby affecting the surface smoothness of the extruded tube, comparative example 4 is not added with antioxidant 1330, but adopts a combination of antioxidant 168 and antioxidant 1010 which are more conventional, the extrusion temperature is increased to 250 ℃, the tube is just started or normally produced, the flame retardant begins to degrade after 10min, the surface of the tube becomes rough, the thickness is not uniform, and the tube has obvious deformation and shrinkage; comparative example 5 the mold wall temperature of the vacuum forming apparatus was set to 35 c, and the tube was rapidly cooled after extrusion, and the tube was shrunk and deformed. It can be seen that the selection of the PP base material, the type of the filler, the reasonable matching of the lubricant and the antioxidant, the temperature setting of the extruder, the cooling temperature setting and the length-diameter ratio of the extruder all affect the preparation of the flame-retardant polypropylene material and the pipe thereof.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (7)
1. A flame retardant polypropylene material characterized by: the composite material is prepared from the following raw materials in parts by mass: 50 to 70 parts of polypropylene resin, 24 to 29 parts of compound flame retardant, 5 to 15 parts of filler, 0.8 part of lubricant and 0.6 part of antioxidant; the lubricant is polyethylene wax: silicone master batch =1:1, compounding; the antioxidant is antioxidant 168: antioxidant 1010: antioxidant 1330=3:2:1 is compounded; the compound flame retardant is piperazine pyrophosphate: melamine polyphosphoric acid: nanoscale zinc oxide = (40-60): (25-45): (1-3) compounding; the melt index of the polypropylene resin under the test condition of 230 ℃ and 2.16kg is (2-5) g/10min, and the notched impact strength of the cantilever beam is more than 500J/m; the length-diameter ratio of the filler is 20:1, wollastonite.
2. A method for preparing the flame-retardant polypropylene material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1: preparing a compound flame retardant, a filler, an antioxidant and a lubricant into an auxiliary agent package according to a proportion;
s2: and mixing the polypropylene resin and the auxiliary agent bag according to a ratio, transferring the mixture into a double-screw/single-screw double-stage mixing granulator set, and extruding and granulating to obtain the flame-retardant polypropylene material.
3. The method for preparing a flame retardant polypropylene material according to claim 2, wherein: the extrusion temperature of the double-screw/single-screw double-stage mixing granulator set is 190-225 ℃.
4. The method for preparing a flame retardant polypropylene material according to claim 2, wherein: in the double-screw/single-screw double-stage mixing granulator unit, the diameter of a screw of a double-screw extruder is 50-95 mm, and the length-diameter ratio is 24-48.
5. The method for preparing a flame retardant polypropylene material according to claim 4, wherein: in the double-screw/single-screw double-stage mixing granulator set, the screw diameter of a single-screw extruder is 120-200 mm, and the length-diameter ratio is 7-20.
6. A pipe, characterized in that: the pipe is prepared by melting the flame-retardant polypropylene material of claim 1 and then cooling and shaping.
7. The pipe according to claim 6, wherein: the cooling temperature is 50-70 ℃.
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| CN115725136B (en) * | 2022-11-29 | 2024-05-03 | 金发科技股份有限公司 | High-oxygen-index flame-retardant PP material and preparation method thereof |
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