CN110615928B - Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof - Google Patents
Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof Download PDFInfo
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
Modified coal gangue powder filled polyolefin flame-retardant composite material and a preparation process thereof belong to the technical field of preparation of polyolefin flame-retardant composite materials. The weight ratio of the modified coal gangue powder to the polyolefin in the composite material is 10-60: 100, and the modified coal gangue powder containing the cyclotriphosphazene derivative has a novel structure and can be used as a surface modifier and a flame retardant. The gangue powder modified by the cyclotriphosphazene is easy to disperse uniformly in the polyolefin matrix, and the interfacial binding force between the gangue powder and the polyolefin matrix can be enhanced, so that the mechanical property of the composite material is remarkably improved, and the composite material has a better flame retardant property. The novel composite material has the advantages of high coal gangue filling amount, low polyolefin consumption, no need of calcining coal gangue powder, energy conservation and low cost. The composite material has excellent comprehensive mechanical property, obvious flame retardant property, simple preparation process, no use of strong acid and strong alkali in the preparation process and no environmental pollution.
Description
Technical Field
The invention belongs to the technical field of preparation of polyolefin flame-retardant composite materials, and particularly relates to a coal gangue modified filled polyolefin flame-retardant composite material and a preparation process thereof.
Background
The polyolefin is a material with wide application range and excellent performance, and is widely applied to the fields of household appliances, automobiles, mechanical manufacturing and the like. However, with the rapid development of various fields, the general polyolefin material cannot meet the increasing demand of performance, and the polyolefin is synthetic resin made of petroleum which is a nonrenewable one-time natural resource, and with the consumption and price rise of petroleum resources, the price of the polyolefin material is always high, so that the polyolefin filling modification not only can effectively improve the comprehensive performance of the polyolefin material, but also can effectively reduce the cost of the polyolefin material and save the petroleum resources.
Along with the recent coal mining, a large amount of coal gangue waste is generated. At present, the treatment of coal gangue waste in China is still in a lower level, the utilization rate is less than 30%, and the treatment is mainly focused on the aspects of building materials, field reclamation, land backfilling and the like. Although the treatment methods can solve part of coal gangue waste, the added value is extremely low, and secondary pollution is generated to the environment. With the development of the technology, the coal gangue is gradually applied to the field of polymer material filling, because the coal gangue contains SiO2、Al2O3And Fe2O3And the surface of the polyolefin material is provided with hydroxyl groups such as silicon hydroxyl (Si-OH), aluminum hydroxyl (Al-OH) and the like, so that favorable conditions are provided for surface modification of the polyolefin material, and therefore, the coal gangue powder is used as a filler for filling and modifying the polyolefin material, so that the polyolefin material has wide application prospect and good economic and social benefits.
The most obvious problem of the modified polyolefin material filled with the coal gangue powder is that the coal gangue powder has poor compatibility in the polyolefin matrix material, is difficult to disperse uniformly, is easy to agglomerate and delaminate, and greatly reduces the mechanical property of the composite material. According to the report of the existing literature, the main method for solving the problem is to modify the surface of the coal gangue powder and refill modified polyolefin materials. A process for refilling a polypropylene material with calcined gangue powder modified by a plurality of micromolecular coupling agents is introduced in P27-31 of 1991 (2), and although the heat resistance and the processing fluidity of the gangue-polypropylene composite material prepared by the process are improved to a certain degree, the strength and the toughness of the composite material are greatly reduced. A technical route for preparing a polymer/coal gangue composite material by a melt blending method is introduced in the Chinese plastics 2006 (7) P35-39, a small amount of non-calcined coal gangue powder is filled, the strength and the modulus of the composite material are well improved, but when the filling amount of the coal gangue powder is increased to 25%, the strength and the modulus of the composite material are obviously reduced. Although the process in the prior document improves the mechanical comprehensive performance of the coal gangue-polyolefin composite material to a certain extent and reduces the preparation cost to a certain extent, the comprehensive performance of the coal gangue-polyolefin composite material cannot be synchronously improved, and the composite material prepared by the method has low coal gangue filling amount, low cost and limited reutilization of solid wastes.
In addition, polyolefin materials have become indispensable basic materials in daily life and are widely applied to various fields, but most of the polyolefin materials are flammable or combustible materials, and the application space is greatly limited. The conventional flame-retardant filler is a halogen/antimony composite flame-retardant filler, although the flame-retardant filler has excellent flame-retardant effect, a large amount of toxic and corrosive gas is generated during combustion, so that personnel on a fire scene are easily suffocated and die, and the corrosive gas can seriously damage buildings and equipment. Meanwhile, the flame retardant efficiency of the halogen flame retardant is in direct proportion to the filling amount, and the premise is that the mechanical property of the polyolefin material is damaged. Conventional flame retardant fillers are considered to be non-hazardous flame retardants such as: aluminum hydroxide or magnesium hydroxide, but such flame retardants need to be added in a large amount to obtain better flame retardant performance and need to be supplemented with a flame retardant synergist, which can greatly reduce the mechanical properties of polyolefin materials and increase the preparation cost, and in addition, such flame retardant fillers can greatly reduce the filling amount of coal gangue powder, so that the problem needs to be solved urgently. Aiming at the defects of the two flame retardants, the phosphazene flame retardant filler is proposed and popularized, and the phosphazene flame retardant filler is a high polymer material formed by alternately arranging phosphorus and nitrogen elements, has a stable phosphorus-nitrogen framework structure, and has good thermal stability and flame retardance due to the unique phosphorus and nitrogen hybridized structure and high phosphorus and nitrogen content. The phosphazenes have the advantages of low smoke generation amount during combustion, high flame retardant efficiency and no generation of toxic and corrosive gases, and are considered to be a flame retardant with the greatest development prospect.
Disclosure of Invention
The invention aims to provide a novel modified coal gangue powder filled polyolefin flame-retardant composite material aiming at the defects of the prior art, and the composite material has greatly improved mechanical comprehensive properties such as strength, toughness and the like and excellent flame retardance.
The invention also aims to provide a preparation method of the modified coal gangue powder filled polyolefin flame-retardant composite material, so that the filling amount of the modified coal gangue powder is greatly increased, and the cost is obviously reduced.
The invention relates to cyclotriphosphazene, which is hexa (P-hydroxybenzaldehyde) -hexa (aliphatic alkoxy) substituted triphosphazene (HDCP) with a molecular formula of (P ═ N)3(OC6H4CHO)6(OCnH2n+1)6The structural formula is shown as follows:
wherein n is an integer of 2 to 4.
The modified coal gangue powder filled polyolefin flame-retardant composite material is characterized in that the weight ratio of the modified coal gangue powder to polyolefin is 10-60: 100, the modified coal gangue powder contains HDCP, and the weight ratio of the HDCP to the coal gangue powder is 1-10: 100. The HDCP contained in the polyolefin composite material provided by the invention is a reactive amphoteric macromolecular compound, the p-hydroxybenzaldehyde substituent group of the HDCP can generate a stronger effect with silicon hydroxyl (Si-OH), aluminum hydroxyl (Al-OH) and other polar groups on the surface of coal gangue, and the aliphatic alkoxy group has good compatibility with the polyolefin matrix, so that the modified coal gangue powder can be effectively and uniformly dispersed in the polyolefin matrix, and the interface bonding force between the modified coal gangue powder and the polyolefin matrix material is remarkably improved, thereby remarkably improving the mechanical comprehensive properties of the polyolefin composite material, such as strength and toughness. Meanwhile, the HDCP is filled into the polyolefin composite material as a flame-retardant filler, so that the composite material has excellent flame-retardant property and thermal stability.
The invention provides a preparation route of a modified coal gangue powder filled polyolefin flame-retardant composite material, which is characterized by comprising the following process steps and conditions:
(1) drying, namely drying the 300-mesh 400-mesh coal gangue powder at 110-120 ℃ until the water content is less than 0.1%;
(2) high-speed mixing, namely adding HDCP and coal gangue powder into a high-speed mixer according to the mass ratio of 1-10: 100, wherein the rotating speed of the high-speed mixer is 1000-1400 r/min, and stirring and mixing at a high speed for 10-20 minutes;
(3) mixing polyolefin and modified coal gangue powder, adding the coal gangue powder subjected to surface modification treatment and a polyolefin base material into a double-screw extruder, melting, blending, extruding and granulating at the temperature of 160-260 ℃ and the rotating speed of 100-150 rpm;
(4) and (3) adding the granules in the step (3) into an injection molding machine for injection molding, wherein the injection molding temperature is 190-250 ℃, and the injection molding pressure is 40-70 MPa, and the injection molding is carried out according to a product mold.
The invention has the following advantages:
1. because the polyolefin composite material contains HDCP, the coal gangue powder can be uniformly dispersed in the polyolefin matrix, and the interface bonding force between the coal gangue powder and the polyolefin matrix material can be effectively improved, so that the mechanical property is greatly improved compared with that of the coal gangue-polyolefin composite material which is not subjected to modification treatment, the elastic modulus is improved by 30-40%, the strength can be improved by 20-40%, the toughness can be improved by 30-60%, and the flow processability of the composite material is also improved; compared with the coal gangue-polyolefin composite material prepared by the prior art, the elastic modulus of the composite material is obviously improved, the strength is obviously improved, the toughness is also well enhanced, the mechanical comprehensive performance of the modified coal gangue filled polyolefin composite material is obviously improved, in addition, the coal gangue is not calcined at high temperature, the cost is greatly reduced, the energy is saved, and the environment is protected.
2. The method provided by the invention adopts the HDCP as the surface modifier of the coal gangue powder, the HDCP has flame retardance and can be used as a flame retardant filler, the addition amount is small, the polyolefin composite material can pass a UL94V-2 flame retardant test only by adding 1-10%, the heat distortion temperature is 250-300 ℃, the limiting oxygen index is improved to 30-35, and the flame retardant composite material has the advantages of small carbonization area in case of fire, no residual flame, no smoldering and the like, so that the polyolefin composite material has an excellent flame retardant effect.
3. The raw materials of the coal gangue, the polyolefin and the HDCP are easy to obtain, the price is low, the preparation route is simple, and the process is simple, convenient and easy to operate. According to the invention, only one surface modifier HDCP is added, so that the mechanical comprehensive performance of the polyolefin composite material can be obviously improved, the composite material has good flame retardant property, the consumption of the surface modifier is small, and the cost can be greatly saved.
4. The preparation route of the invention not only has less HDCP dosage, but also can reasonably allocate the dosage of the HDCP, and effectively adjust the performance of the composite material so as to meet different use requirements.
5. The invention can be filled with a large amount of coal gangue powder, not only can effectively solve the waste of the coal gangue, thereby improving the added value of products, promoting economic benefits and social benefits, but also can reduce the using amount of polyolefin materials, thereby saving non-renewable disposable resources of petroleum. The composite material can effectively solve the problem of resource conservation of solid wastes, is green and environment-friendly, does not use strong acid and strong alkali in the preparation process, and has no pollution to the environment.
Detailed Description
The following examples are given to illustrate the present invention in more detail, and it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that those skilled in the art may make modifications and variations of the present invention without departing from the spirit and scope of the present invention.
Example 1
Drying the coal gangue powder at the temperature of 110-120 ℃ at room temperature until the water content is less than 0.1%, adding the HDCP and the dried coal gangue powder into a high-speed mixer according to the weight ratio of 1:100, and mixing at the high speed of 1000r/min for 10min to obtain the modified coal gangue powder. Filling the modified coal gangue powder and the polyolefin into a double-screw extruder according to the weight ratio of 30:100, wherein the rotating speed of a main screw is 140rpm, the rotating speed of a pump is 10rpm, the temperature is 190-200 ℃, after melt blending extrusion, the granules are cooled and cut into granules by a granulator, the granules are filled into an injection molding machine, the injection molding temperature is 190 ℃, and the injection molding pressure is 40MPa, the modified coal gangue powder filled polyolefin flame-retardant composite material product can be prepared by injection molding extrusion, the elastic modulus is improved by 20%, the strength can be improved by 10%, the toughness can be improved by 20%, the thermal deformation temperature is 260 ℃, and the limiting oxygen index is 31.
Example 2
Drying the coal gangue powder at the temperature of 110-120 ℃ at room temperature until the water content is less than 0.1%, adding the HDCP and the dried coal gangue powder into a high-speed mixer according to the weight ratio of 10:100, and mixing at the rotating speed of 1300r/min for 20min at a high speed to obtain the modified coal gangue powder. Filling the modified coal gangue powder and the polyolefin into a double-screw extruder according to the weight ratio of 30:100, wherein the rotating speed of a main screw is 120rpm, the rotating speed of a pump is 9rpm, the temperature is 220-240 ℃, after melt blending extrusion, the granules are cooled and cut into granules by a granulator, the granules are filled into an injection molding machine, the injection molding temperature is 230 ℃, and the injection molding pressure is 60MPa, the modified coal gangue powder filled polyolefin flame-retardant composite material product can be prepared by injection molding extrusion, the elastic modulus is improved by 35%, the strength can be improved by 28%, the toughness can be improved by 45%, the thermal deformation temperature is 280 ℃, and the limiting oxygen index is 33.
Example 3
Drying the coal gangue powder at the temperature of 110-120 ℃ at room temperature until the water content is less than 0.1%, adding the HDCP and the dried coal gangue powder into a high-speed mixer according to the weight ratio of 8:100, and mixing at the high speed of 1200r/min for 15min to obtain the modified coal gangue powder. Filling the modified coal gangue powder and the polyolefin into a double-screw extruder according to the weight ratio of 30:100, wherein the rotating speed of a main screw is 100rpm, the rotating speed of a pump is 8rpm, the temperature is 210-220 ℃, after melt blending extrusion, the granules are cooled and cut into granules by a granulator, the granules are filled into an injection molding machine, the injection molding temperature is 210 ℃, and the injection molding pressure is 50MPa, the modified coal gangue powder filled polyolefin flame-retardant composite material product can be prepared by injection molding extrusion, the elastic modulus is improved by 40%, the strength can be improved by 35%, the toughness can be improved by 55%, the thermal deformation temperature is 290 ℃, and the limiting oxygen index is 35.
Claims (2)
1. The modified coal gangue powder filled polyolefin flame-retardant composite material is characterized in that:
the weight ratio of the modified coal gangue powder to the polyolefin is 10-60: 100, the modified coal gangue powder contains a substance with the following structural formula, and the weight ratio of the substance to the coal gangue powder is 1-10: 100;
the structural formula is as follows:
wherein n is an integer of 2 to 4.
2. The preparation process of the modified coal gangue powder filled polyolefin flame-retardant composite material is characterized by comprising the following steps of:
(1) drying, namely drying the 300-mesh 400-mesh coal gangue powder at 110-120 ℃ until the water content is less than 0.1%;
(2) high speed mixing
Adding the substances with the following structural formula and coal gangue powder into a high-speed mixer according to the mass ratio of 1-10: 100, wherein the rotating speed of the high-speed mixer is 1000-1400 r/min, and stirring and mixing at a high speed for 10-20 minutes to obtain coal gangue powder with the surface modified;
the structural formula of the substance is as follows:
wherein n is an integer of 2-4;
(3) mixing polyolefin with modified coal gangue powder
Adding the gangue powder subjected to surface modification treatment and a polyolefin base material into a double-screw extruder, melting, blending, extruding and granulating to obtain granules, wherein the temperature is 160-260 ℃, the rotating speed is 100-150 rpm;
(4) and (3) adding the granules in the step (3) into an injection molding machine for injection molding, wherein the injection molding temperature is 190-250 ℃, and the injection molding pressure is 40-70 MPa, and the injection molding is carried out according to a product mold.
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| CN113045839B (en) * | 2021-03-02 | 2022-06-28 | 中国地质大学（北京） | Composite material for reinforcing thermoplastic polymer resin and preparation method thereof |
| CN114133626A (en) * | 2021-10-24 | 2022-03-04 | 北京工业大学 | High-added-value utilization method of coal gangue |
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| WO2004083295A1 (en) * | 2003-03-19 | 2004-09-30 | Fuji Electric Holdings Co. Ltd. | Reactive flame retardants and flame-retarded resin products made by using the same |
| CN1631956A (en) * | 2004-11-26 | 2005-06-29 | 四川大学 | Polyolefin composite material filled with modified gangue powder and method for preparing same |
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| JP2012177777A (en) * | 2011-02-25 | 2012-09-13 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method and printed substrate |
| CN104829650A (en) * | 2015-05-15 | 2015-08-12 | 湘潭大学 | Hindered amine light stabilizer with thermal stability and preparation method thereof |
| CN105348578A (en) * | 2015-11-27 | 2016-02-24 | 沈阳顺风新城建筑材料有限公司 | Preparation method of novel nanoscale fire retardant |
| CN107337696A (en) * | 2016-05-03 | 2017-11-10 | 广东广山新材料股份有限公司 | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical |
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- 2019-09-30 CN CN201910939080.XA patent/CN110615928B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6020081A (en) * | 1996-04-27 | 2000-02-01 | Daimler-Benz Aktiengesellschaft | Polymerizable phosphazene derivatives: a process for preparing them and their uses |
| WO2004083295A1 (en) * | 2003-03-19 | 2004-09-30 | Fuji Electric Holdings Co. Ltd. | Reactive flame retardants and flame-retarded resin products made by using the same |
| CN1631956A (en) * | 2004-11-26 | 2005-06-29 | 四川大学 | Polyolefin composite material filled with modified gangue powder and method for preparing same |
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| JP2012177777A (en) * | 2011-02-25 | 2012-09-13 | Fujifilm Corp | Photosensitive composition, photosensitive film, photosensitive laminate, permanent pattern formation method and printed substrate |
| CN104829650A (en) * | 2015-05-15 | 2015-08-12 | 湘潭大学 | Hindered amine light stabilizer with thermal stability and preparation method thereof |
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