阅读说明：本技术 一种阻燃线管材料、阻燃线管及其制备方法 (Flame-retardant wire pipe material, flame-retardant wire pipe and preparation method thereof ) 是由 张旭 李明 焦素文 张明 尤建昌 陈洪捷 张友亮 于 2020-06-10 设计创作，主要内容包括：本发明提供一种阻燃线管材料、阻燃线管及其制备方法,由下列重量份配比的原料组成：树脂225份、羧基丁腈胶粉30-45份、轻质碳酸钙50份、硬脂酸0.3-0.5份、PE蜡1.0-1.5份、CPE 13.5-14.5份、钙锌稳定剂8.0-8.4份、钛白粉1.3-1.5份、增白剂6-8份复合阻燃剂1.5-2.5份。通过原料混合-塑化造粒-坯料挤出-真空冷却成型的制备工序,将具有核壳结构的羧基丁腈胶粉和树脂进行物理交联,有效增加分子链间的联系,将线管的延伸率提高到165％,拉伸强度提高到42Mpa。相对现有市面的管材具有优良的化学稳定性,同时,采用特殊的偶联剂表面处理阻燃剂Mg(OH)<Sub>2</Sub>,再与改性的阻燃助剂制得复合阻燃剂,协同使用该复合阻燃剂可以制得加工性能、力学性能及阻燃抑烟性能都比较优异的线管。(The invention provides a flame-retardant wire tube material, a flame-retardant wire tube and a preparation method thereof, wherein the flame-retardant wire tube material is prepared from the following raw materials in parts by weight: 225 parts of resin, 30-45 parts of carboxyl nitrile rubber powder, 50 parts of light calcium carbonate, 0.3-0.5 part of stearic acid, 1.0-1.5 parts of PE wax, 13.5-14.5 parts of CPE, 8.0-8.4 parts of calcium-zinc stabilizer, 1.3-1.5 parts of titanium dioxide and 6-8 parts of whitening agent, and 1.5-2.5 parts of composite flame retardant. Through the preparation procedures of raw material mixing, plasticizing granulation, blank extrusion and vacuum cooling molding, the carboxyl butyronitrile rubber powder with the core-shell structure and resin are physically crosslinked, the relation between molecular chains is effectively increased, the elongation of a line pipe is improved to 165%, and the tensile strength is improved to 42 Mpa. Compared with the existing pipe in the market, the pipe has excellent chemical stability, and simultaneously, a special coupling agent is adopted to treat the surface of a flame retardant Mg (OH) 2 And then the modified flame retardant additive is used to prepare the composite flame retardant which is used cooperatively to prepare the wire tube with excellent processing performance, mechanical property and flame-retardant and smoke-suppressing performance.)

1. The flame-retardant wire tube material is characterized by comprising the following raw materials in parts by weight:

225 parts of resin;

30-45 parts of carboxyl butyronitrile rubber powder;

50 parts of light calcium carbonate;

0.3-0.5 part of stearic acid;

1.0-1.5 parts of PE wax;

13.5-14.5 parts of CPE;

8.0-8.4 parts of calcium zinc stabilizer;

1.3-1.5 parts of titanium dioxide and 6-8 parts of whitening agent;

1.5-2.5 parts of composite flame retardant.

2. The flame-retardant wire tube material according to claim 1, which is characterized by comprising the following raw materials in parts by weight:

225 parts of resin;

35 parts of carboxyl butyronitrile rubber powder;

75 parts of light calcium carbonate;

0.4 part of stearic acid;

1.0 part of PE wax;

13.5 parts of CPE;

8.4 parts of a calcium zinc stabilizer;

1.3 parts of titanium dioxide and 6 parts of whitening agent;

and 2 parts of a composite flame retardant.

3. The flame-retardant wire tube material as claimed in claim 1 or 2, wherein the composite flame retardant comprises a flame retardant and a flame-retardant auxiliary, and the flame retardant is a titanate coupling agent NDZ-311 surface-treated Mg (OH)₂(ii) a The flame-retardant auxiliary agent is Sb subjected to surface treatment by adopting titanate coupling agent₂O₃Or ZnO surface-treated with a silane coupling agent.

4. The flame-retardant wire tube material as claimed in claim 3, wherein the weight ratio of the flame retardant to the flame-retardant auxiliary in the composite flame retardant is 2-3: 1.

5. a fire retardant wire material according to claim 3 wherein said mg (oh) is used₂Titanate coupling agent NDZ-311 to Mg (OH) with mass fraction of 0.3% -2%₂Surface-treated with Sb₂O₃Titanate coupling agent pair Sb with mass fraction of 0.3-2%₂O₃And (3) performing surface treatment, namely performing surface treatment on the ZnO by using a silane coupling agent accounting for 0.3-2% of the mass fraction of the ZnO.

6. The flame retardant wire material of claim 5, wherein the Sb is modified₂O₃The titanate coupling agent is selected from NDZ-101, KR-TTS, KR-38S, HY-101 or AG-K38; the silane coupling agent is selected from KH-550, KH-560, KH-570, KH-903, A-171, A-151 or A-189.

7. The flame-retardant wire tube material of claim 1, wherein the carboxylated nitrile rubber powder is in a core-shell structure, wherein the core is nitrile rubber and the shell is a plastic carboxylated unsaturated hydrocarbon polymer.

8. The flame-retardant wire tube material as claimed in claim 7, wherein the preparation method of the carboxyl nitrile rubber powder comprises the following steps: copolymerizing butadiene and acrylonitrile by an emulsion copolymerization method, then adding unsaturated hydrocarbon containing carboxyl, grafting into powder by a suspension grafting method, and then washing, drying and crushing to obtain the modified butadiene-acrylonitrile copolymer; wherein, the unsaturated hydrocarbon containing carboxyl is at least one of acrylic acid, crotonic acid and methacrylic acid.

9. A flame retardant conduit prepared using the flame retardant conduit material according to any one of claims 1 to 8.

10. A method of making a fire retardant conduit according to claim 9 comprising the steps of:

the method comprises the following steps: mixing the raw materials, weighing the raw materials according to the proportion, putting the raw materials into a material jar of a high-low temperature mixer, carrying out high-temperature mixing, taking out the high-temperature mixture into a cold jar when the temperature of the mixture in the hot jar reaches 120-130 ℃, and discharging the mixed material when the temperature of the mixture in the cold jar is reduced to 40-50 ℃ to prepare the mixture for later use;

step two: plasticizing and granulating, namely putting the mixture discharged in the step one into a granulator, wherein the rotating speed of a main machine of the granulator is 30 revolutions per minute, the temperature of a charging barrel zone of the granulator is 180-190 ℃, and the temperature of a granulating die is 200-210 ℃ to prepare granules with the particle size of 1.5 mm;

step three: extruding a pipe blank, namely feeding the granular material prepared in the step two into a double-screw extruder when the temperature of the granular material is reduced to 40-50 ℃, wherein the rotating speed of an extrusion screw is 25 revolutions per minute, the rotating speed of a feeding screw is 55 revolutions per minute, the temperature of an extrusion area is 160 plus materials, the torque of the screw is 43 N.m, and the pipe blank is extruded;

step four: and (3) carrying out vacuum cooling molding on the pipe, immediately sizing and cooling the pipe blank when the pipe blank is extruded out of the die, putting the extruded pipe blank into a vacuum molding cooling box, and molding the blank by adopting an internal pressure external sizing method to prepare the molded middle flame-retardant sleeve.

Technical Field

The invention belongs to the technical field of PVC (polyvinyl chloride) pipe production, and particularly relates to a flame-retardant wire pipe material, a flame-retardant wire pipe and a preparation method thereof.

Background

The raw material polyvinyl chloride (PVC) used in the PVC-U line pipe belongs to self-extinguishing materials, but the PVC can emit a large amount of black smoke and toxic gases when being burnt. Such as HCl, CO, small amounts of phosgene, benzene, naphthalene, and other aromatic compounds. In case of fire, a great deal of people are suffocated due to smoke, so that the application range of the PVC is limited. Meanwhile, the flame retardant property and smoke suppression property of the material can be reduced by adding auxiliary agents such as a plasticizer, a lubricant and the like in the processing process of the PVC wire pipe, so that the research on smoke suppression and flame retardation modification of the PVC wire pipe is more and more focused. Therefore, it is necessary to develop flame-retardant and smoke-suppressing technology suitable for PVC conduit pipe.

In view of the above, there is a need for a new modified PVC conduit, which has improved toughness, elongation and tensile strength, and flame retardancy.

Disclosure of Invention

Aiming at the problems existing in the prior technical scheme, the invention aims to provide a flame-retardant wire pipe material, a flame-retardant wire pipe and a preparation method thereof, which can improve the elongation rate and tensile strength of the pipe material, enhance the toughness, reduce black smoke and toxic gas released by the PVC pipe material during combustion, and greatly reduce a large amount of casualties caused by smoke suffocation in a fire accident.

In order to achieve the purpose, the invention provides the following technical scheme:

the flame-retardant wire tube material is composed of the following raw materials in parts by weight:

225 parts of resin;

30-45 parts of carboxyl butyronitrile rubber powder;

50 parts of light calcium carbonate;

0.3-0.5 part of stearic acid;

1.0-1.5 parts of PE wax;

13.5-14.5 parts of CPE;

8.0-8.4 parts of calcium zinc stabilizer;

1.3-1.5 parts of titanium dioxide and 6-8 parts of whitening agent

1.5-2.5 parts of composite flame retardant.

Further, the flame-retardant wire tube is composed of the following raw materials in parts by weight:

225 parts of resin;

35 parts of carboxyl butyronitrile rubber powder;

75 parts of light calcium carbonate;

0.4 part of stearic acid;

1.0 part of PE wax;

13.5 parts of CPE;

8.4 parts of a calcium zinc stabilizer;

1.3 parts of titanium dioxide and 6 parts of whitening agent;

and 2 parts of a composite flame retardant.

Go toThe composite flame retardant consists of a flame retardant and a flame retardant auxiliary agent, wherein the flame retardant is Mg (OH) subjected to surface treatment by adopting a titanate coupling agent NDZ-311₂(ii) a The flame-retardant auxiliary agent is Sb subjected to surface treatment by adopting titanate coupling agent₂O₃Or ZnO surface-treated with a silane coupling agent.

Further, in the composite flame retardant, the weight ratio of the flame retardant to the flame-retardant auxiliary agent is 2-3: 1.

further, use is made of said Mg (OH)₂Titanate coupling agent NDZ-311 to Mg (OH) with mass fraction of 0.3% -2%₂Surface-treated with Sb₂O₃Titanate coupling agent pair Sb with mass fraction of 0.3-2%₂O₃And (3) performing surface treatment, namely performing surface treatment on the ZnO by using a silane coupling agent accounting for 0.3-2% of the mass fraction of the ZnO.

Further, the Sb for modification₂O₃The titanate coupling agent is selected from NDZ-101, KR-TTS, KR-38S, HY-101 or AG-K38; the silane coupling agent is selected from KH-550, KH-560, KH-570, KH-903, A-171, A-151 or A-189.

Furthermore, the carboxyl nitrile rubber powder is in a core-shell structure, wherein the core is nitrile rubber, and the shell is a plastic carboxyl unsaturated hydrocarbon polymer.

Further, the preparation method of the carboxyl butyronitrile rubber powder comprises the following steps: copolymerizing butadiene and acrylonitrile by an emulsion copolymerization method, then adding unsaturated hydrocarbon containing carboxyl, grafting into powder by a suspension grafting method, and then washing, drying and crushing to obtain the modified butadiene-acrylonitrile copolymer; wherein, the unsaturated hydrocarbon containing carboxyl is at least one of acrylic acid, crotonic acid and methacrylic acid.

The flame-retardant wire pipe is prepared by utilizing the flame-retardant wire pipe material.

The preparation method of the flame-retardant wire tube comprises the following steps:

the method comprises the following steps: mixing the raw materials, weighing the raw materials according to the proportion, putting the raw materials into a material jar of a high-low temperature mixer, carrying out high-temperature mixing, taking out the high-temperature mixture into a cold jar when the temperature of the mixture in the hot jar reaches 120-130 ℃, and discharging the mixed material when the temperature of the mixture in the cold jar is reduced to 40-50 ℃ to prepare the mixture for later use;

step two: plasticizing and granulating, namely putting the mixture discharged in the step one into a granulator, wherein the rotating speed of a main machine of the granulator is 30 revolutions per minute, the temperature of a charging barrel zone of the granulator is 180-190 ℃, and the temperature of a granulating die is 200-210 ℃ to prepare granules with the particle size of 1.5 mm;

step three: extruding a pipe blank, namely feeding the granular material prepared in the step two into a double-screw extruder when the temperature of the granular material is reduced to 40-50 ℃, wherein the rotating speed of an extrusion screw is 25 revolutions per minute, the rotating speed of a feeding screw is 55 revolutions per minute, the temperature of an extrusion area is 160 plus materials, the torque of the screw is 43 N.m, and the pipe blank is extruded;

step four: and (3) carrying out vacuum cooling molding on the pipe, immediately sizing and cooling the pipe blank when the pipe blank is extruded out of the die, putting the extruded pipe blank into a vacuum molding cooling box, and molding the blank by adopting an internal pressure external sizing method to prepare the molded middle flame-retardant sleeve.

The raw materials are selected and combined, so that the effects of the raw materials generate a synergistic effect, the tensile strength, the hardness, the impact resistance and the fracture elongation of the product can be effectively improved, and the functional effects of the raw materials are as follows:

resin: the resin is a plastic assistant with dual functions of impact resistance modification and processing modification, and the PVC product has excellent impact resistance, low-temperature toughness, compatibility with PVC, weather resistance, stability and processability due to the core/shell structure, and moderate performance to price ratio, so that the fluidity and thermal deformation of PVC melt can be obviously improved, the plasticization is promoted, and the surface of the product is smooth and attractive.

Titanium dioxide: the PVC composite material is applied to the PVC drainage pipe industry, and can effectively improve the heat resistance, light resistance and weather resistance of the PVC pipe, improve the physical and chemical properties of the PVC pipe, enhance the color of the PVC pipe and prolong the service life of the PVC pipe.

Calcium carbonate: the filler is applied to the PVC drainage pipe industry, can ensure that the surface performance of the pipe is good, improve the formability of the pipe, ensure that the pipe is easy to shape, and can reduce the cost.

The raw materials all belong to the existing perfect technology, and the invention adds the following formula raw materials on the basis of the raw materials, and the functions and the effects of the raw materials are as follows:

the carboxyl nitrile rubber powder is in a core-shell structure, wherein the core is nitrile rubber, and the shell is a plastic carboxyl unsaturated hydrocarbon polymer.

The carboxyl butyronitrile rubber powder with the core-shell structure has obvious interface effect, the active surface strongly adsorbs molecular chains of a PVC matrix, and usually, a plurality of molecular chains are connected on the surface of one particle to form physical crosslinking among chains. The particles with adsorbed molecular chains can play a role in uniformly distributing load, and reduce the possibility of breaking the polymer. On the other hand, the PVC resin has a microphase separation structure on the microscopic scale, hard segment molecules are strongly associated together to form a plurality of microdomains to be dispersed in a soft segment phase matrix, the soft segment phase provides elasticity, and the hard segment phase plays a role in reinforcing filling and crosslinking. PVC is a linear polymer formed by connecting VCM monomers in a head-tail structure, and more hydrogen bonds can be formed between-COOH carried on the shell of carboxyl nitrile rubber powder particles and PVC groups, so that the binding force between the particles and a matrix is increased. When a small amount of carboxyl butyronitrile rubber powder is added, the nano-scale particles serve as hard segments and serve as a part of physical crosslinking points to effectively increase the relation among molecular chains, and when external force is applied, the nano-scale particles serve as stress concentrators to induce a large amount of silver lines and shear bands, absorb energy, control and stop the silver line development by the rubber powder particles and the shear bands, so that the silver lines are prevented from forming destructive cracks, and the enhancement and toughening are realized.

Meanwhile, if Mg (OH) without surface treatment is directly added₂、Sb₂O₃Or ZnO is used as the flame-retardant smoke inhibitor, and has the defects of high consumption and easy reduction of the processing performance and the mechanical property of the material. The coupling agent is adopted to carry out surface treatment on the flame retardant and the flame retardant auxiliary agent, so that the dispersity of the flame retardant and the flame retardant auxiliary agent can be improved, and the processing performance of the flame retardant and the flame retardant auxiliary agent can be improved. However, the influence of the coupling agent on the flame retardant performance and the smoke suppression performance is rarely reported in the prior art, and the inventor unexpectedly finds that the proper coupling agent is selectedThe flame retardant and the flame retardant auxiliary agent are modified, so that the flame retardant and smoke suppression effect of the composite flame retardant is fully exerted, and the flame retardant and smoke suppression effects are improved. For flame retardant Mg (OH)₂Surface treatment is carried out by adopting titanate coupling agent NDZ-311, and then the surface treatment is carried out with flame retardant auxiliary agent Sb₂O₃Or ZnO is used cooperatively, the prepared PVC drainpipe has better flame-retardant and smoke-inhibiting performance, but other types of titanate coupling agents (such as NDZ-101, KR-38S and the like) are used for surface treatment of Mg (OH)₂The flame retardant and smoke suppressant properties of PVC drainpipes are reduced, so titanate coupling agent NDZ-311 is the best choice for surface treatment of Mg (OH) 2.

The flame-retardant auxiliary Sb of the invention₂O₃The surface treatment is carried out by adopting the conventional titanate coupling agent in the field, and if other coupling agents are adopted, the flame-retardant smoke-suppression effect of the subsequently prepared product is obviously reduced.

The flame retardant auxiliary agent ZnO is subjected to surface treatment by adopting a conventional silane coupling agent in the field, and if other coupling agents are adopted, the flame retardant and smoke suppression effects of subsequently prepared products are remarkably reduced.

The pipe prepared from the raw materials has excellent chemical stability, effectively improves the tensile strength, impact resistance and fracture elongation of the product, and is environment-friendly and pollution-free.

Compared with the prior art, the invention has the beneficial effects that: according to the wire tube, the carboxyl butyronitrile rubber powder with the core-shell structure and the resin are physically crosslinked, so that the relation between molecular chains is effectively increased, the toughness of the material is improved, the elongation of the wire tube is improved to 165%, and the tensile strength of the wire tube is improved to 42 Mpa. Has stronger thermal shock resistance and lower thermal deformation rate, has excellent chemical stability compared with the prior pipe on the market, and simultaneously adopts a special coupling agent for surface treatment of a flame retardant Mg (OH)₂And then the modified flame retardant additive is used to prepare the composite flame retardant which is used cooperatively to prepare the wire tube with excellent processing performance, mechanical property and flame-retardant and smoke-suppressing performance.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments.