CN110527178B - Ultraviolet light crosslinked black low-smoke halogen-free cable sheath material and preparation method thereof - Google Patents
Ultraviolet light crosslinked black low-smoke halogen-free cable sheath material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet light crosslinking black low-smoke halogen-free cable sheath material which comprises the following components in parts by weight: 100 parts of polyolefin resin; 10-20 parts of a compatilizer; 145 parts of hydroxide flame retardant 115; 28-56 parts of a nano flame retardant; 4-8 parts of a silicon flame retardant synergist; 5-7 parts of a photosensitizer; 2-4 parts of an auxiliary crosslinking agent; 0.5-1.5 parts of antioxidant; 1-3 parts of a lubricant; 0.5-1.0 part of pigment carbon black; the nano flame retardant is a compound of montmorillonite and ferrocene or montmorillonite. The invention applies the nano flame retardant technology to the material, and combines the nano synergy and the ultraviolet crosslinking technology; the interfacial area between the polymer and the nanometer flame retardant particles is very large, and the chemical combination between the base material and the inorganic filler exists between the interfaces, so that the cable material has ideal bonding performance, can eliminate the problem of mismatch of thermal expansion coefficients of the inorganic substance and the polymer matrix, has flame retardance and lower total heat release amount, and has the advantage of ultraviolet crosslinking, and the fused strip line surface is smooth and the extruded surface is good.
Description
Technical Field
The invention relates to an ultraviolet light crosslinking black low-smoke halogen-free cable sheath material and a preparation method thereof.
Background
Taking digital statistics as an example, a fire can occur together every 17 seconds on average nationwide, and particularly the use of synthetic polymers greatly exacerbates the fire hazard and injury from combustion. In fire death accidents, about 80 percent of people die from the suffocation of toxic gas and smoke, and the low-smoke halogen-free material is produced at the same time. The requirements of the wire and cable industry on flame resistance are particularly outstanding, and relevant departments clearly stipulate that LSZH cable materials must be used in public places. While promoting the non-halogenation of wires, telephone cables and data cables inside buildings. Although the low-smoke halogen-free flame-retardant polyolefin has better flame retardant property and small smoke emission, and does not release toxic gas during combustion, the low-smoke halogen-free flame-retardant polyolefin has the defects of low mechanical property and thermal deformation temperature and difficulty in meeting the requirements of certain occasions. Crosslinking is a method for improving mechanical properties and heat distortion temperature. The currently used crosslinking methods mainly include peroxide crosslinking, silane crosslinking, radiation crosslinking and ultraviolet crosslinking. Wherein electron beam crosslinking and ultraviolet crosslinking are known as '5E' technology.
Although the radiation crosslinking has high production efficiency and low cost, and no crosslinking assistant is needed to be added in the crosslinking process, the cleanness and the electrical property of the material are maintained, but the radiation crosslinking has the defects of large one-time investment and safety protection problem in operation. Ultraviolet (UV) curing is an advanced technology for surface treatment of materials emerging in the 60's of the 20 th century, and is collectively referred to as radiation crosslinking technology with Electron Beam (EB) curing. The photocuring technology is a high-efficiency, environment-friendly, energy-saving and high-quality material surface treatment technology, and is praised as a new technology facing the green industry of the 21 st century. With the deepening of polyolefin photo-crosslinking theory and application research, ultraviolet light crosslinking technology is applied to the wire and cable industry for the first time by Dianthus superbus and the like, and a series of new wire and cable products are developed. Compared with other crosslinking methods, the ultraviolet crosslinking technology has unique advantages. The equipment investment cost is low, and the operation and the protection are simple. The C-C bond of polyolefin is basically not destroyed in the irradiation process, the radiation damage to the polyolefin is small, and the polyolefin ultraviolet light crosslinking technology is more and more paid attention by people.
When the ultraviolet crosslinking technology is applied to halogen-free flame-retardant cable materials, due to the fact that the colors are numerous, the problems that the absorption wavelengths of ultraviolet regions with different colors are different and the shielding effects of different toners on ultraviolet are different need to be solved. Especially, the black pigment has very low transmittance in an ultraviolet-visible wave band, and almost has no obvious 'transmission window'; in addition, a large amount of fillers in the low-smoke halogen-free flame-retardant cable material also influence the crosslinking efficiency of the system to a certain extent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an ultraviolet crosslinking black low-smoke zero-halogen cable sheath material and a preparation method thereof, which are used for overcoming the technical difficulty of low ultraviolet crosslinking efficiency of the black low-smoke zero-halogen cable material.
The invention aims to provide an ultraviolet crosslinking black low-smoke halogen-free cable sheath material which comprises the following components in parts by weight:
the nano flame retardant is a compound of montmorillonite and ferrocene or montmorillonite.
Specifically, the nano flame retardant is montmorillonite and ferrocene, and the mass part ratio of the montmorillonite to the ferrocene is 2.5-4: 1.
Specifically, the photosensitizer is a compound of a photosensitizer 1173, a photosensitizer TPO and a photosensitizer ITX.
Preferably, the mass part ratio of the photosensitizer 1173 to the photosensitizer TPO to the photosensitizer ITX is 1:1-2: 1.
Specifically, the pigment carbon black is one selected from the group consisting of Zaozun Xin chemical industry ink UV curing carbon black XY-100, XY-230 and XY-880.
Specifically, the polyolefin is a mixture of an ethylene-vinyl acetate copolymer having a VA content of 18%, an ethylene-vinyl acetate copolymer having a VA content of 28%, and a metallocene linear low density polyethylene.
Preferably, the weight part ratio of the ethylene-vinyl acetate copolymer with 18% of VA content, the ethylene-vinyl acetate copolymer with 28% of VA content and the metallocene linear low density polyethylene is 1.2-1.8:1: 1.
Specifically, the compatibilizer is one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
Specifically, the hydroxide flame retardant is aluminum hydroxide, and the silicon flame retardant synergist is polydimethylsiloxane and silicone master batch.
Preferably, the weight part ratio of the polydimethylsiloxane to the silicone master batch is 1-2: 1.
Specifically, the antioxidant is antioxidant 1010 and antioxidant DLTP.
Preferably, the weight part ratio of the antioxidant 1010 to the antioxidant DLTP is 0.8-1.2: 1.
Specifically, the lubricant is selected from the group consisting of 4000 molecular weight polyethylene wax and EVA wax.
Preferably, the ratio of the parts by weight of the 4000 molecular weight polyethylene wax to the parts by weight of the EVA wax is 0.8-1.2: 1.
Specifically, the auxiliary crosslinking agent is triallyl isocyanurate.
The second purpose of the invention is to provide a preparation method of the ultraviolet crosslinking black low-smoke zero-halogen cable sheath material, which comprises the following steps:
(a) weighing polyolefin resin, a compatilizer, a hydroxide flame retardant, a nano flame retardant, a lubricant and an antioxidant according to the formula ratio, adding the weighed polyolefin resin, the compatilizer, the hydroxide flame retardant, the nano flame retardant, the lubricant and the antioxidant into a high-speed mixer, mixing for 3-5 minutes under the condition of 30-50 revolutions per minute, adding a silicon-based flame retardant synergist, a photosensitizer and an auxiliary crosslinking agent according to the formula ratio, mixing for 5-10 minutes at the low rotating speed, and finally adding pigment carbon black according to the formula ratio, and continuously mixing for 3-5 minutes to obtain a mixture;
(b) putting the mixed material into a bin, and feeding the mixed material into a double-screw extruder from the bin for extrusion granulation, wherein the length-diameter ratio of the double-screw extruder is not less than 35: 1; the temperature of each section of the machine body of the double-screw extruder is as follows in sequence: 120-125 ℃, 120-130 ℃, 130-135 ℃, 135-140 ℃, 140-145 ℃, 145-150 ℃ and the temperature of the machine head is 150 ℃.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the invention applies the nano flame retardant technology to the ultraviolet crosslinking black low-smoke halogen-free cable sheath material, and combines the nano synergy and the ultraviolet crosslinking technology; the nanometer flame retardant has incomparable advantages, the interface area between the polymer and the nanometer flame retardant particles is very large, chemical combination between the base material and the inorganic filler exists between the interfaces, the nanometer flame retardant has ideal bonding performance, the problem of mismatch of thermal expansion coefficients of the inorganic substance and the polymer matrix can be solved, the obtained cable material has flame retardance and lower total heat release amount, and simultaneously has the advantage of ultraviolet crosslinking, the surface of a fused strip line is smooth, and the extrusion surface is good.
Detailed Description
The following provides a detailed description of preferred embodiments of the invention.
The invention provides an ultraviolet crosslinking black low-smoke halogen-free cable sheath material which comprises the following components in parts by weight:
the nano flame retardant is a compound of montmorillonite and ferrocene or montmorillonite. Preferably, the nano flame retardant is montmorillonite and ferrocene, and the mass part ratio of the montmorillonite to the ferrocene is 2.5-4: 1.
The photosensitizer is a compound of photosensitizer 1173, photosensitizer TPO and photosensitizer ITX. Preferably, the mass part ratio of the photosensitizer 1173 to the photosensitizer TPO to the photosensitizer ITX is 1:1-2: 1.
The pigment carbon black is selected from one of UV-cured carbon black XY-100, XY-230 and XY-880 of Zaozhuangxin chemical ink.
The polyolefin is a mixture of ethylene-vinyl acetate copolymer with VA content of 18%, ethylene-vinyl acetate copolymer with VA content of 28% and metallocene linear low density polyethylene. The weight portion ratio of the ethylene-vinyl acetate copolymer with 18 percent of VA content, the ethylene-vinyl acetate copolymer with 28 percent of VA content and the metallocene linear low-density polyethylene is 1.2-1.8:1: 1.
The compatilizer is one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
The hydroxide flame retardant is aluminum hydroxide, and the silicon flame retardant synergist is polydimethylsiloxane and silicone master batch.
The weight portion ratio of the polydimethylsiloxane to the silicone master batch is 1-2: 1.
The antioxidant is antioxidant 1010 and antioxidant DLTP. The weight portion ratio of the antioxidant 1010 to the antioxidant DLTP is 0.8-1.2: 1.
The lubricant is selected from 4000 molecular weight polyethylene wax and EVA wax. The weight portion ratio of the polyethylene wax with the molecular weight of 4000 to the EVA wax is 0.8-1.2: 1.
The auxiliary crosslinking agent is triallyl isocyanurate.
The invention also provides a preparation method of the ultraviolet crosslinking black low-smoke halogen-free cable sheath material, which comprises the following steps:
(a) weighing polyolefin resin, a compatilizer, a hydroxide flame retardant, a nano flame retardant, a lubricant and an antioxidant according to the formula ratio, adding the weighed polyolefin resin, the compatilizer, the hydroxide flame retardant, the nano flame retardant, the lubricant and the antioxidant into a high-speed mixer, mixing for 3-5 minutes under the condition of 30-50 revolutions per minute, adding a silicon-based flame retardant synergist, a photosensitizer and an auxiliary crosslinking agent according to the formula ratio, mixing for 5-10 minutes at the low rotating speed, and finally adding pigment carbon black according to the formula ratio, and continuously mixing for 3-5 minutes to obtain a mixture;
(b) putting the mixed material into a bin, and extruding and granulating the mixed material into a double-screw extruder from the bin, wherein the length-diameter ratio of the double-screw extruder is not less than 35: 1; the temperature of each section of the machine body of the double-screw extruder is as follows in sequence: 120-125 ℃, 120-130 ℃, 130-135 ℃, 135-140 ℃, 140-145 ℃, 145-150 ℃ and the temperature of the machine head is 150 ℃.
The following provides a detailed description of preferred embodiments of the invention.
Embodiment 1 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which comprises the following components in parts by weight:
100 parts of polyolefin resin; (the mass ratio of the ethylene-vinyl acetate copolymer having a VA content of 18%, the ethylene-vinyl acetate copolymer having a VA content of 28%, and the metallocene linear low density polyethylene is 1.5:1:1)
15 parts of a compatilizer; (maleic anhydride-grafted ethylene-vinyl acetate copolymer)
115 parts of hydroxide flame retardant; (aluminum hydroxide)
56 parts of a nano flame retardant; (the mass ratio of the montmorillonite to the ferrocene is 4:1),
6 parts of a silicon flame retardant synergist; (the mass ratio of polydimethylsiloxane to silicone master batch is 1.5:1)
7 parts of a photosensitizer; (1173 ITX, TPO in a mass ratio of 1:1:1)
3 parts of an auxiliary crosslinking agent; (Triallylisocyanuric acid ester)
1 part of an antioxidant; (the mass ratio of the antioxidant 1010 to the antioxidant DLTP is 1:1)
1.5 parts of a lubricant; (the mass ratio of the polyethylene wax with the molecular weight of 4000 to the EVA wax is 1:1)
0.7 part of pigment carbon black; (XY-880)
Embodiment 2 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has a preparation method completely the same as that of embodiment 1, except that the ultraviolet crosslinked black low-smoke halogen-free cable sheath material comprises the following components in parts by weight:
100 parts of polyolefin resin; (the mass ratio of the ethylene-vinyl acetate copolymer having a VA content of 18%, the ethylene-vinyl acetate copolymer having a VA content of 28%, and the metallocene linear low density polyethylene is 1.2:1:1)
10 parts of a compatilizer; (maleic anhydride-grafted ethylene-vinyl acetate copolymer)
130 parts of hydroxide flame retardant; (aluminum hydroxide)
28 parts of a nano flame retardant; (the mass ratio of the montmorillonite to the ferrocene is 4:1),
8 parts of a silicon flame retardant synergist; (the mass ratio of polydimethylsiloxane to silicone master batch is 1.5:1)
5 parts of a photosensitizer; (1173 ITX, TPO in a mass ratio of 1:1:1)
2 parts of an auxiliary crosslinking agent; (Triallylisocyanuric acid ester)
0.5 part of antioxidant; (the mass ratio of the antioxidant 1010 to the antioxidant DLTP is 1:1)
1 part of a lubricant; (the mass ratio of the polyethylene wax with the molecular weight of 4000 to the EVA wax is 0.8:1)
1.0 part of pigment carbon black; (XY-100)
Embodiment 3 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has a preparation method completely the same as that of embodiment 1, except that the material components have different contents, and the ultraviolet crosslinked black low-smoke halogen-free cable sheath material comprises the following components in parts by weight:
100 parts of polyolefin resin; (the mass ratio of the ethylene-vinyl acetate copolymer having a VA content of 18%, the ethylene-vinyl acetate copolymer having a VA content of 28%, and the metallocene linear low density polyethylene is 1.8:1:1)
20 parts of a compatilizer; (maleic anhydride-grafted polyethylene)
145 parts of hydroxide flame retardant; (aluminum hydroxide)
42 parts of a nano flame retardant; (the mass ratio of montmorillonite to ferrocene is 4:1)
4 parts of a silicon flame retardant synergist; (the mass ratio of polydimethylsiloxane to silicone master batch is 1.5:1)
6 parts of a photosensitizer; (1173 ITX, TPO in a mass ratio of 1:1:1)
4 parts of an auxiliary crosslinking agent; (Triallylisocyanuric acid ester)
1.5 parts of an antioxidant; (the mass ratio of the antioxidant 1010 to the antioxidant DLTP is 1:1)
3 parts of a lubricant; (the mass ratio of the polyethylene wax with the molecular weight of 4000 to the EVA wax is 1.2:1)
0.5 part of pigment carbon black; (XY-230).
Embodiment 4 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has the same formula components as embodiment 1, and the same preparation method, except that: 5 parts of a photosensitizer; (1173, ITX, TPO in a mass ratio of 1:1: 1).
Embodiment 5 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has the same formula components as embodiment 1, and the same preparation method, except that: 6 parts of a photosensitizer; (1173, ITX, TPO in a mass ratio of 1:1: 1).
Embodiment 6 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has the same formula components as embodiment 1, and the same preparation method, except that: 1173. the mass ratio of ITX and TPO is 1:1.5: 1.
Embodiment 7 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has substantially the same formula components as embodiment 1, and completely the same preparation method, except that: 1173. the mass ratio of ITX and TPO is 1:2: 1.
Embodiment 8 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has the same formula components as embodiment 1, and the same preparation method, except that: 28 parts of nano flame retardant (the mass ratio of montmorillonite to ferrocene is 4: 1).
Embodiment 9 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has substantially the same formula components as embodiment 1, and completely the same preparation method, except that: 28 parts of nano flame retardant (the mass ratio of montmorillonite to ferrocene is 2.5: 1).
Embodiment 10 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, which has the same formula components as embodiment 1, and the same preparation method, except that: the nano flame retardant is selected from 28 parts of montmorillonite.
Comparative example 1 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those of example 1, and the preparation method is completely the same, and the differences are only that: no photosensitizer is added.
Comparative example 2 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those of example 1, and the preparation method is completely the same, and the difference is only that: the photosensitizer is a single photosensitizer, and 7 parts of photosensitizer 1173.
Comparative example 3 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those of example 1, and the preparation method is completely the same, and the difference is only that: the photosensitizer is a compound photosensitizer, 3.5 parts of photosensitizer TPO and 3.5 parts of photosensitizer ITX.
Comparative example 4 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those in example 1, the proportions of the photosensitizer type and different photosensitizers are not changed, the preparation methods are completely the same, and the differences are only that: the adding content of the photosensitizer is 3 parts.
Comparative example 5 provides an ultraviolet crosslinking black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those in example 1, the proportions of the photosensitizer type and different photosensitizers are not changed, the preparation methods are completely the same, and the difference is only that: the adding content of the photosensitizer is 15 parts.
Comparative example 6 provides an ultraviolet crosslinked black low-smoke halogen-free cable sheath material, the formula components of which are basically the same as those of example 1, and the preparation method is completely the same, and the difference is only that: the addition part of the nano flame retardant is 10 parts.
Comparative example 7 provides a halogen-free cable material with low smoke density and high flame retardant property, the formula components of which are basically the same as those of example 1, and the preparation method is completely the same, and the differences are only that: 28 parts of ferrocene as the nano flame retardant.
TABLE 1 results of physical Property test of examples 1 to 10 and comparative examples 1 to 7
From examples 1, 4-5 and comparative example 4, it can be seen that the ultraviolet crosslinking black low-smoke halogen-free cable sheath material prepared by the invention has larger thermal extension under the same irradiation condition with the reduction of the photosensitizer (1173: ITX: TPO ═ 1:1:1), which indicates that the crosslinking speed is slower, the crosslinking degree is lower and the crosslinking is difficult. As can be seen from comparative example 5, the photosensitizer content is too high, which results in excessive lubrication during processing, reduced shear, poor material plastic, and the residue of the photosensitizer which has not completely reacted presents a potential problem to the aging properties of the material.
From examples 1, 6-7, and comparative examples 1-3, it can be seen that the crosslinking behavior of the material can be changed without adding a photosensitizer, or selecting a single or a compound photosensitizer, or even without ultraviolet crosslinking. It can be seen from examples 1 and 6 that increasing the reduction in the amount of photosensitizer 1173 reduces the degree of crosslinking, but that as the ITX content in example 7 is further increased, the degree of crosslinking increases.
As can be seen from examples 1, 2-3, and 8-9, the ultraviolet crosslinking black low-smoke halogen-free cable sheath material prepared by the invention has gradually increased total heat release amount along with the reduction of the nano flame retardant amount. Comparing examples 8-9 with example 10, although example 10 only added montmorillonite as a nano flame retardant, the total amount of heat release was reduced, since ferrocene is also a cationic photosensitizer, which assists in uv crosslinking, and this reduction in composition also retards the crosslinking reaction.
As can be seen from example 1 and comparative example 6, when the content of the nano flame retardant in the ultraviolet crosslinking black low-smoke halogen-free cable sheath material prepared by the invention is low, the flame retardant synergistic effect can not be exerted, and the heat release performance is not improved; however, if the content of the nano flame retardant is too large, the melt viscosity is too high during the twin-screw processing, and the extrusion is difficult. From example 1 and comparative example 7, it can be seen that the addition of ferrocene alone as the nanocatalyst, but not montmorillonite, results in a material with an undesirably large total amount of heat release.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The ultraviolet crosslinking black low-smoke halogen-free cable sheath material is characterized by comprising the following components in parts by weight:
100 parts of polyolefin resin;
10-20 parts of a compatilizer;
145 parts of hydroxide flame retardant 115;
28-56 parts of a nano flame retardant;
4-8 parts of a silicon flame-retardant synergist;
5-7 parts of a photosensitizer;
2-4 parts of an auxiliary crosslinking agent;
0.5-1.5 parts of antioxidant;
1-3 parts of a lubricant;
0.5-1.0 part of pigment carbon black;
the nano flame retardant is a compound of montmorillonite and ferrocene or montmorillonite;
the photosensitizer is a compound of a photosensitizer 1173, a photosensitizer TPO and a photosensitizer ITX.
2. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the nano flame retardant is montmorillonite and ferrocene, and the mass part ratio of the montmorillonite to the ferrocene is 2.5-4: 1.
3. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the pigment carbon black is one selected from the group consisting of Zaozhuang Xin source chemical ink UV curing carbon black XY-100, XY-230 and XY-880.
4. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the polyolefin is a mixture of an ethylene-vinyl acetate copolymer with a VA content of 18%, an ethylene-vinyl acetate copolymer with a VA content of 28% and metallocene linear low density polyethylene.
5. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the compatilizer is one selected from maleic anhydride grafted ethylene-vinyl acetate copolymer and maleic anhydride grafted polyethylene.
6. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the hydroxide flame retardant is aluminum hydroxide, and the silicon flame retardant synergist is polydimethylsiloxane and silicone master batch.
7. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the antioxidant is antioxidant 1010 and antioxidant DLTP, and the lubricant is selected from polyethylene wax with the molecular weight of 4000 and EVA wax.
8. The ultraviolet light crosslinked black low-smoke zero-halogen cable sheath material as claimed in claim 1, is characterized in that: the auxiliary crosslinking agent is triallyl isocyanurate.
9. The ultraviolet crosslinked black low-smoke zero-halogen cable sheath material according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(a) weighing polyolefin resin, a compatilizer, a hydroxide flame retardant, a nano flame retardant, a lubricant and an antioxidant according to the formula ratio, adding the weighed polyolefin resin, the compatilizer, the hydroxide flame retardant, the nano flame retardant, the lubricant and the antioxidant into a high-speed mixer, mixing for 3-5 minutes under the condition of 30-50 revolutions per minute, adding a silicon-based flame retardant synergist, a photosensitizer and an auxiliary crosslinking agent according to the formula ratio, mixing for 5-10 minutes at the low rotating speed, and finally adding pigment carbon black according to the formula ratio, and continuously mixing for 3-5 minutes to obtain a mixture;
(b) putting the mixed material into a bin, and feeding the mixed material into a double-screw extruder from the bin for extrusion granulation, wherein the length-diameter ratio of the double-screw extruder is not less than 35: 1; the temperature of each section of the machine body of the double-screw extruder is as follows in sequence: 120-125 ℃, 120-130 ℃, 130-135 ℃, 135-140 ℃, 140-145 ℃, 145-150 ℃ and the temperature of the machine head is 150 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153802A (en) * | 2011-03-07 | 2011-08-17 | 沭阳优唯新材料有限公司 | Ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable material and method for preparing ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer from same |
| JP2013129845A (en) * | 2013-03-07 | 2013-07-04 | Asahi Rubber Inc | Silicone resin base material |
| CN104893088A (en) * | 2015-06-17 | 2015-09-09 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof |
| CN105237865A (en) * | 2015-10-21 | 2016-01-13 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material |
| CN105419072A (en) * | 2015-12-18 | 2016-03-23 | 华南理工大学 | Flexible low-smoke halogen-free flame-retardant wire and cable material and preparation method thereof |
| CN106632866A (en) * | 2017-01-05 | 2017-05-10 | 合肥光冉高分子材料科技有限公司 | Ultraviolet-light crosslinked polyethylene wire-cable material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2311967C2 (en) * | 2002-03-06 | 2007-12-10 | Акцо Нобель Коатингс Интернэшнл Б.В. | Heat-seal coating composition for the methods of transfer of the film and the cast product |
| CN104004262A (en) * | 2014-06-06 | 2014-08-27 | 杭州双马高分子材料科技有限公司 | Irradiation crosslinking oil-resistance low-smoke halogen-free flame-retardant polyolefin sheath material and preparation method thereof |
| CN104403190A (en) * | 2014-12-09 | 2015-03-11 | 黑龙江省润特科技有限公司 | Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
-
2019
- 2019-10-08 CN CN201910947715.0A patent/CN110527178B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153802A (en) * | 2011-03-07 | 2011-08-17 | 沭阳优唯新材料有限公司 | Ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable material and method for preparing ultraviolet-light deeply cross-linked halogen-free flame-retardant polyolefin cable insulating or sheathing layer from same |
| JP2013129845A (en) * | 2013-03-07 | 2013-07-04 | Asahi Rubber Inc | Silicone resin base material |
| CN104893088A (en) * | 2015-06-17 | 2015-09-09 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof |
| CN105237865A (en) * | 2015-10-21 | 2016-01-13 | 上海至正道化高分子材料股份有限公司 | Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material |
| CN105419072A (en) * | 2015-12-18 | 2016-03-23 | 华南理工大学 | Flexible low-smoke halogen-free flame-retardant wire and cable material and preparation method thereof |
| CN106632866A (en) * | 2017-01-05 | 2017-05-10 | 合肥光冉高分子材料科技有限公司 | Ultraviolet-light crosslinked polyethylene wire-cable material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 光引发剂的进展;金养智;《影像技术》;20110630(第03期);第8-18页 * |
| 环境友好型阻燃剂的研究及进展;唐皓;《消防技术与产品信息》;20080228(第02期);第23-25页 * |
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