CN114316403A - Ultraviolet light crosslinking heat-shrinkable tube material and preparation method thereof - Google Patents
Ultraviolet light crosslinking heat-shrinkable tube material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an ultraviolet light crosslinking heat-shrinkable tube material and a preparation method thereof. According to the invention, by matching and using the near-infrared light initiator and the ultraviolet light initiator, the wavelength range of ultraviolet light absorption of the product is widened, so that the light absorption efficiency of the product is greatly improved; and in the dark product, refined quartz sand is added, because the crystal structure of the quartz sand can refract the irradiated ultraviolet light and near infrared light, partial light can penetrate into the dark product, the light absorption efficiency is improved, the dark or even black product can achieve the crosslinking effect, and the technical problem that the previous product can only carry out ultraviolet crosslinking on light products is solved.
Description
Technical Field
The invention belongs to the field of power cable insulating materials, and particularly relates to an ultraviolet light crosslinking heat-shrinkable tube material and a preparation method thereof.
Background
The heat-shrinkable tube is widely applied to insulation protection of wire harnesses, welding spots and inductors, rust prevention and corrosion prevention protection of metal tubes, handles, pen holder sleeves and the like. The heat shrinkable sleeve needs to be subjected to the processes of extrusion molding, crosslinking, expansion, cooling and shaping and the like, and then can be shrunk to play roles in fastening, sealing and protecting when being heated to a high elastic state in use.
Since the 90 s, heat-shrinkable tubes have been produced by irradiation crosslinking. For large-scale manufacturers, it is a common choice to invest in irradiation accelerators to perform irradiation crosslinking processing. As the investment capital of the irradiation crosslinking equipment is generally 300-. In this case, the problems of troublesome transportation, long irradiation processing period and high cost do limit the development and production of heat shrinkable tubes.
Subsequently, the uv cross-linking technique has entered the field of view of the general public. The ultraviolet crosslinking technology makes up the defects of irradiation processing, adopts ultraviolet light as an irradiation source, has low investment on required crosslinking equipment, simple process, convenient operation and maintenance, energy conservation and environmental protection, high production efficiency and low product cost, and the produced heat shrinkable tube has the same characteristics as the heat shrinkable tube produced by a high-energy ray radiation crosslinking method, such as good high-temperature resistance and mechanical property.
However, the ultraviolet crosslinked products on the market can only be used in light-colored products, but the ideal crosslinking effect cannot be achieved for dark-colored and black-colored products due to poor light transmittance.
Disclosure of Invention
The invention provides an ultraviolet crosslinking heat-shrinkable tube material and a preparation method thereof, aiming at solving the problem that the prior dark color and black color products can not achieve the ideal crosslinking effect due to poor light transmittance.
The published Chinese patent documents relate to the research of ultraviolet light crosslinking thermal shrinkage material products, but the ultraviolet light crosslinking thermal shrinkage material products can only realize crosslinking in light color products, and do not relate to the research of dark color products, and the near infrared light and purple light initiator matching and quartz sand refraction mechanism used in the invention are not related.
In order to achieve the purpose, the invention adopts the technical scheme that:
an ultraviolet light crosslinking thermal shrinkage pipe material is characterized in that: the material is mainly prepared from the following raw materials in parts by weight:
85-95 parts of polyolefin resin;
5-15 parts of modified grafting material;
0.5-1 part of near infrared photoinitiator;
1.5-3 parts of an ultraviolet initiator;
1-3 parts of a crosslinking sensitizer;
3-6 parts of refined quartz sand;
the polyolefin resin is one or a composition of more of polyethylene, ethylene-octene copolymer, ethylene-butene copolymer, ethylene propylene diene monomer, ethylene-vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-methyl acrylate copolymer and ethylene-butyl acrylate copolymer;
the modified grafting material is one or a composition of more of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, maleic anhydride grafted ethylene octene copolymer, maleic anhydride grafted ethylene propylene rubber and ethylene-acrylate-maleic anhydride terpolymer;
the near-infrared photoinitiator is a mixture of 1- { 2, 2-bis [4- (diethylamino) phenyl ] vinyl } -3, 3-bis [4- (diethylamino) phenyl ] prop-2-en-1-ium P-toluenesulfonate (IRT) and an organic ammonium salt in a mass ratio of 1:1 to 2:1, wherein the organic ammonium salt is tetrabutylammonium triphenylbutyl borate (P3B) or tetrabutylammonium trinaphthyl butyl borate (N3B);
the ultraviolet initiator is one or a combination of benzophenone and derivatives thereof, Irgacure 651, Irgacure 184, Darocur TPO, Darocur ITX and Darocur 1173;
the crosslinking sensitizer is: triallyl isocyanurate (TAIC), trimethylolpropane trimethacrylate (TMPTMA), and 1, 2-polybutadiene.
The heat-shrinkable tube material further comprises 50-150 parts by weight of a halogen-free flame retardant, wherein the halogen-free flame retardant is one or a composition of more of aluminum hydroxide, magnesium hydroxide, zinc borate, ammonium polyphosphate, triphenyl phosphate, melamine polyphosphate, organic aluminum hypophosphite, inorganic aluminum hypophosphite and red phosphorus.
The thermal shrinkage pipe material also comprises 1-3 parts by weight of antioxidant, wherein the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [ 2.4-di-tert-butylphenyl ] phosphite ester, dioctadecyl thiodipropionate, dilauryl thiodipropionate, (4.4 '-bis (alpha, alpha-dimethylbenzyl) diphenylamine) and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
The heat-shrinkable tube material further comprises 1-4 parts by weight of a lubricant, wherein the lubricant is one or a combination of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, Ethylene Bis Stearamide (EBS), silicone oil and silicone.
Wherein the mesh number of the refined quartz sand is 1000-2500 meshes.
Wherein, 1- { 2, 2-bis [4- (diethylamino) phenyl ] vinyl } -3, 3-bis [4- (diethylamino) phenyl ] prop-2-en-1-ium p-toluenesulfonate (IRT for short, CAS number 96233-24-8) has a structural formula
Wherein the organic ammonium salt is tetrabutylammonium triphenylbutyl borate (P3B for short and CAS number 120307-06-4),
structural formula is
；
Tetrabutylammonium trinaphthylbutylborate (abbreviated to N3B, CAS number 219125-19-6),
structural formula is
The technical scheme also provides a preparation method for the heat-shrinkable tube material, which is characterized by comprising the following steps: the method comprises the following steps:
pouring 85-95 parts by weight of polyolefin resin and 5-15 parts by weight of modified grafting material into an internal mixer, starting the internal mixer at normal pressure to stir uniformly, then pouring 0.5-1 part by weight of near infrared light initiator, 1.5-3 parts by weight of ultraviolet light initiator and 1-3 parts by weight of crosslinking sensitizer into the internal mixer to mix together for 10-15 seconds, then pouring 3-6 parts by weight of refined quartz sand, starting the internal mixer, putting a pressing hammer down to perform pressure mixing to 120-125 ℃, lifting the pressing hammer up, cleaning an internal mixing chamber, putting the pressing hammer down after the materials in the internal mixer are turned over, performing pressure mixing to 135-140 ℃, lifting the pressing hammer up again after the materials in the internal mixer are turned over, putting the pressing hammer down after the materials in the internal mixer are turned over, discharging and feeding the materials into a conical feeding machine after the internal mixing is performed to 150-155 ℃, performing melt extrusion and dispersion by a double screw at an extrusion temperature of 140-155 ℃, and then performing single screw extrusion granulation at an extrusion temperature of 140-150 ℃, and (3) carrying out hot cutting, air cooling and sieving to obtain the ultraviolet crosslinking oil-resistant heat-shrinkable tube material.
Wherein, 50 to 150 weight parts of halogen-free flame retardant, 1 to 3 weight parts of antioxidant and 1 to 4 weight parts of lubricant are added into an internal mixer together with refined quartz sand.
The design principle and the effect of the invention are as follows:
1. because the range of light absorption wavelength and light absorption efficiency are limited, the ultraviolet crosslinking heat-shrinkable tube material on the current market can only realize ultraviolet crosslinking on light-colored products, but cannot meet the requirement of required crosslinking degree in dark-colored products. The heat shrinkable tube produced by the heat shrinkable tube material prepared by the invention can be applied to dark products.
2. The key point of the invention is that near infrared light initiator, ultraviolet light initiator, crosslinking sensitizer and refined quartz sand are introduced, so that the dark color and black products can achieve the ultraviolet light crosslinking effect successfully, the problem that the original dark color and black products can not be crosslinked by ultraviolet light is solved, the production efficiency is improved, and the cost is reduced:
(1) the introduction of the near infrared light initiator, the ultraviolet light initiator, the crosslinking sensitizer and the quartz sand ensures that the dark color and black heat shrinkable tube has the capability of ultraviolet light crosslinking, thereby widening the application range of ultraviolet light crosslinking;
(2) the use of low density polyethylene LDPE in polyolefin resin, ethylene-vinyl acetate copolymer EVA and ethylene propylene diene monomer EPDM ensures the expansion and shrinkage process performance of the heat shrinkable tube;
(3) the introduction of flame retardants such as aluminum hydroxide, magnesium hydroxide and red phosphorus improves the flame retardant property of the material, so that the product meets the green and environment-friendly characteristics of low smoke, zero halogen and flame retardance.
3. The shrinkage test of the finished product proves that the product has the ultraviolet crosslinking effect by the processes of tube extrusion, ultraviolet crosslinking and expansion, the problem that dark and black products cannot be crosslinked by ultraviolet is solved, and the prepared heat-shrinkable tube meets the relevant requirements of UL224 and UL758 standards.
4. According to the invention, by matching and using the near-infrared light initiator and the ultraviolet light initiator, the wavelength range of ultraviolet light absorption of the product is widened, so that the light absorption efficiency of the product is greatly improved; and in the dark product, refined quartz sand is added, because the crystal structure of the quartz sand can refract the irradiated ultraviolet light and near infrared light, partial light can penetrate into the dark product, the light absorption efficiency is improved, the dark or even black product can achieve the crosslinking effect, and the technical problem that the previous product can only carry out ultraviolet crosslinking on light products is solved.
Detailed Description
The invention is further described below in connection with examples 1-5:
example (b):
table one: examples 1-5 Heat shrinkable tubing compositions
In the following table, 1- { 2, 2-bis [4- (diethylamino) phenyl ] vinyl } -3, 3-bis [4- (diethylamino) phenyl ] prop-2-en-1-ium p-toluenesulfonate is abbreviated as IRT;
the abbreviation of tetrabutylammonium triphenylbutylborate is P3B;
the abbreviation of tetrabutylammonium trinaphthylbutylborate is N3B;
the abbreviation for triallyl isocyanurate is TAIC.
Example (b):
table two: examples 1-5 Heat shrink tubing Properties List:
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 (7)
1. An ultraviolet light crosslinking thermal shrinkage pipe material is characterized in that: the material is mainly prepared from the following raw materials in parts by weight:
85-95 parts of polyolefin resin;
5-15 parts of modified grafting material;
0.5-1 part of near infrared photoinitiator;
1.5-3 parts of an ultraviolet initiator;
1-3 parts of a crosslinking sensitizer;
3-6 parts of refined quartz sand;
the polyolefin resin is one or a composition of more of polyethylene, ethylene-octene copolymer, ethylene-butene copolymer, ethylene propylene diene monomer, ethylene-vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene-methyl acrylate copolymer and ethylene-butyl acrylate copolymer;
the modified grafting material is one or a composition of more of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene vinyl acetate, maleic anhydride grafted ethylene octene copolymer, maleic anhydride grafted ethylene propylene rubber and ethylene-acrylate-maleic anhydride terpolymer;
the near-infrared photoinitiator is a mixture of 1- { 2, 2-bis [4- (diethylamino) phenyl ] vinyl } -3, 3-bis [4- (diethylamino) phenyl ] prop-2-en-1-ium p-toluenesulfonate and an organic ammonium salt in a mass ratio of 1:1 to 2:1, wherein the organic ammonium salt is tetrabutylammonium triphenylbutyl borate or tetrabutylammonium trinaphthyl butyl borate;
the ultraviolet initiator is one or a combination of benzophenone and derivatives thereof, Irgacure 651, Irgacure 184, Darocur TPO, Darocur ITX and Darocur 1173;
the crosslinking sensitizer is: one or a plurality of triallyl isocyanurate, trimethylolpropane trimethacrylate and 1, 2-polybutadiene.
2. The heat-shrinkable tubing of claim 1, wherein: the heat-shrinkable tube material also comprises 50-150 parts by weight of a halogen-free flame retardant, wherein the halogen-free flame retardant is one or a combination of more of aluminum hydroxide, magnesium hydroxide, zinc borate, ammonium polyphosphate, triphenyl phosphate, melamine polyphosphate, organic aluminum hypophosphite, inorganic aluminum hypophosphite and red phosphorus.
3. The heat-shrinkable tubing of claim 1, wherein: the thermal shrinkage pipe material also comprises 1-3 parts by weight of antioxidant, wherein the antioxidant is one or more of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [ 2.4-di-tert-butylphenyl ] phosphite ester, dioctadecyl thiodipropionate, dilauryl thiodipropionate, (4.4 '-bis (alpha, alpha-dimethylbenzyl) diphenylamine) and 4,4' -thiobis (6-tert-butyl-3-methylphenol).
4. The heat-shrinkable tubing of claim 1, wherein: the heat-shrinkable tube material also comprises 1-4 parts by weight of a lubricant, wherein the lubricant is one or a combination of zinc stearate, calcium stearate, magnesium stearate, polyethylene wax, ethylene bis-stearamide, silicone oil and silicone.
5. The heat-shrinkable tubing of claim 1, wherein: the mesh number of the refined quartz sand is 1000-.
6. A method for preparing a heat shrinkable tubing material as claimed in any one of claims 1 to 5, characterized by: the method comprises the following steps:
pouring 85-95 parts by weight of polyolefin resin and 5-15 parts by weight of modified grafting material into an internal mixer, starting the internal mixer at normal pressure to stir uniformly, then pouring 0.5-1 part by weight of near infrared light initiator, 1.5-3 parts by weight of ultraviolet light initiator and 1-3 parts by weight of crosslinking sensitizer into the internal mixer to mix together for 10-15 seconds, then pouring 3-6 parts by weight of refined quartz sand, starting the internal mixer, putting a pressing hammer down to perform pressure mixing to 120-125 ℃, lifting the pressing hammer up, cleaning an internal mixing chamber, putting the pressing hammer down after the materials in the internal mixer are turned over, performing pressure mixing to 135-140 ℃, lifting the pressing hammer up again after the materials in the internal mixer are turned over, putting the pressing hammer down after the materials in the internal mixer are turned over, discharging and feeding the materials into a conical feeding machine after the internal mixing is performed to 150-155 ℃, performing melt extrusion and dispersion by a double screw at an extrusion temperature of 140-155 ℃, and then performing single screw extrusion granulation at an extrusion temperature of 140-150 ℃, and (3) carrying out hot cutting, air cooling and sieving to obtain the ultraviolet crosslinking oil-resistant heat-shrinkable tube material.
7. The method of claim 6, wherein: adding 50-150 parts by weight of halogen-free flame retardant, 1-3 parts by weight of antioxidant and 1-4 parts by weight of lubricant into an internal mixer together with refined quartz sand.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012939A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | Ultraviolet light cross-linking heat-shrinkage pipe material and method for producing ultraviolet light cross-linking heat-shrinkage pipe |
| 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 |
| CN112662046A (en) * | 2020-12-22 | 2021-04-16 | 上海新上化高分子材料有限公司 | Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012939A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | Ultraviolet light cross-linking heat-shrinkage pipe material and method for producing ultraviolet light cross-linking heat-shrinkage pipe |
| 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 |
| CN112662046A (en) * | 2020-12-22 | 2021-04-16 | 上海新上化高分子材料有限公司 | Ultraviolet light crosslinking low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| 华林林;吕建平;谢飞;叶磊;吴强华;瞿保钧;: "光引发交联改性对尼龙6性能的影响", 高分子材料科学与工程 * |
| 徐志前;吕建平;谢飞;王亚柯;汤存对;: "紫外光辐射交联甲基乙烯基硅橡胶/线性低密度聚乙烯热塑弹性体的性能", 高分子材料科学与工程 * |
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