CN114316403B - Ultraviolet light crosslinking heat-shrinkable tubing and preparation method thereof - Google Patents
Ultraviolet light crosslinking heat-shrinkable tubing and preparation method thereof Download PDFInfo
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- CN114316403B CN114316403B CN202111490199.7A CN202111490199A CN114316403B CN 114316403 B CN114316403 B CN 114316403B CN 202111490199 A CN202111490199 A CN 202111490199A CN 114316403 B CN114316403 B CN 114316403B
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Abstract
The invention relates to an ultraviolet light crosslinking heat-shrinkable tube material and a preparation method thereof. The invention widens the wavelength range of the product for absorbing ultraviolet light through the collocation of the near infrared photoinitiator and the ultraviolet photoinitiator, so that the absorption efficiency of the product for light is greatly improved; in addition, refined quartz sand is added into the dark product, and the crystal structure of the quartz sand can refract the irradiated ultraviolet light and near infrared light, so that part of light can penetrate into the dark product, the light absorption efficiency is improved, the dark and even black products can achieve the crosslinking effect, and the technical problem that the traditional product can only carry out ultraviolet crosslinking on the light product is solved.
Description
Technical Field
The invention belongs to the field of power cable insulating materials, and particularly relates to an ultraviolet 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 protection of metal tubes, handles, pen holder sleeves and the like. The heat-shrinkable sleeve is required to be subjected to the procedures of extrusion molding, crosslinking, expansion, cooling shaping and the like, and then can be shrunk to play roles of fastening, sealing and protecting when being heated to a high-elastic state during use.
Since the 90 s, heat shrinkable tubes have been produced by irradiation crosslinking. For large-scale manufacturers, it is a common option to invest in irradiation accelerators for irradiation crosslinking processing. Because the investment funds of the irradiation crosslinking equipment are generally 300-1000 ten thousand, and because of the high price, many small-scale manufacturers can only send to an irradiation processing plant for irradiation processing without an irradiation accelerator. In this case, the problems of troublesome transportation, long irradiation processing period and high cost do limit the development and production of the heat shrinkable tube.
Subsequently, ultraviolet crosslinking technology has come into the public view. The ultraviolet crosslinking technology makes up the defect of irradiation processing, ultraviolet light is adopted as an irradiation source, the required crosslinking equipment investment is low, the process is simple, the operation and maintenance are convenient, the energy is saved, the environment is protected, the production efficiency is high, the cost of the product is low, and the produced heat-shrinkable tube has the same characteristics as the heat-shrinkable tube produced by the high-energy ray radiation crosslinking method, such as good high-temperature resistance and mechanical property.
However, the uv-crosslinking products on the market at present can only be used in light products, but the ideal crosslinking effect cannot be achieved for dark and black products due to poor light transmittance.
Disclosure of Invention
The invention provides an ultraviolet light crosslinking heat shrinkage tube material and a preparation method thereof, which aim to solve the problem that the ideal crosslinking effect of the existing dark and black products cannot be achieved due to poor light transmittance.
The disclosed Chinese patent literature has researches on ultraviolet crosslinking thermal shrinkage material products, but only can achieve crosslinking in light products, and does not relate to the researches on dark products, and the matching of near infrared light and a purple photoinitiator and the refraction mechanism of quartz sand used by the invention are not related.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultraviolet light crosslinking heat shrinkage tubing 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 initiator;
1.5-3 parts of ultraviolet initiator;
1-3 parts of a crosslinking sensitizer;
3-6 parts of refined quartz sand;
the polyolefin resin is one or a combination 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 combination 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-acrylic ester-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, wherein the mass ratio of the two is 1:1-2:1, and the organic ammonium salt is tributyl ammonium triphenylbutylborate (P3B) or tetraphthyl butylborate (N3B);
the ultraviolet initiator is one or a combination of more 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), 1, 2-polybutadiene.
The heat-shrinkable tubing also comprises 50-150 parts by weight of 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.
Wherein the heat-shrinkable tubing also comprises 1-3 parts by weight of antioxidant, and 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 tubing also comprises 1-4 parts by weight of a lubricant, wherein the lubricant is one or a combination of more 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 the structural formula
Wherein the organic ammonium salt is tributyl ammonium triphenylbutyl borate (P3B for short, CAS number is 120307-06-4),
the structure is that
Tetrabutylammonium trinaphthylbutyl borate (abbreviated as N3B, CAS number 219125-19-6),
the structure is that
The technical scheme also provides a preparation method for the heat-shrinkable tubing, which is characterized in that: the method comprises the following steps:
the 85-95 parts of polyolefin resin and 5-15 parts of modified grafting material by weight are poured into an internal mixer, the internal mixer is started under normal pressure to be uniformly stirred, then 0.5-1 part of near infrared photoinitiator, 1.5-3 parts of ultraviolet photoinitiator and 1-3 parts of crosslinking sensitizer are poured into the internal mixer to be mixed together for 10-15 seconds, then 3-6 parts of refined quartz sand are poured into the internal mixer, the internal mixer is started, a pressing hammer is placed under pressure to be banburying to 120-125 ℃, the pressing hammer is lifted up, a pressing hammer is placed under cleaning the internal mixer after materials in the internal mixer are overturned, the pressing hammer is lifted up again when the materials in the internal mixer are overturned under the pressure to 135-140 ℃, the internal mixer is discharged when the materials in the internal mixer are overturned to 150-155 ℃, the materials are fed into a conical feeder, the materials are fed into the internal mixer, and the materials are subjected to single-screw extrusion granulation with 140-150 ℃ after the double-screw melt extrusion dispersion with the extrusion temperature, and the extrusion granulation is carried out, and the ultraviolet crosslinking oil-resistant type heat shrinkage pipe material is obtained after hot cutting, air cooling and sieving.
Wherein 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 are added into an internal mixer together with refined quartz sand.
The design principle and effect of the invention are:
1. because of the limitation on the light absorption wavelength range and the light absorption efficiency, the ultraviolet crosslinking heat shrinkage tubing in the current market can only realize ultraviolet crosslinking in light products, but cannot meet the required crosslinking degree requirement in dark products. The heat-shrinkable tube produced by the heat-shrinkable tube material prepared by the invention can be applied to dark products.
2. The invention has the key points that the near infrared photoinitiator, the ultraviolet photoinitiator, the crosslinking sensitizer and the refined quartz sand are introduced to successfully lead the dark and black products to achieve the ultraviolet crosslinking effect, solve the problem that the original dark and black products cannot be crosslinked by ultraviolet, improve the production efficiency and reduce the cost:
(1) The introduction of the near infrared photoinitiator, the ultraviolet photoinitiator, the crosslinking sensitizer and the quartz sand ensures that the dark and black heat-shrinkable tubes have ultraviolet crosslinking capability, and the ultraviolet crosslinking application range is widened;
(2) The use of low-density polyethylene LDPE, ethylene-vinyl acetate copolymer EVA and ethylene propylene diene monomer EPDM in the polyolefin resin ensures the expansion and contraction process performance of the heat-shrinkable tube;
(3) The introduction of the flame retardants such as aluminum hydroxide, magnesium hydroxide, red phosphorus and the like improves the flame retardant property of the material, so that the product meets the green and environment-friendly characteristics of low-smoke halogen-free flame retardance.
3. Through the verification of tube extrusion, ultraviolet crosslinking and expansion processes, the shrinkage test of the finished product has an ultraviolet crosslinking effect, the problem that dark and black products cannot be crosslinked by ultraviolet is solved, and the prepared heat-shrinkable tube meets the related requirements of UL224 and UL758 standards.
4. The invention widens the wavelength range of the product for absorbing ultraviolet light through the collocation of the near infrared photoinitiator and the ultraviolet photoinitiator, so that the absorption efficiency of the product for light is greatly improved; in addition, refined quartz sand is added into the dark product, and the crystal structure of the quartz sand can refract the irradiated ultraviolet light and near infrared light, so that part of light can penetrate into the dark product, the light absorption efficiency is improved, the dark and even black products can achieve the crosslinking effect, and the technical problem that the traditional product can only carry out ultraviolet crosslinking on the light product is solved.
Detailed Description
The invention is further described in connection with examples 1-5 below:
examples:
table one: examples 1-5 Heat shrink tubing Components
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 IRT;
the short name of the tributyl ammonium triphenylbutyl borate is P3B;
the short name of the tetranaphthylbutyl tetrabutylammonium borate is N3B;
the abbreviation for triallyl isocyanurate is TAIC.
Examples:
and (II) table: examples 1-5 list of heat shrink tubing properties:
the above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (7)
1. An ultraviolet light crosslinking heat shrinkage tubing 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 initiator;
1.5-3 parts of ultraviolet initiator;
1-3 parts of a crosslinking sensitizer;
3-6 parts of refined quartz sand;
the polyolefin resin is one or a combination of more of polyethylene, ethylene propylene diene monomer and ethylene-vinyl acetate copolymer;
the modified grafting material is maleic anhydride grafted polyethylene;
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, wherein the mass ratio of the two is 1:1-2:1, and the organic ammonium salt is tributylammonium triphenylbutylborate or tetrabutylammonium trinaphthylbutylborate;
the ultraviolet initiator is a combination of 2, 4-dihydroxybenzophenone and Irgacure 651;
the crosslinking sensitizer is triallyl isocyanurate.
2. The heat shrink tubing of claim 1, wherein: the heat-shrinkable tubing also comprises 50-150 parts by weight of halogen-free flame retardant, wherein the halogen-free flame retardant is one or a combination of more of aluminum hydroxide and magnesium hydroxide.
3. The heat shrink tubing of claim 1, wherein: the heat-shrinkable tubing also comprises 1-3 parts by weight of an antioxidant, wherein the antioxidant is pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
4. The heat shrink tubing of claim 1, wherein: the heat-shrinkable tubing also comprises 1-4 parts by weight of a lubricant, wherein the lubricant is silicone.
5. The heat shrink tubing of claim 1, wherein: the mesh number of the refined quartz sand is 1000-2500 mesh.
6. A process for the preparation of heat shrinkable tubing as defined in any one of claims 1 to 5, characterized in that: the method comprises the following steps:
the 85-95 parts of polyolefin resin and 5-15 parts of modified grafting material by weight are poured into an internal mixer, the internal mixer is started under normal pressure to be uniformly stirred, then 0.5-1 part of near infrared photoinitiator, 1.5-3 parts of ultraviolet photoinitiator and 1-3 parts of crosslinking sensitizer are poured into the internal mixer to be mixed together for 10-15 seconds, then 3-6 parts of refined quartz sand are poured into the internal mixer, the internal mixer is started, a pressing hammer is placed under pressure to be banburying to 120-125 ℃, the pressing hammer is lifted up, a pressing hammer is placed under cleaning the internal mixer after materials in the internal mixer are overturned, the pressing hammer is lifted up again when the materials in the internal mixer are overturned under the pressure to 135-140 ℃, the internal mixer is discharged when the materials in the internal mixer are overturned to 150-155 ℃, the materials are fed into a conical feeder, the materials are fed into the internal mixer, and the materials are subjected to single-screw extrusion granulation with 140-150 ℃ after the double-screw melt extrusion dispersion with the extrusion temperature, and the extrusion granulation is carried out, and the ultraviolet crosslinking oil-resistant type heat shrinkage pipe material is obtained after hot cutting, air cooling and sieving.
7. The method of manufacturing according to claim 6, wherein: 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 are added into an internal mixer together with refined quartz sand.
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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 |
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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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| 光引发交联改性对尼龙6性能的影响;华林林;吕建平;谢飞;叶磊;吴强华;瞿保钧;;高分子材料科学与工程(第03期);全文 * |
| 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;徐志前;吕建平;谢飞;王亚柯;汤存对;;高分子材料科学与工程(第10期);全文 * |
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