CN107459728B - Light-storing luminous polyvinyl chloride extrusion composition and preparation method thereof - Google Patents
Light-storing luminous polyvinyl chloride extrusion composition and preparation method thereof Download PDFInfo
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- CN107459728B CN107459728B CN201610389302.1A CN201610389302A CN107459728B CN 107459728 B CN107459728 B CN 107459728B CN 201610389302 A CN201610389302 A CN 201610389302A CN 107459728 B CN107459728 B CN 107459728B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
A light-storing luminous polyvinyl chloride extrusion composition and a preparation method thereof belong to the technical field of high polymer material processing and application. The composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 1.5-10 parts of plasticizer, 1-7 parts of stabilizer, 1-6 parts of auxiliary stabilizer, 6-10 parts of impact modifier, 0.5-3.0 parts of lubricant, 5-30 parts of light-storing luminescent material and 0.03-0.9 part of titanate coupling agent. The preparation method comprises the steps of 1) mixing a titanate coupling agent with a light-storing luminescent material, mixing and infiltrating the titanate coupling agent with a plasticizer, adding a lubricant, mixing, and grinding by three rollers to obtain a light-storing luminescent premix; 2) stirring and mixing polyvinyl chloride, a stabilizer, an auxiliary stabilizer and an impact modifier at 90-110 ℃, adding a light-storing and light-emitting premix, heating to 110 ℃, stirring at a low speed, cooling to below 40 ℃, and discharging. The light-storing luminous polyvinyl chloride extrusion composition has long luminous time, bright light emission, difficult blackening and better flexibility, and can be coated outside a curved surface.
Description
Technical Field
The invention belongs to the technical field of processing and application of high polymer materials, and particularly relates to a light-storing luminous polyvinyl chloride extrusion composition and a preparation method thereof.
Background
The light storage material is a material which stores energy in the material after being irradiated by sunlight or lamplight and releases the energy in a luminous mode at night or in a dark place, and the light storage material is mainly used for safety signs, advertising boards, artware, traffic instructions, guardrails, fences and the like. Most of the light-storing materials are light-storing and light-emitting type coating products, and due to the characteristics of the light-storing materials, few light-storing products are formed by an extrusion process.
Patent publication No. CN101817961A discloses a technology for preparing articles with negative ion releasing effect by using compositions such as PVC paste resin, Anion series negative ion additive, plasticizer, stabilizer and the like. At present, light-storing materials are mostly used for powder coatings and plastic spraying materials, and reports for polyvinyl chloride extrusion compositions are not found, and the main reasons are that the light-storing luminescent powder is poor in high-temperature resistance and high in hardness, and products are prone to blacking after the light-storing luminescent powder is strongly rubbed with the metal wall of a mixer in a mixed material. By adopting the pretreatment methods of soaking, grinding and the like on the light-storing and light-emitting powder, on one hand, the agglomeration phenomenon of light-storing and light-emitting is solved, so that the light-storing and light-emitting powder can be uniformly dispersed in the polymer; on the other hand, the degree of blackening of the product caused by friction between the luminescent material and processing machinery is greatly reduced, and the problem of poor luminescence of the luminescent material caused by high-temperature processing is greatly relieved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the light storage and emission type polyvinyl chloride extrusion composition is long in light emission time, bright in light emission, not prone to blackening, good in flexibility and capable of being coated outside a curved surface.
The invention is realized by the following technical scheme: the light-storing luminous polyvinyl chloride extrusion composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 1.5-10 parts of plasticizer, 1-7 parts of stabilizer, 1-6 parts of auxiliary stabilizer, 6-10 parts of impact modifier, 0.5-3.0 parts of lubricant, 5-30 parts of light-storing luminescent material and 0.03-0.9 part of titanate coupling agent.
The light-storing luminous polyvinyl chloride extrusion composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 2.5-6 parts of plasticizer, 2-5 parts of stabilizer, 2-5 parts of auxiliary stabilizer, 7-10 parts of impact modifier, 1-2 parts of lubricant, 8-15 parts of light-storing luminescent material and 0.03-0.2 part of titanate coupling agent.
The light-storing luminous polyvinyl chloride extrusion composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 2.8-3 parts of plasticizer, 2-2.4 parts of stabilizer, 3-4 parts of auxiliary stabilizer, 8-10 parts of impact modifier, 1.6-1.8 parts of lubricant, 8-9 parts of light-storing luminescent material and 0.032-0.043 part of titanate coupling agent.
The weight ratio of the plasticizer to the light-emitting and light-storing material is 1: 3-6, and the weight ratio of the titanate coupling agent to the light-storing and light-storing material is 0.3-3: 50.
the polyvinyl chloride is suspension polyvinyl chloride, and the polymerization degree is 1000-1300.
The plasticizer is phthalate plasticizer; the light-storing luminescent material is 100-300-mesh rare earth long-acting aluminate light-storing luminescent powder.
The titanate coupling agent is coordination tetraisopropyl dilauryl phosphite titanate.
The stabilizer is a calcium zinc stabilizer or an organic tin stabilizer, and the auxiliary stabilizer is epoxidized soybean oil.
The lubricant is one or two of calcium stearate, stearic acid and oxidized polyethylene wax.
The preparation method of the light-storing luminous polyvinyl chloride extrusion composition is characterized by comprising the following steps:
1) mixing titanate coupling agent and light-storing luminescent material, adding the titanate coupling agent into plasticizer, mixing and infiltrating to form paste, adding lubricant, mixing, and grinding by three rollers to obtain light-storing luminescent premix;
2) and (2) putting the polyvinyl chloride, the stabilizer, the auxiliary stabilizer and the impact modifier into a high-speed mixer for high-speed mixing, heating to 90-110 ℃, adding the light-storing and light-emitting premix, heating to 110 ℃, discharging into a low-speed mixer for cooling and continuing to stir, and discharging after the temperature is lower than 40 ℃ to obtain the light-storing and light-emitting polyvinyl chloride composition.
The invention is described below:
the light-storing luminous polyvinyl chloride composition for extrusion is prepared with polyvinyl chloride resin as main material and through mixing, stirring and cooling.
The applicant has found that polyvinyl chloride is not prone to have too high a degree of polymerisation, which would result in too high a processing temperature of the composition, adversely affecting the brightness of the luminescence of the composition. According to the research of the applicant, the optimal polyvinyl chloride is suspension polyvinyl chloride resin, the polymerization degree is 1000-1300, the processing temperature of the composition is suitable, and the light storage and emission performance of the finally produced composition is excellent. The polyvinyl chloride resin having a polymerization degree of 1000 is preferable. The stabilizer is a thiol organotin stabilizer. Preferably, the mercaptan organotin stabilizer 17MOK-N octyl tin mercaptide has good heat stabilizing effect and low odor.
The light-storing luminescent material, also called light-storing luminescent pigment, is a rare earth long-acting aluminate light-storing luminescent powder, belonging to alkaline earth aluminate long-afterglow luminescent materials. The light-storing luminescent material belongs to nontoxic and nonradioactive environment-friendly pigment, has the characteristics of long luminescence time and long service life, so that a product processed by the composition can emit visible light at night for a long time, and the energy is saved. The light-storing luminescent material with the size of 100-300 meshes is mixed uniformly in the liquid phthalate plasticizer in advance, and then is slowly added into the stirring machine for low-speed stirring in the later period of mixing, so that the friction force and time between the light-storing luminescent material and the stirring machine are reduced and shortened, and the phenomenon that the composition is blackened is solved. Finally, the light-storing and light-emitting premix obtained in the step 1) is a fine powder material, so that the mixing processing in the step 2) is facilitated.
The plasticizer is phthalate plasticizer. The plasticizer has the effect in polyvinyl chloride, and mainly reduces the acting force among macromolecules of the polyvinyl chloride, so that the glass transition temperature and the rigidity of the polyvinyl chloride are reduced, and the polyvinyl chloride is easy to process; the dosage of the polyvinyl chloride is basically more than 35 parts per hundred parts. In the invention, the plasticizer is mainly used for infiltration and three-roller grinding of the light-emitting and light-storing material, and has extremely limited plasticizing effect on polyvinyl chloride due to small using amount, but has promotion effect on dispersion of the light-storing and light-emitting material. The ratio of the plasticizer to the light-emitting and light-storing material is 1: 3-6, and the preferable ratio is 1: 3.5-4. Preferably, the phthalate plasticizer is liquid at normal temperature, the liquid phthalate plasticizer has better dispersibility, and can be uniformly mixed with the titanate coupling agent and the light-storing luminescent material in the mixing of the step 1) to promote the dispersion of the light-storing luminescent material in the composition. Preferably, the phthalate plasticizer is one or two of dioctyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate and diisobutyl phthalate. Preferably, the weight ratio of the plasticizer to the light-emitting and light-storing material is 1: 3.5-4. And (2) adding a lubricant into the paste to mix, and fully mixing the plasticizer, the light-storing luminescent material and the titanate coupling agent through three-roller grinding to obtain the light-storing luminescent premix.
The titanate coupling agent is coordination tetraisopropyl dilauryl phosphite titanate, which can play a firm bridge role between polyvinyl chloride, filler and light-storing luminescent material, and does not generate ester exchange reaction with auxiliary agent. The weight ratio of the titanate coupling agent to the light-storing luminescent material is 0.3-3: 50 (namely the using amount of the titanate coupling agent is 0.6-6% of the light-storing luminescent material by mass percent), preferably, the weight ratio of the titanate coupling agent to the light-storing luminescent material is 1-4: 100. the coordination type titanate coupling agent has low activity of ester exchange reaction, no initial viscosity effect, good initial dispersibility and greatly increased filling amount.
Compared with the prior art, the light-storing luminous polyvinyl chloride extrusion composition has the beneficial effects that:
1. the light-storing luminous polyvinyl chloride extrusion composition has long luminous time, is bright in light emission and not easy to blacken, and can be coated on the outer surface of a material for use. The composition for light-storing luminous polyvinyl chloride extrusion is prepared by taking polyvinyl chloride resin as a main raw material by a suspension method, adding a stabilizer, a lubricant, an impact modifier and a non-toxic and non-radioactive rare earth long-acting aluminate long-afterglow light-storing luminous powder pigment, mixing, stirring, cooling and granulating by an extruder. The invention adopts 100-300-mesh rare earth long-acting aluminate light-storage luminescent powder and titanate coupling agent for treatment, and then the rare earth long-acting aluminate light-storage luminescent powder and the titanate coupling agent are mixed and soaked in liquid auxiliary agent to form paste-shaped substance, and then the paste-shaped substance is mixed with lubricant. After three-roller grinding, the agglomeration phenomenon of the light-storing luminescent material is greatly reduced, and the dispersion effect of the light-storing luminescent material in the polyvinyl chloride resin is promoted. The plasticizer and the lubricant are wrapped outside the light-storing luminescent material, so that the phenomenon that the luminescent performance of the light-storing luminescent material is reduced and even blackened due to friction with the metal surface of equipment is reduced. And in the later stage of mixing, slowly adding the light-storing luminescent material into a low-speed stirring stirrer when the temperature reaches 90-100 ℃, cooling the material in a low-speed cooling stirrer when the temperature reaches 110 ℃, continuously stirring the material until the material is discharged at room temperature, and extruding and granulating the material. Therefore, the friction force and time between the light-storing luminescent powder and the stirring machine are reduced and shortened, and the adverse effect on the light-storing luminescent material in the production and processing process is further relieved.
2. The light-storing luminous polyvinyl chloride extrusion composition is bright in light emitting, long in light emitting time and wide in application. The non-toxic and non-radioactive rare earth long-acting aluminate long-afterglow light-storing luminescent powder is added into the polyvinyl chloride extrusion composition as a pigment, so that a product processed by the composition can emit visible light at night for a long time, and energy is saved.
3. The light-storing luminous polyvinyl chloride extrusion composition also has good mechanical property, can be coated on the outer surface of a material, and has good practical value. The extrusion coating can be used for extrusion coating of highway guardrails and protecting net wires, can also be used for guardrails and warning marks in public places such as parks, halls, hotels and the like, and has the characteristics of high strength, corrosion resistance, aging resistance and the like.
Detailed Description
Examples 1 to 5 are specific embodiments of the light-storing light-emitting polyvinyl chloride extrusion composition of the present invention. Of these, example 1 is the most preferred example. The titanate coupling agent used in examples 1 to 5 was KR-36S, a coordination type tetraisopropyl dilauryl phosphite titanate, produced by Kenrich Petrochemicals, Inc. The light-storing luminescent materials used in the embodiments 1 to 5 adopt 100 to 300 mesh rare earth long-acting aluminate light-storing luminescent powder.
TABLE 1 formulation of examples and comparative examples (in parts by weight)
The preparation method of the embodiment 1-5 adopts the following steps:
1) under the condition of normal temperature, weighing titanate coupling agent according to the weight parts, mixing the titanate coupling agent with the light-storing luminescent material, performing coupling treatment, then putting the titanate coupling agent into a plasticizer, mixing and infiltrating to form paste, adding a lubricant, mixing, and grinding by a three-roll grinder to form light-storing luminescent premix for later use;
2) weighing polyvinyl chloride, a stabilizer, an auxiliary stabilizer and an impact modifier according to the weight parts, putting the polyvinyl chloride, the stabilizer, the auxiliary stabilizer and the impact modifier into a high-speed stirrer for heating and high-speed stirring and mixing, when the rotating speed is 1000-1400 r/min and the temperature is increased to 90-100 ℃, reducing the rotating speed to 600-800 r/min, putting a light-storing and light-emitting premix into the high-speed stirrer for stirring and mixing, when the temperature is continuously increased to 110 ℃, putting the mixture into a low-speed stirrer for stirring and cooling, and discharging when the temperature is reduced to below 40 ℃ to obtain the light-storing and light-emitting polyvinyl chloride.
Comparative example 1
The preparation method of the comparative example is the same as that of examples 1 to 5.
Comparative example 2
The light-storing luminescent material in the preparation method of the comparative example is not subjected to the plasticizer soaking treatment in the step 1), and the steps 2) to 3) are the same as the examples, so that the color is not greatly different from that of each example, and the performance is obviously reduced.
Performance testing
Extruding and granulating the light-storing luminous polyvinyl chloride composition by a conical double-screw extruder or a parallel double-screw extruder, properly adjusting the process conditions according to different equipment models and parameters, and then putting the mixture into an extruding device to extrude to obtain a sheet. The compositions obtained in the examples and comparative examples were formed into sheets having the same shape as the samples, and the results of the performance tests were shown in the following table.
Table 2 results of performance testing
As shown in Table 2, the light-storing luminescent material in comparative example 1 was treated with a coupling agent, impregnated with a plasticizer, ground, directly mixed with other materials in the formulation, stirred at a high speed, cooled, and granulated, and the obtained granules were dark in color and mixed with black dots. In comparative example 2, the light-storing luminescent material was not impregnated with the plasticizer, but the remaining process conditions were the same as those in the above examples, and the color was not much different from those in the examples, and the performance was significantly reduced. In example 5, the polymerization degree of polyvinyl chloride is higher than that of polyvinyl chloride in other examples, the granulation temperature and the processing and forming temperature are slightly higher by 5 to 10 ℃, and although the performance is slightly higher than that of other examples, the color and the brightness are slightly different by naked eyes. Compared with comparative examples 1-2, the impact resistance, tensile property and elongation at break of the compositions in examples 1-5 are obviously improved, and the compositions in examples 1-5 have bright light storage color after the preparation method is adopted.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. The light-storing luminous polyvinyl chloride extrusion composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 1.5-10 parts of plasticizer, 1-7 parts of stabilizer, 1-6 parts of auxiliary stabilizer, 6-10 parts of impact modifier, 0.5-3.0 parts of lubricant, 5-30 parts of light-storing luminescent material and 0.03-0.9 part of titanate coupling agent;
the polyvinyl chloride is suspension polyvinyl chloride, and the polymerization degree is 1000-1300;
the titanate coupling agent is coordination tetraisopropyl dilauryl phosphite titanate.
2. The light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, which is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 2.5-6 parts of plasticizer, 2-5 parts of stabilizer, 2-5 parts of auxiliary stabilizer, 7-10 parts of impact modifier, 1-2 parts of lubricant, 8-15 parts of light-storing luminescent material and 0.03-0.2 part of titanate coupling agent.
3. The light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, which is prepared from the following raw materials in parts by weight: 100 parts of polyvinyl chloride, 2.8-3 parts of plasticizer, 2-2.4 parts of stabilizer, 3-4 parts of auxiliary stabilizer, 8-10 parts of impact modifier, 1.6-1.8 parts of lubricant, 8-9 parts of light-storing luminescent material and 0.032-0.043 part of titanate coupling agent.
4. The light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, wherein: the weight ratio of the plasticizer to the light-emitting and light-storing material is 1: 3-6, and the weight ratio of the titanate coupling agent to the light-storing and light-storing material is 0.3-3: 50.
5. the light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, wherein: the plasticizer is phthalate plasticizer; the light-storing luminescent material is 100-300-mesh rare earth long-acting aluminate light-storing luminescent powder.
6. The light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, wherein: the stabilizer is a calcium zinc stabilizer or an organic tin stabilizer, and the auxiliary stabilizer is epoxidized soybean oil.
7. The light-storing light-emitting polyvinyl chloride extrusion composition according to claim 1, wherein: the lubricant is one or two of calcium stearate, stearic acid and oxidized polyethylene wax.
8. The method for preparing a light-storing light-emitting polyvinyl chloride extrusion composition according to any one of claims 1 to 7, wherein the method comprises the following steps:
1) under the condition of normal temperature, titanate coupling agent is mixed with light-storing luminescent material, the titanate coupling agent and the light-storing luminescent material are put into plasticizer to be mixed and soaked to form paste, lubricant is added to be mixed, and light-storing luminescent premix is obtained through three-roller grinding;
2) and (2) putting the polyvinyl chloride, the stabilizer, the auxiliary stabilizer and the impact modifier into a high-speed mixer for high-speed mixing, heating to 90-110 ℃, adding the light-storing and light-emitting premix, heating to 110 ℃, discharging into a low-speed mixer for cooling and continuing to stir, and discharging after the temperature is lower than 40 ℃ to obtain the light-storing and light-emitting polyvinyl chloride composition.
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| CN109233154A (en) * | 2018-10-10 | 2019-01-18 | 世联汽车内饰（苏州）有限公司 | Automobile-used flexible self-luminous atmosphere lamp of one kind and preparation method thereof |
| CN111057294A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Light-storage foaming type polyethylene floating ball composition and preparation method thereof |
| CN109795143A (en) * | 2018-12-17 | 2019-05-24 | 滁州市宏源喷涂有限公司 | A kind of production method of color light-accumulation luminescent PVC board |
| CN111816356B (en) * | 2020-08-07 | 2022-02-11 | 居盛文 | Flat flexible cable of insulating sheath based on butyronitrile polyvinyl chloride |
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| CN101475803A (en) * | 2009-01-19 | 2009-07-08 | 上海富顺单向透视材料有限公司 | Self-luminescent material and preparation thereof |
| CN104250409A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Light storage luminous typepolyvinyl chloride dip composite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101475803A (en) * | 2009-01-19 | 2009-07-08 | 上海富顺单向透视材料有限公司 | Self-luminescent material and preparation thereof |
| CN104250409A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Light storage luminous typepolyvinyl chloride dip composite and preparation method thereof |
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