CN106700312B - Heat-preservation and heat-insulation polyvinyl chloride composition - Google Patents
Heat-preservation and heat-insulation polyvinyl chloride composition Download PDFInfo
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- CN106700312B CN106700312B CN201510780927.6A CN201510780927A CN106700312B CN 106700312 B CN106700312 B CN 106700312B CN 201510780927 A CN201510780927 A CN 201510780927A CN 106700312 B CN106700312 B CN 106700312B
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Abstract
A heat-insulating polyvinyl chloride composition belongs to the technical field of processing and application of high polymer materials. The composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 2-4.5 parts of stabilizer, 40-60 parts of plasticizer, 0.3-3 parts of coupling agent, 100-150 parts of hollow glass microsphere and 0.2-1 part of lubricant; the outer surface of the hollow glass bead is subjected to roughening treatment. The heat-insulation polyvinyl chloride composition has good heat-insulation performance, good flexibility, can be coated outside a curved surface, and has good practical value.
Description
Technical Field
The invention belongs to the technical field of processing and application of high polymer materials, and particularly relates to a heat-insulation polyvinyl chloride composition.
Background
At present, rock wool, glass wool, expanded perlite and other traditional heat-insulating materials still occupy main markets in China, although the materials are low in price, the loss of laid thick materials is large, the moisture absorption is high, the seismic performance and the environmental protection performance are poor, and in addition, building heat-insulating materials such as the rock wool, the glass wool and the like have a large amount of harmful substances and cannot meet the health requirements of human beings.
PVC has the advantages of corrosion resistance, difficult combustion, good insulativity, good transparency and the like, but the defects of poor toughness, poor flowability and heat resistance in the processing process and the like of PVC which belongs to a brittle material limit the wide application of the PVC. Inorganic fillers generally have a relatively high melting temperature, improve the thermal properties of the product when added to a polymer, and have been used as PVC fillers for a long time to reduce the cost of the product. Since the 80 s in the 20 th century, the appearance and development of the inorganic rigid particle toughening theory make the inorganic filler a functional material capable of obviously improving the performance of PVC.
The main component of the high-performance hollow glass bead (hereinafter referred to as hollow glass bead) is soda lime borosilicate, and the high-performance hollow glass bead is used as a novel energy-saving, clean and light filler and has the characteristics of being hollow, light in weight, heat-insulating, heat-preserving, high in electric insulation strength, wear-resistant, corrosion-resistant, radiation-proof, sound-proof, low in water absorption, stable in chemical performance and the like. The hollow glass microspheres are used as multifunctional filling agents of composite materials in foreign countries, and are widely applied to the fields of rubber and plastic, coatings, glass fiber reinforced plastics, emulsion explosives, oil drilling and the like. The application of the high-performance hollow glass beads in China is started later, but the application of the high-performance hollow glass beads is concerned by more and more fields along with the gradual deep-going understanding of the structural characteristics of the high-performance hollow glass beads by the Chinese. The material has the advantages of large self thermal resistance, low thermal conductivity, reduced absorption of radiant heat, and reduced temperature of the coated surface and the internal space, so that the material is consistently recognized by the experts as one of high-efficiency energy-saving materials with development prospects.
In China, the composition of PVC and hollow glass beads is mostly used for heat-insulating coatings and is not used for a few materials, a high-temperature-resistant power protection tube with application number of 201410326127.2 adopts a small amount (15 parts) of hollow glass beads, but the temperature resistance of the material is improved mainly by using chlorinated polyvinyl chloride with higher cost.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the heat-preservation and heat-insulation type polyvinyl chloride composition has good heat-preservation performance, good flexibility, capability of being coated outside a curved surface and good practical value.
The invention is realized by the following technical scheme: the heat-preservation and heat-insulation polyvinyl chloride composition is characterized by comprising the following raw materials in parts by weight: the composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 2-4.5 parts of stabilizer, 40-60 parts of plasticizer, 0.3-3 parts of coupling agent, 100-150 parts of hollow glass microsphere and 0.2-1 part of lubricant; the outer surface of the hollow glass bead is subjected to roughening treatment.
The heat-preservation and heat-insulation polyvinyl chloride composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 2-3 parts of stabilizer, 45-55 parts of plasticizer, 0.3-3 parts of coupling agent, 110-150 parts of hollow glass microsphere and 0.4-0.8 part of lubricant; the outer surface of the hollow glass bead is subjected to roughening treatment.
Preferably, the polyvinyl chloride resin is suspension-method high-polymerization-degree polyvinyl chloride resin (HPVC for short), and the polymerization degree is 2500. The HPVC has higher molecular weight, more physical cross-linking points and ordered regions among molecules, and poor processing flowability, so that the plasticizer absorption of the HPVC is higher than that of the polyvinyl chloride resin with the common polymerization degree. The plasticizer is added into the polyvinyl chloride as a small molecule flexible chain to increase the interval of PVC molecular chains, and the hydrogen bond action, the ordered region and the crystallization ratio among molecules are reduced; the polymerization degree is high, the number of micromolecule flexible chains capable of being accommodated among PVC molecular chains is large, the space of PVC molecular chains is enlarged, and the PVC resin and products thereof are soft and elastic.
Preferably, the plasticizer is dioctyl phthalate (TOTM) or a mixture of diisodecyl phthalate and trioctyl trimellitate. The dioctyl phthalate or the mixture of diisodecyl phthalate and trioctyl trimellitate ensures that the compound plasticizer meets the requirement of high temperature resistance in the composition.
Preferably, the lubricant is a mixture of any two of stearic acid, glyceryl monostearate and polyethylene wax.
Preferably, the coupling agent is a mixture of a silane coupling agent and a titanate coupling agent.
Preferably, the coupling agent is a silane coupling agent and a titanate coupling agent in a weight ratio of (11-18): 4 to 9.
Preferably, the hollow glass beads are made of soda lime borosilicate materials, and the particle size ranges from 10 to 100 microns.
Preferably, the lubricant is polyethylene wax and oxidized polyethylene wax according to a weight ratio of 1: 1 to 1.5.
Preferably, the roughening treatment is performed by the following specific operations: the method comprises the following steps of placing clean hollow glass beads in a stirrer for stirring, uniformly spraying an acidic micro-fluorine dilute solution on the hollow glass beads by adopting a mist spraying method, stirring for 1-3 minutes, unloading, rinsing with clear water, and drying to perform coupling treatment.
Preferably, the dilute acidic micro-fluorine solution is a mixed solution of water, ammonium hydrofluoride, oxalic acid, ammonium sulfate, glycerol and barium sulfate.
Preferably, the preparation method of the heat-preservation and heat-insulation type polyvinyl chloride composition comprises the following steps:
1) roughening the hollow glass beads: placing the clean hollow glass microspheres in a stirrer for stirring, uniformly spraying the acid micro-fluorine dilute solution on the hollow glass microspheres by adopting a mist spraying method, stirring for 1-3 minutes, unloading, rinsing with clear water, and drying to perform coupling treatment;
2) modifying hollow glass beads: adding the coupling agent into the diluent according to the weight ratio, uniformly mixing, adding the coupling agent and the glass beads into a high-speed stirrer, stirring, and drying to obtain modified hollow glass beads;
3) preparation of the composition: putting polyvinyl chloride resin, a stabilizer, a plasticizer and a lubricant into a high-speed stirrer according to the weight ratio, stirring at a high speed, fully absorbing, adding the glass beads treated in the step 2) after all components are uniformly mixed, continuously mixing until the components are uniform, discharging to obtain a mixed ingredient, adding the mixed ingredient into an extruder, extruding and granulating at the temperature of 160-200 ℃, and obtaining the granules of the heat-preservation and heat-insulation polyvinyl chloride composition.
The invention is described below: according to the invention, the surface roughening treatment is carried out on the hollow glass beads by adopting the acid micro fluorine dilute solution, so that the specific surface area of the hollow glass beads combined with the polyvinyl chloride is further increased, and the bonding strength of the hollow glass beads and the polyvinyl chloride is enhanced. Then, the hollow glass beads are coupled by a step-by-step method. Firstly, putting high-performance hollow glass beads into a stirrer for stirring at a low speed, pouring a mixed solution of a silane coupling agent and alcohol into the low-speed stirred hollow glass beads after the mixed solution is uniform, and uniformly coating the coupling agent on the hollow glass beads through a heating system of the stirrer and the self friction heat generation of the hollow glass beads and drying the hollow glass beads; then spraying the titanate diluent on the hollow glass beads stirred at a low speed in a spraying mode, and drying. The high-strength hollow glass beads are stirred at a low speed, so that the breakage rate of the hollow glass beads is greatly reduced, and the heat-insulating property of the material is ensured.
After the surface roughening treatment is carried out on the hollow glass beads by the acid micro fluorine dilute solution, the hollow glass beads have higher specific surface area than non-roughened hollow glass beads, so that the specific surface area of the hollow glass beads combined with polyvinyl chloride is further increased. Therefore, the addition amount of the hollow glass beads can be further increased, and the density of the composition is reduced; the rolling between the hollow glass beads after the addition amount is increased is also avoided, so that the composition is easier to plasticize. Preferably, the acidic micro-fluorine dilute solution is prepared by uniformly stirring 50-60 ℃ water 18.4%, ammonium hydrofluoride 23.5%, oxalic acid 12.4%, ammonium sulfate 15.7%, glycerol 6.5% and barium sulfate 23.5%.
The silane coupling agent is a main surface treating agent for treating silicon-containing inorganic fillers such as hollow glass beads and the like, and the adopted hollow glass beads are alkali borosilicate, so that the silane coupling agent with acidic functional groups can be firmly combined with the hollow glass beads and PVC molecules. 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. The dosage of the coupling agent is 0.5-3% of the weight of the hollow glass bead, and the recommended dosage is 0.8-1.5%.
After the high-performance hollow glass beads treated by the method are combined with polyvinyl chloride resin, the mechanical property is obviously improved. The composition has the characteristics of low price, chemical corrosion resistance, hollowness, light weight, heat preservation and insulation, radiation protection, sound insulation, low water absorption rate and the like of the hollow glass microspheres, can be extruded into a belt-shaped coating or winding pipeline for coating and the heat preservation and insulation of a container and a stirring kettle, and greatly expands the application of the polyvinyl chloride in the field of heat preservation and insulation.
Compared with the prior art, the heat-preservation and heat-insulation type polyvinyl chloride composition has the beneficial effects that: the heat-insulation polyvinyl chloride composition has good heat-insulation performance, good flexibility, capability of being coated outside a curved surface and good practical value. The hollow glass beads are added in a large proportion, and compared with the design that the addition amount of the hollow glass beads is less than 100 parts, the heat insulation performance of the composition can be obviously improved. The applicant designs that the hollow glass beads subjected to roughening treatment by the micro-fluorine dilute acid solution are modified by the coupling agent, so that the bending property and the tensile property of the composition are obviously improved, the composition can realize bending, rolling and curved surface coating while adding the hollow glass beads with a large weight ratio, and the composition is suitable for serving as an external thermal insulation material of a pipe.
Detailed Description
Examples 1 to 4 are specific embodiments of the heat insulating polyvinyl chloride composition of the present invention. Of these, example 1 is the most preferred example.
TABLE 1 formulation of the examples (in parts by weight)
The preparation method of the embodiment 1-4 comprises the following steps:
1) roughening the hollow glass beads: placing clean hollow glass beads into a stirrer for stirring, uniformly spraying an acidic micro-fluorine dilute solution on the hollow glass beads by adopting a mist spraying method, stirring for 1-3 minutes, unloading, rinsing with clear water, and drying to perform coupling treatment;
2) modifying hollow glass beads: adding the coupling agent into the diluent according to the weight ratio, uniformly mixing, adding the coupling agent and the glass beads into a high-speed stirrer, stirring, and drying to obtain modified hollow glass beads;
3) preparation of the composition: putting polyvinyl chloride resin, a stabilizer, a plasticizer and a lubricant into a high-speed stirrer according to the weight ratio, stirring at a high speed, fully absorbing, adding the glass beads treated in the step 2) after all components are uniformly mixed, continuously mixing until the components are uniform, discharging to obtain a mixed ingredient, adding the mixed ingredient into an extruder, extruding and granulating at the temperature of 160-200 ℃, and obtaining the granules of the heat-preservation and heat-insulation polyvinyl chloride composition.
Comparative example
Comparative examples 1 to 5 are comparative formulations, and the component ratios of the comparative formulations are shown in table 2.
TABLE 2 formulation of the comparative examples (in parts by weight)
The preparation methods of comparative examples 1 to 5 include only steps 2) to 3) of the preparation methods of examples, and do not include step 1) of the preparation methods of examples.
Performance testing
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 3 results of performance testing
As can be seen from Table 3, compared with comparative proportions of 1-5, the hollow glass beads with roughened outer surfaces adopted in examples 1-4 have good bending performance and obviously improved tensile property, which indicates that the composition of the invention has good flexibility and is more suitable for coating curved surfaces, such as outer walls of pipes.
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 (3)
1. The heat-preservation and heat-insulation polyvinyl chloride composition is characterized by comprising the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 2-3 parts of stabilizer, 45-55 parts of plasticizer, 0.3-3 parts of coupling agent, 110-150 parts of hollow glass microsphere and 0.4-0.8 part of lubricant; the outer surface of the hollow glass bead is subjected to roughening treatment;
the polyvinyl chloride resin is suspension-method high-polymerization-degree polyvinyl chloride resin, and the polymerization degree is 2500;
the coupling agent is a silane coupling agent and a titanate coupling agent in a weight ratio of (11-18): 4-9 of a mixture;
the roughening treatment comprises the following specific operations: placing clean hollow glass beads into a stirrer for stirring, uniformly spraying an acidic micro-fluorine dilute solution on the hollow glass beads by adopting a mist spraying method, stirring for 1-3 minutes, unloading, rinsing with clear water, and drying to perform coupling treatment;
the hollow glass beads are made of soda lime borosilicate materials, and the particle size ranges from 10 to 100 mu m;
the acid micro-fluorine dilute solution is a mixed solution of water, ammonium hydrofluoride, oxalic acid, ammonium sulfate, glycerol and barium sulfate;
the plasticizer is dioctyl phthalate or a mixture of diisodecyl phthalate and trioctyl trimellitate.
2. A thermal insulating polyvinyl chloride composition according to claim 1, wherein: the lubricant is a mixture of two optional lubricants in stearic acid, glycerin monostearate and polyethylene wax.
3. A thermal insulating polyvinyl chloride composition according to claim 1, wherein: the lubricant is polyethylene wax and oxidized polyethylene wax according to the weight ratio of 1: 1 to 1.5.
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| CN107699162A (en) * | 2017-09-08 | 2018-02-16 | 张家港爱科思汽车配件有限公司 | A kind of weld seam glue |
| CN109608790A (en) * | 2018-12-26 | 2019-04-12 | 浙江维派管业有限公司 | Effective hard polyvinyl chloride composition of a kind of noise reduction low noise draining and preparation method thereof |
| CN109971092A (en) * | 2019-03-21 | 2019-07-05 | 安徽万朗磁塑股份有限公司 | A kind of microballon composite door closure material and preparation method |
| CN112745686B (en) * | 2019-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | Composite cementing material for frozen earth pavement and preparation method thereof |
| CN115449164A (en) * | 2022-08-30 | 2022-12-09 | 安徽合汇金源科技有限公司 | PVC sealing material for refrigerator door and preparation method thereof |
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| CN102020877B (en) * | 2010-10-13 | 2013-02-27 | 天津大学 | Rear-earth surface-modified hollow glass microsphere and preparation method thereof |
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| CN102958305A (en) * | 2011-08-21 | 2013-03-06 | 比亚迪股份有限公司 | Glass window and decorating method thereof |
| CN102993554A (en) * | 2011-09-14 | 2013-03-27 | 辽宁辽杰科技有限公司 | Glass-microsphere-filled modified thermoplastic structural panel and preparation method thereof |
| CN102850697A (en) * | 2012-09-24 | 2013-01-02 | 佛山市日丰企业有限公司 | Polyvinyl chloride drain pipe and preparation method thereof |
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