CN111548564A - Ultralow-temperature flexible cold insulation material and preparation method thereof - Google Patents
Ultralow-temperature flexible cold insulation material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultralow temperature flexible cold insulation material and a preparation method thereof, belonging to the technical field of materials, wherein the ultralow temperature flexible cold insulation material consists of 95-99 wt% of an ultrahigh molecular weight polypropylene composite material and 1-5 wt% of a chemical foaming agent; the ultrahigh molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents. The ultralow-temperature flexible cold insulation material has excellent cold insulation effect and excellent low-temperature flexibility, can play an effective cold insulation role on low-temperature materials, and has low production cost, simple production process and wide application prospect in the field of low-temperature cold insulation.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to an ultralow-temperature flexible cold insulation material and a preparation method thereof.
Background
The cold insulation material is a material with extremely low thermal conductivity coefficient at low temperature, can effectively reduce the heat absorbed from the surrounding environment, and is commonly used as a cold insulation layer on the surface of a low-temperature pipeline and a storage tank. The cold-insulating material must generally be chosen to meet the following requirements: (1) the heat conductivity coefficient is small, the water absorption and moisture absorption rate is low, the low temperature resistance is good, the construction is easy, the manufacturing cost is low, and the comprehensive economic benefit is high; (2) the minimum safe use temperature of the cold insulation material is lower than the minimum temperature of the medium during normal operation; (3) the high-density high-strength steel has the advantages of low density, high mechanical strength, stable chemical performance, no corrosion to main materials, capability of keeping normal operation for a long time at working temperature and the like.
Natural gas is used as a green and environment-friendly clean energy source, is widely applied and developed in China quickly, and plays a great role in promoting the development of a natural gas industrial chain, various domestic Liquefied Natural Gas (LNG) pipeline projects develop in coastal areas of China like bamboo shoots in spring after rain, but LNG pipelines required to be built and used for transporting natural gas need to have excellent cold insulation performance to ensure the stability of the liquefied natural gas in transportation, so that the low-temperature cold insulation material has a wide application prospect, and simultaneously plays a great role in the fields of storage tanks, ships and the like requiring low-temperature cold insulation, so that the development of a novel low-temperature cold insulation material which is good in low-temperature cold insulation performance, simple in construction, convenient to transport and store and low in cost has great significance.
At present, several cold insulation materials commonly used in China are rigid polyurethane foam (PUR), foam glass and polyisocyanurate foam (PIR). However, several existing cold insulation materials have some disadvantages, which either affect the cold insulation effect or increase the construction, transportation and storage costs, for example, the foam glass as the cold insulation material has a very large brittleness, and is easily broken by a slight strong vibration or shaking, so the foam glass material is more demanding in selecting the low-temperature cold insulation application environment, and is also inconvenient to transport and store, which greatly hinders the application of the foam glass; hard PUR and PIR mostly selected by cold insulation materials used by the traditional LNG pipeline also have the defects difficult to make up, for example, the use and the working life are not long, the cold insulation structure is complicated and the construction operation is complex, the splicing parts are more in the construction process, for some special-shaped parts, both the PUR and the PIR can be cast and foamed on site, but in the foaming processing and manufacturing process, the influence of factors such as weather conditions, foaming time, multi-component stirring and the like is caused, the air hole damage rate is high, the water absorption and moisture resistance performance is poor, and the final cold insulation effect is reduced. Therefore, the development of a novel cold insulation material with ultralow temperature flexibility can not only improve the cold insulation effect, but also avoid the inconvenience in transportation, storage and construction, so that the cold insulation material has a wider application prospect.
Disclosure of Invention
The invention aims to provide an ultralow temperature flexible cold insulation material which has excellent low temperature flexibility, can be used at low temperature for a long time and has simple manufacturing process.
The purpose of the invention is realized by the following technical scheme: the ultra-low temperature flexible cold insulation material consists of 95-99 wt% of ultra-high molecular weight polypropylene composite material and 1-5 wt% of chemical foaming agent; the ultrahigh molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents.
Wherein, the viscosity-average molecular weight of the ultra-high molecular weight polypropylene is 30-1000 ten thousand; preferably, the viscosity average molecular weight of the ultra-high molecular weight polypropylene is 50 to 800 ten thousand; more preferably, the viscosity average molecular weight of the ultra-high molecular weight polypropylene is 100 to 500 ten thousand; most preferably, the ultra-high molecular weight polypropylene has a viscosity average molecular weight of 200 to 400 ten thousand.
Wherein, the rubber of the ultralow temperature flexible cold insulation material is more than one of ethylene propylene rubber, styrene butadiene rubber, nitrile rubber, natural rubber, butyl rubber, butadiene rubber, isoprene rubber, chloroprene rubber, silicone rubber, fluororubber, polyurethane rubber, acrylate rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber or chlorinated polyethylene rubber.
Wherein, the antioxidant is more than one of hindered phenol antioxidant, phosphite antioxidant and thiosulfate antioxidant;
the hindered phenol antioxidant is antioxidant 1010 or antioxidant 1076; the phosphite antioxidant is antioxidant 168, antioxidant 626 or antioxidant 618; the thiosulphate antioxidant is antioxidant DSTP or antioxidant DLTP.
Wherein, in the ultralow temperature flexible cold insulation material, the crosslinking agent is an organic peroxide crosslinking agent and/or an auxiliary crosslinking agent;
the organic peroxide crosslinking agent is DCP, DTBP or BPO; the auxiliary crosslinking agent is DAP, TAC, maleimide, p-quinone dioxime, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, N' -m-phenyl bismaleimide, liquid polybutadiene, divinylbenzene, p-benzoquinone dioxime or triallyl cyanurate.
Wherein, the lubricant is more than one of zinc stearate, PE wax, pentaerythritol stearate, monoglyceride or oxidized PE wax.
Wherein, the other auxiliary agents of the ultralow temperature flexible cold insulation material are more than one of antistatic agent, light stabilizer, ultraviolet absorber, colorant or surface brightener.
Wherein, the chemical foaming agent of the ultralow temperature flexible cold insulation material is more than one of citric acid, azodiisobutyronitrile, azodicarbonamide and barium azodicarboxylate.
The invention also provides a preparation method of the ultralow temperature flexible cold insulation material, which comprises the following steps:
a, preparing premix: weighing 95-99 wt% of the ultrahigh molecular weight polypropylene composite material and 1-5 wt% of the chemical foaming agent, and uniformly mixing to obtain a premix;
b, preparing an internal mixing material: adding the premix into an internal mixer, and blending for 3-10 minutes at the temperature of 165-200 ℃ and the rotating speed of 30-60r/min to obtain an internal mixture;
c, pre-crosslinking: placing the internal mixing material in a mould of a mould press for mould pressing presetting, wherein the temperature in the mould pressing presetting process is 165-220 ℃, the pressure is 3-6MPa, the pressure maintaining time is 5-10 minutes, and the internal mixing material is deflated for 3-5 times in the process to obtain a pre-crosslinking mould pressing material;
d, foaming and forming of the ultralow-temperature flexible cold insulation material: and (3) placing the mold filled with the pre-crosslinking mold pressing material in a mold pressing machine at the temperature of 250-280 ℃ for pressurizing to 10-15MPa, maintaining the pressure for 2-5 minutes, and then opening the mold for pressure relief to obtain the ultralow-temperature flexible cold insulation material.
In the preparation method, the ultrahigh molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the ultra-high molecular weight polypropylene with a branched chain structure and the rubber material with good air tightness are used for preparing the ultra-low temperature flexible cold insulation material, and the antioxidant, the lubricant, the cross-linking agent, the foaming agent and other auxiliary agents are added for foaming, so that the prepared product has the characteristics of small density, light weight, good air tightness, high impact resistance, water absorption and low moisture absorption rate, is convenient to store and transport, and has wide application prospects in the field of low temperature cold insulation. Meanwhile, the preparation process of the ultralow temperature flexible cold insulation material is simple, and the production cost is low.
Drawings
FIG. 1 is a schematic view of the ultra-low temperature flexible cold insulation material obtained in example 1;
FIG. 2 is a schematic view showing the bending of the ultra-low temperature flexible cold-keeping material obtained in example 1 after quenching with liquid nitrogen.
Detailed Description
Specifically, the ultralow temperature flexible cold insulation material consists of 95-99 wt% of an ultrahigh molecular weight polypropylene composite material and 1-5 wt% of a chemical foaming agent; the ultrahigh molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents.
The inventor successfully prepares the ultralow temperature flexible cold insulation material with excellent cold insulation effect and excellent low temperature flexibility by adding a chemical foaming agent and adjusting a foaming formula.
The ultralow-temperature flexible cold insulation material takes the ultrahigh-molecular-weight polypropylene as a main component, the viscosity of the ultrahigh-molecular-weight polypropylene is moderate in the foaming process due to the branched chain structure, a cellular structure is favorably formed, and meanwhile, the ultrahigh-molecular-weight polypropylene has excellent low-temperature flexibility due to the ultra-long molecular chain of the ultrahigh-molecular-weight polypropylene, so that the construction difficulty of the cold insulation material is effectively reduced, the service life of the cold insulation material is prolonged, and meanwhile, the ultralow-molecular-weight polypropylene is a non-polar material, so that the ultralow-temperature flexible cold insulation material has the characteristic of low water absorption; the rubber is used as the second component, so that the excellent air tightness and elasticity of the ultralow-temperature flexible cold insulation material can be brought, and the air tightness and impact resistance of the material are improved.
The preparation method disclosed by the invention has the advantages that the equipment and the process used in the foaming process are simple, high-pressure equipment such as an autoclave is avoided, the safety in the foaming process is improved, and the material production cost is greatly reduced.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
In the embodiment, the ultra-high molecular weight polypropylene composite material is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
(1) weighing 85 parts of ultrahigh molecular weight polypropylene powder (with the viscosity-average molecular weight of 250 ten thousand), 20 parts of ethylene propylene rubber, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168, 2 parts of DCP and 2 parts of PE wax into a self-sealing bag, adding 95 wt% of ultrahigh molecular weight polypropylene composite material and 5 wt% of azodicarbonamide foaming agent into a high-speed mixer together, and mixing and stirring uniformly to obtain a premix;
(2) putting the premix into an internal mixer for further mixing, and taking out the mixture after blending for 5 minutes to obtain an internal mixer, wherein the internal mixing temperature of the internal mixer is set to 185 ℃, and the rotating speed of a rotor is set to 60 r/min;
(3) placing the internal mixing material in a mould pressing mould, placing the mould in a mould pressing machine for mould pressing and pre-shaping, wherein the temperature of the pre-shaping mould pressing process is set to be 165 ℃, the pressure is set to be 5MPa, the pressure maintaining time is set to be 5 minutes, and the internal mixing material is deflated for 3 times in the process to obtain a pre-crosslinking mould pressing material;
(4) and immediately transferring the die filled with the pre-crosslinking die pressing material to another die pressing machine at the temperature of 280 ℃ to pressurize to 10MPa, and opening the die to release pressure after keeping the pressure for 5 minutes to obtain the ultralow-temperature flexible cold insulation material with a complete structure.
The obtained ultralow temperature flexible cold insulation material can be used in liquid nitrogen (-196 ℃)The sample bar of the flexible cold-insulation material can keep very good flexibility, is quenched in liquid nitrogen for 2 minutes, and has the impact strength of 39.49K J/m after being taken out for 5s2The product is folded in two directions at 360 degrees in liquid nitrogen for 500 times without cracks and fractures, the foaming ratio is 50 times, and the density is 0.0192g/cm3The ultra-low temperature flexible cold insulation material can work for a long time within the range of-196 ℃ to 158 ℃, the thermal conductivity coefficient is 0.024W/mK, the compressive strength of the ultra-low temperature flexible cold insulation material is 184KPa under the condition of-60 ℃, the tensile strength is 250KPa, the water vapor permeability coefficient is extremely small and is 0.9 ng/Pa.mS, water vapor can hardly permeate, and the material does not wrinkle, crack, pinhole or deform after 150-hour anti-aging test.
Example 2
In the embodiment, the ultra-high molecular weight polypropylene composite material is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
(1) weighing 53 parts of ultrahigh molecular weight polypropylene powder (with the viscosity-average molecular weight of 250 ten thousand), 40 parts of chlorinated polyethylene rubber, 0.15 part of antioxidant DLSP, 0.15 part of antioxidant 168, 2 parts of TAC, 0.5 part of pentaerythritol stearate, 0.5 part of ultraviolet absorbent and 0.5 part of light stabilizer into a self-sealing bag, adding 99 wt% of ultrahigh molecular weight polypropylene composite material and 1 wt% of citric acid foaming agent into a high-speed mixer together, mixing and stirring uniformly to obtain a premix;
(2) putting the premix into an internal mixer for further mixing, and taking out the mixture after blending for 6 minutes to obtain an internal mixer, wherein the internal mixing temperature of the internal mixer is set to be 200 ℃, and the rotating speed of a rotor is set to be 50 r/min;
(3) placing the internal mixing material in a mould pressing mould, placing the mould in a mould pressing machine for mould pressing and pre-shaping, wherein the temperature of the pre-shaping mould pressing process is 220 ℃, the pressure is 3MPa, the pressure maintaining time is 3 minutes, and the internal mixing material is deflated for 5 times in the process to obtain a pre-crosslinking mould pressing material;
(4) and immediately transferring the die filled with the pre-crosslinking die pressing material to another die pressing machine at the temperature of 260 ℃ to pressurize to 12MPa, and opening the die to relieve pressure after keeping the pressure for 4 minutes to obtain the ultralow-temperature flexible cold insulation material with a complete structure.
The obtained ultralow-temperature flexible cold insulation material can keep very good flexibility in liquid nitrogen (-196 ℃), a sample strip of the ultralow-temperature flexible cold insulation material is quenched in the liquid nitrogen for 2 minutes, and the impact strength of the sample strip after 5s of taking out the sample strip is 48.56KJ/m2The product is folded in two directions at 360 degrees in liquid nitrogen for 500 times without cracks and fractures, the foaming ratio is 30 times, and the density is 0.0321g/cm3The ultra-low temperature flexible cold insulation material can work for a long time within the range of-196 ℃ to 158 ℃, the thermal conductivity coefficient is 0.029W/mK, the compressive strength of the ultra-low temperature flexible cold insulation material is 204KPa under the condition of-60 ℃, the tensile strength is 299KPa, the water vapor permeability coefficient is extremely small and is 1.8 ng/Pa.mS, water vapor can hardly penetrate, and the material does not wrinkle, crack, pinhole or deform after 150-hour anti-aging test.
Comparative example:
the ultra-high molecular weight polypropylene composite material in the comparative example is prepared from the following raw materials in parts by weight:
the preparation method comprises the following steps:
(1) weighing 85 parts of ultrahigh molecular weight polypropylene powder (with the viscosity-average molecular weight of 250 ten thousand), 20 parts of ethylene propylene rubber, 0.1 part of antioxidant 1010, 0.1 part of antioxidant 168 and 2 parts of PE wax into a self-sealing bag, adding 95 wt% of ultrahigh molecular weight polypropylene composite material and 5 wt% of azodicarbonamide foaming agent into a high-speed mixer together, and mixing and stirring uniformly to obtain a premix;
(2) putting the premix into an internal mixer for further mixing, and taking out the mixture after blending for 5 minutes to obtain an internal mixer, wherein the internal mixing temperature of the internal mixer is set to 185 ℃, and the rotating speed of a rotor is set to 60 r/min;
(3) placing the internal mixing material in a mould pressing mould, placing the mould in a mould pressing machine for mould pressing and presetting, wherein the temperature of the presetting mould pressing process is set to be 165 ℃, the pressure is set to be 5MPa, the pressure maintaining time is set to be 5 minutes, and the internal mixing material is deflated for 3 times in the process to obtain a mould pressing material;
(4) and immediately transferring the die filled with the die pressing material to another die pressing machine at the temperature of 280 ℃ to pressurize to 10MPa, and opening the die to release pressure after 5 minutes of pressure maintaining.
The formula of the material of the comparative example is not added with a chemical cross-linking agent, the material is not subjected to cross-linking reaction in the foaming process of the material, and a three-dimensional network mechanism which is easy to retain gas is not formed in the material, so that the non-cross-linked material produced by the formula basically has no expansion of volume, and a usable low-density foam material is not formed after foaming.
Claims (10)
1. The ultralow temperature flexible cold insulation material is characterized in that the material consists of 95-99 wt% of ultrahigh molecular weight polypropylene composite material and 1-5 wt% of chemical foaming agent; the ultrahigh molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents.
2. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the viscosity average molecular weight of the ultra-high molecular weight polypropylene is 30 to 1000 ten thousand; preferably, the viscosity average molecular weight of the ultra-high molecular weight polypropylene is 50 to 800 ten thousand; more preferably, the viscosity average molecular weight of the ultra-high molecular weight polypropylene is 100 to 500 ten thousand; most preferably, the ultra-high molecular weight polypropylene has a viscosity average molecular weight of 200 to 400 ten thousand.
3. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the rubber is one or more of ethylene propylene rubber, styrene butadiene rubber, nitrile rubber, natural rubber, butyl rubber, butadiene rubber, isoprene rubber, chloroprene rubber, silicone rubber, fluorine rubber, polyurethane rubber, acrylate rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber or chlorinated polyethylene rubber.
4. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant and thiosulfate antioxidant;
the hindered phenol antioxidant is antioxidant 1010 or antioxidant 1076; the phosphite antioxidant is antioxidant 168, antioxidant 626 or antioxidant 618; the thiosulphate antioxidant is antioxidant DSTP or antioxidant DLTP.
5. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the cross-linking agent is an organic peroxide cross-linking agent and/or an auxiliary cross-linking agent;
the organic peroxide crosslinking agent is DCP, DTBP or BPO; the auxiliary crosslinking agent is DAP, TAC, maleimide, p-quinone dioxime, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, N' -m-phenyl bismaleimide, liquid polybutadiene, divinylbenzene, p-benzoquinone dioxime or triallyl cyanurate.
6. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the lubricant is one or more of zinc stearate, PE wax, pentaerythritol stearate, monoglyceride or oxidized PE wax.
7. The ultra-low temperature flexible cold insulation material as claimed in claim 1, wherein the other auxiliary agent is one or more of antistatic agent, light stabilizer, ultraviolet light absorber, colorant or surface brightening agent.
8. The ultra-low temperature flexible cold insulation material as claimed in any one of claims 1 to 7, wherein the chemical foaming agent is one or more of citric acid, azobisisobutyronitrile, azodicarbonamide and barium azodicarboxylate.
9. The preparation method of the ultralow temperature flexible cold insulation material as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps:
a, preparing premix: weighing 95-99 wt% of the ultrahigh molecular weight polypropylene composite material and 1-5 wt% of the chemical foaming agent, and uniformly mixing to obtain a premix;
b, preparing an internal mixing material: adding the premix into an internal mixer, and blending for 3-10 minutes at the temperature of 165-200 ℃ and the rotating speed of 30-60r/min to obtain an internal mixture;
c, pre-crosslinking: placing the internal mixing material in a mould of a mould press for mould pressing presetting, wherein the temperature in the mould pressing presetting process is 165-220 ℃, the pressure is 3-6MPa, the pressure maintaining time is 5-10 minutes, and the internal mixing material is deflated for 3-5 times in the process to obtain a pre-crosslinking mould pressing material;
d, foaming and forming of the ultralow-temperature flexible cold insulation material: and (3) placing the mold filled with the pre-crosslinking mold pressing material in a mold pressing machine at the temperature of 250-280 ℃ for pressurizing to 10-15MPa, maintaining the pressure for 2-5 minutes, and then opening the mold for pressure relief to obtain the ultralow-temperature flexible cold insulation material.
10. The preparation method of claim 9, wherein the ultra-high molecular weight polypropylene composite material is prepared from the following components in parts by weight: 53-85 parts of ultrahigh molecular weight polypropylene, 20-40 parts of rubber, 0.2-0.4 part of antioxidant, 1-2 parts of cross-linking agent, 0.5-1 part of lubricant and 0-2 parts of other auxiliary agents.
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