CN114316414A - Silicone oil filled composite rubber phase change material and preparation method thereof - Google Patents
Silicone oil filled composite rubber phase change material and preparation method thereof Download PDFInfo
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- 239000012782 phase change material Substances 0.000 title claims abstract description 102
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 100
- 229920001971 elastomer Polymers 0.000 title claims abstract description 34
- 239000005060 rubber Substances 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 114
- 239000011347 resin Substances 0.000 claims abstract description 114
- 230000008859 change Effects 0.000 claims abstract description 54
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- 239000000463 material Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 24
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000005011 phenolic resin Substances 0.000 claims description 46
- 229920001568 phenolic resin Polymers 0.000 claims description 45
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 28
- 229920001903 high density polyethylene Polymers 0.000 claims description 25
- 239000004700 high-density polyethylene Substances 0.000 claims description 25
- 229920001684 low density polyethylene Polymers 0.000 claims description 19
- 239000004702 low-density polyethylene Substances 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 8
- 239000013132 MOF-5 Substances 0.000 claims description 6
- -1 cyclic vinyl siloxane Chemical class 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application relates to the technical field of heat-conducting phase-change materials, and particularly discloses a silicone oil filled composite rubber phase-change material and a preparation method thereof. The phase-change material is prepared by polymerizing the following raw materials in parts by weight: 15-25 parts of base material resin; 5-10 parts of a silicone oil additive; 40-70 parts of phase change filler; 0.5-0.8 part of inhibitor; 1.1-1.5 parts of a cross-linking agent; 0.8-1.7 parts of a reinforcer; 1.0-1.2 parts of a catalyst; the preparation method comprises the following steps: melting matrix resin, adding a reinforcer and a part of inhibitor, stirring, mixing, keeping the temperature at 210 ℃ for 1h, adding a silicone oil additive and a catalyst, stirring, mixing, adding a phase-change filler for 6-7 times, stirring, mixing, adding the rest of inhibitor, keeping the temperature at 210 ℃ under 1.5 atmospheres for 2h, and pouring into a mold to obtain the phase-change material. The phase-change material can be used for thermal protection energy storage of electronic products and has the advantages of high impact strength and strong aging resistance.
Description
Technical Field
The application relates to the technical field of heat-conducting phase-change materials, in particular to a silicone oil filled composite rubber phase-change material and a preparation method thereof.
Background
The phase-change material serving as a novel energy-saving and environment-friendly material can be used in the fields of passive solar houses, industrial waste heat recycling, electronic product heat protection and heat storage, intelligent temperature-regulating fibers, energy-storage and temperature-regulating building materials and the like. The phase-change material can be divided into a high-temperature phase-change material (the phase-change temperature is more than 150 ℃) and a medium-low temperature phase-change material (the phase-change temperature is less than 150 ℃) according to the using temperature, the high-temperature phase-change material comprises fused salt, metal alloy and other compounds, the phase-change material realizes the storage and the release of heat energy through solid-liquid phase change, the phase-change temperature and the phase-change enthalpy are both high, but the leakage problem exists, and the phase-change material has strong corrosivity in the liquid phase and has high requirements on packaging materials and packaging technologies; the medium-low temperature phase-change material comprises crystalline hydrated salt, paraffin, fatty acid, polyhydric alcohol and the like, but the phase-change material generates a liquid phase in the phase-change process and is inconvenient to use practically.
The phase change material commonly used at present is a shape-stabilized phase change material, which is mainly a composite energy storage material consisting of the phase change material, a polymer support and a packaging material, and due to the packaging and supporting effects of the polymer support material, when the phase change material is subjected to phase transition to be changed into a liquid phase, the phase change material cannot flow out, and the whole composite material can also keep the original shape in a high-temperature environment without changing and has certain structural strength, so that the performance of the phase change heat storage material is changed to a certain extent.
However, when phase change material is in the continuous use, the phase change material surface receives the impact easily, and after polymer supporting material continuously received the impact, the ageing phenomenon appeared easily in the macromolecular material, appears damaged breakage easily, and then leads to phase change material appearing leaking easily when taking place the phase transition, when bringing the potential safety hazard, can reduce phase change material's heat-retaining performance.
Disclosure of Invention
In order to improve the impact resistance and the impact aging resistance of the phase change material, the application provides a silicone oil filled composite rubber phase change material and a preparation method thereof.
In a first aspect, the present application provides a silicone oil filled composite rubber phase change material, which adopts the following technical scheme:
the phase-change material is prepared by polymerizing the following raw materials in parts by weight: 15-25 parts of base material resin; 5-10 parts of a silicone oil additive; 40-70 parts of phase change filler; 0.5-0.8 part of inhibitor; 1.1-1.5 parts of a cross-linking agent; 0.8-1.7 parts of a reinforcer; 1.0-1.2 parts of a catalyst; the matrix resin is high-density polyethylene resin, low-density polyethylene resin and phenolic resin in a weight ratio of (1-10): (1-10): the composition of (1-10).
By adopting the technical scheme, the base material resin plays a role of a support in the phase change material, the base material resin includes the silicone oil additive and the phase change filler, the phase change filler plays a role of absorbing heat in the phase change material, and the phase change filler performs phase change to absorb heat; the inhibitor, the cross-linking agent and the catalyst can promote various cross-linking reactions among the base material resin, the silicone oil additive and the phase-change filler, so that the overall performance of the phase-change material is improved; the base material resin is prepared by mixing high-density polyethylene resin, low-density polyethylene resin and phenolic resin according to a certain weight part ratio, the phenolic resin can improve the integral hardness and protective capacity of the base material resin, and the cross-linking agent can promote the cross-linking reaction among the three resins.
Preferably, the silicone oil additive comprises two compositions of terminal vinyl silicone oil and hydrogen-containing silicone oil, and the weight part ratio of the terminal vinyl silicone oil to the hydrogen-containing silicone oil is 9: 1.
preferably, the vinyl-terminated silicone oil has a vinyl content of 0.1-0.65%; the hydrogen content in the hydrogen-containing silicone oil is 0.05-0.75%.
Preferably, the inhibitor is a cyclic vinyl siloxane.
Preferably, the crosslinking agent is methyltrimethoxysilane.
Preferably, the enhancer is fumed silica, and the specific surface area of the fumed silica is 100-150m2/g。
Preferably, the catalyst is MOF-5.
By adopting the technical scheme, the MOF-5 serving as a metal organic framework material can promote the reaction, has better heat conductivity, and can improve the integral heat conductivity of the phase change material when dispersed in the phase change material.
Preferably, the matrix resin is prepared by the following preparation steps: solidifying the phenolic resin, grinding, and sieving with a 100-mesh sieve for later use; melting and mixing the high-density polyethylene resin and the low-density polyethylene resin, adding the phenolic resin powder and the cross-linking agent, stirring and mixing, and cooling to obtain the matrix resin.
By adopting the technical scheme, the phenolic resin is difficult to generate a crosslinking reaction with the high-density polyethylene resin and the low-density polyethylene resin under the common condition, however, the phenolic resin is ground into powder, and then the crosslinking agent is added, so that the phenolic resin can be dispersed in the base resin, and the effect of reinforcing the structure of the base resin is achieved.
Preferably, the phase change material comprises 1.0-1.2 parts of stannous octoate by weight.
In a second aspect, the application provides a preparation method of a silicone oil filled composite rubber phase change material, which adopts the following technical scheme:
a preparation method of a silicone oil filled composite rubber phase change material comprises the following steps: melting matrix resin, adding a reinforcer and a part of inhibitor, stirring, mixing, keeping the temperature at 210 ℃ for 1h, adding a silicone oil additive and a catalyst, stirring, mixing, adding a phase-change filler for 6-7 times, stirring, mixing, adding the rest of inhibitor, keeping the temperature at 210 ℃ under 1.5 atmospheres for 2h, and pouring into a mold to obtain the phase-change material.
In summary, the present application has the following beneficial effects: the phase-change material is prepared by polymerizing the following raw materials in parts by weight: 15-25 parts of base material resin; 5-10 parts of a silicone oil additive; 40-70 parts of phase change filler; 0.5-0.8 part of inhibitor; 1.1-1.5 parts of a cross-linking agent; 0.8-1.7 parts of a reinforcer; 1.0-1.2 parts of a catalyst; the matrix resin is high-density polyethylene resin, low-density polyethylene resin and phenolic resin in a weight ratio of (1-10): (1-10): the composition of (1-10); the base material resin plays a role of a support in the phase change material, the base material resin includes the silicone oil additive and the phase change filler, the phase change filler plays a role of absorbing heat in the phase change material, and the phase change filler performs phase change to absorb heat; the inhibitor, the cross-linking agent and the catalyst can promote various cross-linking reactions among the base material resin, the silicone oil additive and the phase-change filler, so that the overall performance of the phase-change material is improved; the base material resin is prepared by mixing high-density polyethylene resin, low-density polyethylene resin and phenolic resin according to a certain weight part ratio, the phenolic resin can improve the integral hardness and protective capacity of the base material resin, and the cross-linking agent can promote the cross-linking reaction among the three resins.
Detailed Description
The present application will be described in further detail below with reference to examples 1 to 10 and comparative examples 1 to 7.
Examples
Examples 1 to 5
The weight parts of the raw materials of the silicone oil filled rubber phase change material in examples 1-5 of the present application are shown in table 1.
TABLE 1 weight parts of the raw materials of the silicone oil-filled rubber phase change materials of examples 1-5
In examples 1-5, the vinyl content of the vinyl-terminated silicone oil is 0.1-0.65%, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.75%, the phase-change filler is fatty acid, the inhibitor is ring-shaped vinyl siloxane, the cross-linking agent is methyltrimethoxysilane, and the enhancer is 150m with a specific surface area of 100-2The catalyst is MOF-5.
In examples 1 to 4, the base resin was prepared by the following preparation steps: grinding phenolic resin in a grinder at 70 ℃, and screening the ground phenolic resin through a 100-mesh screen for later use; melting the high-density polyethylene resin and the low-density polyethylene resin, stirring at the rotation speed of 100r/min for 1h, uniformly adding the ground phenolic powder 4-5 times, adding the cross-linking agent after the phenolic powder is added, stirring at the rotation speed of 120r/min for 1h, and taking out to obtain the base material resin.
In example 5, the base resin was prepared by the following preparation steps: melting and mixing the phenolic resin, the high-density polyethylene resin and the low-density polyethylene resin, taking out and placing in a stirrer, adding the cross-linking agent into the mixture, stirring at the rotating speed of 120r/min, keeping the temperature for 1h, and taking out to obtain the base material resin.
In embodiments 1 to 5, a method for preparing a silicone oil filled composite rubber phase change material includes the following steps: placing base material resin in a stirrer for melting and heat preservation for 10min, adding the whole amount of reinforcer and the whole amount of inhibitor 1/3, stirring at a rotating speed of 100r/min at 210 ℃ for 1h, adding the whole amount of silicone oil additive and the whole amount of catalyst, stirring at a rotating speed of 120r/min for 30min, standing and heat preservation for 30min, adding phase change filler into the stirrer in a trend of being less, more and less for 6-7 times, controlling the adding time of the phase change filler within 20-30min, stirring and mixing the materials by the stirrer at a rotating speed of 150r/min continuously in the adding process of the phase change filler, adding the rest amount of inhibitor after the phase change filler is added and the stirrer is stirred for 10min, stirring the materials at a rotating speed of 20r/min for 2h in an environment of 210 ℃ and 1.5 atmospheres, pouring the mixture into a mold to obtain the phase-change material.
Examples 6 to 10
The weight parts of the raw materials of the silicone oil filled rubber phase change material in examples 6-10 of the present application are shown in table 2.
TABLE 2 weight parts of the raw materials of the silicone oil-filled rubber phase change materials in examples 6-10
In the examples 6-10, the vinyl-terminated silicone oil contains 0.1-0.65% of vinyl groups, the hydrogen-containing silicone oil contains 0.05-0.75% of hydrogen, the phase-change filler is fatty acid, and the inhibitor is selected fromUsing ring vinyl siloxane, methyl trimethoxy silane as cross-linking agent, and 150m specific surface area as reinforcing agent2The catalyst is MOF-5.
In examples 6 to 10, the base resin was prepared in the same manner as in examples 1 to 4.
In examples 6 to 9, the preparation method of the silicone oil-filled composite rubber phase change material was the same as that of the silicone oil-filled composite rubber phase change material in examples 1 to 5.
In this embodiment 10, a method for preparing a silicone oil filled composite rubber phase change material includes the following steps: placing base material resin in a stirrer for melting and heat preservation for 10min, adding the whole amount of reinforcer and 1/3 amount of inhibitor, stirring at a rotating speed of 100r/min at 210 ℃ for 1h, adding the whole amount of silicone oil additive and the whole amount of catalyst, stirring at a rotating speed of 120r/min for 30min, standing and heat preservation for 30min, adding phase change filler into the stirrer in a trend of being less, more and less for 6-7 times, controlling the adding time of the phase change filler within 20-30min, stirring and mixing the materials by the stirrer at a rotating speed of 150r/min continuously in the adding process of the phase change filler, adding the rest amount of inhibitor and the whole amount of stannous octoate after the phase change filler is added and the stirrer is stirred for 10min, stirring at a rotating speed of 20r/min by the stirrer for 2h in an environment of 210 ℃ and 1.5 atmospheres, pouring the mixture into a mold to obtain the phase-change material.
Comparative example
Comparative examples 1 to 5
The weight parts of the raw materials of the silicone oil filled rubber phase change material in comparative examples 1-5 of the present application are shown in table 3.
TABLE 3 weight parts of raw materials of phase change materials of silicone oil-filled rubbers in comparative examples 1 to 5
Comparative examples 6 to 7
The weight parts of the raw materials of the silicone oil filled rubber phase change materials in comparative examples 6-7 of the present application are shown in table 4.
TABLE 4 weight parts of raw materials of phase change materials of silicone oil-filled rubbers in comparative examples 6 to 7
In the comparative examples 1-7, the vinyl-terminated silicone oil contains 0.1-0.65% of vinyl, the hydrogen-containing silicone oil contains 0.05-0.75% of hydrogen, the phase-change filler is fatty acid, the inhibitor is annular vinyl siloxane, the cross-linking agent is methyltrimethoxysilane, and the reinforcing agent is 150-inch calcium with a specific surface area of 100-2The catalyst is MOF-5.
In this comparative example 4, the matrix resin was prepared by the following preparation steps: melting the high-density polyethylene resin and the low-density polyethylene resin at high temperature, adding the cross-linking agent, stirring, mixing, keeping the temperature for 1h, and taking out to obtain the base resin.
In this comparative example 5, the matrix resin was prepared by the following preparation steps: grinding phenolic resin in a grinder at 70 ℃, and screening the ground phenolic resin through a 100-mesh screen for later use; melting the high-density polyethylene resin, stirring at a rotation speed of 100r/min for 1h, uniformly adding the ground phenolic powder 4-5 times, adding the cross-linking agent after the phenolic powder is added, stirring at a rotation speed of 120r/min for 1h, and taking out to obtain the base material resin.
In this comparative example 6, the matrix resin was prepared by the following preparation steps: grinding phenolic resin in a grinder at 70 ℃, and screening the ground phenolic resin through a 100-mesh screen for later use; melting the low-density polyethylene resin, stirring at a rotation speed of 100r/min for 1h, uniformly adding the ground phenolic powder 4-5 times, adding the cross-linking agent after the phenolic powder is added, stirring at a rotation speed of 120r/min for 1h, and taking out to obtain the base material resin.
In this comparative example 7, the preparation procedure of the base resin was the same as that of examples 1 to 4.
In the comparative examples 1 to 6, the preparation method of the silicone oil filled composite rubber phase change material was the same as that of the silicone oil filled composite rubber phase change materials in the examples 1 to 5.
In the comparative example 7, the preparation method of the silicone oil filled composite rubber phase change material comprises the following steps: placing the base material resin in a stirrer for melting and heat preservation for 10min, adding the whole amount of the enhancer and the 1/3 amount of the inhibitor, stirring at 210 ℃ for 1h at the rotating speed of 100r/min, adding the whole amount of silicone oil additive, stirring at a rotation speed of 120r/min for 30min, standing and maintaining the temperature for 30min, adding the phase change filler into the stirrer in a trend of less filler, more filler and less filler for 6-7 times, controlling the adding time of the phase change filler within 20-30min, in the adding process of the phase-change filler, the stirrer continuously stirs and mixes the materials at the rotating speed of 150r/min, after the phase change filler is added and the stirring of the stirrer is kept for 10min, adding the rest inhibitor, and (3) in an environment with the temperature of 210 ℃ and the atmospheric pressure of 1.5, stirring the materials by a stirrer at the rotation speed of 20r/min for 2 hours, and pouring the materials into a mould to obtain the phase-change material.
Performance test
Test method
The silicone oil filled composite rubber phase change materials in examples 1-10 and comparative examples 1-7 were prepared to a thickness of 2mm, and then heat-preserved at 100 ℃ for 30min, and cut into rectangular sheets of 5cm × 10 cm. The sheets of examples 1 to 10 and comparative examples 1 to 7 were measured for thermal conductivity according to the method described in ATSM 5470; the tensile strength of the sheet was measured according to the method described in ASTM D412; the tear strength of the sheet was measured according to the method described in ASTM D624; measuring the enthalpy of phase change of the sheet according to the method described in ASTM C1784; after the sheet is placed in an environment with the temperature of 150 ℃ and is aged for 240h at high temperature, the weight before and after aging is measured, the weight loss rate of the sheet is calculated, the phase change enthalpy of the sheet is measured according to the method recorded in ASTM C1784, and the attenuation rate of the phase change enthalpy after heat aging treatment is calculated; placing the sheet on a plane, using a 1KG heavy iron ball to drop onto the sheet from a position 1m away from the sheet in a free-falling mode, repeatedly impacting for 100 times, measuring the phase change enthalpy of the sheet according to the method recorded in ASTM C1784, and calculating the attenuation rate of the phase change enthalpy after impact aging; the test results are shown in tables 5, 6 and 7.
TABLE 5 data of the results of the tests on the sheets of examples 1 to 6
TABLE 6 data of the results of the tests on the sheets of examples 7 to 10 and comparative examples 1 to 2
TABLE 7 data of the results of the tests on the sheets of comparative examples 3 to 7
In combination with examples 1 to 4 and table 5, it can be seen that the different addition ratios of the high-density polyethylene resin, the low-density polyethylene resin and the phenolic resin in the matrix resin have a great influence on the whole phase change material. The added amount of the phenolic resin was the smallest in example 1 and was only 1/15 for the entire matrix resin, in example 2, the added amounts of the phenolic resins were all 1/5 for the entire matrix resin, in example 3, the added amount of the phenolic resin was the largest and was 10/17 for the entire matrix resin, and in example 4, the added amount of the phenolic resin was 7/16 for the entire matrix resin.
As can be seen from table 5, as the addition ratio of the phenolic resin is increased, the tensile strength and the tear strength of the phase change material both tend to increase, mainly because the addition amount of the phenolic resin is relatively excessive, the hardness of the phase change material is increased, and the thermal conductivity of the whole phase change material is reduced because the thermal conductivity of the phenolic resin is poor. Meanwhile, as the thermal stability of the phenolic resin at 150 ℃ is good, the wrapping performance of the base resin on the phase-change filler is better along with the increase of the addition ratio of the phenolic resin, the amount of the silicone oil and the phase-change material leaked from the sheet can be reduced, namely, the weight loss rate after thermal aging is lower, and thus the value of the phase-change enthalpy decay rate of the sheet after thermal aging treatment is reduced. However, as described above, an increase in the amount of the phenolic resin added leads to an increase in the hardness of the sheet, which leads to a decrease in the toughness of the sheet, a decrease in the impact absorption capacity, and a tendency that the sheet is broken after an impact, and a decrease in the enthalpy of phase transition after the impact aging of the sheet is excessive.
Therefore, combining examples 1-4 and table 5, it can be concluded that the addition of the phenolic resin is less than 1/2 of the entire addition of the matrix resin, which can ensure that the tensile strength, tear strength, thermal aging performance and impact aging resistance of the phase change material are at a better level.
Combining example 2 and example 5, and table 5, it can be seen that the preparation step of the matrix resin has a greater influence on the whole sheet, since the matrix resin plays a role in wrapping and supporting the phase change filler, in example 5, the high-density polyethylene resin, the low-density polyethylene resin and the phenolic resin are melt-mixed, however, in this melting process, it is difficult to mix the phenolic resin and the other two polyethylene resins, so that the phenolic resin is delaminated in the matrix resin, and then the wrapping protection of the phase change filler is reduced, which results in a substantial decrease in the thermal conductivity, tensile strength and tear strength of the sheet in example 5; similarly, as the wrapping protection of the matrix resin on the phase-change filler and the silicone oil additive is reduced in example 5, the silicone oil and the phase-change filler are easy to seep out of the sheet after the sheet is thermally aged, so that the thermal aging weight loss rate of the sheet is greatly improved compared with example 2, the thermal aging phase-change enthalpy attenuation rate is also obviously improved, but the impact resistance and aging resistance of the sheet are not obviously influenced.
Combining example 2 and example 6, and combining table 5, it can be seen that in example 6, when vinyl-terminated silicone oil is singly used as a silicone oil additive to be added into the phase change material, the thermal conductivity of the sheet in example 6 is reduced compared with that of example 2, and the tensile strength and tear strength are also reduced, because the strength of the base resin is lower due to the lack of the enhancement of the base resin by the hydrogen-containing silicone oil, so that the strength of the phase change material as a whole is lower; the enthalpy of phase change of the sheet in example 6 is also significantly reduced, and the weight loss rate after heat aging is slightly reduced compared with that in example 2, mainly because the terminal vinyl silicone oil is not easy to separate out from the sheet when used alone, and the decay values of the enthalpy of phase change of the sheet in example 6 after heat aging and impact aging have no significant changes.
When the example 2 and the example 7 are combined and the table 5 and the table 6 are combined, it can be seen that in the example 7, when the hydrogen-containing silicone oil is singly used as the silicone oil additive to be added into the phase-change material, the heat conductivity coefficient of the sheet in the example 7 is obviously reduced compared with the example 2, mainly because the heat conductivity of the hydrogen-containing silicone oil is poor, and when the content of the hydrogen-containing silicone oil is high, the heat conduction of the phase-change material is inhibited; the tensile strength and tear strength of the sheet in example 7 were not significantly reduced, mainly because a large amount of hydrogen-containing silicone oil and the base resin were subjected to a crosslinking reaction, thereby improving the overall strength of the phase change material; the phase change enthalpy and the thermal aging weight loss rate of the sheet in example 7 are obviously changed from those in example 2, because the hydrogen-containing silicone oil itself cannot completely react with the base resin, the phase change material also contains a large amount of hydrogen-containing silicone oil, so that the phase change enthalpy of the phase change material is inhibited, and simultaneously, after thermal aging, the hydrogen-containing silicone oil is separated out from the phase change material, so that the weight loss rate is increased.
By combining the example 2 and the examples 6 to 7 and combining the table 5 and the table 6, it can be seen that when the terminal vinyl silicone oil and the hydrogen-containing silicone oil are used in a composite manner, the hydrogen-containing silicone oil and the terminal vinyl silicone oil generate a bridging reaction, the amount of unreacted hydrogen-containing silicone oil in the phase change material can be reduced, and after the combined action, the thermal conductivity, the tensile strength and the tear strength of the sheet can be improved, the influence of a silicone oil additive on phase change enthalpy can be reduced, the thermal aging weight loss rate of the sheet can be reduced, and the high temperature aging resistance and the impact aging resistance of the sheet can be improved.
When the hydrogen-containing silicone oil is added in an excessively high amount, it can be seen from the combination of example 2 and examples 8 to 9 and from tables 5 and 6 that the hydrogen-containing silicone oil is difficult to complete the crosslinking reaction of the entire phase change material, so that the hydrogen-containing silicone oil is easy to exude from the phase change material when the phase change material is thermally aged, and the hydrogen-containing silicone oil content is excessively high, so that the impact aging resistance of the phase change material is reduced.
By combining example 2 and example 10, and by combining tables 5 and 6, it can be seen that the addition of stannous octoate to the phase change material in example 10 can significantly improve various properties of the phase change material, because the stannous octoate contains metal tin ions, the heat conductivity coefficient of the phase change material can be improved, and after the stannous octoate is added, can promote the cross-linking reaction between the vinyl-terminated silicone oil, the hydrogen-containing silicone oil and the base resin, thereby improving the connection tightness of the silicone oil additive and the base material resin, improving the wrapping effect on the phase change filler, simultaneously promoting the cross-linking reaction between the phase change filler and the base material resin by the stannous octoate, thereby improving the stability of the phase change filler, preventing the probability of the phase change filler and the silicone oil additive from seeping out of the phase change material, meanwhile, the stannous octoate improves the toughness of the phase change material, and then the impact and aging resistance of the sheet is improved.
When the high-density polyethylene resin is used alone as the base resin, the thermal conductivity of the sheet in comparative example 1 is greatly reduced compared with that of the sheet in example 2, and the tensile strength, tear strength and enthalpy of phase transition are also significantly reduced, as can be seen by combining example 2 with comparative example 1, and by combining tables 5 and 6; due to the fact that the wrapping performance of the single high-density polyethylene resin on the phase change filler and the silicone oil additive is poor, after the sheet is aged at high temperature, the silicone oil and the phase change filler are easy to seep out of the sheet, the thermal aging weight loss rate of the sheet is too high, and the phase change enthalpy attenuation value of the sheet after thermal aging treatment are affected; the sheet material has flexibility due to the single use of the high-density polyethylene resin, the sheet material has insufficient hardness, and when an impact aging test is carried out, the surface of the sheet material is easy to have a perforation phenomenon, so that the attenuation value of the phase change enthalpy of the sheet material after the impact aging is too high.
When the low-density polyethylene resin is used alone as the base resin, the thermal conductivity is slightly improved as compared with the high-density polyethylene resin used alone in comparative example 1, but the tensile strength, tear strength and enthalpy of phase change are inferior to those of the sheet in comparative example 1, and it can be seen that the sheet is affected similarly when the high-density polyethylene resin and the low-density polyethylene resin are used alone, in terms of the weight loss rate by heat aging, the attenuation rate of enthalpy of phase change, and the attenuation rate of enthalpy of phase change by impact aging.
Combining example 2 with comparative examples 1-3, and tables 5 and 6-7, it can be seen that when phenolic resin is used alone in the base resin, the sheet in comparative example 3 has a significantly deteriorated thermal conductivity compared to the sheets in comparative examples 1-2, but the sheet in comparative example 3 is superior to the sheets in comparative examples 1-2 in tensile strength and tear strength, mainly because the phenolic resin has a higher hardness and requires a greater tensile force to stretch-tear the sheet; however, the enthalpy of phase change of the sheet in the comparative example 3 is lower than that of the sheet in the comparative examples 1-2 due to the properties of the phenolic resin, but the weight loss rate after heat aging and the decay rate of the enthalpy of phase change after heat aging are better than those of the sheet in the comparative examples 1-2, but the hardness of the phenolic resin is high enough, the flexibility is insufficient, the sheet is not resistant to impact, and the decay rate of the enthalpy of phase change after impact aging is greatly higher than that of the sheet in the comparative examples 1-2.
By combining example 2, comparative examples 1-2 and comparative example 4, and by combining tables 5-7, it can be seen that in comparative example 4, the base resin is selected from the high-density polyethylene resin and the low-density polyethylene resin, and the finally obtained phase-change material has obviously improved thermal conductivity, improved tensile strength, improved tear strength and improved phase-change enthalpy compared with comparative examples 1-2, but the improvement is not obvious; compared with comparative examples 1-2, the heat aging weight loss rate, the heat aging phase change enthalpy attenuation rate and the impact aging phase change enthalpy attenuation value of the sheet in comparative example 4 have no obvious advantages and disadvantages, which shows that the performance of the sheet is not obviously improved by using the high-density polyethylene resin and the low-density polyethylene resin in combination.
By combining the example 2, the comparative example 1, the comparative example 3 and the comparative example 5, and combining tables 5-7, it can be seen that, in the comparative example 5, the substrate resin is formed by combining the high-density polyethylene resin and the phenolic resin, and the heat-conducting property of the finally obtained sheet is not obviously improved, mainly because the phenolic resin has an inhibiting effect on the whole heat-conducting property, but the phenolic resin is dispersed in the high-density polyethylene resin, and the phenolic resin and the high-density polyethylene resin are subjected to a crosslinking reaction, so that the whole strength of the substrate resin can be improved, and a certain flexibility is maintained, so that the tensile strength and the tear strength of the sheet in the comparative example 5 are obviously improved compared with those of the sheet in the comparative example 1, but are not obviously improved compared with those of the sheet in the comparative example 3; however, in comparative example 5, the phenolic resin and the high-density polyethylene resin in the base resin are crosslinked with each other, so that the phase change enthalpy of the sheet can be greatly increased, and the heat aging capability and the impact aging resistance capability of the sheet can be improved.
In comparative example 6, in which the base resin is a combination of a low-density polyethylene resin and a phenol resin, the effect is slightly inferior to that in comparative example 5, but the properties are improved to a different degree from those in comparative examples 2 and 3, as can be seen by combining example 2, comparative example 3, comparative example 5 and comparative example 6, and by combining tables 5 to 7.
By combining the example 2 and the comparative example 7 and combining the table 5 and the table 7, it can be seen that, when no catalyst is added in the comparative example 7, the performance of the prepared sheet is greatly reduced compared with that of the example 2, mainly because the effect of the catalyst is lacked, the crosslinking reaction between the silicone oil additive and the base resin is not thorough, the connection relationship between the support and the wrap in the phase-change material is influenced, and the weight loss rate and the heat aging capability of the phase-change material are reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The silicone oil filled composite rubber phase change material is characterized by being prepared by polymerizing the following raw materials in parts by weight: 15-25 parts of base material resin; 5-10 parts of a silicone oil additive; 40-70 parts of phase change filler; 0.5-0.8 part of inhibitor; 1.1-1.5 parts of a cross-linking agent; 0.8-1.7 parts of a reinforcer; 1.0-1.2 parts of a catalyst; the matrix resin is high-density polyethylene resin, low-density polyethylene resin and phenolic resin in a weight ratio of (1-10): (1-10): the composition of (1-10).
2. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the silicone oil additive comprises two compositions of terminal vinyl silicone oil and hydrogen-containing silicone oil, and the weight part ratio of the terminal vinyl silicone oil to the hydrogen-containing silicone oil is 9: 1.
3. the silicone oil filled compounded rubber phase change material as claimed in claim 2, wherein: the vinyl-terminated silicone oil contains 0.1 to 0.65 percent of vinyl; the hydrogen content in the hydrogen-containing silicone oil is 0.05-0.75%.
4. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the inhibitor is a cyclic vinyl siloxane.
5. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the cross-linking agent is methyl trimethoxy silane.
6. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the enhancer is fumed silica, and the specific surface area of the fumed silica is 100-150m2/g。
7. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the catalyst is MOF-5.
8. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein the matrix resin is prepared by the following preparation steps: solidifying the phenolic resin, grinding, and sieving with a 100-mesh sieve for later use; melting and mixing the high-density polyethylene resin and the low-density polyethylene resin, adding the phenolic resin powder and the cross-linking agent, stirring and mixing, and cooling to obtain the matrix resin.
9. The silicone oil filled compounded rubber phase change material as claimed in claim 1, wherein: the phase change material comprises, by weight, 1.0-1.2 parts of stannous octoate.
10. The method for preparing the silicone oil filled compounded rubber phase change material as claimed in any one of claims 1 to 8, wherein the method comprises the following steps: melting matrix resin, adding a reinforcer and a part of inhibitor, stirring, mixing, keeping the temperature at 210 ℃ for 1h, adding a silicone oil additive and a catalyst, stirring, mixing, adding a phase-change filler for 6-7 times, stirring, mixing, adding the rest of inhibitor, keeping the temperature at 210 ℃ under 1.5 atmospheres for 2h, and pouring into a mold to obtain the phase-change material.
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Application publication date: 20220412 |