WO2019127990A1

WO2019127990A1 - Heat-storage polystyrene foam, preparation method therefor, and application thereof

Info

Publication number: WO2019127990A1
Application number: PCT/CN2018/083695
Authority: WO
Inventors: 刘若鹏; 赵治亚; 王盼; 刘光烜; 胡宇; 李自东; 肖成伟; 白雪; 张运湘
Original assignee: 洛阳尖端技术研究院; 洛阳尖端装备技术有限公司
Priority date: 2017-12-27
Filing date: 2018-04-19
Publication date: 2019-07-04
Also published as: CN109971080A; CN109971080B

Abstract

The present invention provides a heat-storage polystyrene foam, a preparation method therefor, and application thereof. The method comprises: mixing deionized water, a styrene monomer, a phase change microcapsule, and a first additive to obtain a polystyrene particle containing the phase change microcapsule; adding deionized water and a second additive into the polystyrene particle containing the phase change microcapsule, and performing impregnation to obtain expanded polystyrene containing the phase change microcapsule; and pre-foaming, ripening, and foaming the expanded polystyrene containing the phase change microcapsule to obtain the polystyrene foam. By means of the polystyrene foam prepared with the method of the present invention, the wearing comfort of a helmet is improved, the heat-storage performance of the polystyrene foam is improved, and the addition of the phase change microcapsule also maintains the mechanical property of the polystyrene foam so that the polystyrene foam satisfies mechanical property requirements.

Description

Thermal storage polystyrene foam and preparation method and application thereof

Technical field

The present invention relates to a polystyrene foam inside a helmet, and more particularly to a heat storage temperature-regulating polystyrene foam and a preparation method and application thereof.

Background technique

The helmet cushion layer is used to better protect the helmet wearer from reducing or preventing head damage in the event of accidental injury. It is usually used as a buffer layer of foam or foam rubber to disperse and absorb impact kinetic energy. However, the shock-proof foaming material (foam or foam rubber) as a buffer layer is a poor heat-conducting material, and when worn in a high-temperature environment in summer, a relatively closed thermal environment is formed on the head, and the head is inferior in comfort; the wearer avoids Sweating discomfort, sometimes giving up wearing a helmet increases the risk of accidental injuries.

At present, the purpose of heat dissipation is usually achieved by providing a vent hole in the top of the outer casing of the motorcycle helmet. Although this solution improves the difficulty of heat dissipation during riding to a certain extent, it is difficult to dissipate heat when the vehicle speed is slow or stationary. The problem still exists, the buffer layer insulation effect is not solved, and the shell opening reduces the helmet safety factor and the mechanical properties are low.

Summary of the invention

In view of the above problems, the present invention absorbs the heat released from the head in time by adding phase change microcapsules to the buffer foam, thereby avoiding heat accumulation in the helmet and causing sweating of the head.

The present invention provides a method of preparing a polystyrene foam, the method comprising:

Deionizing water, styrene monomer, phase change microcapsule and first auxiliary agent are mixed to obtain polystyrene particles containing phase change microcapsules; and deionization is added to the polystyrene particles containing phase change microcapsules Water and a second auxiliary agent, impregnated, to obtain expandable (ie, foamable properties) polystyrene containing phase change microcapsules; and precipitating the expandable polystyrene containing phase change microcapsules Foaming, aging, and foaming to obtain a polystyrene foam.

In the above method, the phase change microcapsule has a phase transition temperature of 25 to 30 °C.

In the above method, the first auxiliary agent includes a dispersing agent, a suspending agent, an emulsifier, a plasticizer, and an initiator.

In the above method, the dispersing agent comprises one or more of calcium phosphate, sodium phosphate and sodium acetate; the suspending agent comprises one of polyvinyl alcohol, hydroxypropyl methylcellulose and starch ether or a plurality of; the emulsifier comprises one or more of sodium dodecylbenzenesulfonate, tridecyl polyether-4carboxylic acid, and sodium lauryl sulfate; the plasticizer includes phosphoric acid III One or more of butyl ester, di(2-ethylhexyl) phthalate and diisononyl phthalate; the initiator includes benzoyl peroxide, benzoic acid benzoate One or more of butyl ester and azobisisobutyronitrile.

In the above method, the second auxiliary agent includes a dispersing agent and a foaming agent.

In the above method, the dispersing agent includes one or more of calcium phosphate, sodium phosphate, and sodium acetate; and the foaming agent includes one or more of pentane, isobutane, and n-butane.

In the above method, the immersion temperature is 100 to 120 ° C, the immersion pressure is 0.5 to 0.8 MPa, and the immersion time is 2 to 3 hours.

In the above method, the pre-expansion temperature is 80 to 110 ° C, and the pre-expansion is 30 to 50 times.

In the above method, the aging time is 20 to 24 hours, and the curing temperature is normal temperature.

In the above method, the temperature of the foaming is from 115 to 125 °C.

In the above method, the mass ratio of the deionized water, the styrene monomer, the phase change microcapsule and the first auxiliary agent is 800 to 1200:800 to 1200:100 to 500:8 to 10 .

In the above method, the mass ratio of the polycrystalline silicon particles containing the phase change microcapsules, the deionized water and the second auxiliary agent is 800 to 1200:800 to 1200:1 to 3.

The present invention also provides a polystyrene foam prepared according to the above method.

The invention also provides for the use of polystyrene foam in a helmet cushion.

The invention adopts the phase change microcapsules in the buffer foam, uses the phase change microcapsules to contact the head to adjust the temperature, releases heat in the cold, absorbs heat when the heat is hot, and makes the head at a comfortable temperature. In addition, the addition of phase change microcapsules enhances the heat storage capacity of polystyrene foam (EPS). When EPS containing phase change microcapsules is used as a helmet buffer layer, the addition of phase change microcapsules effectively improves the buffer layer for the head. The heat preservation problem of the department can absorb the heat inside the helmet when the exercise is intense or the outside temperature is high; when the internal temperature of the helmet is low, the heat can be released to improve the wearing comfort of the helmet; in addition, the phase change microcapsule is added. The mechanical properties of the polystyrene foam are maintained to meet the mechanical properties.

DRAWINGS

Figure 1 is a process flow diagram for preparing a polystyrene foam.

Detailed ways

The following examples are intended to provide a more complete understanding of the invention, and are not intended to limit the invention in any way.

The present invention provides a phase change by adding one or more of an inorganic phase change microcapsule material, an organic phase change microcapsule material, and an organic/inorganic composite phase change microcapsule material to, but not limited to, polystyrene foam (EPS). The microcapsules use the phase transition temperature (25 to 30 ° C) of the phase change microcapsules to maintain the head temperature at about 25 to 30 ° C by absorbing or releasing heat.

In addition, the combination of phase change microcapsules and EPS enables the phase change microcapsules to absorb heat inside the helmet when the temperature of the outside is increased or the temperature in the helmet rises to reach the phase change microcapsule phase transition temperature due to severe physical activity; When the outside temperature is lowered or the body is at rest for a long time, causing the temperature to drop below the phase transition temperature of the phase change microcapsules, the phase change microcapsules will release the previously stored energy through such a "dynamic" thermal energy storage and The thermal energy release process adjusts the temperature balance and maintains the head temperature to create a temperature-friendly environment.

Deionized water, styrene monomer, phase change microcapsules are added to the polymerization reactor, and then the first auxiliary agent is added (including the mass ratio of 1 to 1.5: 0.2 to 0.5: 0.8 to 1: 2 to 2.5: 4). 4.5 dispersant, suspending agent, emulsifier, plasticizer and initiator), stirred at 300-80 ° C at 300-500r / min for 1 ~ 3h, polymerized to obtain phase change microcapsules of polystyrene particles Dry at 80 to 100 ° C for 10 to 12 hours to remove moisture.

Thereafter, the polystyrene particles containing the phase change microcapsules are sent to an impregnation kettle to which deionized water and a second auxiliary agent (including a dispersant and a foaming agent in a mass ratio of 0.8 to 2: 0.2 to 1) are added. Under the pressure of 0.5-0.8 MPa, immersing at 100-120 ° C for 2-3 h, the polystyrene containing the phase change microcapsules can be obtained, and the polystyrene containing the phase change microcapsules can be made at 80~. Pre-expansion at 30 ° C for 30 to 50 times, and then aged at room temperature for 20 to 24 hours; then the pre-expanded material which has been aged is placed in a mold and heated to 115 to 125 ° C for foaming to obtain polyphenylene. Ethylene foam.

In the above method, the use of an auxiliary agent comprising a dispersing agent, a suspending agent, an emulsifier, a plasticizer and an initiator further promotes the combination of styrene and phase change microcapsules, so that the phase change microcapsules can be better. Dispersed in polyethylene and helps to improve the stability of the phase change temperature control material.

In the above method, the use of an auxiliary agent including a dispersing agent and a foaming agent can contribute to subsequent impregnation and foaming.

In the above method, the temperature, pressure and time of the impregnation, the temperature and the multiple of the pre-expansion, the temperature and time of the aging, and the setting of the temperature of the foaming are all providing a good foaming environment for preparing the polystyrene foam, wherein The impregnation, pre-expansion and maturation are all prepared for the expansion of polystyrene, so that the surface of the particles can be fused together into a foamed plastic part by the action of heat while the material is expanded, thereby preparing a polystyrene foam with good performance. .

In the above method, the mass ratio of deionized water, styrene monomer, phase change microcapsule and first auxiliary agent is in the range of 800 to 1200:800 to 1200:100 to 500:8 to 10, so that the phase change microcapsule Good combination with styrene, if the phase change microcapsule content is too high, it is not conducive to the subsequent foaming, if the phase change microcapsule content is too low, it is not conducive to adjust the temperature inside the helmet; if deionized water and / or help Too high a content of the agent is not conducive to the formation of polystyrene foam.

In the above method, the mass ratio of the polystyrene particles containing the phase change microcapsules, the deionized water and the second auxiliary agent is in the range of 800 to 1200:800 to 1200:1 to 3, if the polyphenylene of the phase change microcapsules If the content of the ethylene particles is too high, it is disadvantageous for dispersion, and if the content of the polystyrene particles of the phase change microcapsules is too low, it is disadvantageous for foaming.

The invention also provides for the use of the polystyrene foam in a helmet cushion.

Example 1

1000 g of deionized water, 1000 g of styrene monomer, 100 g of inorganic phase change microcapsule material were added to the polymerization reactor, and then 1.2 g of dispersant calcium phosphate, 0.27 g of suspending agent polyvinyl alcohol, and 0.87 g of emulsifier dodecane were added. Sodium benzenesulfonate, 2 g plasticizer tributyl phosphate and 4.17 g initiator (4 g benzoyl peroxide and 0.17 g t-butyl peroxybenzoate), stirred and polymerized to obtain polyphenylene containing phase change microcapsules Ethylene pellets and dried to remove moisture.

Thereafter, 1000 g of polystyrene particles containing phase change microcapsules were sent to an impregnation kettle to which 1000 g of deionized water, 1.2 g of dispersant calcium phosphate, and 0.45 g of a blowing agent pentane were added, under a pressure of 0.6 MPa, The polystyrene containing the phase change microcapsules can be prepared by immersing at 100 ° C for 3 h, and the polystyrene containing the phase change microcapsules can be pre-expanded 40 times at 100 ° C, and then placed at room temperature for 24 hours. The aging is carried out; the pre-foamed material which has been aged is placed in a mold, and heated to 115 ° C for foaming to obtain a polystyrene foam.

Example 2

900 g of deionized water, 1000 g of styrene monomer, 100 g of organic phase change microcapsule material were added to the polymerization reactor, and 1.3 g of dispersant sodium phosphate, 0.25 g of suspension hydroxypropyl methylcellulose, and 0.87 g of emulsification were added. Sodium dodecyl benzene sulfonate, 2 g of plasticizer tributyl phosphate and 4.17 g of initiator (4 g of benzoyl peroxide and 0.17 g of t-butyl peroxybenzoate), stirred and polymerized to obtain a phase change micro Capsules of polystyrene particles and dry to remove moisture.

Thereafter, 1000 g of polystyrene particles containing phase change microcapsules were sent to an impregnation kettle to which 1000 g of deionized water, 1.2 g of dispersant calcium phosphate, and 0.45 g of a blowing agent pentane were added, under a pressure of 0.7 MPa, The polystyrene containing the phase change microcapsules was prepared by impregnation at 110 ° C for 2.5 h, and the polystyrene containing the phase change microcapsules was pre-expanded 40 times at 100 ° C, and then placed at room temperature for 20 h. It is aged; the pre-expanded material which has been aged is placed in a mold, and heated to 120 ° C for foaming to obtain a polystyrene foam.

Example 3

1100 g of deionized water, 900 g of styrene monomer, 100 g of inorganic phase change microcapsule material were added to the polymerization reactor, and 1.2 g of dispersant sodium acetate, 0.4 g of suspension starch ether, and 0.9 g of emulsifier tridecyl alcohol were further added. Polyether-4 carboxylic acid, 2.2 g plasticizer tributyl phosphate and 4.17 g initiator (4 g benzoyl peroxide and 0.17 g tert-butyl peroxybenzoate), stirred and polymerized to obtain phase change microcapsules Polystyrene granules and dried to remove moisture.

Thereafter, 1000 g of polystyrene particles containing phase change microcapsules were sent to an impregnation kettle to which 1000 g of deionized water, 1.2 g of dispersant calcium phosphate, and 0.45 g of a blowing agent pentane were added, under a pressure of 0.6 MPa, The polystyrene containing the phase change microcapsules was prepared by immersing at 100 ° C for 3 h, and the polystyrene containing the phase change microcapsules was pre-expanded 30 times at 90 ° C, and then placed at room temperature for 22 h. The aging is carried out; the pre-foamed material which has been aged is placed in a mold, and heated to 115 ° C for foaming to obtain a polystyrene foam.

Example 4

1000 g of deionized water, 1100 g of styrene monomer, 100 g of inorganic phase change microcapsule material were added to the polymerization reactor, and then 1.2 g of dispersant calcium phosphate, 0.27 g of a suspending agent (0.1 g of polyvinyl alcohol and 0.17 g of hydroxypropyl group) were added. Methyl cellulose), 0.87g emulsifier sodium dodecyl benzene sulfonate, 2g plasticizer diisodecyl phthalate and 4.5g initiator azobisisobutyronitrile, stirred, polymerized to obtain phase Change the microcapsules of polystyrene particles and dry to remove moisture.

Thereafter, 1000 g of phase change microcapsule-containing polystyrene pellets were sent to an impregnation kettle to which 1000 g of deionized water, 1.2 g of a dispersant (0.6 g of sodium phosphate and 0.6 g of sodium acetate), and 0.45 g of a blowing agent pentane were added. The polystyrene containing the phase change microcapsules can be obtained by immersing at 100 ° C for 3 h under a pressure of 0.6 MPa, and the polystyrene containing the phase change microcapsules can be 40 times at 100 ° C. Pre-expanded, and then allowed to stand at room temperature for 24 hours to be matured; then the pre-expanded material which had been aged was placed in a mold and heated to 125 ° C for foaming to obtain a polystyrene foam.

Example 5

800g of deionized water, 800g of styrene monomer, 400g of inorganic phase change microcapsule material was added to the polymerization reactor, and then 1g of dispersant calcium phosphate, 0.2g of suspension of polyvinyl alcohol, 0.8g of emulsifier (0.4g ten) was added. Sodium dialkyl sulfate and 0.4 g sodium lauryl sulfate), 2 g plasticizer di(2-ethylhexyl) phthalate and 4 g initiator (2 g benzoyl peroxide and 2 g benzoic acid) Tert-butyl ester), stirred, polymerized to obtain polystyrene particles containing phase change microcapsules, and dried to remove water.

Thereafter, 800 g of phase change microcapsule-containing polystyrene pellets were fed to an impregnation supplemented with 800 g of deionized water, 0.8 g of dispersant calcium phosphate, and 0.2 g of a blowing agent (0.1 g of isobutane and 0.1 g of n-butane). In the kettle, the polystyrene containing the phase change microcapsules was prepared by immersing at 100 ° C for 3 h under a pressure of 0.5 MPa, and the polystyrene containing the phase change microcapsules was made at 80 ° C. The pre-expansion was doubled and then allowed to stand at room temperature for 20 hours to be aged; the pre-expanded material which had been aged was placed in a mold, and heated to 115 ° C for foaming to obtain a polystyrene foam.

Example 6

Add 1200g of deionized water, 1200g of styrene monomer, 500g of organic/inorganic composite phase change microcapsule material to the polymerization reactor, and then add 1.5g of dispersant calcium phosphate, 0.5g of suspending agent polyvinyl alcohol, 1g of emulsifier Sodium dialkylbenzene sulfonate, 2.5 g plasticizer (2 g tributyl phosphate and 0.5 g diisodecyl phthalate) and 4.5 g initiator benzoyl peroxide, stirred and polymerized to obtain phase change Microcapsules of polystyrene particles and dried to remove moisture.

Thereafter, 1200 g of phase change microcapsule-containing polystyrene pellets were sent to an impregnation kettle to which 1200 g of deionized water, 2 g of dispersant calcium phosphate, and 1 g of a blowing agent pentane were added, at a pressure of 0.8 MPa at 120 ° C. After immersing for 2 h, the polystyrene containing the phase change microcapsules was prepared, and the polystyrene containing the phase change microcapsules was pre-expanded 50 times at 110 ° C, and then aged at room temperature for 24 hours. The pre-foamed material which has been aged is placed in a mold and heated to 125 ° C for foaming to obtain a polystyrene foam.

Comparative example 1

The same as in Example 1, except that the inorganic composite phase change microcapsule material was not added.

Differential thermal analysis of the polystyrene foam samples prepared in Examples 1 to 6 was carried out by differential scanning calorimetry (DSC) commonly used in the art, and the test range was 0 to 80 ° C, and the scanning rate was ± 10 ° C. /min, environment: nitrogen to protect the environment.

According to the measurement standard of tensile strength and elongation at break of the flexible foam polymer material of GB/T6344-1996, the polyphenylene obtained in Examples 1 to 6 was tested by a microcomputer-controlled electronic universal testing machine commonly used in the art. The elongation at break of the ethylene foam, the test results are shown in Table 1 below:

Table 1

It can be seen from Table 1 that the EPS (polystyrene foam) containing no inorganic composite phase change microcapsule material has no absorption and release heat peaks during the ascending and cooling processes, but has absorption and release in the EPS containing phase change microcapsules. The heat peak appears, and the phase transition temperature can be maintained at about 28 ° C, indicating that the phase change microcapsule can keep the ambient temperature stable within a constant range according to the increase of the external environment temperature and the absorption or release of heat. The phase change microcapsules are added into the foam, and the phase change microcapsules are used to adjust the temperature by contacting the head, and the heat is released in the cold, and the heat is absorbed in the hot state, so that the head is at a comfortable temperature, thereby improving the wearing comfort of the helmet; The addition of phase change microcapsules with a phase change of 120-150 J/g makes the phase change of EPS up to 27 J/g, which greatly improves the heat storage capacity of EPS.

In addition, the elongation at break (85%-90%) of EPS containing phase change microcapsules is similar to the elongation at break of EPS containing no inorganic composite phase change microcapsule material, which maintains the mechanics of EPS. The performance is due to the fact that the added phase change microcapsules can be combined with polystyrene to ensure the size and uniformity of the EPS foaming pore size, thereby maintaining the mechanical properties of EPS.

In summary, the polystyrene foam prepared by the method of the present invention can be applied to a helmet cushion layer.

Those skilled in the art will appreciate that the above-described embodiments are merely exemplary embodiments, and various changes, substitutions and changes may be made without departing from the spirit and scope of the invention.

Claims

A method of preparing a polystyrene foam, the method comprising:

Deionizing water, styrene monomer, phase change microcapsule and first auxiliary agent are mixed to obtain polystyrene particles containing phase change microcapsules;

Deionizing water and a second auxiliary agent are added to the polystyrene particles containing phase change microcapsules, and impregnated to obtain expandable polystyrene containing phase change microcapsules;

The expandable polystyrene containing phase change microcapsules is pre-expanded, aged, and foamed to obtain a polystyrene foam.
The method according to claim 1, wherein the phase change microcapsule has a phase transition temperature of 25 to 30 °C.
The method according to claim 1, wherein said first auxiliary agent comprises a dispersing agent, a suspending agent, an emulsifier, a plasticizer, and an initiator.

Wherein the dispersing agent comprises one or more of calcium phosphate, sodium phosphate and sodium acetate; the suspending agent comprises one or more of polyvinyl alcohol, hydroxypropyl methylcellulose and starch ether; The emulsifier includes one or more of sodium dodecylbenzenesulfonate, tridecyl polyether-4carboxylic acid, and sodium lauryl sulfate; the plasticizer includes tributyl phosphate, One or more of di(2-ethylhexyl) phthalate and diisononyl phthalate; the initiator includes benzoyl peroxide, t-butyl peroxybenzoate, and One or more of azobisisobutyronitrile.
The method according to claim 1, wherein said second auxiliary agent comprises a dispersing agent and a blowing agent,

Wherein the dispersing agent comprises one or more of calcium phosphate, sodium phosphate and sodium acetate; the foaming agent comprises one or more of pentane, isobutane and n-butane.
The method according to claim 1, wherein said immersion temperature is 100 to 120 ° C, said immersion pressure is 0.5 to 0.8 MPa, and said immersion time is 2 to 3 hours.
The method according to claim 1, wherein said pre-expansion temperature is 80 to 110 ° C, and said pre-expansion is 30 to 50 times, and said foaming temperature is 115 to 125 °C.
The method according to claim 1, wherein the curing time is 20 to 24 hours, and the curing temperature is normal temperature.
The method according to claim 1, wherein the mass ratio of the deionized water, the styrene monomer, the phase change microcapsule and the first auxiliary agent is 800 to 1200:800 to 1200. : 100 to 500: 8 to 10.
The method according to claim 1, wherein the mass ratio of the polycrystalline silicon particles containing phase change microcapsules, the deionized water and the second auxiliary agent is 800 to 1200:800 to 1200. : 1 to 3.
A polystyrene foam prepared by the method of any one of claims 1-9.
Use of a polystyrene foam according to claim 10 in a helmet cushion.