CN111533878A - Heat-dissipation breathable memory cotton and preparation method and application thereof - Google Patents
Heat-dissipation breathable memory cotton and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/m3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2280/00—Compositions for creating shape memory
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- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of household articles, in particular to heat-dissipation and breathable memory cotton and a preparation method and application thereof, wherein the heat-dissipation and breathable memory cotton is prepared from the following raw materials in parts by weight: 20-35 parts of polyoxyethylene triol, 10-20 parts of polyether polyol, 10-20 parts of toluene diisocyanate, 1-2.5 parts of a pore-forming agent, 0.2-0.4 part of silicone oil, 0.003-0.005 part of stannous octoate, 0.5-1.5 parts of modified graphene, 8-15 parts of ethylene glycol, 3-5 parts of water, 0.5-1.5 parts of a nonionic surfactant and 1-3 parts of a silane coupling agent, wherein the modified graphene is diamino end-sealed polyethylene glycol grafted graphene; the heat-dissipation breathable memory cotton has the advantages of heat dissipation, breathability and good resilience.
Description
Technical Field
The invention relates to the technical field of household articles, in particular to heat-dissipation breathable memory cotton and a preparation method and application thereof.
Background
The memory foam is also called 'slow rebound sponge', 'inert sponge' and 'zero pressure foam', and is viscoelastic polyurethane soft foam with an open pore structure. When the memory cotton is impacted by pressure, two kinds of deformation can occur simultaneously: one is elastic deformation (energy storage deformation), and the accumulated partial energy can slowly recover the shape of the memory foam material before being pressed after the external force is removed; the other is plastic deformation (energy-consuming deformation), which can absorb more than 90% of impact energy and has little rebound force on a pressing object in contact with the deformation; therefore, the memory cotton has the characteristics of absorbing pressure and being repeatedly used without deformation.
The polyurethane soft foam is a polymer consisting of hard molecular chain segments and soft molecular chain segments which are subjected to thermodynamic micro-phase separation, and contains a fixed phase and a reversible phase. The function of the stationary phase is to memorize the original shape of the foam, and to restore the original shape after the foam is deformed, and to make the foam have the required bearing capacity. The reversible phase is an amorphous region rich in macromolecular soft segments and functions to reversibly change the foam softening/hardening with temperature, thereby effecting a change in the shape of the foam while imparting the desired resiliency to the foam.
At present, most of domestic memory cotton is temperature-sensitive memory cotton, and the memory cotton can be shaped according to the body temperature of a human body, memorize the curve of the human body, can automatically shape a comfortable effect according to the needs of the human body no matter lying on the back or lying on the side, and effectively solves the human body pressure into zero pressure. For example, the memory mattress avoids the fatigue and stiff neck caused by the overhead bending of the neck and the waist of the traditional mattress, so that the cervical vertebra and the vertebra are completely relaxed and rested, the unnecessary turning times during sleeping are reduced, and the situations of snoring, muscle ache and the like are alleviated. However, the memory foam senses not only the temperature of the human body, but also the temperature due to season changes. When the temperature is lower than 10 ℃, the memory cotton material can be hardened, and can be as hard as stone below 0 ℃, so that the crack resistance and the use comfort of the memory cotton material are influenced; when the ambient temperature is higher, the heat absorbed by the heat-accumulating memory sponge is not easy to dissipate due to the function of the heat-accumulating memory sponge, so that the feeling of air impermeability is given to people.
The invention patent application with the publication number of CN 103819645B discloses a slow-rebound polyurethane foam material, which comprises the following components in parts by weight: 90-100 parts of polyether, 0.2-1 part of catalyst, 0.8-1.5 parts of silicone oil, 2.5-4 parts of cell opener, 2-4 parts of water and toluene diisocyanate, wherein the molar ratio of the polyether to the toluene diisocyanate is 75-85; the content of ethylene oxide in the polyether is 10-30%, the polyether is a mixture of any two or three of ordinary polyether, soft foam polyether and soft foam graft polyether with the molecular weight of 300-800, wherein the weight parts of the ordinary ether, KGF3010 and KGP345 are KGF3010 and KGP345, and the weight parts of the ordinary ether, KGF3010 and KGP345 are 5:2:2-3:1: 1. The prior art effectively improves the low-temperature hardening problem of the slow-rebound polyurethane foam material by changing the molecular weight of polyether and the content of ethylene oxide, adjusting the ratio of polyether to toluene diisocyanate and adding a catalyst, silicone oil and a pore-forming agent in proper proportion.
However, the above prior art has the following drawbacks: firstly, the low-temperature hardening problem of the memory cotton can be improved by changing the raw materials and the proportion of the soft section and the hard section and matching with additives such as a catalyst and the like, but the heat storage performance of the memory cotton is not changed, and the problems of poor heat dissipation and air impermeability still exist when the temperature is higher; secondly, due to the heat storage property of the memory cotton, when the temperature is higher, the heat inside the memory cotton cannot be dissipated in time, so that the temperature inside the memory cotton is continuously increased or in a higher state, the memory cotton is in a softening state for a long time, and the rebound speed is influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide the heat-dissipation breathable memory cotton which has the advantages of good heat-conducting property and good air permeability.
The second purpose of the invention is to provide a preparation method of the heat-dissipation breathable memory cotton.
The third purpose of the invention is to provide the application of the heat-dissipation breathable memory cotton.
The first purpose of the invention is realized by the following technical scheme:
the heat-dissipation breathable memory cotton is prepared from the following raw materials in parts by weight: 20-35 parts of polyoxyethylene triol, 10-20 parts of polyether polyol, 10-20 parts of toluene diisocyanate, 1-2.5 parts of a pore-forming agent, 0.2-0.4 part of silicone oil, 0.003-0.005 part of stannous octoate, 0.5-1.5 parts of modified graphene, 8-15 parts of ethylene glycol, 3-5 parts of water, 0.5-1.5 parts of a nonionic surfactant and 1-3 parts of a silane coupling agent, wherein the modified graphene is diamino end-sealed polyethylene glycol grafted graphene.
By adopting the technical scheme, the graphene is used as a novel two-dimensional material and is formed by sp2The carbon atoms on the hexagonal reticular plane layer have residual electrons, and the residual electrons of the carbon atoms on the adjacent planes exist between the reticular planes as electron clouds, so that the graphene has good thermal conductivity, and the thermal conductivity coefficient of the graphene is as high as 5300W/(m.K); when the memory cotton is applied to the memory cotton, the function of immunocytes of human skin can be enhanced, the effects of diminishing inflammation and inhibiting bacteria are achieved, and the heat conductivity of the memory cotton can be effectively improved. However, graphene sheets with a single atomic layer thickness have a large specific surface area, and strong van der waals interaction force exists between the sheets, so that the performance of the graphene sheets is affected due to the fact that the sheet stacking and aggregation effects are easily generated between the graphene sheets.
The graphene is grafted by adopting the diamino end-sealed polyethylene glycol, and is modified by utilizing the diamino end-sealed polyethylene glycol, so that the dispersity of the graphene in the system disclosed by the invention can be effectively improved, and the heat-conducting property of the memory cotton disclosed by the invention is improved. Ethylene glycol is used as a low molecular weight chain extender of a hard segment in the memory cotton; on the other hand, the modified graphene is used as a dispersing agent, a dispersion liquid of the diamino end-sealed polyethylene glycol grafted graphene is formed after the dispersing agent is mixed with water, and the surface of the modified graphene is treated by matching with a non-ionic surfactant and a silane coupling agent, so that the dispersion uniformity of the modified graphene in the memory cotton system can be improved.
Preferably, the method comprises the following steps: the composition is prepared from the following raw materials in parts by weight: 25-32 parts of polyoxyethylene triol, 12-18 parts of polyether polyol, 12-18 parts of toluene diisocyanate, 1-2.5 parts of a pore-forming agent, 0.2-0.4 part of silicone oil, 0.003-0.005 part of stannous octoate, 0.5-1.5 parts of modified graphene, 8-15 parts of ethylene glycol, 3-5 parts of water, 0.5-1.5 parts of a nonionic surfactant and 1-3 parts of a silane coupling agent.
Preferably, the method comprises the following steps: the double-amino end-sealed polyethylene glycol grafted graphene is prepared by the following method: in the presence of a condensing agent and N-hydroxysuccinimide, mixing diamino end-sealed polyethylene glycol and graphene oxide for condensation reaction; reducing the diamino end-sealed polyethylene glycol grafted graphene oxide into diamino end-sealed polyethylene glycol grafted graphene by hydrazine hydrate, thus obtaining the double amino end-sealed polyethylene glycol grafted graphene.
By adopting the technical scheme, a large number of tests prove that the compatibility of the diamino end-sealed polyethylene glycol and the graphene oxide is better. The double-amino end-sealed polyethylene glycol is subjected to grafting reaction with graphene oxide to form an intermediate with a graphene laminated structure, and then the intermediate is reduced to modified graphene with a laminated structure, so that the modified graphene has the thermal conductivity of graphene and excellent dispersing performance.
Preferably, the method comprises the following steps: the graphene oxide is prepared by taking graphene as a raw material and using a Hummers method.
Preferably, the method comprises the following steps: the molecular weight of polyethylene glycol in the double-amino end-sealed polyethylene glycol is 2000.
By adopting the technical scheme, researches show that the larger the molecular weight of the diamino end-capped polyethylene glycol is, the better the overall thermal conductivity after the diamino end-capped polyethylene glycol is grafted on graphene is. However, as the molecular weight of the polyethylene glycol increases, steric hindrance between the polyethylene glycol and the graphene oxide increases, which increases grafting difficulty on the graphene oxide, reduces the number of grafts, and affects grafting effect, so the molecular weight of the polyethylene glycol is 2000.
Preferably, the method comprises the following steps: the nonionic surfactant is an amphoteric triblock polymer Pluronic P-123.
By adopting the technical scheme, the ionic surfactant can be adsorbed on the surface of the graphene, and the graphene is stabilized by virtue of electrostatic repulsion; the nonionic surfactant mainly depends on the interaction between a hydrophobic group and the surface of graphene, and utilizes a hydrophilic group to increase the dispersibility of the nonionic surfactant in water. The results of the study show that the dispersing ability of the nonionic surfactant is higher than that of the ionic surfactant, and a large number of experiments show that the Pluronic triblock surfactant has the highest dispersing ability in the system of the invention.
Preferably, the method comprises the following steps: the silane coupling agent is selected from one or more of KH-550, KH560 and KH 570.
Preferably, the method comprises the following steps: the silicone oil is polysiloxane-polyalkylene oxide-block copolymer, the viscosity at 25 ℃ is 510mPas, and the density is 1.03g/cm3。
By adopting the technical scheme, the polysiloxane-polyalkylene oxide-block copolymer has ultra-wide processing latitude and is suitable for high-density and slow-rebound systems. Compared with the conventional silicone oil, the memory cotton with better air permeability can be obtained by using the copolymer.
The second object of the present invention is achieved by the following technical solutions:
a preparation method of heat-dissipation breathable memory cotton comprises the following steps:
mixing 70% of the total weight of glycol with water, a nonionic surfactant and a silane coupling agent, and uniformly stirring to obtain a mixed solution A;
adding the modified graphene into the mixed solution A, and uniformly stirring to obtain a mixed solution B;
adding toluene diisocyanate into the mixture B, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, polyether polyol, a pore-forming agent, silicone oil and stannous octoate, and uniformly stirring at 75-90 ℃ to obtain a mixture D;
and adding the mixture C and the residual glycol into the mixture D, stirring uniformly at 80-85 ℃, degassing, filling into a mold, foaming, curing, and demolding to obtain the heat-dissipation breathable memory cotton.
By adopting the technical scheme, firstly, mixing ethylene glycol, a nonionic surfactant and a silane coupling agent to obtain a dispersion liquid of modified graphene; adding modified graphene, and fully dispersing the modified graphene in the dispersion liquid; then adding toluene diisocyanate which is the main component of the hard segment to disperse the modified graphene in a stationary phase; after preparing the soft section material, mixing the soft section and the hard section, and adding the chain extender to prepare the heat-dissipation breathable memory cotton.
The third object of the present invention is achieved by the following technical solutions:
the application of the heat-dissipation and breathable memory cotton is characterized in that the heat-dissipation and breathable memory cotton is used in production and processing of household articles and bedding articles to obtain the household articles and the bedding articles.
By adopting the technical scheme, the memory cotton can be applied to production and processing of cushions, mattresses, pillows, earplugs and the like, and can be used for obtaining household and bedding which is harmless to human bodies and has the advantages of good air permeability, strong heat conductivity and the like.
In summary, the invention includes at least one of the following beneficial technical effects:
(1) the density of the memory cotton reaches 102kg/m3The above belongs to high-quality memory cotton; the rebound resilience is excellent, and the rebound resilience is moderate;
(2) the memory cotton has the recovery time of 5-7s, and belongs to high-grade memory cotton; the 75% compression set is optimally 7.0%; the indentation ratio of 65%/25% can reach 3.1% at most, which shows that the memory cotton has higher bearing capacity;
(3) the heat conductivity coefficient of the memory cotton can reach 3.46W/(m.K) at most, the heat conductivity is greatly improved, and the heat in the memory cotton is favorably dissipated; the air permeability is 4000 g/(m)2× day) and can reach 4500 g/(m)2× day), excellent air permeability;
(4) the memory cotton has excellent heat dissipation performance and good air permeability, can dissipate heat in the memory cotton in time, and has high bearing capacity and excellent rebound speed.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The following raw materials in the invention are all commercial products, and specifically comprise: the polyoxyethylene triol is Caradol SC 56-23; the polyether polyol is selected from slow-rebound 1030 polyether polyol; the toluene diisocyanate is selected from T80-CN 0250; the type of the pore forming agent is 1206; the silicone oil is selected from S-5822, which is polysiloxane-polyalkylene oxide-block copolymer, has viscosity of 510mPas at 25 deg.C, and density of 1.03g/cm3(ii) a The stannous octoate is selected from T-9; the nonionic surfactant is an amphoteric triblock polymer Pluronic P-123; the polyethylene glycol is selected from Dow PEG-2000, and the effective content is 99.9%; the graphene is selected from chemical reagents of national drug group, and the specification is 99% (Vocko).
Graphene oxide in the modified graphene raw material is prepared by taking graphene as a raw material and using a traditional Hummers method. The diamino end-sealed polyethylene glycol is prepared by the following method: 40g of polyethylene glycol was dissolved in 200mL of methylene Chloride (CH)2Cl2) 100mL of triethylamine containing 11.4g of p-toluenesulfonyl chloride (TsCl) was slowly added to the solution, and the reaction was stirred at 24 ℃ for 12 hours; washing the organic phase for 3 times by using 3mol/L HCl, then slowly adding solid sodium bicarbonate into the organic phase, violently stirring until no bubbles exist, filtering, and carrying out reduced pressure distillation on the filtrate; stirring, adding diethyl ether into the concentrated solution until no precipitate is separated out, filtering, collecting precipitate, and vacuum drying to obtain diamino end-sealed polyethylene glycol.
The modified graphene is prepared by the following steps:
taking 1g of graphene oxide, dispersing in 150mL of deionized water, carrying out ultrasonic treatment for 30min, transferring into a three-neck flask, and adding N2Pre-purifying; transferring the aqueous solution containing 0.2g of diamino end-capped polyethylene glycol into the three-neck flask, adding 0.019g of water-soluble condensing agent EDC & HCl and 0.019g of N-hydroxysuccinimide, heating the mixture to 55 ℃ under continuous stirring, and adding N-hydroxysuccinimide into the three-neck flask2Condensing and refluxing for 24 h; adding 3g of hydrazine hydrate, heating to 95 ℃, stirring, and carrying out condensation reflux for 2 h; vacuum filtering for 3 times, placing the filter cake in a vacuum drying oven at 50 ℃, and drying for 24 hours to obtain the modified graphene。
Example 1
The heat-dissipation breathable memory cotton is prepared by the following steps:
heating polyether polyol to 100 ℃, sealing and stirring, drying under the vacuum condition of 1MPa, cooling to 50 ℃, and protecting with inert gas for later use;
according to the mixing amount shown in table 1, 70% of the total weight of ethylene glycol is mixed with water, a nonionic surfactant and a silane coupling agent, and the mixture is uniformly stirred to obtain a mixed solution A;
adding the modified graphene into the mixed solution A, and uniformly stirring to obtain a mixed solution B;
adding toluene diisocyanate into the mixture B, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, dehydrated polyether polyol, a pore-opening agent, silicone oil and stannous octoate, and stirring and mixing for 1.5 hours at the temperature of 75 ℃ to obtain a mixture D;
adding the mixture C and the rest glycol into the mixture D, stirring and mixing for 2 hours at 80 ℃, and degassing; then pouring the mixture into a foaming mold, closing the mold, and vulcanizing for 1h at the temperature of 120 ℃ in a vulcanizing machine; transferring the mould into an oven, and vulcanizing for 8 hours at the temperature of 98 ℃; foaming and curing for 10 days at 25 ℃, and then cooling and demolding to obtain the heat-dissipation breathable memory cotton.
Example 2
The heat-dissipation breathable memory cotton is prepared by the following steps:
heating polyether polyol to 100 ℃, sealing and stirring, drying under the vacuum condition of 1MPa, cooling to 50 ℃, and protecting with inert gas for later use;
according to the mixing amount shown in table 1, 70% of the total weight of ethylene glycol is mixed with water, a nonionic surfactant and a silane coupling agent, and the mixture is uniformly stirred to obtain a mixed solution A;
adding the modified graphene into the mixed solution A, and uniformly stirring to obtain a mixed solution B;
adding toluene diisocyanate into the mixture B, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, dehydrated polyether polyol, a pore-forming agent, silicone oil and stannous octoate, and stirring and mixing for 1.5 hours at 83 ℃ to obtain a mixture D;
adding the mixture C and the rest glycol into the mixture D, stirring and mixing for 2 hours at 85 ℃, and degassing; then pouring the mixture into a foaming mold, closing the mold, and vulcanizing for 1h at the temperature of 120 ℃ in a vulcanizing machine; transferring the mould into an oven, and vulcanizing for 8 hours at 100 ℃; foaming and curing for 10 days at 24 ℃, and then cooling and demolding to obtain the heat-dissipation breathable memory cotton.
Example 3
The heat-dissipation breathable memory cotton is prepared by the following steps:
heating polyether polyol to 100 ℃, sealing and stirring, drying under the vacuum condition of 1MPa, cooling to 50 ℃, and protecting with inert gas for later use;
according to the mixing amount shown in table 1, 70% of the total weight of ethylene glycol is mixed with water, a nonionic surfactant and a silane coupling agent, and the mixture is uniformly stirred to obtain a mixed solution A;
adding the modified graphene into the mixed solution A, and uniformly stirring to obtain a mixed solution B;
adding toluene diisocyanate into the mixture B, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, dehydrated polyether polyol, a pore-opening agent, silicone oil and stannous octoate, and stirring and mixing for 1.5 hours at 90 ℃ to obtain a mixture D;
adding the mixture C and the rest glycol into the mixture D, stirring and mixing for 2 hours at 80 ℃, and degassing; then pouring the mixture into a foaming mold, closing the mold, and vulcanizing for 1h at the temperature of 120 ℃ in a vulcanizing machine; transferring the mould into an oven, and vulcanizing for 8 hours at 100 ℃; foaming and curing for 10 days at 24 ℃, and then cooling and demolding to obtain the heat-dissipation breathable memory cotton.
Examples 4 to 7
Examples 4 to 7 were prepared in the same manner as in example 2 except that the types and amounts of the respective raw materials were different, as shown in Table 1.
TABLE 1 EXAMPLES 1-9 blending amount (unit/kg) of each material of the heat-dissipating air-permeable memory cotton
Examples 8 to 12
Examples 8 to 12 were prepared in exactly the same manner as in example 2, except that the types and amounts of the respective raw materials were different, as shown in Table 2.
TABLE 2 examples 8-12 blending amount (unit/kg) of each material of the heat-dissipating air-permeable memory cotton
Examples 13 to 18
Examples 13 to 18 were prepared in exactly the same manner as in example 2, except that the types and amounts of the respective raw materials were different, as shown in Table 3.
TABLE 3 examples 13-18 blending amount (unit/kg) of each material of the heat-dissipating air-permeable memory cotton
Examples 19 to 23
Examples 19 to 23 were prepared in exactly the same manner as in example 2, except that the types and amounts of the respective raw materials were different, as shown in Table 4.
TABLE 4 examples 19-23 blending amount (unit/kg) of each material of the heat-dissipating air-permeable memory cotton
Comparative example 1
In the patent application for patent publication No. CN 103819645B, the polyurethane foam of example 8.
Comparative example 2
The memory cotton of comparative example 2 was prepared in the same manner as in example 1 except that: the modified graphene in the raw materials is replaced by the same amount of graphene, and the rest raw materials and the doping amount are the same as those in the example 1.
Comparative example 3
The memory cotton of comparative example 3 was prepared in the same manner as in example 1 except that: the amount of ethylene glycol added to the raw materials was 2kg, and the other raw materials and the amounts added were the same as in example 1.
Comparative example 4
The memory cotton of comparative example 4 was prepared in the same manner as in example 1 except that: the same amount of ethylene glycol in the raw material was replaced with 1, 4-butanediol, and the other raw materials and the blending amount were the same as in example 1.
Comparative example 5
The memory cotton of comparative example 5 was prepared in the same manner as in example 1 except that: the same amount of the nonionic surfactant in the raw materials was replaced with ethylene glycol, and the other raw materials and the amount of the added materials were the same as in example 1.
Comparative example 6
The memory cotton of comparative example 6 is the same as the memory cotton of example 1 in terms of raw materials and mixing amount, except that the preparation method is different:
heating polyether polyol to 100 ℃, sealing and stirring, drying under the vacuum condition of 1MPa, cooling to 50 ℃, and protecting with inert gas for later use;
according to the mixing amount shown in table 1, 70% of the total weight of ethylene glycol is mixed with water, a nonionic surfactant and a silane coupling agent, and the mixture is uniformly stirred to obtain a mixed solution A;
adding toluene diisocyanate into the mixture A, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, dehydrated polyether polyol, a pore-opening agent, silicone oil, stannous octoate and modified graphene, and stirring and mixing for 1.5 hours at 75 ℃ to obtain a mixture D;
adding the mixture C and the rest glycol into the mixture D, stirring and mixing for 2 hours at 80 ℃, and degassing; then pouring the mixture into a foaming mold, closing the mold, and vulcanizing for 1h at the temperature of 120 ℃ in a vulcanizing machine; transferring the mould into an oven, and vulcanizing for 8 hours at the temperature of 98 ℃; foaming and curing for 10 days at 25 ℃, and then cooling and demolding to obtain the heat-dissipation breathable memory cotton.
Performance detection
The performance of the memory cotton of the examples 1 to 23 and the comparative examples 1 to 6 is tested by adopting the following test standards:
density (unit: kg/m)3): a weighing method;
75% compression set (unit:%): GB/T6669-2008, the standard requirement is less than or equal to 12 percent;
rebound resilience (unit:%): GB/T6670 plus 2008, the standard requirement is less than or equal to 12 percent;
65%/25% indentation ratio (unit:%): GB/T10807-one 2006, the standard requirement is more than or equal to 1.8 percent;
recovery time (unit: s): GB/T26392-2011;
air permeability (unit: g/m)2× day), ASTMD 1653, covering the testing sample on the cup mouth of the moisture-permeable testing cup, sealing with paraffin, placing in a temperature-controllable constant temperature and humidity apparatus with air flow rate of 5 m/s;
thermal conductivity (unit: W/(m.K)): TPS thermal conductivity tester; the results of the performance tests are shown in Table 5.
TABLE 5 Performance test results for different memory cottons
The detection results in Table 5 show that the density of the memory cotton reaches 102kg/m3The above belongs to high-quality memory cotton; has excellent rebound resilience and moderate rebound resilience. The contact part of a user is easy to be rigid due to too long recovery time of the memory cotton, and the slow rebound effect cannot be achieved due to too short recovery time; the memory cotton has the recovery time of 5-7s, and belongs to high-grade memory cotton; the 75% compression set is optimally 7.0%; the indentation ratio of 65%/25% can reach 3.1% at most, which is superior to the prior art (comparative example)1) 2.0% in the specification, which shows that the memory cotton has higher bearing capacity.
Compared with the traditional memory cotton, the memory cotton has the advantages that the heat conductivity coefficient is increased by two orders of magnitude and can reach 3.46W/(m.K) at most, the heat conductivity is greatly improved, and the heat dissipation in the memory cotton is facilitated; and the air permeability is 4000 g/(m)2× day) and can reach 4500 g/(m)2× day), the air permeability is good compared with the prior art (comparison document 1), the memory cotton of the invention has good heat radiation performance and air permeability, can timely radiate the heat in the memory cotton, and has good rebound speed while having higher bearing capacity.
The detection result of comparative example 2 shows that the modified graphene in the invention has a great influence on the air permeability and the thermal conductivity of the memory cotton, and the air permeability and the heat dissipation capacity of the memory cotton are seriously influenced after the graphene is replaced by the same amount, but the influence on the density, the resilience performance and the like of the memory cotton is slightly small. From the results of comparative examples 3 to 4, it can be seen that the addition amount of ethylene glycol and the presence or absence thereof have a large influence on the air permeability, the thermal conductivity and the rebound time of the memory cotton, possibly due to the dispersion effect of the ethylene glycol on the modified graphene. The detection result of the comparative example 5 shows that the nonionic surfactant has a certain effect on the dispersibility of the modified graphene, and equivalent replacement of the nonionic surfactant can reduce the dispersibility of the system on the modified graphene, so that the bearing capacity, resilience, air permeability and heat dissipation capacity of the memory cotton are reduced. From the results of comparative example 6, it is understood that, in the present invention, if the modified graphene is added to the soft segment, the finally obtained memory cotton has reduced load bearing capacity, rebound resilience and air permeability.
Application example
The memory cotton prepared in the embodiment 22 of the invention is applied to the production and processing of household articles and bedding articles to obtain the household articles and bedding articles; the specific production and processing method of different products adopts a mature processing method in the prior art, the household articles can be products such as a cushion, a sofa cushion and the like, the bedding articles can be products such as a mattress, a pillow and the like, and the method can also be applied to processing earplugs. The processed product has the advantages of good air permeability, good heat conductivity and excellent resilience; the problem of traditional memory cotton when using in summer, because of the not good moist heat airtight that leads to the user and the contact position of memory cotton of heat dissipation is overcome.
The embodiments of the present invention are preferred embodiments, and the scope of the present invention is not limited by the embodiments, and therefore: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (10)
1. The heat-dissipation breathable memory cotton is characterized by being prepared from the following raw materials in parts by weight: 20-35 parts of polyoxyethylene triol, 10-20 parts of polyether polyol, 10-20 parts of toluene diisocyanate, 1-2.5 parts of a pore-forming agent, 0.2-0.4 part of silicone oil, 0.003-0.005 part of stannous octoate, 0.5-1.5 parts of modified graphene, 8-15 parts of ethylene glycol, 3-5 parts of water, 0.5-1.5 parts of a nonionic surfactant and 1-3 parts of a silane coupling agent, wherein the modified graphene is diamino end-sealed polyethylene glycol grafted graphene.
2. The heat-dissipation breathable memory cotton is characterized by being prepared from the following raw materials in parts by weight: 25-32 parts of polyoxyethylene triol, 12-18 parts of polyether polyol, 12-18 parts of toluene diisocyanate, 1-2.5 parts of a pore-forming agent, 0.2-0.4 part of silicone oil, 0.003-0.005 part of stannous octoate, 0.5-1.5 parts of modified graphene, 8-15 parts of ethylene glycol, 3-5 parts of water, 0.5-1.5 parts of a nonionic surfactant and 1-3 parts of a silane coupling agent.
3. The heat-dissipation breathable memory cotton according to claim 1, wherein the bis-amino end-capped polyethylene glycol grafted graphene is prepared by the following method: in the presence of a condensing agent and N-hydroxysuccinimide, mixing diamino end-sealed polyethylene glycol and graphene oxide for condensation reaction; reducing the diamino end-sealed polyethylene glycol grafted graphene oxide into diamino end-sealed polyethylene glycol grafted graphene by hydrazine hydrate, thus obtaining the double amino end-sealed polyethylene glycol grafted graphene.
4. The heat-dissipating breathable memory foam according to claim 3, wherein: the graphene oxide is prepared by taking graphene as a raw material and using a Hummers method.
5. The heat-dissipating breathable memory foam according to claim 3, wherein: the molecular weight of polyethylene glycol in the double-amino end-sealed polyethylene glycol is 2000.
6. The heat-dissipating breathable memory foam according to claim 1, wherein: the nonionic surfactant is an amphoteric triblock polymer Pluronic P-123.
7. The heat-dissipating breathable memory foam according to claim 1, wherein: the silane coupling agent is selected from one or more of KH-550, KH560 and KH 570.
8. The heat-dissipating breathable memory foam according to claim 1, wherein: the silicone oil is polysiloxane-polyalkylene oxide-block copolymer, the viscosity at 25 ℃ is 510mPas, and the density is 1.03g/cm3。
9. The preparation method of the heat-dissipation breathable memory cotton is characterized by comprising the following steps:
mixing 70% of the total weight of glycol with water, a nonionic surfactant and a silane coupling agent, and uniformly stirring to obtain a mixed solution A;
adding the modified graphene into the mixed solution A, and uniformly stirring to obtain a mixed solution B;
adding toluene diisocyanate into the mixture B, and uniformly stirring to obtain a mixture C for later use;
mixing polyoxyethylene triol, polyether polyol, a pore-forming agent, silicone oil and stannous octoate, and uniformly stirring at 75-90 ℃ to obtain a mixture D;
and adding the mixture C and the residual glycol into the mixture D, stirring uniformly at 80-85 ℃, degassing, filling into a mold, foaming, curing, and demolding to obtain the heat-dissipation breathable memory cotton.
10. The use of the heat-dissipating breathable memory foam according to any one of claims 1 to 8, wherein: the heat-dissipation breathable memory cotton is used in production and processing of household articles and bedding articles to obtain the household articles and bedding articles.
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