Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof
阅读说明：本技术 抗静电耐低温慢回弹聚氨酯海绵材料及其制备方法 (Antistatic low-temperature-resistant slow-rebound polyurethane sponge material and preparation method thereof ) 是由 郑玉婴 王利 于 2021-08-12 设计创作，主要内容包括：本发明属于聚氨酯材料制备技术领域,具体涉及一种抗静电耐低温慢回弹聚氨酯海绵材料及其制备方法,其制备方法是首先制备表面插层十八烷基二甲基羟乙基季铵硝酸盐的还原氧化石墨烯SN-RGO作为导电增强剂,然后制备苯胺甲基三乙氧基硅烷改性氧化乙炔炭黑ND-42@o-ACET,与自制聚醚改性硅油进行接枝反应,作为改性耐低温剂,加入得到抗静电耐低温慢回弹聚氨酯海绵材料。在不改变原有慢回弹聚氨酯海绵结构、力学性能的基础上,大大增强了其强度、耐低温性、抗静电性、抗静电稳定性等性能。(The invention belongs to the technical field of preparation of polyurethane materials, and particularly relates to an antistatic low-temperature-resistant slow-rebound polyurethane sponge material and a preparation method thereof. On the basis of not changing the original slow-rebound polyurethane sponge structure and mechanical properties, the strength, low temperature resistance, antistatic property, antistatic stability and other properties of the polyurethane sponge are greatly enhanced.)
1. The utility model provides an antistatic low temperature resistant polyurethane sponge material that kick-backs slowly which characterized in that: comprises the following raw materials in parts by weight:
polyether polyol DALTOPED FF 1183440-60 parts
40-60 parts of polypropylene glycol PPG
0-20 parts of polymer polyol POP
331.2-2.4 parts of catalyst A
10-15 parts of assistant
1.0 to 2.0 portions of deionized water
5-10 parts of modified low temperature resistant agent
5-10 parts of conductive reinforcing agent
40-65 parts of diphenylmethane diisocyanate MDI.
2. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 1, wherein: the sum of the weight parts of polyether polyol DALTOPED FF, polypropylene glycol PPG and polymer polyol POP is 100 parts.
3. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 1, wherein: the conductive reinforcing agent is reduced graphene oxide SN-RGO with surface intercalated octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and the modified low-temperature resistant agent is aniline methyl triethoxysilane modified acetylene oxide carbon black [email protected] o-ACET grafted polyether modified silicone oil.
4. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 3, wherein: the preparation steps of the conductive reinforcing agent are as follows:
(1) preparation of SN-GO: preparing graphene oxide GO by an improved Hummers method, adding 0.2g of GO into a round-bottom flask filled with 20mL of anhydrous DMF, and carrying out 100W ultrasonic treatment in an ultrasonic cleaning machine for 1 h; then adding 2mL of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate into the GO dispersion liquid, stirring for 24 hours in a nitrogen atmosphere by using magnetons, and finally washing and freeze-drying a product to obtain SN-GO;
(2) preparation of SN-RGO: adding 0.2g of SN-GO into a beaker filled with 50mL of deionized water, carrying out ultrasonic dispersion for 30min, then stirring for 1h at 500r/min, then adding 0.2g of anhydrous glucose, carrying out magneton stirring reaction for 30min, then adding 1mL of ammonium hydroxide, then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reduction for 4h in a vacuum drying oven at 170 ℃, centrifuging the product to be neutral, and freeze-drying to obtain SN-RGO.
5. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 3, wherein: the preparation steps of the modified low temperature resistant agent are as follows:
(1) preparation of o-ACET: adding 10g of acetylene black ACET into a three-neck flask filled with 210mL of concentrated nitric acid, refluxing and condensing in an oil bath kettle at 100 ℃, stirring and reacting for 12 hours by using magnetons, filtering the mixed solution, washing the mixed solution to be neutral, and finally putting the mixed solution into a vacuum drying oven at 80 ℃ for 24 hours to obtain oxidized acetylene black o-ACET;
(2) preparation of [email protected] o-ACET: firstly, mixing 1.2g o-ACET, 8mL of deionized water, 24mL of absolute ethyl alcohol and 0.5mL of aniline methyl triethoxysilane ND-42 in a beaker, then placing the beaker in an ultrasonic cleaning machine for ultrasonic dispersion for 1h, transferring the dispersion liquid to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a vacuum drying oven at 110 ℃ for reaction for 6h, naturally cooling to room temperature, then carrying out suction filtration on the product, washing with absolute ethyl alcohol for at least three times, and freeze-drying to obtain aniline methyl triethoxysilane modified acetylene oxide carbon black [email protected] o-ACET;
(3) preparation of [email protected] o-ACET grafted polyether modified silicone oil:
adding 21.92g of cis-1, 2-dimethylolethylene and 0.4g of sodium methoxide into a 0.3L stainless steel high-pressure reaction kettle with a visual constant-pressure funnel, replacing 3 times with nitrogen, controlling the reaction temperature to be 110 ℃, continuously adding a mixture of 70.472g of propylene oxide and 6.128g of ethylene oxide into the constant-pressure funnel, cooling to 80 ℃ after the addition is finished, sequentially adding 0.835g of 85wt% phosphoric acid aqueous solution and 5g of deionized water into the constant-pressure funnel, stirring for 2 hours, heating to 120 ℃, performing vacuum for 0.5 hour to remove water and micromolecules to obtain cis-1, 2-dimethylolethylene polyether polyol, and placing the product in a dry and dark place for 24 hours for later use;
sequentially adding 65mL of cis-1, 2-dimethylol vinyl polyether polyol and 7.5ppm of 1wt% chloroplatinic acid-isopropanol solution into a three-neck flask provided with a condenser tube, a dropping funnel and a nitrogen bag, stirring by using a magneton, controlling the reaction temperature to be 110 ℃, continuously adding 10.75mL of polymethylhydrosiloxane through the dropping funnel after 1h, cooling to 80 ℃ after 2h of reaction, adding 0.5g of [email protected] o-ACET, reacting for 5h, and after the reaction is finished, removing water and micromolecules in vacuum for 2h to obtain the [email protected] o-ACET grafted polyether modified silicone oil.
6. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 1, wherein: the auxiliary agent is prepared from stannous octoate T9: surfactant (b): cell opener =1: 4.2:5.5 mixture.
7. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 1, wherein: the surfactant is a polyurethane foam stabilizer L-580 produced by Meitu company of America.
8. The antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 1, wherein: the pore former is a slow rebound pore former GLK-15 produced by Shanghai Gaoqiao petrochemical company.
9. The preparation method of the antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in any one of claims 1 to 8, wherein the preparation method comprises the following steps: the method comprises the following steps:
(1) adding polyether polyol DALTOPED FF 11834, polypropylene glycol PPG and polymer polyol POP into a container according to a proportion, then adding a catalyst A33, an auxiliary agent, deionized water, a modified low temperature resistant agent and a conductive reinforcing agent according to a formula, stirring for 30-60 seconds, and marking as a component A;
(2) pouring MDI into a container filled with the component A, stirring for 6-8 seconds in a stirrer with the rotation speed of 2500-.
10. The preparation method of the antistatic low-temperature-resistant slow-rebound polyurethane sponge material as claimed in claim 9, wherein the preparation method comprises the following steps: the stirring speed in the step (1) is 1000-.
Technical Field
The invention belongs to the technical field of organic polymer synthesis, relates to a production method of a polyurethane polymer material, and particularly relates to an antistatic low-temperature-resistant slow-rebound polyurethane sponge and a production method thereof.
Background
A slow rebound polyurethane sponge is a flexible foam with viscoelasticity, and is also called a memory sponge because of its shape memory function. The foam is a special material in foam plastics and has the characteristic of 'fingerprint', namely, when the foam is deformed under the action of external force, the strain lags behind the change of stress, so that the foam is not immediately recovered when external force is applied to the foam by the outside, but slowly recovers to the original shape after 3-15 seconds, and the special foam is called as slow-rebound foam and is also called as memory foam. The birth of slow rebound polyurethane sponge dates back to a research of the U.S. space agency (NASA) in 1962: the united states has introduced a high-cushioning material in the apollo series of airships that makes astronauts feel more comfortable during flight. The material is used on the seats of the airship and is used for absorbing the huge impact force on astronauts during the takeoff and return to the atmosphere of the airship due to the characteristics of high compression rate and low compression modulus.
The slow-rebound polyurethane sponge has good shape memory property, strong energy absorption, shock resistance and the like, so the slow-rebound polyurethane sponge is widely applied to the field of buffer materials, such as medical treatment, medicine, arrow targets, helmet inner pads, racing car cushions, functional insoles, bedding, furniture and the like. Especially, when the polyurethane foam is used as a seat cushion and a headrest in a high-grade car in a large amount for more than ten years, is used as a high-grade slow rebound pillow and mattress in the home and is used as a slow rebound buffering insole in a sports shoe material, the hardness and the physical properties of the common slow rebound polyurethane foam can generate obvious changes along with the changes of the environmental temperature: hardening at low temperature and slowing down rebound; softening at high temperature and fast rebound.Especially when used as a seat, a mattress, a pillow and other products in winter, people can feel uncomfortable and even uncomfortable hard feeling, and because the traditional slow-rebound polyurethane foam plastic is a high polymer material with poor conductivity, the surface resistance of the material per se is usually 1012～1015Between omega, electrostatic effect is easy to generate, and most of isocyanate used in the preparation process is TDI (toluene diisocyanate) which has high toxicity, so that the application range of the isocyanate is greatly limited. Therefore, how to prepare the slow rebound polyurethane sponge which is antistatic, low temperature resistant, safe and nontoxic is very necessary.
The traditional method for improving the antistatic performance of the slow-rebound polyurethane sponge is to add an antistatic agent or physically dip a conductive filler, but after the antistatic agent is added, because micromolecular substances are easily precipitated in a polymer matrix, the long-term antistatic performance of the slow-rebound polyurethane sponge is poor; the surface resistivity of the polyurethane can be effectively reduced after physical impregnation, but the stability is poor. Both methods result in problems of excessive sponge odor, poor storage stability of raw materials, migration of antistatic agents, and the like. According to the invention, reduced graphene oxide SN-RGO with surface intercalated octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is firstly prepared as a conductive reinforcing agent, and then aniline methyl triethoxysilane modified acetylene oxide carbon black [email protected] o-ACET is prepared to perform a grafting reaction with self-made polyether modified silicone oil to be used as a modified low temperature resistant agent. Adding a certain formula to obtain the antistatic low-temperature-resistant slow-rebound polyurethane sponge material. On the basis of not changing the original slow-rebound polyurethane sponge structure and mechanical properties, the strength, low temperature resistance, antistatic property, antistatic stability and other properties of the polyurethane sponge are greatly enhanced.
Disclosure of Invention
The invention aims to provide a preparation method of an antistatic low-temperature-resistant slow-rebound polyurethane sponge material, which has good slow-rebound performance, can effectively resist static electricity and has no obvious improvement in hardness at low temperature.
In order to achieve the technical purpose and achieve the technical effect, the invention adopts the following technical scheme:
an antistatic low-temperature-resistant slow-rebound polyurethane sponge material comprises the following raw materials in parts by weight:
wherein the polyether polyolFF. The sum of the parts by weight of the polypropylene glycol PPG and the polymer polyol POP is 100 parts.
The conductive reinforcing agent is reduced graphene oxide SN-RGO with surface intercalated octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and the modified low-temperature resistant agent is aniline methyl triethoxysilane modified acetylene black ([email protected] o-ACET) grafted polyether modified silicone oil. The auxiliary agent is stannous octoate T9: surfactant (b): the cell opening agent is a mixture of 1:4.2:5.5 (mass ratio), the surfactant is a polyurethane foam stabilizer L-580 produced by American Meigram company, and the cell opening agent is a slow rebound cell opening agent GLK-15 produced by Shanghai Gaoqiao petrochemical company.
The preparation steps of the conductive reinforcing agent are as follows:
(1) preparation of SN-GO: graphene oxide GO was prepared by an improved Hummers method. 0.2g of GO is added into a round-bottom flask filled with 20mL of anhydrous DMF, and the mixture is subjected to 100W ultrasonic treatment in an ultrasonic cleaning machine for 1 h. Then adding 2mL of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate into the GO dispersion liquid, stirring for 24h in a nitrogen atmosphere by a magneton, and finally washing and freeze-drying a product to obtain SN-GO.
(2) Preparation of SN-RGO: adding 0.2g of SN-GO into a beaker filled with 50mL of deionized water, carrying out ultrasonic dispersion for 30min, then stirring for 1h at 500r/min, then adding 0.2g of anhydrous glucose, carrying out magneton stirring reaction for 30min, then adding 1mL of ammonium hydroxide, then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reduction for 4h in a vacuum drying oven at 170 ℃, then centrifuging the product to be neutral, and freeze-drying to obtain SN-RGO.
The preparation steps of the modified low temperature resistant agent are as follows:
(1) preparation of o-ACET: adding 10g of acetylene black (ACET) into a three-neck flask filled with 210mL of concentrated nitric acid, refluxing and condensing in an oil bath kettle at 100 ℃, stirring and reacting for 12 hours by magnetons, filtering the mixed solution, washing with water to be neutral, and finally placing in a vacuum drying oven at 80 ℃ for 24 hours to obtain the acetylene oxide black o-ACET.
(2) Preparation of [email protected] o-ACET: firstly, mixing 1.2g o-ACET, 8mL of deionized water, 24mL of absolute ethyl alcohol and 0.5mL of aniline methyl triethoxysilane (ND-42) in a beaker, then placing the beaker in an ultrasonic cleaning machine for ultrasonic dispersion for 1h, transferring the dispersion liquid to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a vacuum drying oven at 110 ℃ for reaction for 6h, naturally cooling to room temperature, then carrying out suction filtration on the product, washing with absolute ethyl alcohol for at least three times, and freeze-drying to obtain the aniline methyl triethoxysilane modified acetylene black [email protected] o-ACET.
(3) Preparation of [email protected] o-ACET grafted polyether modified silicone oil:
adding 21.92g of cis-1, 2-dimethylolethylene and 0.4g of sodium methoxide into a 0.3L stainless steel high-pressure reaction kettle with a visual constant-pressure funnel, replacing 3 times with nitrogen, controlling the reaction temperature to be 110 ℃, continuously adding a mixture of 70.472g of propylene oxide and 6.128g of ethylene oxide into the constant-pressure funnel, cooling to 80 ℃ after the addition is finished, sequentially adding 0.835g of 85wt% phosphoric acid aqueous solution and 5g of deionized water into the constant-pressure funnel, stirring for 2 hours, heating to 120 ℃, performing vacuum for 0.5 hour to remove water and micromolecules to obtain cis-1, 2-dimethylolethylene polyether polyol, and placing the product in a dry and dark place for 24 hours for later use;
sequentially adding 65mL of cis-1, 2-dimethylol vinyl polyether polyol and 7.5ppm of 1wt% chloroplatinic acid-isopropanol solution into a three-neck flask provided with a condenser tube, a dropping funnel and a nitrogen bag, stirring by a magneton, controlling the reaction temperature to be 110 ℃, continuously adding 10.75mL polymethylhydrosiloxane (after 1h of addition) through the dropping funnel, after 2h of reaction, cooling to 80 ℃, adding 0.5g of [email protected] o-ACET, reacting for 5h, and after the reaction is finished, removing water and micromolecules in vacuum for 2h to obtain the [email protected] o-ACET grafted polyether modified silicone oil.
The invention also provides a preparation method of the antistatic low-temperature-resistant slow-rebound polyurethane sponge material, which comprises the following steps:
(1) mixing polyether polyolFF 11834, polypropylene glycol PPG and polymer polyol POP are added into a container in proportion, then a catalyst A33, an auxiliary agent, deionized water, a modified low temperature resistant agent and a conductive reinforcing agent are added according to the formula, and the mixture is stirred for 30 to 60 seconds in a stirrer with the rotating speed of 1000-1500r/min and is marked as component A;
(2) pouring MDI into a container filled with the component A, stirring for 6-8 seconds in a stirrer with the rotation speed of 2500-.
The invention has the beneficial effects that:
(1) through a reasonably designed production formula and process, nontoxic water is used as a foaming agent, and the slow-rebound polyurethane sponge prepared by using safer diphenylmethane diisocyanate has the benefits of health and environmental protection.
(2) Because the slow-rebound polyurethane sponge raw material system has large viscosity and large foaming volume, the antistatic agent SN and the carbon black which can be applied to polyurethane hard foam can not form a conductive network in the sponge system, and can not achieve the antistatic effect, and when the addition amount of the carbon black is too large, the raw material system is easy to agglomerate due to the small specific surface area of the carbon black, and has overlarge viscosity, so that the foaming can not be realized. According to the invention, SN is intercalated into GO and further reduced to obtain a conductive reinforcing agent SN-RGO, acetylene black is oxidized to enhance the dispersibility, ND-42 is used for modifying the surface of the GO, aniline groups are introduced while the dispersibility is enhanced, a certain amount of polyaniline can be formed in the system, and polyether modified silicone oil is grafted to jointly connect a strong conductive network, so that the problems of low temperature resistance, static resistance and static resistance stability of the slow-rebound polyurethane sponge are solved.
(3) The invention has the characteristics of the traditional slow rebound polyurethane sponge, and has excellent flexibility, low temperature resistance and antistatic property, namely, the polyurethane sponge still keeps better slow rebound property at the temperature of-5 ℃, and the phenomena of low temperature hardening, slow rebound, hardness increase and the like can not occur. At the foundationIn addition, the material also has better mechanical strength, antistatic property and antistatic stability, namely the material is not easy to damage and deform at high and low temperatures and has the surface resistance of less than 109Omega (even up to<107Ω) and can remain unchanged for a long period of time (30 days essentially unchanged).
Drawings
FIG. 1 is a production flow diagram.
FIG. 2 XRD patterns of SN-GO and SN-RGO.
FIG. 3 SEM image of [email protected] o-ACET.
FIG. 4 is a scanning electron microscope image of the antistatic low temperature resistant slow rebound polyurethane sponge.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparation of the conductive reinforcing agent:
step 1, preparation of SN-GO: graphene oxide GO was prepared by an improved Hummers method. 0.2g of GO is added into a round-bottom flask filled with 20mL of anhydrous DMF, and the mixture is subjected to 100W ultrasonic treatment in an ultrasonic cleaning machine for 1 h. Then adding 2mL of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate into the GO dispersion liquid, stirring for 24h in a nitrogen atmosphere by a magneton, and finally washing and freeze-drying a product to obtain SN-GO.
Step 2, preparation of SN-RGO: adding 0.2g of SN-GO into a beaker filled with 50mL of deionized water, carrying out ultrasonic dispersion for 30min, then stirring for 1h at 500r/min, then adding 0.2g of anhydrous glucose, carrying out magneton stirring reaction for 30min, then adding 1mL of ammonium hydroxide, then transferring the mixed solution into a reaction kettle, carrying out hydrothermal reduction for 4h in a vacuum drying oven at 170 ℃, then centrifuging the product to be neutral, and freeze-drying to obtain SN-RGO.
(2) The preparation steps of the modified low temperature resistant agent are as follows:
step 1, preparation of o-ACET: adding 10g of acetylene black (ACET) into a three-neck flask filled with 210mL of concentrated nitric acid, condensing and stirring in an oil bath kettle at 100 ℃ for reaction for 12 hours, filtering the mixed solution, washing with water to be neutral, and finally placing in a vacuum drying oven at 80 ℃ for 24 hours to obtain the oxidized acetylene black o-ACET.
Step 2, preparing [email protected] o-ACET: firstly, mixing 1.2g o-ACET, 8mL deionized water, 24mL absolute ethyl alcohol and 0.5mL LND-42 in a beaker, then placing the beaker in an ultrasonic cleaning machine for ultrasonic dispersion for 1h, transferring the dispersion liquid to a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a vacuum drying oven at 110 ℃ for reaction for 6h, naturally cooling to room temperature, carrying out suction filtration on the product, washing the product with absolute ethyl alcohol for at least three times, and freeze-drying to obtain the aniline methyl triethoxysilane modified acetylene black [email protected] o-ACET.
Step 3, preparing [email protected] o-ACET grafted polyether modified silicone oil:
adding 21.92g of cis-1, 2-dimethylolethylene and 0.4g of sodium methoxide into a 0.3L stainless steel high-pressure reaction kettle with a visual constant-pressure funnel, after nitrogen is replaced for 3 times, controlling the reaction temperature to be 110 ℃, continuously adding a mixture of 70.472g of propylene oxide and 6.128g of ethylene oxide into the constant-pressure funnel, after the addition is finished, cooling to 80 ℃, sequentially adding 0.835g of 85% phosphoric acid aqueous solution and 5g of deionized water into the constant-pressure funnel, stirring for 2 hours, heating to 120 ℃, performing vacuum for 0.5 hour to remove water and micromolecules to obtain cis-1, 2-dimethylolethylene polyether polyol, and placing the product in a dry and dark place for 24 hours for later use;
sequentially adding the obtained cis-1, 2-dimethylol vinyl polyether polyol and 7.5ppm chloroplatinic acid-isopropanol solution into a three-neck flask provided with a condenser tube, a dropping funnel and a nitrogen bag, stirring by using magnetons, controlling the reaction temperature to be 110 ℃, continuously adding 10.75mL polymethylhydrosiloxane (after 1h is added) through the dropping funnel, cooling to 80 ℃ after 2h of reaction, adding 0.5g [email protected] o-ACET, reacting for 5h, and after the reaction is finished, removing water and micromolecules in vacuum for 2h to obtain the [email protected] o-ACET grafted polyether modified silicone oil.
(3) Accurately weighing the following raw materials in percentage by weight:
the conductive reinforcing agent is reduced graphene oxide SN-RGO with surface intercalated octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, and the modified low-temperature resistant agent is aniline methyl triethoxysilane modified acetylene black ([email protected] o-ACET) grafted polyether modified silicone oil. The auxiliary agent is stannous octoate T9: surfactant L-580: cell opener GLK-15 is a mixture of 1:4.2: 5.5.
Mixing polyether polyolFF 11834, polypropylene glycol PPG and polymer polyol POP are added into a container according to a proportion, then a catalyst A33, an auxiliary agent, deionized water, a modified low temperature resistant agent and a conductive reinforcing agent are added according to a formula, and the mixture is stirred for 30 seconds in a stirrer with the rotating speed of 1200r/min and is marked as a component A;
pouring MDI into a container filled with the component A, stirring for 6-8 seconds under a stirrer with the rotation speed of 2500r/min until the system turns white, pouring the system into a mold, controlling the temperature of the mold at 25 +/-0.5 ℃, and cutting after 24-72 hours to obtain the product.
Example 2
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparation of the conductive reinforcing agent: the same as in example 1.
(2) Preparing a modified low-temperature resistant agent: the same as in example 1.
(3) Accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 5 parts of a modified low temperature resistant agent, 10 parts of a conductive reinforcing agent and 62 parts of MDI.
The foaming process was the same as in example 1.
Example 3
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparation of the conductive reinforcing agent: the same as in example 1.
(2) Preparing a modified low-temperature resistant agent: the same as in example 1.
(3) Accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of a modified low temperature resistant agent, 5 parts of a conductive reinforcing agent and 62 parts of MDI.
The foaming process was the same as in example 1.
Example 4
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparation of the conductive reinforcing agent: the same as in example 1.
(2) Preparing a modified low-temperature resistant agent: the same as in example 1.
(3) Accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of a modified low temperature resistant agent, 10 parts of a conductive reinforcing agent and 62 parts of MDI.
The foaming process was the same as in example 1.
Comparative example 1
The slow rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) accurately weighing the following raw materials in percentage by weight:FF 1183440, PPG 40, POP-204520, A331.210.7 parts of an auxiliary agent (a mixture of stannous octoate T9, a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water and 62 parts of MDI.
(2) Will be provided withFF 11834, PPG and POP-2045 are added into a container according to the formula, then A33, an auxiliary agent and deionized water are added, and the mixture is stirred for 60 seconds in a stirrer with the rotating speed of 1200r/min and is marked as component A;
(3) free foaming: pouring the component B MDI into a container filled with the component A, stirring for 7 seconds in a stirrer with the rotation speed of 2500r/min, pouring the system into a mold after the system turns white, controlling the temperature of the mold at 25 +/-0.5 ℃, and cutting after 24 hours to obtain the product.
Comparative example 2
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparing a modified low-temperature resistant agent: the same as in example 1.
(2) Accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of a modified low temperature resistant agent and 62 parts of MDI.
The foaming process was the same as in example 1.
Comparative example 3
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparation of the conductive reinforcing agent: the same as in example 1.
(2) Accurately weighing the following raw materials in percentage by weight:FF 1183440, PPG 40, POP-204520, and,332.4 parts of A, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580: a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of a conductivity enhancer and 62 parts of MDI.
The foaming process was the same as in example 1.
Comparative example 4
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparing polyether modified silicone oil: adding 21.92g of cis-1, 2-dimethylolethylene and 0.4g of sodium methoxide into a 0.3L stainless steel high-pressure reaction kettle with a visual constant-pressure funnel, replacing 3 times with nitrogen, controlling the reaction temperature to be 110 ℃, continuously adding a mixture of 70.472g of propylene oxide and 6.128g of ethylene oxide into the constant-pressure funnel, cooling to 80 ℃ after the addition is finished, sequentially adding 0.835g of 85wt% phosphoric acid aqueous solution and 5g of deionized water into the constant-pressure funnel, stirring for 2 hours, heating to 120 ℃, performing vacuum for 0.5 hour to remove water and micromolecules to obtain cis-1, 2-dimethylolethylene polyether polyol, and placing the product in a dry and dark place for 24 hours for later use;
and sequentially adding 65mL of the cis-1, 2-dimethylol vinyl polyether polyol and 7.5ppm of 1% chloroplatinic acid-isopropanol solution into a three-neck flask provided with a condenser tube, a dropping funnel and a nitrogen bag, stirring by using magnetons, controlling the reaction temperature to be 110 ℃, continuously adding 10.75mL of polymethylhydrosiloxane (after 1h of addition) through the dropping funnel, reacting for 2 hours, and naturally cooling to obtain the polyether modified silicone oil.
(2) Accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of polyether modified silicone oil, 10 parts of an antistatic agent SN, and 62 parts of MDI.
(3) Will be provided withFF 11834, PPG and POP-2045 are added into a container according to the formula, then A33, an auxiliary agent, deionized water, polyether modified silicone oil and an antistatic agent SN are added, and the mixture is stirred for 60 seconds in a stirrer with the rotating speed of 1200r/min and is marked as component A;
(4) free foaming: pouring the component B MDI into a container filled with the component A, stirring for 7 seconds in a stirrer with the rotation speed of 2500r/min, pouring the system into a mold after the system turns white, controlling the temperature of the mold at 25 +/-0.5 ℃, and cutting after 24 hours to obtain the product.
Comparative example 5
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparing polyether modified silicone oil: the same as comparative example 4;
(2) accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of polyether modified silicone oil and 62 parts of MDI.
(3) Will be provided withFF 11834, PPG and POP-2045 are added into a container according to the formula, then A33, an auxiliary agent, deionized water and polyether modified silicone oil are added, and the mixture is stirred for 60 seconds in a stirrer at the rotating speed of 1200r/min and is marked as component A;
(4) free foaming: pouring the component B MDI into a container filled with the component A, stirring for 7 seconds in a stirrer with the rotation speed of 2500r/min, pouring the system into a mold after the system turns white, controlling the temperature of the mold at 25 +/-0.5 ℃, and cutting after 24 hours to obtain the product for later use.
(5) Impregnating graphene in an aqueous dispersion: cutting the obtained sponge into 5 samples of 12 multiplied by 1cm, immersing the samples in the graphene water dispersion, carrying out ultrasonic treatment at 300W for 1h, taking out the sponge, extruding excessive water, and drying the sponge in a vacuum drying oven at 60 ℃ for 12h to obtain the product.
Comparative example 6
The antistatic low-temperature-resistant slow-rebound polyurethane sponge material and the preparation method thereof comprise the following steps:
(1) preparing polyether modified silicone oil: as in comparative example 4,
(2) accurately weighing the following raw materials in percentage by weight:FF 1183440 parts, PPG 40 parts, POP-204520 parts, A332.4 parts, 10.7 parts of an auxiliary agent (stannous octoate T9: a mixture of a surfactant L-580 and a cell opener GLK-15: 1:4.2: 5.5), 1.3 parts of deionized water, 10 parts of polyether modified silicone oil, 5 parts of conductive carbon black and 62 parts of MDI.
(2) Will be provided withFF 11834, PPG and POP-2045 are added into a container according to the formula, then A33, an auxiliary agent, deionized water and polyether modified silicone oil are added, and the mixture is stirred for 60 seconds in a stirrer at the rotating speed of 1200r/min and is marked as component A;
(3) free foaming: pouring the component B MDI into a container filled with the component A, stirring for 7 seconds in a stirrer with the rotation speed of 2500r/min, pouring the system into a mold after the system turns white, controlling the temperature of the mold at 25 +/-0.5 ℃, and cutting after 24 hours to obtain the product.
Table 1 detection of the properties of the slow rebound polyurethane sponge finished product:
the data in table 1 show that: the antistatic low-temperature-resistant slow-rebound polyurethane sponge (examples 1-4) is temperature-sensitive and humidity-sensitive according to GB/T24451-The sensory index measuring method tests each product, when the temperature changes (5 ℃ and 40 ℃), even further tests the hardness change at-5 ℃, not only the sponge hardness change amplitude is very little (the hardness change is not more than 3 percent at most), but also the sponge is insensitive to the temperature, and compared with most common slow-rebound sponges sold in the market, the sponge hardness change amplitude is larger, and the low-temperature resistance of the sponge is greatly improved; the composite material has more excellent tensile strength and compression set, namely, the mechanical strength is greatly improved; and the surface resistance is greatly reduced compared with that of comparative example 1, and the antistatic requirement (less than 10) is met9Omega, even less than 107Omega), compared with most of antistatic sponges sold in the market, the antistatic stability is innovatively concerned, the surface resistance is basically unchanged after 30 days, and as can be seen from comparative examples 2 and 3 by a single variable method, the antistatic performance of the modified low-temperature resistant agent added with the conductive filler is not excellent, the antistatic stability of comparative example 2 is not good enough, but the surface resistance is directly reduced by two to three orders of magnitude when the conductive filler and the modified low-temperature resistant agent are added simultaneously, which proves that the conductive fillers and the modified low-temperature resistant agent form a dense conductive network in a polyurethane sponge system. The surface resistance of the antistatic agent SN used in the comparative example 4 is changed greatly after 30d, because small molecules are easily separated out by using the antistatic agent singly, the stability of the antistatic agent SN is greatly improved by inserting the SN into GO in the invention; the comparative example 5 adopts a physical impregnation method, but the residual graphene on the surface of the finished sponge product is too much, so that the practical application is not satisfied; comparative example 6 since the specific surface area of the conductive carbon black is large, the viscosity was too large to foam when mixing the A component and the B component. In conclusion, the antistatic performance and the antistatic stability of the sponge are greatly improved.