CN111635500A - Low-temperature-resistant neck-protecting memory cotton and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of polyurethane materials, and particularly discloses low-temperature-resistant neck-protecting memory cotton which is prepared from the following raw materials in parts by weight: 70-80 parts of polyether, 55-60 parts of toluene diisocyanate, 0.3-1 part of catalyst, 1-3 parts of pore-forming agent, 0.3-0.6 part of silicone oil, 2-3 parts of water, 1-3 parts of perfluorohexyl glycol and 0.5-2 parts of hydroxyl silicone oil; the low-temperature-resistant neck-protecting memory cotton has the advantages that the hardness of the memory cotton at a low temperature can be reduced, and the elasticity is kept good; also provides a preparation method of the low-temperature-resistant neck-protecting memory cotton.

Description

Low-temperature-resistant neck-protecting memory cotton and preparation method thereof

Technical Field

The invention relates to the technical field of polyurethane materials, in particular to low-temperature-resistant neck-protecting memory cotton and a preparation method thereof.

Background

Polyurethane slow resilience foams are also known as memory foam, viscoelastic foam, low resilience foam, and the like. After the memory cotton is stressed, the memory cotton can conform to the shapes of different parts, the contact area with a force application object is maximized, the stress gradient is minimized, a stress concentration point is relieved, the memory cotton is slowly restored when external force is removed, and the recovery time can be from several seconds to tens of seconds. Therefore, the memory cotton is widely used for various cushion materials, such as pillows, mattresses, waist pillows, neck protectors, earplugs and the like, and compared with the traditional cushion material, the memory cotton can reduce the sense of extrusion on human bodies, is beneficial to blood circulation and has higher comfort.

The existing memory cotton used for pillows, mattresses and the like has the problem of hardening at low temperature, so that the elasticity of the memory cotton in a low-temperature environment is sharply reduced, and the use is influenced.

In the prior art, memory cotton improved in low-temperature hardening is available, for example, chinese patent publication No. CN103819645B discloses a slow-rebound polyurethane foam material, which comprises the following components: 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 preparation method comprises the following steps: the polyether, the catalyst, the silicone oil, the pore-forming agent and the water in the formula ratio are fully mixed at normal temperature according to the weight portion ratio, and then are uniformly stirred and reacted with the toluene diisocyanate to obtain the slow-rebound polyurethane foam material.

By the formula, the problem of low-temperature hardening of the memory cotton can be solved. However, the above formulation has the following drawbacks: firstly, the hardness of the memory cotton is reduced to some extent compared with the hardness of the traditional memory cotton at low temperature (4 ℃), but the hardness of the memory cotton is obviously increased below 4 ℃, so that the memory cotton is not comfortable enough in winter in the north; secondly, when the temperature is lower, the elasticity of the rubber is greatly reduced, so that the user experience is poor.

Disclosure of Invention

In view of the defects of the prior art, the first object of the invention is to provide a low temperature resistant neck protection memory cotton which has the advantages that the hardness of the memory cotton at low temperature can be reduced, and the elasticity can be kept good.

The second purpose of the invention is to provide a preparation method of the low-temperature-resistant neck-protecting memory cotton.

In order to achieve the first object, the invention provides the following technical scheme:

the low-temperature-resistant neck-protecting memory cotton is prepared from the following raw materials in parts by weight: 70-80 parts of polyether, 55-60 parts of toluene diisocyanate, 0.3-1 part of catalyst, 1-3 parts of pore-forming agent, 0.3-0.6 part of silicone oil, 2-3 parts of water, 1-3 parts of perfluorohexyl glycol and 0.5-2 parts of hydroxyl silicone oil.

By adopting the technical scheme, the weather resistance, the oxidation resistance and the like of the organic fluorine polymer can be improved due to the existence of fluorine atoms in the organic fluorine polymer; the organosilicon compound is a semi-organic and semi-inorganic compound with low glass transition temperature; the formula of the low-temperature-resistant neck-protecting memory cotton contains hydroxyl silicone oil and perfluorohexyl dihydric alcohol, and in the synthesis process of polyurethane, the hydroxyl silicone oil and the perfluorohexyl dihydric alcohol can react with-NCO in toluene diisocyanate in the polyurethane through hydroxyl in molecules to generate covalent bonds, so that the polyurethane molecules have fluorine, silicon and other atoms, the low-temperature-resistant neck-protecting memory cotton is modified, the low-temperature-resistant performance is effectively improved, the hardness is obviously reduced in a low-temperature environment, and the elasticity is kept well.

Preferably, the preparation method of the perfluorohexyl diol comprises the following steps:

1) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane into an ammonium chloride solution with the concentration of 3-5mol/L, uniformly stirring, wherein the molar ratio of the 3-perfluoro-n-hexyl-1, 2-epoxypropane to a solute in ammonia water is 1:2-1:4, adding ethanol with the volume same as that of the ammonium chloride solution, dropwise adding a sodium hydroxide solution while stirring, wherein the molar amount of the solute in the dropwise added sodium hydroxide solution is the same as that of the solute in the ammonium chloride solution, after dropwise adding, stirring and reacting for 3-5 hours, and then performing rotary evaporation at 35-45 ℃ until the volume is 0.1-0.05 times of that of the original solution to obtain a mixed solution A;

2) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane and ethanol, the volume of which is 2-5 times of the volume of the mixed solution, into the mixed solution A, and stirring for reaction for 7-10h to obtain a mixed solution B;

3) adding diethyl ether and deionized water with the same volume as the mixed solution into the mixed solution B for extraction, and taking an organic layer to obtain a solution A;

4) and concentrating the solution A to obtain a solid A, and recrystallizing the solid A by using chloroform to obtain the perfluorohexyl diol.

By adopting the technical scheme, the dropwise added sodium hydroxide can increase the hydrolysis of ammonium ions to generate ammonium monohydrate, nitrogen atoms in the ammonium monohydrate attack carbon atoms at the tail end of a carbon chain connected with oxygen atoms in the 3-perfluoro-n-hexyl-1, 2-epoxypropane to break carbon-oxygen bonds, and then the ammonium monohydrate reacts with the 3-perfluoro-n-hexyl-1, 2-epoxypropane to generate perfluorohexyl dihydric alcohol molecules; compared with the method of directly using ammonia water for reaction, the method can reduce the volatilization of the ammonia water, and can control the reaction speed by the speed of dropwise adding sodium hydroxide.

Preferably, the step 4) of concentrating the solution a comprises the steps of: the concentration of the solution A in the step 4) comprises the following steps:

adding a drying agent into the solution A, drying for 10-15h, and filtering to obtain a solution B;

and carrying out rotary evaporation on the solution B at the temperature of 30-45 ℃ to obtain a solid A.

By adopting the technical scheme, compared with drying, the rotary evaporation can save the solvent volatilization time, so that the concentration step is faster; the water in solution a can be removed by drying.

Preferably, the drying agent in the step 2) is one of anhydrous sodium sulfate, anhydrous calcium sulfate and anhydrous magnesium sulfate.

By adopting the technical scheme, the drying agent can well remove the water in the concentrated solution A without damaging the molecular structure of the perfluorohexyl glycol.

Preferably, the silicone oil is a silicone surfactant S-5822.

By adopting the technical scheme, the silicone surfactant S-5822 is a polysiloxane-polyalkylene oxide block copolymer, is suitable for a polyether polyurethane soft foam formula, can provide a wider processing gradient, and compared with conventional silicone oil, the silicone surfactant S-5822 can obtain better air permeability and can reduce the tendency of foam cracking.

Preferably, the catalyst is one of dibutyltin dilaurate and stannous octoate T-9.

By adopting the technical scheme, better effects can be obtained when dibutyltin dilaurate and stannous octoate T-9 are used as catalysts in the polyurethane reaction.

The second purpose of the invention is realized by the following technical scheme: a preparation method of low-temperature-resistant neck-protection memory cotton comprises the following preparation steps:

mixing polyether, perfluorohexyl dihydric alcohol, silicone oil, hydroxyl silicone oil, a pore-forming agent, a catalyst, water and the like, and stirring uniformly; and adding toluene diisocyanate, and stirring for reaction to obtain the low-temperature-resistant neck-protecting memory cotton.

By adopting the technical scheme, the raw materials except the toluene diisocyanate are uniformly stirred at first, and then the toluene diisocyanate is added for reaction, so that the low-temperature-resistant neck-protecting memory cotton is uniform in texture.

In conclusion, the invention has the following beneficial effects:

(1) the low-temperature-resistant neck protection memory cotton has the advantages that the temperature sensitivity coefficient is low, the use temperature range is wide, the hardness of the memory cotton does not change obviously in a low-temperature environment, good elasticity can be kept, and the experience of a user is good; the memory cotton has the lowest temperature sensitive coefficient of 1.010, so that the memory cotton has wider application temperature.

(2) When the perfluorohexyl dihydric alcohol is prepared, sodium hydroxide is dropwise added into an ammonium chloride solution to gradually generate ammonia monohydrate in the solution, and the ammonia monohydrate reacts with the 3-perfluorohexyl-1, 2-epoxypropane.

Detailed Description

The present invention will be described in further detail with reference to examples.

Raw materials

The polyether in the invention is selected from Shanghai Baion chemical engineering and technology limited, the model is 1030, and the hydroxyl value is 230-; the toluene diisocyanate is selected from the chemical company of Jinan brilliant Hao, and the purity is about 99.9%; the stannous octoate T-9 selected as the catalyst is selected from Nantong Runfeng petrochemical company Limited, and the purity is 99 percent; dibutyl tin dilaurate selected from Shandong Deno New Material science and technology limited with a purity of 99.9%; the type of the pore forming agent is KY-1206, and is selected from Shanghai Baion chemical technology Co., Ltd; the silicone oil is selected from silicone surfactant S-5822, which is selected from Wen chemical company of Foshan; the hydroxyl silicone oil is selected from Wuhan Tian Zexin science and technology limited company, and the refractive index is 1.400; the 3-perfluoro-n-hexyl-1, 2-epoxypropane is selected from Wuhansai Wall chemical industry Co., Ltd, and the melting point is-51.7 ℃.

Preparation example 1

The perfluorohexyl glycol is prepared by the following steps:

1) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane into an ammonium chloride solution with the concentration of 3mol/L, uniformly stirring, wherein the molar ratio of the 3-perfluoro-n-hexyl-1, 2-epoxypropane to a solute in the ammonium chloride solution is 1:3, adding ethanol with the volume same as that of the ammonium chloride solution, dropwise adding a sodium hydroxide solution while stirring, wherein the molar amount of the solute in the dropwise added sodium hydroxide solution is the same as that of the solute in the ammonium chloride solution, stirring for reacting for 4 hours after dropwise adding, and performing rotary evaporation at 35 ℃ until the volume is 0.05 times of that of the original solution to obtain a mixed solution A;

2) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane and ethanol, the volume of which is 2 times of that of the mixed solution A, into the mixed solution A, wherein the amount of the 3-perfluoro-n-hexyl-1, 2-epoxypropane is equal to that in the step 1), and stirring for reaction for 7 hours to obtain a mixed solution B;

3) adding diethyl ether and deionized water with the same volume as the mixed solution B into the mixed solution B for extraction, and taking an organic layer to obtain a solution A;

4) adding anhydrous sodium sulfate into the solution A for drying, and filtering after drying for 10 hours to obtain a solution B; and (3) carrying out rotary evaporation on the solution B at the temperature of 30 ℃ to obtain a solid A, and recrystallizing the solid A by using chloroform to obtain the perfluorohexyl glycol.

Preparation example 2

The perfluorohexyl glycol is prepared by the following steps:

1) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane into an ammonium chloride solution with the concentration of 4mol/L, uniformly stirring, wherein the molar ratio of the 3-perfluoro-n-hexyl-1, 2-epoxypropane to a solute in the ammonium chloride solution is 1:2, adding ethanol with the volume same as that of the ammonium chloride solution, dropwise adding a sodium hydroxide solution while stirring, wherein the molar amount of the solute in the dropwise added sodium hydroxide solution is the same as that of the solute in the ammonium chloride solution, stirring and reacting for 5 hours after dropwise adding, and performing rotary evaporation at 40 ℃ until the volume is 0.05 times of that of the original solution to obtain a mixed solution A;

2) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane and ethanol, the volume of which is 3 times that of the mixed solution A, into the mixed solution A, wherein the amount of the 3-perfluoro-n-hexyl-1, 2-epoxypropane is equal to that in the step 1), and stirring for reaction for 9 hours to obtain a mixed solution B;

3) adding diethyl ether and deionized water with the same volume as the mixed solution B into the mixed solution B for extraction, and taking an organic layer to obtain a solution A;

4) adding anhydrous calcium sulfate into the solution A, drying for 12 hours, and filtering to obtain a solution B; and (3) carrying out rotary evaporation on the solution B at the temperature of 35 ℃ to obtain a solid A, and recrystallizing the solid A by using chloroform to obtain the perfluorohexyl glycol.

Preparation example 3

The perfluorohexyl glycol is prepared by the following steps:

1) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane into an ammonium chloride solution with the concentration of 5mol/L, uniformly stirring, wherein the molar ratio of the 3-perfluoro-n-hexyl-1, 2-epoxypropane to a solute in the ammonium chloride solution is 1:4, adding ethanol with the volume same as that of the ammonium chloride solution, dropwise adding a sodium hydroxide solution while stirring, wherein the molar amount of the solute in the dropwise added sodium hydroxide solution is the same as that of the solute in the ammonium chloride solution, after dropwise adding, stirring and reacting for 3 hours, and then performing rotary evaporation at 45 ℃ until the volume is 0.1 time of the original volume to obtain a mixed solution A;

2) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane and ethanol, the volume of which is 5 times of that of the mixed solution A, into the mixed solution A in an amount which is equal to that in the step 1), and stirring for reaction for 10 hours to obtain a mixed solution B;

3) adding diethyl ether and deionized water with the same volume as the mixed solution B into the mixed solution B for extraction, and taking an organic layer to obtain a solution A;

4) adding anhydrous calcium sulfate into the solution A, drying for 15h, and filtering to obtain a solution B; and (3) carrying out rotary evaporation on the solution B at the temperature of 45 ℃ to obtain a solid A, and recrystallizing the solid A by using chloroform to obtain the perfluorohexyl glycol.

Example 1

The contents of the components of the low-temperature-resistant neck-protection memory cotton of example 1 are shown in table 1, and the processing operation is specifically as follows: mixing and uniformly stirring polyether, perfluorohexyl glycol, silicone oil, hydroxyl silicone oil, a pore-forming agent, a catalyst, water and the like at normal temperature according to the raw materials and the raw material content in the table 1; adding toluene diisocyanate, stirring and reacting for 10 hours to obtain the low-temperature-resistant neck-protecting memory cotton. Wherein, the catalyst adopts stannous octoate T-9, and the perfluorohexyl dihydric alcohol is selected from preparation example 1.

TABLE 1 composition and content of raw materials of low temperature resistant neck-protecting memory cotton

Example 2

The contents of the components of the low-temperature-resistant neck-protection memory cotton of example 2 are shown in table 1, wherein stannous octoate T-9 is used as a catalyst, and perfluorohexyl diol is selected from preparation example 2. The processing steps differ from those of example 1 in that the stirring reaction time of example 2 was 11 hours, and the rest of the steps were the same.

Example 3

The contents of the components of the low-temperature-resistant neck-protection memory cotton of example 3 are shown in table 1, wherein stannous octoate T-9 is used as a catalyst, and perfluorohexyl diol is selected from preparation example 2. The processing procedure was the same as in example 1. The processing steps differ from those of example 1 in that the stirring reaction time of example 3 is 12 hours, and the rest of the steps are the same

Example 4

The contents of the components of the low temperature resistant neck-protecting memory cotton of example 4 are shown in table 1, wherein stannous octoate T-9 is used as a catalyst, and perfluorohexyl diol is selected from preparation example 3. The processing procedure was the same as in example 1.

Examples 5 to 8

The contents of the components of the low temperature resistant neck-protecting memory cotton of examples 5-8 are shown in Table 1, wherein perfluorohexyl glycol is selected from preparation example 2. The processing procedure was the same as in example 1.

Example 9

The contents of the components of the low temperature resistant neck-protecting memory cotton of example 9 are as shown in example 3, wherein the difference from the contents of the components of example 3 is that the addition amount of perfluorohexyldiol is 0, and the processing operation steps are the same as those of example 3.

Example 10

The low temperature resistant neck-protecting memory cotton of example 10 has the contents of the components as shown in example 3, wherein the difference from the contents of the components in example 3 is that the addition amount of the hydroxy silicone oil is 0, and the processing operation steps are the same as those of example 3.

Example 11

The low temperature resistant neck-protecting memory cotton of example 11 has the contents of the respective components as shown in example 3, wherein the contents of the respective components are different from those of example 3 in that the hydroxy silicone oil and the perfluorohexyl glycol are added in amounts of 0, and the processing steps are the same as those of example 3.

Example 12

The low temperature resistant neck-protection memory cotton of example 12 has the same contents of the components as those in example 3, wherein the catalyst is dibutyltin dilaurate, the dibutyltin dilaurate is the same as the substance of the stannous octoate added in example 3, and the processing steps are the same as those in example 3.

Comparative example 1

The slow rebound polyurethane foam of example 12 in chinese invention patent publication No. CN 103819645B.

Comparative example 2

The polyurethane slow recovery foam of example 1 in chinese invention patent publication No. CN 108570138A.

Performance test

The low temperature resistant neck-protecting memory cotton of examples 1-12 and comparative examples 1-2 were extracted, respectively, and molded to prepare a slow recovery foam, the mold was a 380mm × 380mm × 100mm aluminum mold, and after demolding, the article was left for 72 hours and tested according to the following standard or method, and the specific results are shown in table 2.

The rebound resilience: GB/T6670-

The recovery time is as follows: GB/T24451-

Tensile strength: GB/T6344-2008

Elongation at break: GB/T6344-2008

Tear strength: GB/T10808-one 2006

Temperature sensitivity coefficient: GB/T24451-; the temperature sensitivity coefficient refers to the ratio of the hardness of the foam at 50% relative humidity at 5 ℃ to the hardness at 40 ℃. The smaller the temperature sensitive coefficient is, the smaller the influence of the temperature on the foam hardness is, and the wider the application temperature range of the foam is.

TABLE 2 examination results of the low temperature resistant neck-protecting memory cotton of examples 1-13 and comparative examples 1-2

As can be seen from the detection results in Table 2, the low temperature resistant neck-protection memory cotton of the invention is qualified in the aspects of rebound rate, recovery time, tensile strength, elongation at break, tear strength, temperature sensitivity coefficient and the like.

As can be seen from the data of examples 1-8 and comparative examples 1-2, the temperature sensitivity coefficient of the low temperature resistant neck-protection memory cotton of examples 1-8 is obviously smaller than that of comparative examples 1 and 2, which shows that the low temperature resistance of the memory cotton of examples 1-8 is better than that of comparative examples 1-2, the application temperature range is wider, the hardness change at low temperature is smaller, and the memory cotton is suitable for being used at low temperature.

As can be seen from the data of example 3 and examples 5-8, the more the total amount of the hydroxy silicone oil and the perfluorohexyl glycol is added, the stronger the low temperature resistance of the memory cotton is, but the rising trend becomes gradually slower, and the temperature sensitivity coefficient can reach 1.010 at the lowest, which is far lower than that of comparative examples 1-2.

As can be seen from the data of example 3 and examples 9 to 11, the hydroxy silicone oil and the perfluorohexyl glycol respectively have an accelerating effect on the low temperature resistance of the low temperature resistant neck protection memory cotton, and have a synergistic effect when added at the same time.

From the data of example 3 and example 12, it can be seen that when dibutyltin dilaurate or stannous octoate is used as the catalyst, the performance of the low temperature resistant neck-protecting memory cotton is not significantly affected.

As can be seen from the data of examples 1-4 and comparative example 9, all of the perfluorohexyl glycol prepared in preparation examples 1-3 have significantly enhanced low temperature resistance of the low temperature neck protection memory cotton, and the enhancement degree has no significant difference, which indicates that the perfluorohexyl glycol prepared in preparation examples 1-3 has no significant difference in chemical and physical properties.

The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (7)

1. The utility model provides a low temperature resistant rib memory cotton which characterized in that: the composition is prepared from the following raw materials in parts by weight: 70-80 parts of polyether, 55-60 parts of toluene diisocyanate, 0.3-1 part of catalyst, 1-3 parts of pore-forming agent, 0.3-0.6 part of silicone oil, 2-3 parts of water, 1-3 parts of perfluorohexyl glycol and 0.5-2 parts of hydroxyl silicone oil.

2. The low-temperature-resistant neck-protecting memory cotton as claimed in claim 1, wherein: the preparation method of the perfluorohexyl dihydric alcohol comprises the following steps:

1) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane into an ammonium chloride solution with the concentration of 3-5mol/L, uniformly stirring, adding ethanol with the volume same as that of the ammonium chloride solution, dropwise adding a sodium hydroxide solution while stirring, wherein the molar amount of the solute in the dropwise added sodium hydroxide solution is the same as that of the solute in the ammonium chloride solution, after dropwise adding, stirring and reacting for 3-5h, concentrating the mixed solution to the volume of 0.1-0.05 time of the original solution to obtain a mixed solution A, wherein the molar ratio of the 3-perfluoro-n-hexyl-1, 2-epoxypropane to the solute in the ammonium chloride solution is 1:2-1: 4;

2) adding 3-perfluoro-n-hexyl-1, 2-epoxypropane with the same volume as that of the mixed solution A in the step 1) and ethanol with the volume 2-5 times that of the mixed solution A into the mixed solution A, and stirring for reaction for 7-10h to obtain a mixed solution B;

3) adding diethyl ether and deionized water with the same volume as the mixed solution B into the mixed solution B for extraction, and taking an organic layer to obtain a solution A;

4) and concentrating the solution A to obtain a solid A, and recrystallizing the solid A by using chloroform to obtain the perfluorohexyl diol.

3. The low-temperature-resistant neck-protecting memory cotton as claimed in claim 2, wherein: the concentration of the solution A in the step 4) comprises the following steps:

adding a drying agent into the solution A, drying for 10-15h, and filtering to obtain a solution B;

and carrying out rotary evaporation on the solution B at the temperature of 30-45 ℃ to obtain a solid A.

4. The low-temperature-resistant neck-protecting memory cotton as claimed in claim 3, wherein: the drying agent in the step 2) is one of anhydrous sodium sulfate, anhydrous calcium sulfate and anhydrous magnesium sulfate.

5. The low-temperature-resistant neck-protecting memory cotton as claimed in claim 1, wherein: the silicone oil is a silicone surfactant S-5822.

6. The low-temperature-resistant neck-protecting memory cotton as claimed in claim 1, wherein: the catalyst adopts one of dibutyltin dilaurate and stannous octoate T-9.

7. A method for preparing low temperature resistant neck-protecting memory cotton of any one of claims 1 to 6, which is characterized in that: the preparation method comprises the following preparation steps:

mixing polyether, perfluorohexyl dihydric alcohol, silicone oil, hydroxyl silicone oil, a pore-forming agent, a catalyst, water and the like, and stirring uniformly; and adding toluene diisocyanate, and stirring for reaction to obtain the low-temperature-resistant neck-protecting memory cotton.