CN115490905B

CN115490905B - Foam stabilizer for ultra-low density soft foam and preparation method thereof

Info

Publication number: CN115490905B
Application number: CN202211198079.4A
Authority: CN
Inventors: 林斌
Original assignee: Shandong Sider New Material Technology Co ltd
Current assignee: Shandong Sider New Material Technology Co ltd
Priority date: 2022-09-29
Filing date: 2022-09-29
Publication date: 2023-08-25
Anticipated expiration: 2042-09-29
Also published as: CN115490905A

Abstract

The application relates to the technical field of foam stabilizer preparation, and particularly discloses a foam stabilizer for ultra-low density soft foam and a preparation method thereof. The foam stabilizer for the ultra-low density soft foam comprises the following components in parts by weight: 28-32 parts of organosilicon surfactant, 7-9 parts of modified silicon dioxide and 8-10 parts of modified porous microspheres, wherein the organosilicon surfactant is prepared from raw materials including allyl end-capped polyether and hydrogen-containing silicone oil through an addition reaction, the modified silicon dioxide is silicon dioxide powder with hydroxyl grafted on the surface, the components of the modified porous microspheres comprise cell template agent and chitosan, and the components of the cell template agent comprise hydroxyapatite. The application is helpful to form the foam stabilizer with higher foaming effect and stable cell structure through the synergistic effect of the organosilicon surfactant, the modified silicon dioxide and the modified porous microspheres.

Description

Foam stabilizer for ultra-low density soft foam and preparation method thereof

Technical Field

The application relates to the technical field of foam stabilizer preparation, in particular to a foam stabilizer for ultra-low density soft foam and a preparation method thereof.

Background

The polyurethane soft foam is a kind of soft polyurethane foam plastic with certain elasticity. The polyurethane soft foam is of an open-cell structure, has the functions of low density, good elasticity, sound absorption and the like, and is widely used for cushion materials, filtering materials, sound insulation materials, shockproof materials and the like. The foam stabilizer is a key auxiliary agent in the process of forming the polyurethane soft foam, and the foam stabilizer can be regulated to ensure that the foam is uniform and stable, thereby being beneficial to obtaining the polyurethane soft foam with lower foam density.

In the related art, a foam stabilizer for ultra-low density flexible foam comprises the following components in parts by weight: 4g of allyl alcohol, 30g of ethylene oxide, 50g of propylene oxide, 0.3g of potassium hydroxide, 8g of hexamethyldisiloxane, 50g of octamethyl cyclotetrasiloxane, 3g of high hydrogen silicone oil, 0.2g of sulfuric acid and 5mg of noble metal catalyst. The foam stabilizer for ultra-low density flexible foam in the related art is prepared as follows: (1) Mixing allyl alcohol, ethylene oxide and propylene oxide, and heating under the action of potassium hydroxide to obtain allyl end capped polyether; (2) Mixing hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high hydrogen silicone oil, and heating under the action of sulfuric acid to obtain hydrogen silicone oil; (3) 8g of allyl end-capped polyether, 6g of hydrogen-containing silicone oil and 50g of toluene are mixed and heated, an addition reaction is carried out under the action of a platinum catalyst, and the mixture is condensed, refluxed and distilled to obtain the foam stabilizer for the ultra-low density soft foam.

With respect to the above-mentioned related art, the inventors believe that the foam stabilizer in the related art has a weak emulsifying effect on isocyanate and combined polyether when mixed, and limits the formation of nuclei in the foaming system, so that the formed foam is easy to deform or collapse, and is unfavorable for forming a uniform and stable cell structure, thus affecting the foam stabilizing effect of the foam stabilizer.

Disclosure of Invention

In the related art, the foam stabilizer with weak emulsification limits the formation of foam nuclei, which is unfavorable for forming uniform and stable cell structures and affects the foam stabilizing effect of the foam stabilizer. In order to improve these drawbacks, the present application provides a foam stabilizer for ultra-low density flexible foam and a method for preparing the same.

In a first aspect, the present application provides a foam stabilizer for ultra-low density flexible foam, which adopts the following technical scheme:

a foam stabilizer for ultra-low density soft foam comprises the following components in parts by weight: 28-32 parts of organosilicon surfactant, 7-9 parts of modified silicon dioxide and 8-10 parts of modified porous microspheres, wherein the organosilicon surfactant is prepared from raw materials including allyl end-capped polyether and hydrogen-containing silicone oil through an addition reaction, the modified silicon dioxide is silicon dioxide powder with hydroxyl grafted on the surface, the components of the modified porous microspheres comprise cell template agent and chitosan, and the components of the cell template agent comprise hydroxyapatite.

By adopting the technical scheme, in the foam stabilizer disclosed by the application, the polyoxyalkylene chain in the allyl-terminated polyether has hydrophilicity, and the polysiloxane chain in the hydrogen-containing silicone oil has hydrophobicity, so that the organosilicon surfactant obtained by the hydrosilylation reaction of the allyl-terminated polyether and the hydrogen-containing silicone oil has amphipathy, the raw materials with large differences in hydrophilicity and hydrophobicity in a foaming system are emulsified into a uniform system, and hydroxyl groups contained in the modified silicon dioxide can undergo nucleophilic addition reaction with a part of isocyanate in the foaming system, so that the emulsification effect of the foam stabilizer is improved under the action of the organosilicon surfactant and the modified silicon dioxide, further the formation of foam cores is promoted, and meanwhile, more foam cores can promote the formation of tiny and uniform foam holes, and more, smaller and uniform foam holes are not easy to collapse. In addition, the hydroxyapatite in the modified porous microsphere has a stable porous structure, the size and the number of foam holes can be controlled in the foaming process, and a uniform and stable foam hole structure is formed, so that the foam stabilizing effect of the foam stabilizer is improved under the combined action of the organosilicon surfactant, the modified silicon dioxide and the modified porous microsphere.

Preferably, the allyl end-capped polyether is prepared by mixing raw materials including allyl alcohol, ethylene oxide and propylene oxide and then carrying out addition reaction under the condition of an alkaline catalyst, wherein the weight ratio of the ethylene oxide to the propylene oxide is (0.6-0.9): 1.

By adopting the technical scheme, in the copolymer of ethylene oxide and propylene oxide, the polyethylene oxide chain segment has hydrophilicity and foamability, the polypropylene oxide chain segment has hydrophobicity and permeability, the surface tension can be reduced, the proportion of the polyethylene oxide chain segment in the allyl end-capped polyether structure can be regulated by optimizing the consumption of ethylene oxide, the hydrophilicity of the organosilicon surfactant can be regulated, the foam stabilizer can play an emulsification role, and more foam cores can be promoted to be formed.

Preferably, the alkaline catalyst is a water-soluble inorganic salt, and the dosage of the water-soluble inorganic salt is 0.1-0.3% of the sum of the weight of allyl alcohol, ethylene oxide and propylene oxide.

By adopting the technical scheme, the consumption of the catalyst is optimized, the reaction rate and the quantity of byproducts in the formation process of the allyl-terminated polyether are regulated, and the allyl-terminated polyether with higher purity is formed, so that more allyl-terminated polyether is grafted into the molecular chain of the organosilicon surfactant, the hydrophilicity of the organosilicon surfactant is improved, and therefore, the emulsification of the foam stabilizer and the formation of foam cores are promoted.

Preferably, the hydrogen-containing silicone oil is prepared by mixing raw materials including hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high hydrogen-containing silicone oil and then carrying out addition reaction under the condition of an acid catalyst, wherein the weight ratio of the hexamethyldisiloxane to the octamethyl cyclotetrasiloxane is (0.1-0.3): 1.

By adopting the technical scheme, the hexamethyldisiloxane is used as the end-capping agent, and the dosage of the hexamethyldisiloxane is optimized, so that the hydrogen-containing silicone oil with higher branching degree is obtained, and after the hydrogen-containing silicone oil with more polysiloxane chains is grafted onto the molecular chain of the organic silicon surfactant, the hydrophobicity of the organic silicon surfactant can be improved, further the emulsification effect of the foam stabilizer can be promoted, and more foam cores are formed.

Preferably, the component of the cell template further comprises a zirconium-based porous framework material.

By adopting the technical scheme, the zirconium-based porous framework material contains more pore structures, the pore structures can regulate the size and the number of formed foam pores, and meanwhile, in a foaming system containing a large amount of water, the zirconium-based porous framework material also has higher structural stability, so that the zirconium-based porous framework material is favorable for forming uniform and stable foam pore structures.

Preferably, amino groups are grafted on the surface of the pore wall of the zirconium-based porous framework material.

By adopting the technical scheme, the existence of the amino group is favorable for electrostatic interaction between the zirconium-based porous framework material and chitosan in the modified porous microsphere, so that the formation of the modified porous microsphere is promoted.

Preferably, the modified porous microsphere is prepared according to the following method:

(1) Mixing water-soluble calcium salt and water, and regulating the pH value by ammonia water to obtain a mixed solution 1; mixing water-soluble phosphate and water, regulating the pH value by ammonia water to obtain a mixed solution 2, dropwise adding the mixed solution 2 into the mixed solution 1, stirring, aging, centrifugally drying, and calcining to obtain hydroxyapatite;

(2) Adding zirconium salt into N, N-dimethylformamide, and stirring to obtain a mixed solution 3; adding an amino terephthalic acid ligand into the mixed solution 3 to obtain a mixed solution 4, heating the mixed solution 4, cooling, and centrifugally drying to obtain a zirconium-based porous framework material;

(3) Adding an emulsifying agent into liquid paraffin and stirring to obtain a mixed solution 5; preparing an acidic solution, adding chitosan into the acidic solution, stirring the acidic solution uniformly, adding the hydroxyapatite prepared in the step (1) and the zirconium-based porous framework material prepared in the step (2) into the acidic solution, and stirring the mixture uniformly to obtain a mixed solution 6; and (3) dropwise adding the mixed solution 6 into the mixed solution 5 under the condition of stirring, adding a curing agent, and centrifugally drying to obtain the modified porous microspheres.

Through adopting above-mentioned technical scheme, in acidic solution, the inside positive charge of taking amino zirconium-based porous framework material, according to electrostatic interaction, the outside of zirconium-based porous framework material can gather more negative charge, and the amino in the chitosan also takes positive charge, the chitosan that takes positive charge combines with the outside zirconium-based porous framework material that takes negative charge under electrostatic interaction this moment, simultaneously, amino in the chitosan can combine with the hydroxyl in the hydroxyapatite under the hydrogen bonding effect, in addition, under the effect of emulsifier and curing agent, can make the combination reinforcing of three, and then help obtaining the more stable modified porous microsphere of structure.

Preferably, the weight ratio of the hydroxyapatite to the zirconium-based porous framework material is 1 (2.5-2.7).

By adopting the technical scheme, the dosage of the zirconium-based porous framework material is optimized, the number of cells contained in the system can be regulated and controlled, and the uniform and stable cell structure can be formed.

In a second aspect, the application provides a preparation method of a foam stabilizer for ultra-low density flexible foam, which adopts the following technical scheme.

A preparation method of a foam stabilizer for ultra-low density soft foam comprises the following steps:

(1) Mixing allyl alcohol, ethylene oxide and propylene oxide, and heating under the action of an alkaline catalyst to obtain allyl end-capped polyether;

(2) Mixing hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high hydrogen silicone oil, and heating under the action of an acid catalyst to obtain hydrogen silicone oil;

(3) Mixing and heating the allyl-terminated polyether prepared in the step (1), the hydrogen-containing silicone oil prepared in the step (2) and a solvent, performing addition reaction under the action of a noble metal catalyst, condensing and refluxing by using the solvent, distilling at normal pressure, and distilling under reduced pressure to obtain the organosilicon surfactant;

(4) And (3) mixing the modified silicon dioxide, the modified porous microspheres and the organic silicon surfactant prepared in the step (3) to obtain the foam stabilizer for the ultra-low density soft foam.

By adopting the technical scheme, the application prepares the organosilicon surfactant with hydrophilic groups and hydrophobic groups through hydrosilylation reaction of allyl end-capped polyether and hydrogen-containing silicone oil under the action of a noble metal catalyst, and then mixes the organosilicon surfactant, modified silicon dioxide and modified porous microspheres, thereby obtaining the foam stabilizer for the ultra-low density soft foam with a relatively stable cell structure.

Preferably, the weight ratio of the allyl-terminated polyether and the hydrogen-containing silicone oil added in the step (3) for preparing the foam stabilizer for the ultra-low density flexible foam is (1.9-2.1): 1.

by adopting the technical scheme, the use amount of the allyl end-capped polyether is optimized, so that the balance of hydrophobicity and hydrophilicity of the organosilicon surfactant is adjusted, the organosilicon surfactant with a strong emulsification effect is formed, the formation of foam cores is promoted, and a strong foam stabilizing effect is achieved.

In summary, the application has the following beneficial effects:

1. according to the application, through the hydrosilylation reaction of allyl end-capped polyether and hydrogen-containing silicone oil, the amphiphilic organosilicon surfactant is obtained, so that the raw materials with large differences of hydrophilicity and hydrophobicity in a foaming system can be emulsified into a uniform system; in addition, the modified silicon dioxide existing in the foam stabilizer can also react with a part of isocyanate, so that the emulsification effect of the foam stabilizer is further improved, and the formation of foam nuclei is facilitated.

2. In the application, hydroxyapatite and zirconium-based porous framework materials are preferably used as foam templates, which are beneficial to regulating the size and the number of foam pores in the foam forming process, so that a uniform and stable foam pore structure is formed.

3. According to the method, the organic silicon surfactant, the modified silicon dioxide and the modified porous microspheres are mixed, so that the emulsification effect of the foam stabilizer is improved, the formation of foam cores is promoted, and a uniform and stable foam structure can be formed.

Detailed Description

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

The raw materials used in the preparation examples of the present application are all commercially available.

Preparation examples of the silicone surfactant are described below by way of example 1.

Preparation example 1

In this preparation example, the silicone surfactant was prepared as follows:

(1) Adding 50g of allyl alcohol, 265g of ethylene oxide and 530g of propylene oxide into a reaction kettle, adding 0.782g of potassium hydroxide catalyst into the reaction kettle, and reacting for 5 hours at the temperature of 110 ℃ under the pressure of 0.5Mpa to obtain allyl end-capped polyether;

(2) Uniformly mixing 45g of hexamethyldisiloxane, 500g of octamethyl cyclotetrasiloxane, 10g of high-hydrogen silicone oil and 3g of sulfuric acid, and reacting at 50 ℃ for 6 hours to obtain hydrogen silicone oil;

(3) Mixing 90g of allyl-terminated polyether prepared in the step (1), 50g of hydrogen-containing silicone oil prepared in the step (2) and 400g of toluene, adding 50mg of chloroplatinic acid into the mixture, reacting at 115 ℃ for 4 hours, heating while opening a toluene reflux condenser, performing normal pressure distillation, performing reduced pressure distillation, cooling and discharging after the toluene is evaporated, and obtaining the organosilicon surfactant.

As shown in Table 1, preparation examples 1 to 5 differ mainly in the amount of ethylene oxide added in the step (1) of synthesizing the silicone surfactant.

TABLE 1

Sample of	Preparation example 1	Preparation example 2	Preparation example 3	Preparation example 4	Preparation example 5
						Ethylene oxide/g	265	318	397.5	477	503.5

As shown in Table 2, preparation examples 6 to 9 differ from preparation example 3 mainly in the amount of potassium hydroxide added in the step (1) of synthesizing the silicone surfactant.

TABLE 2

Sample of	Preparation example 3	Preparation example 6	Preparation example 7	Preparation example 8	Preparation example 9
						Potassium hydroxide/g	0.782	0.9775	1.955	2.9325	3.91

As shown in Table 3, preparation examples 10 to 13 differ from preparation example 7 mainly in the amount of hexamethyldisiloxane added in the step (2) of synthesizing the silicone surfactant.

TABLE 3 Table 3

Sample of	Preparation example 7	Preparation example 10	PREPARATION EXAMPLE 11	Preparation example 12	Preparation example 13
						Hexamethyldisiloxane/g	45	50	100	150	200

As shown in Table 4, preparation examples 14 to 17 differ from preparation example 11 mainly in the amount of allyl-terminated polyether added in step (3) of synthesizing the silicone surfactant.

TABLE 4 Table 4

Sample of	PREPARATION EXAMPLE 11	PREPARATION EXAMPLE 14	Preparation example 15	PREPARATION EXAMPLE 16	Preparation example 17
						Allyl terminated polyether/g	90	95	100	105	110

Preparation example of modified silica

PREPARATION EXAMPLE 18

In this preparation example, the modified silica was prepared as follows:

mixing 19g of silicon dioxide microspheres with 30g of sodium hydroxide solution in a beaker, stirring and heating in a water bath at 80 ℃, reacting for 2 hours, cooling to room temperature, eluting with deionized water to remove residual sodium hydroxide solution, and then drying at 60 ℃ for 12 hours to obtain the modified silicon dioxide.

Preparation example of modified porous microspheres

Preparation example 19

In this preparation example, the modified porous microspheres were prepared according to the following method:

(1) Mixing 10g of calcium nitrate tetrahydrate with 60g of deionized water, and regulating the pH value to 10 by using ammonia water to obtain a mixed solution 1; 8g of diamine hydrogen phosphate and 60g of deionized water are mixed, and the pH value is adjusted to 10 by ammonia water to obtain a mixed solution 2; under the magnetic stirring condition of 40 ℃ and 600r/min, the mixed solution 2 is added into the mixed solution 1 at a constant speed by using a separating funnel, and the stirring reaction is carried out for 1h. After the reaction is finished, performing ultrasonic dispersion for 40min, aging for 24h, centrifuging, washing with deionized water and absolute ethyl alcohol for 3 times respectively, drying at 80 ℃, and calcining the solid at 700 ℃ for 2h to obtain hydroxyapatite;

(2) 5g of zirconium chloride and 850g of N, N-dimethylformamide were mixed to obtain a mixed solution 3; adding 5.8g of amino terephthalic acid to the mixed solution 3 to obtain a mixed solution 4; heating the mixed solution 4 at 120 ℃ for 24 hours, cooling to room temperature, centrifuging with N, N-dimethylformamide, and then transferring the solid to 80 ℃ for drying for 24 hours to obtain a zirconium-based porous framework material;

(3) 65g of liquid paraffin is added into 80g of sorbitan fatty acid ester at 50 ℃ and stirred uniformly to obtain a mixed solution 5; adding 2g of acetic acid into 100g of water, adding 50g of chitosan into the water, stirring, adding 3g of hydroxyapatite and 7.2g of zirconium-based porous framework material, and uniformly stirring to obtain a mixed solution 6; under the condition of stirring, adding the mixed solution 6 into the mixed solution 5 dropwise, stirring for 1h, adding 3g of glutaraldehyde, continuously stirring for 1h, centrifuging, washing 3 times by using isopropanol, petroleum ether and absolute ethyl alcohol respectively, and finally drying at 60 ℃ for 12h to obtain the modified porous microspheres.

As shown in Table 5, preparation examples 19 to 23 are different in the main point that the amounts of the zirconium-based porous matrix material added in the preparation step (3) of the modified porous microspheres are different.

TABLE 5

Examples

Examples 1 to 5

The following description will take example 1 as an example.

Example 1

In this example, a silicone surfactant was prepared according to preparation example 1, and modified porous microspheres were prepared according to preparation example 19.

In this example, the foam stabilizer for ultra-low density flexible foam was prepared as follows:

and uniformly mixing 18g of organosilicon surfactant, 5g of modified silicon dioxide and 7g of modified porous microspheres to obtain the foam stabilizer for the ultra-low density soft foam.

As shown in Table 6, examples 1 to 5 are different in mainly the proportions of the silicone surfactant, the modified silica and the modified porous microspheres.

TABLE 6

Sample of	Silicone surfactant/g	Modified silica/g	Modified porous microsphere/g
				Example 1	25	5	5
Example 2	28	7	8
				Example 3	30	8	9
Example 4	32	9	10
				Example 5	35	10	11

Examples 6-21 differ from example 3 in the preparation of silicone surfactants as shown in Table 7.

TABLE 7

Examples 22-25 differ from example 13 in the preparation of modified porous microspheres as shown in Table 8.

TABLE 8

Sample of	Preparation example of modified porous microspheres
		Example 13	Preparation example 19
Example 22	Preparation example 20
		Example 23	Preparation example 21
Example 24	PREPARATION EXAMPLE 22
		Example 25	Preparation example 23

Comparative example

Comparative example 1

A foam stabilizer for ultra-low density flexible foam is prepared according to the following method: (1) Reacting 40g of allyl alcohol, 200g of ethylene oxide and 400g of propylene oxide under the action of 0.3g of potassium hydroxide at the temperature of 110 ℃ for 5 hours under the pressure of less than or equal to 0.5Mpa to obtain allyl end capped polyether; (2) Uniformly mixing 80g of hexamethyldisiloxane, 500g of octamethyl cyclotetrasiloxane, 30g of high-hydrogen silicone oil and 2g of sulfuric acid, and reacting at 50 ℃ for 6 hours to obtain hydrogen silicone oil; (3) Mixing 20g of allyl end-capped polyether, 6g of hydrogen-containing silicone oil and 500g of toluene, adding 5mg of chloroplatinic acid into the mixture, reacting for 4 hours at 115 ℃, heating while opening a toluene reflux condenser, performing normal pressure distillation, performing reduced pressure distillation, and cooling and discharging after the toluene is evaporated, thus obtaining the foam stabilizer for the ultra-low density soft foam.

Comparative example 2

This comparative example differs from example 3 in that modified silica is not included.

Comparative example 3

This comparative example differs from example 3 in that modified porous microspheres are not included.

Comparative example 4

This comparative example differs from example 3 in that the zirconium-based porous matrix material used in the modified porous microspheres does not contain amino groups.

Performance detection test method

The operation steps are as follows: (1) Foam stabilizers were prepared as in examples 1-25 and comparative examples 1-4; (2) preparing 29 beakers, numbered 1-29 respectively; (3) The operator prepares 29 wooden boxes of 20cm by 21cm, and a square film tube of 21cm by 130cm is sleeved on the wooden boxes for free rising of foam, and the 29 wooden boxes are respectively numbered 30-58; (4) 100g of polyether triol, 150g of water, 0.2g of triethylenediamine and 0.2g of stannous octoate are respectively added into each beaker at the temperature of 25 ℃, 10g of foam stabilizer prepared according to examples 1-25 is sequentially added into No. 1-25 beakers, 10g of foam stabilizer prepared according to comparative examples 1-4 is sequentially added into No. 26-29 beakers, then each beaker is stirred at a high speed for 1min, 18g of auxiliary foaming agent dichloromethane is respectively added into the 29 beakers, stirring is continued for 30s, 60g of isocyanate is respectively added and stirring is continued for 5s, finally the materials in the No. 1-29 beakers are instantly poured into a wooden box of No. 30-58 in sequence for curing, and are taken out after 1.5 days.

1. Foam stabilizer for ultra-low density flexible foam height and drop height analysis immediately after pouring into the wooden barrel, the maximum foam height of the foam in the wooden barrel and the drop height of 5min were observed and recorded, and the relevant data are recorded in table 9.

TABLE 9

2. Cell number analysis of foam stabilizer for ultra-low density flexible foam

The final foam product was cut into a 20cm by 20cm plane, the number of cells per unit length in a 20cm line was measured, and the relevant data were recorded in table 10.

Table 10

As can be seen from the combination of examples 1 to 5, comparative examples 1 and 2 and table 9, the maximum height of the foam measured in examples 1 to 5 is greater than that in comparative examples 1 and 2, and the height of the foam 5min falling back measured in examples 1 to 5 is smaller than that in comparative examples 1 and 2, it is demonstrated that the emulsification degree of the foaming system can be improved by the combined action of the silicone surfactant and the modified silica, and the foam stabilizer with good emulsification effect can promote the formation of more nuclei, thereby facilitating the formation of fine and uniform cells, and the collapse of the foam is less likely to occur due to the more, smaller and more uniform cells, thereby improving the foam stabilizing effect of the foam stabilizer.

It can be seen from a combination of examples 3 and examples 6-9 in combination with Table 9 that the maximum height of the foam measured in example 7 is higher and the height of the foam measured in example 7 falling back for 5 minutes is smaller, indicating that the use of ethylene oxide is preferred to help promote hydrophilicity of the allyl-terminated polyether and thus emulsification of the silicone surfactant, thus improving the formation of cell nuclei and promoting foam stabilizing effect of the foam stabilizer.

As can be seen from a combination of examples 7 and examples 10-13 in combination with Table 9, the maximum height of the foam measured in example 11 is higher and the height of the foam measured in example 11 falling back for 5 minutes is smaller, which indicates that the allyl-terminated polyether with hydrophilicity can be obtained with higher purity by optimizing the amount of the potassium hydroxide catalyst, thereby being beneficial to improving the emulsification of the organosilicon surfactant and promoting the formation of the foam core.

As can be seen from a combination of examples 11 and examples 14-17 in combination with Table 9, the maximum height of the foam measured in example 15 is higher and the height of the foam measured in example 15 falling back for 5 minutes is smaller, indicating that by optimizing the amount of hexamethyldisiloxane, more polysiloxane chains are advantageously grafted with hydrogen containing silicone oil, and therefore, the hydrophobicity of the silicone surfactant is increased, thereby promoting the emulsification of the foam stabilizer.

As can be seen from the combination of example 15 and examples 18-21 and table 9, the maximum height of the foam measured in example 19 is higher, and the height of the foam measured in example 19 falling back for 5min is smaller, which indicates that the use of the preferred allyl-terminated polyether is beneficial to promoting the amphiphilic balance of the organosilicon surfactant, forming the organosilicon surfactant with stronger emulsification, promoting the formation of foam core and achieving stronger foam stabilizing effect.

As can be seen in combination with examples 1-5, comparative example 1 and comparative example 3 and Table 10, the number of cells measured in examples 1-5 is greater than that measured in comparative example 1 and comparative example 3, indicating that the greater pore structure in the modified porous microspheres regulates the size and number of cells, thereby helping to form a uniform and stable cell structure.

As can be seen from the combination of example 3 and comparative example 4 and the table 10, the number of cells measured in example 3 is slightly greater than that measured in comparative example 4, which indicates that the amino groups contained in the zirconium-based porous skeletal material can promote the formation of modified porous microspheres, so that the pore structure formed by the zirconium-based porous skeletal material and the hydroxyapatite is more uniformly distributed in the foaming system, thereby helping to form a uniform cell structure.

As can be seen from the combination of examples 13 and examples 22-25 and table 10, example 23 shows a higher number of cells, which means that the adjustment of the number of nuclei formed in the foam stabilizer by adjusting the ratio of the zirconium-based porous matrix material in the modified porous microspheres is beneficial to obtaining a foam stabilizer having a higher number of cells.

The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims

1. The foam stabilizer for the ultra-low density soft foam is characterized by comprising the following components in parts by weight: 28-32 parts of organosilicon surfactant, 7-9 parts of modified silicon dioxide and 8-10 parts of modified porous microspheres, wherein the organosilicon surfactant is prepared from raw materials including allyl end-capped polyether and hydrogen-containing silicone oil through an addition reaction, the modified silicon dioxide is silicon dioxide powder with hydroxyl grafted on the surface, the components of the modified porous microspheres comprise cell template agent and chitosan, and the components of the cell template agent comprise hydroxyapatite;

the components of the cell template agent further comprise a zirconium-based porous framework material;

amino groups are grafted on the surface of the pore wall of the zirconium-based porous framework material;

the modified porous microsphere is prepared according to the following method:

2. The foam stabilizer for ultra-low density flexible foam according to claim 1, wherein said allyl-terminated polyether is prepared by mixing raw materials including allyl alcohol, ethylene oxide and propylene oxide and then subjecting the mixture to addition reaction in the presence of an alkaline catalyst, and the weight ratio of said ethylene oxide to said propylene oxide is (0.6-0.9): 1.

3. The foam stabilizer for ultra-low density flexible foam according to claim 2, wherein the basic catalyst is a water-soluble inorganic salt, and the amount of the water-soluble inorganic salt is 0.1 to 0.3% of the sum of the weight of allyl alcohol, ethylene oxide and propylene oxide.

4. The foam stabilizer for ultra-low density flexible foam according to claim 1, wherein the hydrogen-containing silicone oil is prepared by mixing raw materials including hexamethyldisiloxane, octamethyl cyclotetrasiloxane and high hydrogen-containing silicone oil and then carrying out addition reaction in the presence of an acidic catalyst, and the weight ratio of the hexamethyldisiloxane to the octamethyl cyclotetrasiloxane is (0.1-0.3): 1.

5. The foam stabilizer for ultra-low density flexible foam according to claim 1, wherein the weight ratio of the hydroxyapatite to the zirconium-based porous skeletal material is 1 (2.5-2.7).

6. The method for producing a foam stabilizer for ultra-low density flexible foam according to any one of claims 1 to 5, comprising the steps of:

7. The method for preparing a foam stabilizer for ultra-low density flexible foam according to claim 6, wherein the weight ratio of allyl-terminated polyether and hydrogen-containing silicone oil added in the step (3) for preparing the foam stabilizer for ultra-low density flexible foam is (1.9-2.1): 1.