A polyurethane flexible foam composition, a polyurethane flexible foam and a process for the preparation thereof

Abstract

The application provides a polyurethane soft foam composition, a polyurethane soft foam and a preparation method thereof. The polyurethane soft foam composition comprises a first component and a second component, the first component comprises the following components in mass fraction: 85-100 parts of a polyol, 1-20 parts of a borate ester, 1-2 parts of a polyether modified silicone oil, 0.1-0.5 parts of a first amine catalyst, 0.05-0.2 parts of a second amine catalyst and 1-5 parts of water; the second component comprises an isocyanate, and the isocyanate index of the polyurethane soft foam composition is 90-100. Through the design of the polyurethane soft foam composition formula, especially through the synergistic effect of the borate ester and other component materials, the mechanical properties and the flame retardant properties of the polyurethane soft foam are improved.

Description

Technical Field

[0001] This invention relates to a polyurethane flexible foam composition, polyurethane flexible foam, and a method for preparing the same. Background Technology

[0002] Polyurethane foam is a high-molecular polymer made from isocyanate and polyether polyol as the main raw materials, mixed and foamed using specialized equipment under the action of foaming agents, catalysts, and other additives. Flexible polyurethane foam (polyurethane flexible foam) is a particularly important type of polyurethane material, possessing excellent resilience and load-bearing capacity, and is widely used in furniture cushioning, sound insulation, filtration, and lining materials. Ordinary "flexible foam" has a low limiting oxygen index and is flammable, requiring flame-retardant treatment.

[0003] Traditional flame retardants include halogenated flame retardants and phosphate ester flame retardants. Halogenated flame retardants produce dense smoke after combustion, posing a threat to health and safety. Phosphate ester flame retardants have inherent defects that affect the performance of flexible foams, and they also have some unpleasant odors. In addition, these flame retardants often only improve flame retardancy and do not contribute to the improvement of mechanical properties. As the applications of polyurethane flexible foam continue to expand, there is a growing demand for superior mechanical and flame retardant properties. Summary of the Invention

[0004] The purpose of this invention is to provide a polyurethane flexible foam composition with excellent mechanical properties and good stability, a polyurethane flexible foam, and a method for preparing the same.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A polyurethane flexible foam composition comprising a first component and a second component, wherein the first component comprises the following materials in parts by weight:

[0007] 85-100 parts of polyols

[0008] 1-20 parts of borate ester,

[0009] 1-2 parts of polyether-modified silicone oil,

[0010] 0.1–0.5 parts of the first amine catalyst,

[0011] 0.05–0.2 parts of the second amine catalyst,

[0012] 1-5 parts water;

[0013] The second component includes isocyanate, and the isocyanate index of the polyurethane flexible foam composition is 90 to 100.

[0014] Preferably, the mass ratio of the borate ester to the polyol is (0.05-0.15):1.

[0015] Furthermore, the mass ratio of the borate ester to the polyol is (0.1 to 0.15):1, for example, 0.1:1, 0.11:1, 0.12:1, 0.13:1, 0.14:1, 0.15:1, etc.

[0016] In some embodiments, the first component comprises the following parts by mass:

[0017] 100 parts of polyols

[0018] 5-20 parts of borate ester,

[0019] 1-2 parts of polyether-modified silicone oil,

[0020] 0.1–0.5 parts of the first amine catalyst,

[0021] 0.05–0.2 parts of the second amine catalyst,

[0022] 1 to 5 parts water.

[0023] More preferably, the first component comprises the following parts by mass of material:

[0024] 100 parts of polyols

[0025] 10-18 parts of borate ester,

[0026] 1-2 parts of polyether-modified silicone oil,

[0027] 0.1–0.5 parts of the first amine catalyst,

[0028] 0.05–0.2 parts of the second amine catalyst,

[0029] 1 to 5 parts water.

[0030] Preferably, the borate ester is prepared by reacting boric acid with glycerol in the presence of a catalyst and a solvent. The borate ester prepared by this invention has virtually no unpleasant odor, and it not only improves the flame retardant properties of polyurethane flexible foam, but also improves the tensile and tear properties of the foam, and increases the hardness of the foam to a certain extent, thereby improving the overall performance of polyurethane flexible foam.

[0031] Preferably, the molar ratio of boric acid to glycerol is 1:(2-3.3), more preferably 1:(2-2.5), such as 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4 or 1:2.5, etc.

[0032] Preferably, the catalyst is selected from one or more of sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and phosphoric acid.

[0033] Furthermore, the mass of the catalyst fed accounts for 1 to 2% of the total mass of the boric acid and the glycerol, for example, 1%, 1.2%, 1.4%, 1.6%, 1.8% or 2%.

[0034] Preferably, the solvent includes toluene and / or xylene.

[0035] Furthermore, the mass of the solvent used accounts for 30-70% of the total mass of the boric acid and the glycerol, preferably 30-50%, such as 30%, 35%, 40%, 45% or 50%.

[0036] Preferably, the temperature of the reaction is controlled to be 110-140°C, for example, 110°C, 115°C, 120°C, 125°C, 130°C or 140°C.

[0037] Preferably, the reaction time is controlled to be 1 to 6 hours, more preferably 3 to 6 hours, such as 3 hours, 4 hours, 5 hours or 6 hours.

[0038] Preferably, the water produced in the reaction system is removed during or after the reaction.

[0039] Furthermore, water generated in the reaction system is removed during the reaction. By removing water generated in the reaction system during the reaction process, the reaction proceeds in the forward direction.

[0040] Preferably, after the reaction is completed, the catalyst and / or solvent in the reaction system are removed. Methods for removing the solvent include, but are not limited to, vacuum distillation; methods for removing the catalyst include, but are not limited to, adding a base to react with the catalyst.

[0041] Preferably, the first amine catalyst is a gel-type catalyst triethylenediamine or a solution thereof, such as A-33.

[0042] Preferably, the second amine catalyst is dimethylethanolamine, such as DMEA.

[0043] Preferably, the polyether-modified silicone oil is selected from Auschwitz UF-5840 and / or Auschwitz UF-5786.

[0044] Furthermore, when the polyether-modified silicone oil is Auscar UF-5840 and Auscar UF-5786, the mass ratio of Auscar UF-5840 and Auscar UF-5786 is (1-3):1, preferably (1.5-2.5):1, for example 1.5:1, 1.8:1, 2:1, 2.3:1, 2.5:1, etc.

[0045] Preferably, the polyol comprises a first polyether polyol, a second polyether polyol, and a third polyether polyol, wherein the first polyether polyol is a polyether triol with a hydroxyl value of 30-45 mgKOH / g, the second polyether polyol is a polyether triol with a hydroxyl value of 20-30 mgKOH / g, and the third polyether polyol is a slow-rebound polyether with a hydroxyl value of 120-400 mgKOH / g.

[0046] Further, the mass ratio of the first polyether polyol, the second polyether polyol, and the third polyether polyol is (2-3):(0.5-1.5):1, more preferably (2.25-2.75):(0.8-1.2):1, for example 2.25:0.8:1, 2.25:1:1, 2.25:1.2:1, 2.5:0.8:1, 2.5:1:1, 2.5:1.2:1, 2.75:0.8:1, 2.75:1:1, 2.75:1.2:1, etc.

[0047] In some specific embodiments, the first component comprises the following parts by mass:

[0048] 45-55 parts of the first polyether polyol

[0049] 20-25 parts of the second polyether polyol

[0050] 15-20 parts of the third polyether polyol

[0051] 5-15 parts of borate ester,

[0052] UF-5840 0.7 to 1 part,

[0053] UF-5786 0.3-0.5 parts,

[0054] 0.1–0.5 parts of the first amine catalyst,

[0055] 0.05–0.2 parts of the second amine catalyst,

[0056] 1 to 5 parts water.

[0057] Preferably, the isocyanate includes one or more of toluene diisocyanate, diphenylmethane-4,4′-diisocyanate, and polymethylene polyphenyl polyisocyanate.

[0058] A second object of the present invention is to provide a polyurethane flexible foam prepared from the polyurethane flexible foam composition described above.

[0059] A third objective of this invention is to provide a method for preparing polyurethane flexible foam as described above, wherein the method comprises mixing and foaming a polyol, borate ester, polyether-modified silicone oil, a first amine catalyst, a second amine catalyst, and water in a first component with an isocyanate in a second component to obtain the polyurethane flexible foam.

[0060] Preferably, the mixing and foaming are carried out at 15–30°C.

[0061] Preferably, the preparation method includes mixing the polyol, borate ester, polyether-modified silicone oil, first amine catalyst, second amine catalyst and water in the first component with the isocyanate in the second component, and then pouring the mixture into a foaming box for reaction, controlling the stirring speed to be 1500-2500 rpm / min and the time to be 2-10 s.

[0062] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0063] This invention improves the mechanical and flame-retardant properties of polyurethane flexible foam by designing a polyurethane flexible foam composition, especially by leveraging the synergistic effect of borate esters and other components. Detailed Implementation

[0064] Unless otherwise stated, implied from the context, or as is customary in the art, all copies and percentages in this application are based on quality.

[0065] The terms “comprising,” “including,” “having,” and their derivatives do not exclude the presence of any other components, steps, or processes, regardless of whether such other components, steps, or processes are disclosed in this application. To eliminate any doubt, unless expressly stated otherwise, all compositions using the terms “comprising,” “including,” or “having” in this application may contain any additional additives, excipients, or compounds. Conversely, except for those necessary for operational performance, the term “substantially constitutes…” excludes any other components, steps, or processes described below with respect to that term. The term “consisting of…” does not include any components, steps, or processes not specifically described or listed. Unless expressly stated otherwise, the term “or” refers to the individual members listed or any combination thereof.

[0066] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0067] Weigh the materials according to Table 1 below into a mixing vessel, stir at 2100 rpm / min for 5 seconds at 25°C, pour into a foaming box until the reaction is complete, record the foaming time, and the polyurethane foam is obtained.

[0068] Table 1

[0069] Components / parts by weight Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polyether polyol 3602 165 150 135 180 165 165 Polymer polyol 3630 60 60 60 60 60 60 Slow rebound polyether 307 60 60 60 60 60 60 Boric acid compounds 15 30 45 0 15 15 water 8.6 8.6 8.6 8.6 8.6 8.6 UF-5840 2.4 2.4 2.4 2.4 2.4 2.4 UF-5786 1.2 1.2 1.2 1.2 — 1.2 UF-5766 — — — — 1.2 — A-33 1.2 1.2 1.2 1.2 1.2 1.6 DMEA 0.4 0.4 0.4 0.4 0.4 — Isocyanate prepolymer index 95 95 95 95 95 95

[0070] All raw materials used in Table 1 are commercially available. Specifically: Polyether polyol 3602 (polyether triol with a hydroxyl value of 35 mg KOH / g) was purchased from Jiangsu Changhua Polyurethane Technology Co., Ltd.; Polymer polyol 3630 (polyether triol with a hydroxyl value of 22 mg KOH / g) was purchased from Jiangsu Changhua Polyurethane Technology Co., Ltd.; Slow rebound polyether 307 (slow rebound polyether with a hydroxyl value of 240 mg KOH / g) was purchased from Jiangsu Changhua Polyurethane Technology Co., Ltd.; UF-5840 (polyether-modified silicone oil) was purchased from Jiangsu Ausjia Materials Technology Co., Ltd.; and UF-5786 (polyether-modified silicone oil) was purchased from Jiangsu Ausjia Materials Technology Co., Ltd. Purchased from Jiangsu Ausjia Materials Technology Co., Ltd.; UF-5766, low-density expandable silicone oil, purchased from Jiangsu Ausjia Materials Technology Co., Ltd.; A-33, amine catalyst (33% triethylenediamine solution), purchased from Jiangsu Ausjia Materials Technology Co., Ltd.; DEMA, amine catalyst (dimethylethanolamine), purchased from Jiangsu Ausjia Materials Technology Co., Ltd.; Toluene diisocyanate (TDI) was used to adjust the isocyanate index of the system. TDI was purchased from Huntsman Polyurethanes Ltd. The isocyanate prepolymer index = molar ratio of isocyanate to hydroxyl group × 100.

[0071] The boric acid compounds in Table 1 were prepared in-house, and the preparation methods included:

[0072] Add 309 g of boric acid and 920 g of glycerol to a three-necked flask, add 500 ml of xylene, stir and mix thoroughly, then slowly add 10 ml of sulfuric acid. After stirring thoroughly, attach a reflux condenser and water separator, heat to 120 degrees Celsius and reflux for 5 hours, continuously removing the water produced in the reaction, and weigh the water in a timely manner. Stop the reaction, cool down, and remove the solvent (xylene) by vacuum distillation to obtain a yellow, slightly turbid liquid diglyceride borate (i.e., boric acid compound).

[0073] The sample density was tested according to the national standard GB / T 6343-1995; the indentation hardness of the sample was tested according to the national standard GB / T10807-2006B for flexible polyurethane foam; and the flame retardant performance of the polyurethane flexible foam was tested according to the CATB117 California fire retardant standard. The results are shown in Table 2.

[0074] Table 2

[0075] D27 Example 1 Example 2 Example 3 Comparative Example 1 Bubble time / s 156 158 162 151 <![CDATA[Density / (Kg / m 3 )]]> 34.6 34.8 34.7 34.2 25% indentation hardness / N 106 108 109 103 40% indentation hardness / N 170 178 181 161 65% indentation hardness / N 232 245 251 215 Combustion ratio 42％ 35％ 38％ 48％

[0076] Comparative Example 2 showed abnormal foaming, with very large pores and collapsed bubbles, making it unqualified.

[0077] Comparative Example 3 showed significant foam shrinkage and was therefore substandard.

[0078] The solution of the present invention can significantly improve the mechanical properties and flame retardant properties of polyurethane foam. However, with the increase of boric acid compound content, the flame retardant properties of polyurethane foam show a downward trend.

[0079] The present invention has been described in detail above, with the aim of enabling those skilled in the art to understand and implement the invention. However, this description should not be construed as limiting the scope of protection of the invention. All equivalent changes or modifications made in accordance with the spirit and essence of the invention should be included within the scope of protection of the invention.

Claims

1. A polyurethane flexible foam composition, characterized in that: It includes a first component and a second component, wherein the first component comprises the following materials in parts by mass: 85-100 parts of polyols 1-20 parts of borate ester, wherein the borate ester is prepared by reacting boric acid with glycerol in the presence of a catalyst and a solvent, wherein the molar ratio of boric acid to glycerol is 1:(2-3.3). 1-2 parts of polyether-modified silicone oil, wherein the polyether-modified silicone oil is selected from Ausjia UF-5840 and Ausjia UF-5786, and the mass ratio of Ausjia UF-5840 to Ausjia UF-5786 is (1-3):

1. The first amine catalyst is 0.1 to 0.5 parts, and the first amine catalyst is a gel-type amine catalyst, triethylenediamine. The second amine catalyst is 0.05~0.2 parts, and the second amine catalyst is dimethylethanolamine. 1-5 parts water; The second component includes isocyanate, and the isocyanate index of the polyurethane flexible foam composition is 90-100.

2. The polyurethane flexible foam composition according to claim 1, characterized in that: The catalyst is selected from one or more of sulfuric acid, hydrochloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and phosphoric acid, and the mass of the catalyst fed into the reactor accounts for 1 to 2% of the total mass of the boric acid and the glycerol; and / or; The solvent includes toluene and / or xylene, and the mass of the solvent fed into the mixture accounts for 30-70% of the total mass of the boric acid and the glycerol; and / or, The reaction temperature is controlled at 110~140℃, and the time is 1~6h; and / or, During or after the reaction, remove the water produced in the reaction system; and / or, After the reaction is completed, the catalyst and / or solvent in the reaction system are removed.

3. The polyurethane flexible foam composition according to claim 1, characterized in that: The polyols include a first polyether polyol, a second polyether polyol, and a third polyether polyol. The first polyether polyol is a polyether triol with a hydroxyl value of 30-45 mgKOH / g, the second polyether polyol is a polyether triol with a hydroxyl value of 20-30 mgKOH / g, and the third polyether polyol is a slow-rebound polyether with a hydroxyl value of 120-400 mgKOH / g.

4. The polyurethane flexible foam composition according to claim 3, characterized in that: The mass ratio of the first polyether polyol, the second polyether polyol, and the third polyether polyol is (2~3):(0.5~1.5):

1.

5. A polyurethane flexible foam, characterized in that: The polyurethane flexible foam is prepared from the polyurethane flexible foam composition as described in any one of claims 1 to 4.

6. A method for preparing polyurethane flexible foam as described in claim 5, characterized in that: The preparation method includes mixing and foaming the polyol, borate ester, polyether-modified silicone oil, first amine catalyst, second amine catalyst and water in the first component with the isocyanate in the second component to obtain the polyurethane flexible foam.