Method for reducing smell of polyether modified silicone oil, polyether modified silicone oil and application

Abstract

The invention discloses a method for reducing smell of polyether modified silicone oil, which comprises the following steps: uniformly mixing polyether modified silicone oil with an acidic material and dodecylbenzene sulfonic acid, and heating for reaction; and extracting under negative pressure by using inert gas as extraction gas to obtain the purified polyether modified silicone oil. According to the method for reducing the odor of the polyether modified silicone oil, the odor of the polyether modified silicone oil is effectively reduced, meanwhile, the physical performance of soft polyurethane foam is not affected, and the odor performance of the product is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyether modified silicone oil, and specifically relates to a method for reducing the odor of polyether modified silicone oil, the purified polyether modified silicone oil obtained by the method, and the application of the polyether modified silicone oil in polyurethane materials, especially high-resilience materials, which can be used in the fields of furniture cushions, car seats, etc. Background Art

[0002] Polyether siloxane is used as a foam leveler for polyurethane soft foams, and is generally synthesized by reacting hydrogen-containing siloxane and allyl polyether in the presence of a noble metal catalyst such as chloroplatinic acid. However, existing polyether siloxane foam levelers have some unacceptable odors. Summary of the invention

[0003] In view of this, in order to overcome the defects of the prior art, the present invention provides a method for reducing the odor in polyether-modified silicone oil.

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A method for reducing the odor of polyether-modified silicone oil comprises the following steps:

[0006] The polyether modified silicone oil is mixed evenly with the acidic substance and dodecylbenzene sulfonic acid, and the temperature is raised to react;

[0007] An inert gas is used as the extraction gas to perform extraction under negative pressure to obtain purified polyether-modified silicone oil.

[0008] According to some preferred implementation aspects of the present invention, the mass ratio of the polyether-modified silicone oil to the acidic substance and dodecylbenzenesulfonic acid is 1:0.04-0.06:0.02-0.04.

[0009] According to some preferred implementation aspects of the present invention, the acidic substance is hydrochloric acid, and the concentration of the hydrochloric acid is 0.01N-0.1N.

[0010] According to some preferred embodiments of the present invention, the concentration of dodecylbenzenesulfonic acid is 0.01N-0.03N.

[0011] According to some preferred implementation aspects of the present invention, the temperature-raising reaction is carried out at 80-100° C. for 2-5 hours.

[0012] According to some preferred embodiments of the present invention, the mixing and / or reacting is carried out by stirring at a speed of 300-400 rpm.

[0013] According to some preferred embodiments of the present invention, the inert gas is nitrogen.

[0014] According to some preferred implementation aspects of the present invention, the negative pressure is 30-50 mBar.

[0015] According to some preferred embodiments of the present invention, the temperature during the extraction is 110-130°C.

[0016] In some embodiments, the acidic substance and dodecylbenzene sulfonic acid can be first mixed evenly to form a deodorant for reducing the odor of polyether-modified silicone oil, and then the deodorant is mixed with the polyether-modified silicone oil and the temperature is increased to react; an inert gas is used as an extraction gas to perform extraction under negative pressure to obtain a purified polyether-modified silicone oil.

[0017] The present invention also provides a method for preparing a polyurethane material, the method comprising the steps in the method for reducing the odor of polyether-modified silicone oil as described above.

[0018] The present invention also provides a polyether-modified silicone oil obtained by the method for reducing the odor of polyether-modified silicone oil as described above and application of the polyether-modified silicone oil in polyurethane materials.

[0019] Due to the implementation of the above technical scheme, the present invention has the following advantages compared with the prior art: the method for reducing the odor of polyether-modified silicone oil in the present invention effectively reduces the odor of polyether-modified silicone oil, while having no effect on the physical properties of polyurethane soft foam, thereby improving the odor performance of the product. DETAILED DESCRIPTION

[0020] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0021] In the following examples, the commercially available polyether-modified silicone oil is the high-resilience soft foam silicone oil of Aoshijia Material; hydrochloric acid is from Shanghai Lingfeng Chemical Reagent Co., Ltd.; dodecylbenzenesulfonic acid is from Sigma-Aldrich, with a purity of >95%.

[0022] Polyether siloxane is used as a foam leveler for polyurethane soft foams, and is generally synthesized by reacting hydrogen-containing siloxane and allyl polyether in the presence of a noble metal catalyst such as chloroplatinic acid. However, existing polyether siloxane foam levelers themselves have some unacceptable odors. The present invention studies the mechanism of the existence of this odor and finds that this is due to the fact that the odor is caused by the rearrangement of unreacted polyoxyalkylenes remaining in the polyether, and decomposes over time to produce ketones and aldehydes. Specifically, when allyl polyether is used as a polyoxyalkylene and reacts with hydrogen, in the presence of a platinum catalyst, the allyl groups in the siloxane undergo internal rearrangement to form a side reaction, thereby producing propenyl polyether. However, this propenyl polyether does not react with siloxane, so it remains as an impurity in the produced polyether siloxane and exists in the finished product together with the polyether-modified silicone oil; the unreacted allyl polyether also remains in the polyether-modified silicone as an impurity. In addition, the unreacted allyl polyether is gradually isomerized to propenyl polyether under the catalysis of the remaining platinum catalyst.

[0023] When a liquid with a pH value lower than 7 acts on polyether-modified silicone oil containing these impurities, allyl ether is cracked to produce propionaldehyde with an unpleasant odor. In the presence of acidic substances, the reaction rate increases with the decrease of pH value. That is, by treating polyether-modified silicone containing such impurities with a liquid with a pH value lower than 7, this process will produce odorous substances, that is, first fully release the odorous substances, and then by eliminating these substances, the unpleasant odor of polyether-modified silicone can be effectively eliminated or improved.

[0024] The method for purifying the odor of polyether-modified silicone oil of the present invention ensures that the finished product itself has no irritating odor and has no influence on the performance of the foam, thereby improving the odor performance of the final product.

[0025] Specifically, the method for reducing the odor of polyether-modified silicone oil of the present invention comprises the following steps:

[0026] The finished polyether modified silicone oil is mixed with the acidic substance and DBSA (dodecylbenzene sulfonic acid) at a speed of 300-400 rpm, stirred continuously, and reacted at 80-100°C for 2-5 hours. Then, an inert gas is used as an extraction gas at a negative pressure of 30-50 mBar and 110-130°C to obtain a purified polyether silicone oil.

[0027] In some other embodiments, the acidic substance and dodecylbenzene sulfonic acid may be uniformly mixed to form a deodorant for reducing the odor of polyether-modified silicone oil, and then the deodorant is mixed with the polyether-modified silicone oil. The details are as follows:

[0028] The acidic substance and DBSA (dodecylbenzene sulfonic acid) are stirred and mixed at a speed of 300-400 rpm to form a deodorant, and then the deodorant is mixed with the finished polyether modified silicone oil, continuously stirred, and reacted at 80-100°C for 2-5 hours. Then, an inert gas is used as an extraction gas to extract at a negative pressure of 30-50mBar and 110-130°C to obtain a purified polyether silicone oil.

[0029] The mass ratio of the polyether modified silicone oil to the acidic substance and dodecylbenzene sulfonic acid is 1:0.04-0.06:0.02-0.04. The acidic substance is preferably hydrochloric acid, and the concentration of the hydrochloric acid is 0.01N-0.1N; the concentration of the dodecylbenzene sulfonic acid is 0.01N-0.03N.

[0030] Embodiment 1

[0031] Add 1000 g of polyether-modified silicone oil into a flask, followed by 4% of the weight of the silicone oil in 0.1 N hydrochloric acid and 3% of 0.01 N DBSA, and heat to 90°C at 350 rpm with stirring. After reacting for 5 hours, start using nitrogen as the extraction gas, extract at 120°C at a pressure of 50 mBar to obtain purified polyether-modified silicone oil.

[0032] Embodiment 2

[0033] Add 1000 g of polyether-modified silicone oil into a flask, followed by 5% by weight of 0.05 N hydrochloric acid and 2% by weight of 0.02 N DBSA, and heat to 90° C. at 300 rpm with stirring. After reacting for 5 hours, start using nitrogen as the extraction gas at a pressure of 40 mBar and extraction at 130° C. to obtain purified polyether-modified silicone oil.

[0034] Embodiment 3

[0035] Add 1000 g of polyether-modified silicone oil into a flask, followed by 6% by weight of 0.01 N hydrochloric acid and 3% by weight of 0.02 N DBSA, stir at 350 rpm and heat to 80°C. After reacting for 5 hours, start using nitrogen as the extraction gas at a pressure of 40 mBar and extraction at 110°C to obtain purified polyether-modified silicone oil.

[0036] Embodiment 4

[0037] Add 1000 g of polyether-modified silicone oil into a flask, followed by 5% by weight of 0.01 N hydrochloric acid and 4% by weight of 0.03 N DBSA, stir at 400 rpm and heat to 100 ° C. After reacting for 2 hours, start using nitrogen as the extraction gas, extract at 30 mBar pressure and 120 ° C to obtain purified polyether-modified silicone oil.

[0038] Comparative Example 1

[0039] This comparative example is a commercially available polyether-modified silicone oil.

[0040] Comparative Example 2

[0041] The difference between the purified polyether-modified silicone oil in this comparative example and that in Example 1 is that in this comparative example, only hydrochloric acid is used to purify the polyether-modified silicone oil, and dodecylbenzenesulfonic acid is not added. The remaining steps and parameters are basically the same as those in Example 1.

[0042] Comparative Example 3

[0043] The difference between the purified polyether-modified silicone oil in this comparative example and that in Example 1 is that in this comparative example, only dodecylbenzenesulfonic acid is used to purify the polyether-modified silicone oil, and no hydrochloric acid is added. The remaining steps and parameters are basically the same as those in Example 1.

[0044] Comparative Example 4

[0045] The difference between the purified polyether-modified silicone oil in this comparative example and Example 1 is that after the polyether-modified silicone oil is purified by hydrochloric acid and dodecylbenzenesulfonic acid in this comparative example, there is no step of extracting with inert gas. The remaining steps and parameters are basically the same as those in Example 1.

[0046] Results Test

[0047] 1) The polyether-modified silicone oils prepared in the examples and comparative examples were subjected to odor evaluation, with reference to Volkswagen's PV3900 standard: three temperature conditions were used, and dry and wet conditions were compared. The evaluation conditions were as follows:

[0048]

[0049] The results are shown in Table 1:

[0050] Table 1 Results of odor evaluation

[0051]

[0052] The results in Table 1 show that Example 3 has the best comprehensive performance in terms of dry and wet odors, while Example 4 has the second best comprehensive performance in terms of dry and wet odors, but all of the examples are improved over the comparative examples. Therefore, using hydrochloric acid in combination with dodecylbenzenesulfonic acid to purify the polyether-modified silicone oil and using an inert gas such as nitrogen as an extraction gas can significantly improve the dry and wet odor performance of the polyether-modified silicone oil.

[0053] 2) The polyether-modified silicone oil prepared in the example was applied to polyurethane foam. The material was weighed into a stirring kettle, stirred at 25°C at a stirring speed of 2100 rpm / min for 5 seconds, and poured into a foaming box until the reaction was completed. The bubble jumping time was recorded to obtain a high-resilience polyurethane foam material. The formula of the polyurethane foam is as follows:

[0054] Table 2 Polyurethane foam formula (parts by weight)

[0055] Voranol4701 210 CHPH-30 90 water 8 Silicone oil 2 A-33 0.36 T-9 0.39 DEOA 5.2 T-80 112

[0056] Among them, Voranol 4701 comes from Dow Chemical, CHP H-30 comes from Changhua Chemical, A-33 and T-9 come from Jiangsu Aoshijia Material Technology Co., Ltd., DEOA comes from BASF, and T-80 comes from Covestro. The silicone oil is the silicone oil prepared in the examples or comparative examples. The standard sample is comparative example 1, and its silicone oil is a commercially available polyether-modified silicone oil from Jiangsu Aoshijia Material Technology Co., Ltd.

[0057] The prepared polyurethane foam material was tested for density according to the national standard GB6343-1995; the sample resilience was tested according to the national standard GB / T6770-2008 for soft polyurethane foam plastics; the sample depression hardness was tested according to the national standard GB / T10807-2006 B method for soft polyurethane foam plastics; the value of 65% depression hardness divided by 25% depression hardness was taken as the comfort factor; the sample foam odor was tested according to the VDA270 odor test reference standard (Chinese); the results are shown in Table 3:

[0058] Table 3 Test results of polyurethane foam

[0059] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Jump bubble time / s 190 189 186 184 185 183 185 182 <![CDATA[Density / (Kg / m 3 )]]> 35.6 35.2 34.8 34.9 35.3 35.3 35.6 34.7 Rebound / % 51 52 53 52 53 52 52 52 25% indentation hardness / N 89 90 92 91 91 89 89 91 65% indentation hardness / N 247 254 263 257 255 253 253 258 Comfort Factor 2.78 2.82 2.86 2.82 2.8 2.84 2.82 2.83 Foam smell 4 4 3 3.5 4.5 4.5 4.5 4

[0060] The results in Table 3 show that Examples 1, 2, 3, and 4 use hydrochloric acid and dodecylbenzene sulfonic acid to purify the polyether-modified silicone oil, and use inert gases such as nitrogen as extraction gas to improve the odor performance of the high-resilience sponge to a certain extent. At the same time, the data on the rebound rate, depression hardness, and comfort factor of the materials obtained in the Examples and Comparative Examples show that, compared with the standard sample (Comparative Example 1), the physical properties of the soft high-resilience polyurethane foams prepared in the four Examples are basically consistent with those of the standard sample (Comparative Example 1), indicating that the deodorization process does not change the application performance of the polyether-modified silicone oil and does not affect the original application formula process.

[0061] The present invention uses a deodorant formed by mixing dilute hydrochloric acid and DBSA in polyether-modified silicone oil, and applies a nitrogen blast extraction process, thereby effectively reducing the odor of the polyether-modified silicone oil, while having no effect on the physical properties (rebound, hardness, etc.) of the polyurethane soft foam, thereby improving the performance quality of the product.

[0062] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for reducing the odor of polyether-modified silicone oil, characterized in that: The steps include: Mix the polyether modified silicone oil, hydrochloric acid and dodecylbenzene sulfonic acid evenly and heat to react; An inert gas is used as the extraction gas to perform extraction under negative pressure to obtain purified polyether-modified silicone oil.

2. The method according to claim 1, characterized in that The mass ratio of the polyether modified silicone oil to hydrochloric acid and dodecylbenzenesulfonic acid is 1:0.04-0.06:0.02-0.

04.

3. The method according to claim 1, characterized in that The concentration of the hydrochloric acid is 0.01N-0.1N.

4. The method according to claim 1, characterized in that: The concentration of the dodecylbenzenesulfonic acid is 0.01N-0.03N.

5. The method according to claim 1, characterized in that: The temperature-raising reaction is carried out at 80-100° C. for 2-5 hours.

6. The method according to claim 1, characterized in that The mixing and / or reaction is carried out by stirring at a speed of 300-400 rpm.

7. The method according to claim 1, characterized in that The inert gas is nitrogen.

8. The method according to claim 1, characterized in that: The negative pressure is 30-50 mBar.

9. The method according to claim 1, characterized in that: The temperature during the extraction is 110-130°C.

10. A polyether-modified silicone oil obtained by the method for reducing the odor of polyether-modified silicone oil according to any one of claims 1 to 9.

11. A method for preparing a polyurethane material, characterized in that: The preparation method comprises the steps of the method for reducing the odor of polyether-modified silicone oil as described in any one of claims 1 to 9.

12. Use of the polyether-modified silicone oil as claimed in claim 10 in polyurethane materials.

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