Preparation method and application of low-ring-body high-viscosity methyl silicone oil

Abstract

The invention relates to a preparation method of low-ring high-viscosity methyl silicone oil, which comprises the following steps: (S1) carrying out condensation polymerization on 100 parts by mass of hydroxyl-terminated polydimethylsiloxane and 1-20 parts by mass of dimethyl silicone oil under the action of 0.001-0.005 part by mass of phosphonitrile chloride catalyst; (S2) adding 0.004-0.015 part of a neutralizing agent, and carrying out a neutralization reaction; the neutralizer is prepared from 10 to 70 weight percent of crown ether substances and the balance of non-polar solvent; and (S3) raising the temperature to remove the low-viscosity methyl silicone oil to obtain the low-ring-body high-viscosity methyl silicone oil. By adopting the neutralizer including crown ether, the defects of unstable viscosity and high ring content caused by the conventional neutralizer are avoided, the low-ring high-viscosity methyl silicone oil with stable viscosity is obtained, and the low-ring high-viscosity methyl silicone oil is suitable for being prepared into shampoo products.

Description

Technical Field

[0001] This invention belongs to the fields of organosilicon technology and daily chemical technology, and specifically relates to a method for preparing low-cyclic, high-viscosity methyl silicone oil and its application in daily chemical products such as shampoos. Background Technology

[0002] The well-known industrial process for producing high-viscosity dimethyl silicone oil generally involves polymerizing D4 or a mixture of dimethyl cyclosiloxanes (DMC) or organosilicon hydrolysates with a methyl end-capping agent (such as hexamethyldisiloxane or low-viscosity dimethyl silicone oil) under the catalysis of potassium hydroxide silanolate or tetramethylammonium hydroxide silanolate. This type of reaction is an equilibrium reaction, and the crude product contains approximately 15% cyclosiloxanes. Further reduction of the dimethyl cyclosiloxane content is required using a thin-film evaporator at high temperatures to obtain a qualified product. This process involves high equipment investment costs. Using linear polymers with methyl end-capping agents (such as 2-1000mm...) 2 Low-viscosity dimethyl silicone oil (e.g., viscosity 450,000–900,000 cp) is produced by polycondensation of low-cyclic, high-viscosity methyl silicone oil under the action of phosphazene chloride catalyst. This process effectively controls the dimethyl cyclic content without the need for a thin-film evaporator, ensuring that the residual D4, D5, and D6 content meets the requirements of the European Commission's formal revision (EC) No. Annex XVII of the 1907 / 2006 (EU REACH Regulation) restricts the use of D4, D5, and D6 in personal care products (0.1% (w / w)). However, for chlorophosphazene catalysts, weak alkali amine compounds such as triethylamine, propylamine, triethylenenonamine, hexamethyldisilazane, hexamethylcyclotrisilazane, and tetramethyldivinylsilazane are generally used as neutralizing agents. The neutralization products are strong acid-weak base salts that remain in the system and have a significant impact on the viscosity stability of high-viscosity methyl silicone oil. After aging (baking) at 85°C for 4 days, its viscosity will decrease significantly, by 20% to 50%; or after storage at 25°C for 6 months, the viscosity will decrease by 20% to 30%.

[0003] The viscosity of methyl silicone oil is positively correlated with the smooth feeling of hair after washing in shampoos made from it. Chu Liling, in her article "Synthesis of Dimethyl Silicone Oil under Microwave Irradiation and its Application in Shampoo," points out that the viscosity of methyl silicone oil used in shampoos should be around 650,000 cp / mm³. 2 Approximately / s.

[0004] In summary, traditional alkaline methods (e.g., using potassium hydroxide silanolate or tetramethylammonium hydroxide silanolate as catalysts) or acid methods (e.g., using phosphazene chloride as catalysts) cannot simultaneously meet the requirements that D4, D5, and D6 are all less than 1000 ppm and that the viscosity does not decrease significantly after aging at 85°C for 4 days without the aid of thin-film evaporation to produce high-viscosity methyl silicone oils.

[0005] Furthermore, regarding high-viscosity methyl silicone oils prepared using alkaline or acidic methods, the resulting shampoos exhibit differences in foam density during the shampooing process. Summary of the Invention

[0006] In view of this, the purpose of this invention is to address the shortcomings of existing technologies for preparing high-viscosity methyl silicone oil by providing a method that does not require a thin-film evaporator. This method involves polycondensation of a low-viscosity linear polymer and a low-viscosity dimethyl silicone oil under the catalysis of phosphazene chloride, followed by neutralization with a novel neutralizing agent. This process produces a high-viscosity methyl silicone oil with stable viscosity, which is then applied to the production of shampoo. The resulting product not only has low D4, D5, and D6 content and high smoothness, but also exhibits stable storage properties.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] A method for preparing a low-cyclic, high-viscosity methyl silicone oil includes the following steps:

[0009] (S1) 100 parts by weight of hydroxyl-terminated polydimethylsiloxane and 1-20 parts by weight of dimethyl silicone oil undergo polycondensation reaction in the presence of 0.001-0.005 parts by weight of chlorophosphazene catalyst.

[0010] (S2) Add 0.004 to 0.015 parts of neutralizing agent to carry out a neutralization reaction; the neutralizing agent is composed of 10-70 wt% of crown ethers and the remaining nonpolar solvent;

[0011] (S3) Heating to remove low cyclicity and obtain low-cyclicity, high-viscosity methyl silicone oil.

[0012] Preferably, in step (S1), the viscosity of the hydroxyl-terminated polydimethylsiloxane is 60-140 mm. 2 / s, preferably 80-110mm 2 / s; Dimethyl silicone oil viscosity is 2~1000mm 2 / s, preferably 5-500mm 2 / s, more preferably 20-100mm 2 / s.

[0013] Preferably, in step (S1), the phosphazene chloride catalyst is selected from [Cl3PNPCl2NPCl]. + One or a combination of PCl6, OCl2NPCl2NPCl2OH, OCl2(NPCl2)2NPCl2OH, OCl2(NPCl2)3NPCl2OH, OCl2PN(H)PCl2O, OCl2P(NPCl2)N(H)PCl2O, and OCl2P(NPCl2)NPCl3, preferably [Cl3PNPCl2NPCl].+ PCl6; phosphazene chloride is used in an amount of 0.001-0.003 parts by weight; dimethyl silicone oil is used in an amount of 1-13 parts by weight, more preferably 1.5-7.5 parts by weight.

[0014] In a preferred embodiment of the present invention, the mass m1 of the hydroxyl-terminated polydimethylsiloxane, the mass m2 of the dimethyl silicone oil, and the viscosity η of the dimethyl silicone oil satisfy the following relationship: The value is 1200-1400 s / mm 2 The preferred value is 1229 to 1334 s / mm. 2 .

[0015] Preferably, in step (S1), the polycondensation temperature is 120-180℃, more preferably 140-160℃; the polycondensation time is 2-6h, more preferably 3-4h; and the reaction gauge pressure is -0.01 to -0.1MPa.

[0016] Preferably, in step (S2), the nonpolar solvent is selected from at least one of toluene, ethyl acetate, petroleum ether, and C6-C15 alkanes, with ethyl acetate being preferred, and the crown ether is selected from at least one of 12-crown ether-4, 15-crown ether-5, 18-crown ether-6, dicyclohexyl-18-crown ether-6, and dibenzo-18-crown ether-6.

[0017] Preferably, in step (S2), the neutralizing agent consists of a crown ether substance at a concentration of 30-50 wt% and the remaining nonpolar solvent.

[0018] Preferably, in step (S2), the amount of neutralizing agent is 0.005 to 0.010 parts by mass; the neutralization reaction is carried out at 120-160°C for 1-10 hours, preferably at 120-140°C for 1-3 hours.

[0019] Preferably, in step (S3), the de-lowering temperature is 150-190℃, more preferably 160-170℃; the de-lowering time is 1-4h, more preferably 1-2h.

[0020] Following the preparation method described above, 450,000–900,000 mm can be obtained. 2 / s High viscosity dimethyl silicone oil with stable viscosity, and the resulting dimethyl silicone oil has a low content of D3-D10 cyclic compounds. Specifically, the content of cyclic D3 is ≤0.0010 wt%, the content of cyclic D4 is ≤0.004 wt%, the content of cyclic D5 is ≤0.01 wt%, the content of cyclic D6 is ≤0.015 wt%, the content of cyclic D7 is ≤0.05 wt%, the content of cyclic D8 is ≤0.06 wt%, the content of cyclic D9 is ≤0.08 wt%, and the content of cyclic D10 is ≤0.1 wt%. Preferably, the content of cyclic D3 is ≤0.0006 wt%, the content of cyclic D4 is ≤0.0029 wt%, the content of cyclic D5 is ≤0.0098 wt%, the content of cyclic D6 is ≤0.0117 wt%, the content of cyclic D7 is ≤0.0361 wt%, the content of cyclic D8 is ≤0.0488 wt%, the content of cyclic D9 is ≤0.0596 wt%, and the content of cyclic D10 is ≤0.0631 wt%.

[0021] The second aspect of the present invention provides the use of the above-mentioned low-cyclic, high-viscosity methyl silicone oil as a raw material for preparing shampoo.

[0022] A third aspect of the present invention provides a shampoo comprising the aforementioned low-cyclic, high-viscosity methyl silicone oil. Preferably, the shampoo contains 0.1-2 wt% of the low-cyclic, high-viscosity methyl silicone oil, more preferably 0.2-1.5 wt%, and even more preferably 0.5-1 wt%.

[0023] The shampoo comprises the following raw materials in parts by weight: 1.8-2.5 parts low-cyclic high-viscosity methyl silicone oil, 18-25 parts ammonium lauryl ether sulfate (AESA), 9-15 parts ammonium dodecyl sulfate (LSA), 25-35 parts cocamidopropyl betaine (CAB), 0.1-2 parts polyquaternium salt, 0.1-2 parts guar hydroxypropyltrimethylammonium chloride, 0.02-0.5 parts pH adjuster, and 180-320 parts water.

[0024] Preferably, the polyquaternary ammonium salt is polyquaternary ammonium salt-10, and the pH adjuster is selected from NaH2PO4 and / or Na2HPO4.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] First, it requires less equipment investment and consumes less energy.

[0027] Without the need for expensive thin-film evaporators, low-viscosity linear polymers and low-viscosity methyl silicone oils are catalytically polycondensed in a batch reactor for 3-4 hours, followed by depolymerization at a lower temperature (160-170℃) for 1-2 hours, and then neutralized with a novel neutralizing agent for 1-2 hours. The resulting high-viscosity methyl silicone oil has D4, D5, and D6 values ​​all below 1000 ppm.

[0028] II. The high-viscosity methyl silicone oil prepared by this invention has stable viscosity.

[0029] When using phosphazene chloride as a catalyst, traditional neutralizing agents are generally weakly basic compounds such as triethylamine, propylamine, triethylenenonamine, hexamethyldisilazane, hexamethylcyclotrisilazane, and tetramethyldivinylsilazane. The resulting high-viscosity methyl silicone oil has poor viscosity stability. After aging (baking) at 85°C for 4 days, its viscosity will decrease significantly, by 20% to 50% (or after storage at 25°C for 6 months, the viscosity will decrease by 20% to 30%). However, by using a new neutralizing agent, this problem can be significantly improved, achieving a viscosity decrease of less than 1% after aging (baking) at 85°C for 4 days (or a viscosity decrease of <0.3% after storage at 25°C for 6 months).

[0030] Third, the high-viscosity methyl silicone oil prepared by this invention, when applied to products such as shampoo and hairspray, exhibits higher foam density. The high-viscosity methyl silicone oil prepared by the acid method of this invention (using phosphazene chloride as a catalyst) has a higher foam density when applied to shampoo compared to the high-viscosity methyl silicone oil prepared by the alkaline method (for example, using potassium hydroxide silanolate or tetramethylammonium hydroxide silanolate as a catalyst). Attached Figure Description

[0031] Figure 1 The performance of shampoos prepared with methyl silicone oil obtained in Examples 1, 1, and 4 is tested.

[0032] Figure 2 The performance of shampoos prepared with methyl silicone oil obtained in Examples 2, 2, and 5 is tested.

[0033] Figure 3 The performance of shampoos prepared with methyl silicone oil obtained in Examples 3, 3, and 6 is tested. Detailed Implementation

[0034] The technical solution of the present invention will be further explained and illustrated below with specific embodiments and comparative examples.

[0035] The raw materials involved in the examples and comparative examples include:

[0036] D4 and DMC (approximately 75 wt% D4, 15 wt% D5, and approximately 10 wt% D6) were purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0037] Linear hydroxyl-terminated polydimethylsiloxane, viscosity 100 mm 2 / s, purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.;

[0038] DM20 methyl end-capping agent, viscosity approximately 20 mm. 2 / s, volatile matter ≤0.3%, purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.;

[0039] DM50 methyl end-capping agent, viscosity approximately 50 mm. 2 / s, volatile matter ≤0.3%, purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.;

[0040] DM100 methyl end-capping agent, viscosity approximately 100 mm. 2 / s, volatile matter ≤0.3%, purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.;

[0041] Chlorinated phosphazene catalyst ([Cl3PNPCl2NPCl)) + PCl6 was purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0042] Potassium hydroxide silyl alkoxide was purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0043] Silicon phosphate ester, purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0044] Tetramethylammonium hydroxide silanol salt was purchased from Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.

[0045] Hexamethyldisilazane, Jiangxi Lanxing Xinghuo Organosilicon Co., Ltd.;

[0046] All other reagents or equipment not specified can be purchased through Changgu's distributors.

[0047] Example 1

[0048] (S1) Add 600g of linear body and 9.76g of DM20 methyl silicone oil to the reactor, heat to 70℃, -0.1MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 150℃, add 0.0122g of phosphazene chloride catalyst, -0.1MPa, and react for 3.5h.

[0049] (S2) Restore normal pressure, add 0.0732g of neutralizing agent, which is a 50% ethyl acetate solution of 18-crown ether-6, and neutralize for 1 hour;

[0050] (S3) Heat to 160℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 504000cp.

[0051] Example 2

[0052] (S1) Add 600g of linear body and 24g of DM50 methyl silicone oil to the reactor, heat to 70℃, -0.1MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 150℃, add 0.0118g of phosphazene chloride catalyst, -0.1MPa, and react for 4h.

[0053] (S2) Restore normal pressure, add 0.08g of neutralizing agent, which is a 45% ethyl acetate solution of 15-crown ether-5, and neutralize for 1 hour;

[0054] (S3) Heat to 165℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 653000cp.

[0055] Example 3

[0056] (S1) Add 600g of linear body and 45g of DM100 methyl silicone oil to the reactor, heat to 70℃, -0.1MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 150℃, add 0.0115g of phosphazene chloride catalyst, -0.1MPa, and react for 4h.

[0057] (S2) Restore normal pressure, add 0.0877g of neutralizing agent, which is a 40% ethyl acetate solution of 12-crown ether-4, and neutralize for 1 hour;

[0058] (S3) Heat to 170℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 882200cp.

[0059] Example 4

[0060] (S1) Add 600g of linear body and 24g of DM50 methyl silicone oil to the reactor, heat to 70℃, -0.1MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 150℃, add 0.0120g of phosphazene chloride catalyst, -0.1MPa, and react for 4h.

[0061] (S2) Restore normal pressure, add 0.082g of neutralizing agent, which is a 40% ethyl acetate solution of dicyclohexyl-18-crown ether-6, and neutralize for 1 hour;

[0062] (S3) Heat to 165℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 687000cp.

[0063] Comparative Example 1

[0064] (S100) Add 600g of DMC and 9.76g of DM20 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 160℃, add 0.325g of 15% potassium hydroxide silanol catalyst, and react for 4h.

[0065] (S200) Add 0.39g of phosphate silanol salt neutralizing agent and neutralize for 1 hour;

[0066] (S300) is heated to 180℃, -0.1MPa, and depressed for 1h to obtain a high viscosity methyl silicone oil with a viscosity of 504300cp.

[0067] Comparative Example 2

[0068] (S100) Add 600g of DMC and 24g of DM50 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 160℃, add 0.325g of 15% potassium hydroxide silanol catalyst, and react for 4h.

[0069] (S200) Add 0.39g of 15.1% phosphate silanol neutralizer and neutralize for 1 hour;

[0070] (S300) Heat to 180℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 650-300cp.

[0071] Comparative Example 3

[0072] (S100) Add 600g of DMC and 45g of DM100 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 160℃, add 0.325g of 15% potassium hydroxide silanol catalyst, and react for 4h.

[0073] (S200) Add 0.39g of 15.1% phosphate silanol neutralizer and neutralize for 1 hour;

[0074] (S300) is heated to 180℃, -0.1MPa, and depressed for 1h to obtain a high viscosity methyl silicone oil with a viscosity of 892300cp.

[0075] Comparative Example 4

[0076] (S1) Add 600g of DMC and 9.76g of DM20 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 110℃, add 1.626g of 3% tetramethylammonium hydroxide silanolate catalyst, and react for 4h.

[0077] (S2) Heat to 150℃ and keep warm for 1 hour;

[0078] (S3) Heat to 180℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 501900cp.

[0079] Comparative Example 5

[0080] (S1) Add 600g of DMC and 24g of DM50 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 110℃, add 1.626g of 3% tetramethylammonium hydroxide silanolate catalyst, and react for 4h.

[0081] (S2) Heat to 150℃ and keep warm for 1 hour;

[0082] (S3) Heat to 180℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 648700cp.

[0083] Comparative Example 6

[0084] (S1) Add 600g of DMC and 45g of DM100 methyl silicone oil to the reactor, heat to 50℃, -0.06MPa, dehydrate for 1h, restore to normal pressure, raise the temperature to 160℃, add 1.626g of 3% tetramethylammonium hydroxide silanolate catalyst, and react for 4h.

[0085] (S2) Heat to 150℃ and keep warm for 1 hour;

[0086] (S3) Heat to 180℃, -0.1MPa, and remove low viscosity for 1 hour to obtain high viscosity methyl silicone oil with a viscosity of 878900cp.

[0087] Comparative Example 7

[0088] The other conditions and operations are the same as in Example 1, except that in step (S2), the neutralizing agent is 0.0366g of hexamethyldisilazane, and a high viscosity methyl silicone oil with a viscosity of 505400cp is finally obtained.

[0089] Comparative Example 8

[0090] The other conditions and operations are the same as in Example 2, except that in step (S2), the neutralizing agent is 0.0360g of hexamethyldisilazane, and a high viscosity methyl silicone oil with a viscosity of 652100cp is finally obtained.

[0091] Comparative Example 9

[0092] The other conditions and operations are the same as in Example 3, except that in step (S2), the neutralizing agent is 0.0351g of hexamethyldisilazane, and a high viscosity methyl silicone oil with a viscosity of 885700cp is finally obtained.

[0093] Comparative Example 10

[0094] The other conditions and operations are the same as in Example 1, except that in step (S2), the neutralizing agent is 0.0366g of hexadecyl dimethyl tertiary amine, and a high viscosity methyl silicone oil with a viscosity of 501800cp is finally obtained.

[0095] Comparative Example 11

[0096] The other conditions and operations are the same as in Example 2, except that in step (S2), the neutralizing agent is 0.0360g of hexadecyl dimethyl tertiary amine, and a high viscosity methyl silicone oil with a viscosity of 651900cp is finally obtained.

[0097] Comparative Example 12

[0098] The other conditions and operations are the same as in Example 3, except that in step (S2), the neutralizing agent is 0.0351g of hexadecyl dimethyl tertiary amine, and a high viscosity methyl silicone oil with a viscosity of 883800cp is finally obtained.

[0099] The product characterization of the above embodiments and comparative examples is shown in Table 1 below. The contents of cyclic compounds D3 to D10 are by mass percentage.

[0100] Table 1. Cyclic content and aging test results of the examples and comparative examples.

[0101]

[0102]

[0103] As can be seen from Table 1, the high-viscosity methyl silicone oil prepared in the examples can simultaneously possess the advantages of low dimethyl cyclic content and stable viscosity after aging (or long-term storage at room temperature).

[0104] Application examples

[0105] Part 1: Hair Strand Test Assessment

[0106] Comparing the shampoos prepared with the high-viscosity methyl silicone oils of the comparative examples and the comparative examples, the proportions of each component in the shampoos were kept constant, as shown in Table 2:

[0107] Table 2. Shampoo component composition

[0108]

[0109] Application testing results:

[0110] Test conditions:

[0111] Undamaged hair strands from Asians were used as samples, each weighing 50g and containing 2g of test shampoo. The hair was washed twice per cycle, for a total of two cycles. The results were evaluated subjectively by an expert panel, with higher scores indicating a better experience.

[0112] The test results of the shampoos corresponding to the high viscosity methyl silicone oils prepared in the examples and comparative examples are shown in Table 3 and... Figure 1-3 As shown, the high-viscosity dimethyl silicone oil prepared using crown ether neutralizers exhibits significant differences in smoothness, dry combing properties, and softness compared to the comparative sample due to its low cyclic content.

[0113] Table 3 Hair Bundle Test

[0114] serial number Smoothness Dry comb Softness fluffiness Gloss Wet comb Example 1 4.25 4.35 4.00 4.30 3.60 3.75 Example 2 4.35 4.35 4.10 4.35 3.65 3.70 Example 3 4.40 4.50 4.30 4.30 3.65 3.70 Example 4 4.38 4.37 4.23 4.32 3.64 3.72 Comparative Example 1 3.70 3.80 3.80 4.35 3.60 3.70 Comparative Example 2 3.80 3.90 3.90 4.30 3.60 3.70 Comparative Example 3 3.95 4.00 3.95 4.35 3.65 3.70 Comparative Example 4 3.75 3.85 3.80 4.30 3.60 3.70 Comparative Example 5 3.85 3.95 3.90 4.35 3.60 3.75 Comparative Example 6 3.90 4.05 3.95 4.30 3.60 3.75

[0115] It can be seen that the hair strand test results of the example are better than those of the comparative example, especially in terms of smoothness, dry combing, and softness.

[0116] Part Two: Foam Performance Testing and Evaluation

[0117] The foaming performance was determined (GB / T 13173.6-91 Determination of foaming power of detergents (Ross-Miles method), and the results are shown in Table 4 below.

[0118] Table 4. Foaming properties of shampoos

[0119]

[0120]

[0121] t max The time when the maximum bubble height occurs;

[0122] V foam max Maximum foam volume.

[0123] As shown in Table 4, the examples exhibit better foaming properties than the comparative examples, reaching maximum foam height in a shorter time and producing a larger maximum foam volume. Richer foam can, to some extent, reduce shampoo usage and lower cleaning costs. Furthermore, the tactile feel of the foam enhances the user experience and improves the absorption of oil and dirt from the scalp and hair. The physical friction of the foam also improves cleaning efficiency. This is consistent with... Figure 1-3 The data matches.

Claims

1. A method for preparing a low-cyclic, high-viscosity methyl silicone oil, characterized in that, Includes the following steps: (S1) 100 parts by weight of hydroxyl-terminated polydimethylsiloxane and 1-20 parts by weight of dimethyl silicone oil undergo polycondensation reaction in the presence of 0.001-0.005 parts by weight of chlorophosphazene catalyst. (S2) Add 0.004 to 0.015 parts of neutralizing agent to carry out a neutralization reaction; the neutralizing agent is composed of 10-70 wt% of crown ethers and the remaining nonpolar solvent; (S3) Heating to remove low cyclicity and obtain low-cyclicity, high-viscosity methyl silicone oil.

2. The preparation method according to claim 1, characterized in that, In step (S1), the viscosity of the hydroxyl-terminated polydimethylsiloxane is 60-140 mm. 2 / s, preferably 80-110mm 2 / s; Dimethyl silicone oil viscosity is 2~1000mm 2 / s, preferably 5-500mm 2 / s, more preferably 20-100mm 2 / s.

3. The preparation method according to claim 1, characterized in that, In step (S1), the phosphazene chloride catalyst is selected from [Cl3PNPCl2NPCl]. + One or a combination of PCl6, OCl2NPCl2 NPCl2OH, OCl2(NPCl2)2NPCl2OH, OCl2(NPCl2)3NPCl2OH, OCl2PN(H)PCl2O, OCl2P(NPCl2)N(H)PCl2O, and OCl2P(NPCl2)NPCl3, preferably [Cl3PNPCl2NPCl]. + PCl6; phosphazene chloride dosage of 0.001-0.003 parts by weight; and / or The amount of dimethyl silicone oil used is 1-13 parts by weight, more preferably 1.5-7.5 parts by weight.

4. The preparation method according to claim 1, characterized in that, In step (S1), the mass m1 of hydroxyl-terminated polydimethylsiloxane, the mass m2 of dimethyl silicone oil, and the viscosity η of dimethyl silicone oil satisfy the following relationship: m1: The value is 1200-1400 s / mm 2 The preferred value is 1229 to 1334 s / mm. 2 .

5. The preparation method according to claim 1, characterized in that, In step (S1), the polycondensation temperature is 120-180℃, preferably 140-160℃; the polycondensation time is 2-6h, preferably 3-4h; and the reaction gauge pressure is -0.01 to -0.1MPa.

6. The preparation method according to claim 1, characterized in that, In step (S2), the nonpolar solvent is selected from at least one of toluene, ethyl acetate, petroleum ether, and C6-C15 alkanes, preferably ethyl acetate, and the crown ether is selected from at least one of 12-crown ether-4, 15-crown ether-5, 18-crown ether-6, dicyclohexyl-18-crown ether-6, and dibenzo-18-crown ether-6; Preferably, the neutralizing agent consists of 30-50 wt% of a crown ether and the remainder of a nonpolar solvent.

7. The preparation method according to claim 1, characterized in that, In step (S2), the amount of neutralizing agent used is 0.005–0.010 parts by mass; the neutralization reaction is carried out at 120–160°C for 1–10 hours, preferably at 120–140°C for 1–3 hours; and / or In step (S3), the de-lowering temperature is 150-190℃, preferably 160-170℃; the de-lowering time is 1-4h, preferably 1-2h.

8. The preparation method according to claim 1, characterized in that, The viscosity of low-cyclic, high-viscosity methyl silicone oil is 450,000–900,000 mm. 2 / s; and the content of cyclic D3 is ≤0.0010wt%, the content of cyclic D4 is ≤0.004wt%, the content of cyclic D5 is ≤0.01wt%, the content of cyclic D6 is ≤0.015wt%, the content of cyclic D7 is ≤0.05wt%, the content of cyclic D8 is ≤0.06wt%, the content of cyclic D9 is ≤0.08wt%, and the content of cyclic D10 is ≤0.1wt%.

9. The use of the low-cyclic, high-viscosity methyl silicone oil prepared by the preparation method according to any one of claims 1-8 as a raw material for preparing shampoo.

10. A shampoo comprising a low-cyclic, high-viscosity methyl silicone oil prepared by the preparation method according to any one of claims 1-8; preferably, the low-cyclic, high-viscosity methyl silicone oil in the shampoo contains 0.1-2 wt% by mass, more preferably 0.2-1.5 wt%, and more preferably 0.5-1 wt%.

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