Phosphate type quaternary ammonium salt polymer, preparation method and application

Abstract

The invention belongs to the technical field of polymers and application thereof, and particularly relates to a phosphate-type quaternary ammonium salt polymer which is characterized by comprising the following compounds in percentage by mass: 10-20% of 2-methacryloyloxyethyl phosphorylcholine, 10-20% of acrylic acid modified [3-[4-[3-(hydroxymethyl) oxirane-2-yl] butyl-1, 2, 4-triazole-2-yl]-1, 2, 4-triazole-2-yl]-1, 2, 4-triazole-2-yl]-1, 2, 4- The invention discloses a water-soluble adhesive which is prepared from the following components in percentage by weight: 5-15% of 1, 3-dialkynyl] oxirane-2-yl] methanol, 15-25% of ricinoleic acid polyether modified (3-carboxypropyl) trimethyl ammonium chloride and 40-70% of acrylamide. The invention also provides a preparation method and application of the phosphate type quaternary ammonium salt polymer. The phosphate type quaternary ammonium salt polymer disclosed by the invention is soft and good in antistatic property, has moisturizing and conditioning properties, is not easy to remain, and does not influence the foaming property of an anionic surfactant.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymers and their applications, and particularly relates to a phosphate quaternary ammonium salt polymer, a preparation method and an application thereof. Background Art

[0002] Shampoo is the earliest, fastest and most important hair cosmetic among many hair care products. It is mainly composed of surfactants, conditioners, moisturizers, appearance modifiers, as well as fragrances, preservatives, etc. A good shampoo not only has basic functions of removing dirt, dandruff and oil control, but also needs to take into account the softness, combability, fluffiness and dryness of the hair quality after washing.

[0003] The specific surface area of hair is very large. Hair contacts and rubs against each other, making hair prone to generating static electricity (negative charge), which is also the main reason why hair, especially long hair, is easy to knot and difficult to comb. For a long time, the hair care industry has always believed that the hair surface is always negatively charged. To neutralize and shield the negative charge, the conditioners used in shampoos are mostly cationic conditioners. By classifying the known 22 amino acids according to their side chain groups, it is found that among the 13 polar amino acids, 3 amino acids carry positive charges. Thus, it can be determined that the local sites on the hair surface carry positive charges, not all negative charges. Therefore, when choosing hair conditioners, amphoteric conditioners with an appropriate amount of negative charge have better softening and antistatic effects than only cationic conditioners.

[0004] Quaternary ammonium salt cationic conditioners adsorb on the negatively charged hair surface through cationic groups. Long-term use may lead to the accumulation of residues, block hair follicles, cause scalp itching, oiliness, increased dandruff, and even hair loss.

[0005] Chinese Patent CN 104945267 A discloses a cationic quaternary ammonium salt and a preparation method thereof, including the reaction of epichlorohydrin and polyhydroxy compounds under acidic conditions, and then carrying out a quaternization reaction with tertiary amines in a solvent to obtain the cationic quaternary ammonium salt. The cationic quaternary ammonium salt of this patent can simultaneously achieve the functions of a cationic conditioner and a moisturizer, and at the same time solve the problem that moisturizers cannot play a role in wash-off type daily chemical hair care products, providing a new consumer sensory experience for wash-off type daily chemical hair care products; the cationic quaternary ammonium salt of the present invention also has the thickening ability for washing and daily chemical hair care products. However, when the cationic quaternary ammonium salt prepared by this invention is used in combination with anionic surfactants in daily chemical hair care products, it will reduce the foaming performance of the anionic surfactant.

[0006] Based on the above situation, it is necessary to develop a conditioner with good softening and antistatic properties, while having moisturizing and conditioning properties, not easy to leave residues and not affecting the foaming performance of anionic surfactants. Summary of the Invention

[0007] In order to solve the technical problems of the insufficient conditioning, softening and antistatic functions of existing applications and personal care products; the possible accumulation of residues caused by the long-term use of quaternary ammonium cationic conditioners, leading to a series of hair problems; the inability of quaternary ammonium cationic conditioners to have both conditioning and moisturizing effects, and the reduction of the foaming performance of anionic surfactants, the present invention provides a conditioner with good softening and antistatic properties, while having moisturizing and conditioning properties, being not easy to remain and having foaming performance. To achieve the above object, the present invention adopts the following technical solutions:

[0008] A phosphate ester type quaternary ammonium salt polymer, characterized by comprising the following compounds in mass percentages:

[0009] 2-methacryloyloxyethyl phosphorylcholine 10-20%, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol 5-15%, castor oil acid polyether modified (3-carboxypropyl)trimethylammonium chloride 15-25%, acrylamide 40-70%.

[0010] Furthermore, the structural formulas of the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, and castor oil acid polyether modified (3-carboxypropyl)trimethylammonium chloride are respectively:

[0011] 、 and

[0012] wherein, x + y = 20 - 40.

[0013] Furthermore, the preparation method comprises the following steps:

[0014] Step I, synthesize acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol;

[0015] Step II, synthesize castor oil acid polyether modified (3-carboxypropyl)trimethylammonium chloride;

[0016] Step , Dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, and successively add acrylamide and half of dodecyl mercaptan, then stir evenly to prepare monomer solution A; dissolve ricinoleic acid polyether modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, and successively add acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol and the other half of dodecyl mercaptan, then stir evenly to prepare monomer solution B;

[0017] Step , Under the protection of N2, slowly add monomer solution A and monomer solution B to the reaction equipment alternately, the addition time is 2 - 4 h, and at the same time, slowly add potassium persulfate solution dropwise to the reaction equipment, the dropping rate is 3 mL / min - 8 mL / min, control the reaction temperature at 50 °C - 80 °C, after the addition is completed, keep the temperature for 2 - 5 h to obtain the phosphate ester type quaternary ammonium salt polymer.

[0018] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 3wt% - 7wt% of the total amount of monomer solution A and monomer solution B.

[0019] Furthermore, the preparation method of the acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol includes the following steps:

[0020] Under the condition of 70 - 90 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, the dropping time is 40 min - 80 min, after the dropping is completed, raise the temperature to 120 °C - 140 °C, and react for 3 - 8 h to obtain acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol.

[0021] Furthermore, the mass ratio of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride and p-hydroxyanisole is 19:(14 - 17):0.1:0.1.

[0022] Furthermore, the preparation method of the ricinoleic acid polyether modified (3-carboxypropyl) trimethyl ammonium chloride includes the following steps:

[0023] S1. Sequentially add ricinoleic acid and potassium hydroxide into the polymerization reactor. Replace the air with nitrogen three times, stir, and heat up to 100 - 120 °C. After evacuating for 1 h, close the vacuum valve. Slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and simultaneously heat up to 140 - 160 °C. React for 3 h, cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, cool down to 80 °C, and evacuate to obtain polyether of ricinoleic acid.

[0024] S2. Sequentially add polyether of ricinoleic acid and (3 - carboxypropyl) trimethyl ammonium chloride, heat to 50 - 70 °C, stir evenly, slowly add p - toluenesulfonic acid, evacuate, heat up to 120 - 140 °C, react for 4 - 8 h, and close the vacuum valve to obtain polyether of ricinoleic acid modified (3 - carboxypropyl) trimethyl ammonium chloride.

[0025] Further, in S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:(0.06 - 0.1):(15 - 17):(6 - 9), and the relative molecular mass of the polyether of ricinoleic acid is 1200 - 2000.

[0026] Further, in S2, the molar ratio of polyether of ricinoleic acid and (3 - carboxypropyl) trimethyl ammonium chloride is 1:(2.2 - 2.4), and the mass of p - toluenesulfonic acid is 0.3% of the total mass of polyether of ricinoleic acid and (3 - carboxypropyl) trimethyl ammonium chloride.

[0027] Further, the application of the phosphate - type quaternary ammonium salt polymer in personal care.

[0028] The beneficial effects of the present invention are reflected in the following aspects:

[0029] 1. In the present invention, the two epoxy groups on [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol are respectively reacted with acrylic acid to form ester groups and hydroxyl groups, obtaining acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol. This structure has four hydroxyl groups and two ester groups connected to double bonds. The hydroxyl group and carboxyl group on ricinoleic acid are connected with ethylene oxide and propylene oxide to obtain polyether of ricinoleic acid. The hydroxyl group on the polyether of ricinoleic acid undergoes an esterification reaction with the carboxyl group on (3-carboxypropyl)trimethylammonium chloride to obtain ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride. Then, 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride, and acrylamide are polymerized to obtain a phosphate ester type quaternary ammonium salt polymer with a 3D spherical structure.

[0030] 2. The novel phosphate ester type quaternary ammonium salt polymer provided by the present invention contains phosphate ester type quaternary ammonium salts, a large amount of polyethers, and ester groups, has good degradation performance, is not easy to remain, and will not block pores.

[0031] 3. The phosphate ester type quaternary ammonium salt polymer provided by the present invention has both positive and negative charges and is overall positively charged, which can better adsorb to the positive and negative charges on the hair surface to form a protective film, and has better flexibility and antistatic performance than polyquaternary ammonium cations; it has a large number of hydroxyl groups and EOPO chains, and also has good moisturizing properties.

[0032] 4. The phosphate ester type quaternary ammonium salt polymer provided by the present invention contains ester groups, alkynyl groups, long carbon chains of ricinoleic acid, and PO chains with hydrophobicity, and hydroxyl groups, EO chains, quaternary ammonium salts, and phosphate ester type quaternary ammonium salts with hydrophilicity. It has good wettability and does not affect the foaming performance of anions. When used in combination with anionic surfactants, it still has good detergency and foaming properties. Description of the Drawings

[0033] Figure 1 Infrared spectrum of the phosphate ester type quaternary ammonium salt polymer disclosed in the present invention Detailed Embodiments

[0034] To enable those skilled in the art to better understand the technical solution of the present invention and make the above features, objectives, and advantages of the present invention clearer and more understandable, the present invention will be further described below in conjunction with embodiments. However, it is obvious that the described embodiments are part of the embodiments of the present application, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the described embodiments of the present application without creative efforts belong to the scope protected by the present application.

[0035] A quaternary ammonium salt polymer of phosphate type provided by the present invention comprises compounds in the following mass percentages:

[0036] 2-methacryloyloxyethyl phosphorylcholine 10 - 20%, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol 5 - 15%, castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride 15 - 25%, acrylamide 40 - 70%.

[0037] Furthermore, the structural formulas of the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol, and castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride are respectively:

[0038] 、 and

[0039] wherein, x + y = 20 - 40.

[0040] Furthermore, the preparation method comprises the following steps:

[0041] Step I, synthesize acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol;

[0042] In step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and 4-hydroxyanisole are 19:(14 - 17):0.1:0.1. Under the condition of 70 - 90 °C, the catalyst benzyltriethylammonium chloride and the inhibitor 4-hydroxyanisole are added to acrylic acid, stirred and mixed evenly to obtain an acrylic acid mixture; the acrylic acid mixture is added dropwise to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, and the dropping time is 40 min - 80 min. After the dropping is completed, the temperature is raised to 120 °C - 140 °C, and the reaction is carried out for 3 - 8 h to obtain acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol.

[0043] The specific synthesis route is as follows:

[0044] Step II, synthesize ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride;

[0045] In step II of the present invention:

[0046] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:(0.06 - 0.1):(15 - 17):(6 - 9), and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Ricinoleic acid and potassium hydroxide are successively added to the polymerization reactor, the air is replaced with nitrogen 3 times, stirred, and the temperature is raised to 100 - 120 °C. After evacuating for 1 h, the vacuum valve is closed, 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide are slowly added, and at the same time the temperature is raised to 140 - 160 °C, and the reaction is carried out for 3 h. The temperature is lowered to 100 °C, and the remaining ethylene oxide and propylene oxide are added, and the reaction is carried out for 3 h. The temperature is lowered to 80 °C, and the vacuum is evacuated to obtain ricinoleic acid polyether.

[0047] S2, the molar ratio of the ricinoleic acid polyether and (3-carboxypropyl)trimethylammonium chloride is 1:(2.2 - 2.4), and the mass of p-toluenesulfonic acid is 0.3% of the total mass of the ricinoleic acid polyether and (3-carboxypropyl)trimethylammonium chloride. The ricinoleic acid polyether and (3-carboxypropyl)trimethylammonium chloride are successively added, heated to 50 - 70 °C, stirred evenly, p-toluenesulfonic acid is slowly added, the vacuum is evacuated, the temperature is raised to 120 - 140 °C, and the reaction is carried out for 4 - 8 h. The vacuum valve is closed to obtain ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride.

[0048] The specific synthesis route is as follows:

[0049]

[0050] Step , Dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, and successively add acrylamide and half of the dodecyl mercaptan, and stir evenly to prepare monomer solution A; dissolve ricinoleic acid polyether modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, and successively add acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diynyl]oxiranyl]methanol and the other half of the dodecyl mercaptan and stir evenly to prepare monomer solution B;

[0051] Step , Under the protection of N2, slowly add monomer solution A and monomer solution B to the reaction equipment alternately, the addition time is 2-4 h, and at the same time, dropwise add potassium persulfate solution to the reaction equipment at a dropping rate of 3 mL / min - 8 mL / min, control the reaction temperature at 50 °C - 80 °C, after the addition is completed, and continue to keep warm for 2-5 h to obtain the phosphate quaternary ammonium salt polymer.

[0052] The synthesis route of the phosphate quaternary ammonium salt polymer is as follows:

[0053]

[0054] Furthermore, in the said step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 3wt% - 7wt% of the total amount of monomer solution A and monomer solution B.

[0055] Furthermore, the application of the phosphate quaternary ammonium salt polymer in personal care.

[0056] After drying the polymer sample, infrared testing was carried out, see Figure 1 , the test results show that: the broad peak at about 3440 cm⁻¹ can be attributed to the O-H stretching vibration, and there is also a component of intermolecular hydrogen-bonded hydroxyl groups. In addition, the peak at 3440 cm -1 is relatively sharp, which is caused by the N-H stretching vibration, indicating that there is an amino group in the structure. The peak at 3260 cm on the spectrum -1The signals are related to the stretching vibration of N-H on the nearby signals and amides. The strong absorption peak at 1730 cm⁻¹ corresponds to the stretching vibration of C=O on the polymer, which is attributed to carbonyl and ester groups (C=O and C-O-C), indicating the formation of ester groups and amides in the polymer. The asymmetric and symmetric stretching vibrations of C-O-C in the ester group at 1255 cm⁻¹ and 1137 cm⁻¹ respectively, as well as the stretching vibration of P=O on the phosphate group, prove the existence of ester groups and phosphate groups on the polymer. The peak near 2158 cm⁻¹ can be attributed to the stretching vibration of carbon-carbon triple bonds, proving the existence of alkynyl groups in the polymer. In addition, the vibrations of C=C and C-H of propylene at 1638 cm⁻¹ are also detected, which are attributed to isolated double bonds. The vibrations at 962 cm⁻¹ and 914 cm⁻¹ are attributed to the out-of-plane bending vibration of olefin C-H, indicating the existence of double bonds. 2928 cm⁻¹ can be attributed to the asymmetric stretching vibration of CH2 / CH3 in the alkyl chain, indicating the existence of long-chain alkyl groups and methylene groups in the polymer, and the symmetric bending vibration of CH3 at 1354 cm⁻¹ confirms the existence of methyl groups in the structure. The signals in the infrared spectrum in the range of 1400~1200 cm⁻¹ also indicate the existence of C-N stretching vibration in the structure, and the signals in the range of 1060~1021 cm⁻¹ are the stretching vibrations of C-O-C in polyethers, which also conform to the stretching vibration of alkyl-substituted P-O-C on the phosphate group. In addition, the signals near 760 cm⁻¹ can also be attributed to the stretching vibration of P-O-C. Therefore, the target compound contains functional groups such as phosphate groups, ester bonds, carbon-carbon double bonds, alkyl chains, amino groups, and ether bonds, and has the same functional group structural characteristics as lipid quaternary ammonium salt polymers.

[0057] The following specific examples are used to illustrate the present invention in detail.

[0058] It should be noted that, unless otherwise specified, the reagents and drugs used in the following examples and tests are all conventional commercially available products.

[0059] It should be noted that, unless otherwise specified, the operations used in the following examples and tests are all conventional operations in the art.

[0060] Example 1

[0061] A phosphate ester type quaternary ammonium salt polymer, characterized in that it comprises the following compounds in mass percentages:

[0062] 2-methacryloyloxyethyl phosphorylcholine 10%, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxirane-2-yl]but-1,3-diynyl]oxirane-2-yl]methanol 5%, castor oil acid polyether modified (3-carboxypropyl)trimethylammonium chloride 15%, acrylamide 70%.

[0063] Further, the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, and ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride have the following structural formulas respectively:

[0064] , and

[0065] where x + y = 20.

[0066] Further, the preparation method includes the following steps:

[0067] Step I, synthesize acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol;

[0068] In Step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:14:0.1:0.1. Under the condition of 70 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, with the dropping time being 40 min. After the dropping is completed, raise the temperature to 120 °C and react for 3 h to obtain acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol.

[0069] Step II, synthesize ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride;

[0070] In Step II of the present invention:

[0071] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:0.06:15:6, and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Add ricinoleic acid and potassium hydroxide to the polymerization reaction kettle in sequence, displace the air with nitrogen 3 times, stir, and raise the temperature to 100 °C. After evacuating for 1 h, close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 140 °C. React for 3 h, cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, and cool down to 80 °C, then evacuate to obtain ricinoleic acid polyether.

[0072] S2. The molar ratio of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride is 1:2.2, and the mass of p-toluenesulfonic acid is 0.3% of the total mass of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride. The polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride are added in sequence, heated to 50 °C, stirred evenly, p-toluenesulfonic acid is added slowly, the vacuum is pumped, the temperature is raised to 120 °C, and the reaction is carried out for 4 h. Then the vacuum valve is closed to obtain the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride.

[0073] Step , dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, add acrylamide and half of the dodecyl mercaptan in sequence, and stir evenly to prepare monomer solution A; dissolve the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, add acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol and the other half of the dodecyl mercaptan in sequence and stir evenly to prepare monomer solution B;

[0074] Step , under the protection of N2, add monomer solution A and monomer solution B to the reaction equipment alternately and slowly, the addition time is 2 h, and at the same time, add potassium persulfate solution dropwise to the reaction equipment, the dropping rate is 3 mL / min, control the reaction temperature at 50 °C, after the addition is completed, keep the temperature for another 2 h to obtain the phosphate quaternary ammonium salt polymer.

[0075] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 3 wt% of the total amount of monomer solution A and monomer solution B.

[0076] Furthermore, the application of the phosphate quaternary ammonium salt polymer in personal care.

[0077] Example 2

[0078] A phosphate quaternary ammonium salt polymer, characterized in that it comprises the following compounds in mass percentages:

[0079] 2-methacryloyloxyethyl phosphorylcholine 13%, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol 8%, polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride 18%, acrylamide 61%.

[0080] Further, the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, and ricinoleic acid polyether modified (3-carboxypropyl)trimethylammonium chloride have the following structural formulas respectively:

[0081] , and

[0082] where x + y = 25.

[0083] Further, the preparation method includes the following steps:

[0084] Step I, synthesize acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol;

[0085] In Step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:15:0.1:0.1. Under the condition of 75 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, the dropping time is 50 min. After the dropping is completed, raise the temperature to 125 °C and react for 4 h to obtain acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol.

[0086] Step II, synthesize ricinoleic acid polyether modified (3-carboxypropyl)trimethylammonium chloride;

[0087] In Step II of the present invention:

[0088] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:0.07:15:7, and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Add ricinoleic acid and potassium hydroxide to the polymerization reactor in sequence, displace the air with nitrogen 3 times, stir, and raise the temperature to 105 °C. After evacuating for 1 h, close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 145 °C and react for 3 h. Cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, cool down to 80 °C, and evacuate to obtain ricinoleic acid polyether.

[0089] S2. The molar ratio of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride is 1:2.25, and the mass of p-toluenesulfonic acid is 0.3% of the total mass of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride. The polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride are added in sequence, heated to 55 °C, stirred evenly, p-toluenesulfonic acid is added slowly, the vacuum is pumped, the temperature is raised to 125 °C, and the reaction is carried out for 5 h. Then the vacuum valve is closed to obtain polyether ricinoleate modified (3-carboxypropyl) trimethyl ammonium chloride.

[0090] Step , dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, add acrylamide and half of the dodecyl mercaptan in sequence, and stir evenly to prepare monomer solution A; dissolve polyether ricinoleate modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, add acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diyneyl]oxiranyl]methanol and the other half of the dodecyl mercaptan in sequence and stir evenly to prepare monomer solution B;

[0091] Step , under the protection of N2, add monomer solution A and monomer solution B to the reaction equipment alternately and slowly, the addition time is 2.5 h, and at the same time, add potassium persulfate solution dropwise to the reaction equipment, the dropping rate is 4 mL / min, control the reaction temperature at 60 °C, and continue to keep warm for 3 h after the addition is completed to obtain the phosphate ester type quaternary ammonium salt polymer.

[0092] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 4 wt% of the total amount of monomer solution A and monomer solution B.

[0093] Furthermore, the application of the phosphate ester type quaternary ammonium salt polymer in personal care.

[0094] Example 3

[0095] A phosphate ester type quaternary ammonium salt polymer, characterized in that it comprises the following compounds in mass percentages:

[0096] 3-methacryloyloxyethyl phosphorylcholine 15%, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diyneyl]oxiranyl]methanol 10%, polyether ricinoleate modified (3-carboxypropyl) trimethyl ammonium chloride 20%, acrylamide 55%.

[0097] Further, the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, and ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride have the following structural formulas respectively:

[0098] , and

[0099] where x + y = 30.

[0100] Further, the preparation method includes the following steps:

[0101] Step I, synthesize acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol;

[0102] In Step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:16:0.1:0.1. Under the condition of 80 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, with the dropping time being 60 min. After the dropping is completed, raise the temperature to 130 °C and react for 5 h to obtain acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol.

[0103] Step II, synthesize ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride;

[0104] In Step II of the present invention:

[0105] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:0.08:16:8, and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Add ricinoleic acid and potassium hydroxide to the polymerization reaction kettle in sequence, displace the air with nitrogen 3 times, stir, and raise the temperature to 110 °C. After evacuating for 1 h, close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 150 °C and react for 3 h. Then cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, and cool down to 80 °C and evacuate to obtain ricinoleic acid polyether.

[0106] In S2, the molar ratio of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride is 1:2.3, and the mass of p-toluenesulfonic acid is 0.3% of the total mass of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride. The polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride are added in sequence, heated to 60 °C, stirred evenly, p-toluenesulfonic acid is slowly added, the vacuum is pumped, the temperature is raised to 130 °C, and the reaction is carried out for 6 h. Then the vacuum valve is closed to obtain the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride.

[0107] Step , dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, and sequentially add acrylamide and half of the dodecyl mercaptan, and stir evenly to prepare monomer solution A; dissolve the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, and sequentially add acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diynyl]oxiranyl]methanol and the other half of the dodecyl mercaptan and stir evenly to prepare monomer solution B;

[0108] Step , under the protection of N2, slowly add monomer solution A and monomer solution B to the reaction equipment alternately, the addition time is 3 h, and at the same time, slowly dropwise add potassium persulfate solution to the reaction equipment, the dropping rate is 6 mL / min, control the reaction temperature at 70 °C, and continue to keep warm for 4 h after the addition is completed to obtain the phosphate ester type quaternary ammonium salt polymer.

[0109] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 5 wt% of the total amount of monomer solution A and monomer solution B.

[0110] Furthermore, the application of the phosphate ester type quaternary ammonium salt polymer in personal care.

[0111] Example 4

[0112] A phosphate ester type quaternary ammonium salt polymer, characterized in that it comprises the following compounds in mass percentages:

[0113] 2-methacryloyloxyethyl phosphorylcholine 18%, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diynyl]oxiranyl]methanol 12%, polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride 23%, acrylamide 47%.

[0114] Further, the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol, and ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride have the following structural formulas respectively:

[0115] , and

[0116] where x + y = 35.

[0117] Further, the preparation method includes the following steps:

[0118] Step I, synthesize acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol;

[0119] In Step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:16:0.1:0.1. Under the condition of 85 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol, the dropping time is 70 min. After the dropping is completed, raise the temperature to 135 °C and react for 7 h to obtain acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol.

[0120] Step II, synthesize ricinoleic acid polyether-modified (3-carboxypropyl)trimethylammonium chloride;

[0121] In Step II of the present invention:

[0122] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:0.09:16:8, and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Add ricinoleic acid and potassium hydroxide to the polymerization reaction kettle in sequence, displace the air with nitrogen 3 times, stir, and raise the temperature to 115 °C. After evacuating for 1 h, close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 155 °C, react for 3 h, cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, cool down to 80 °C, and evacuate to obtain ricinoleic acid polyether.

[0123] S2. The molar ratio of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride is 1:2.35, and the mass of p-toluenesulfonic acid is 0.3% of the total mass of the polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride. The polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride are added in sequence, heated to 65 °C, stirred evenly, p-toluenesulfonic acid is added slowly, the vacuum is pumped, the temperature is raised to 135 °C, and the reaction is carried out for 7 h. Then the vacuum valve is closed to obtain the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride.

[0124] Step , dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, add acrylamide and half of the dodecyl mercaptan in sequence, and stir evenly to prepare monomer solution A; dissolve the polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride in deionized water, and add acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diynyl]oxiranyl] methanol and the other half of the dodecyl mercaptan in sequence and stir evenly to prepare monomer solution B;

[0125] Step , under the protection of N2, add monomer solution A and monomer solution B to the reaction equipment alternately and slowly, the addition time is 3 h, and at the same time, add potassium persulfate solution dropwise to the reaction equipment, the dropping rate is 7 mL / min, control the reaction temperature at 70 °C, and after the addition is completed, keep the temperature for another 4 h to obtain the phosphate ester type quaternary ammonium salt polymer.

[0126] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 6 wt% of the total amount of monomer solution A and monomer solution B.

[0127] Furthermore, the application of the phosphate ester type quaternary ammonium salt polymer in personal care.

[0128] Example 5

[0129] A phosphate ester type quaternary ammonium salt polymer, characterized in that it comprises the following compounds in mass percentages:

[0130] 2-methacryloyloxyethyl phosphorylcholine 20%, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiranyl]but-1,3-diynyl]oxiranyl] methanol 15%, polyether ricinoleate-modified (3-carboxypropyl) trimethyl ammonium chloride 25%, acrylamide 40%.

[0131] Furthermore, the structural formulas of 2-methacryloyloxyethyl phosphorylcholine, acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, and ricinoleic acid polyether modified (3-carboxypropyl)trimethylammonium chloride are as follows:

[0132] 、 and

[0133] where x + y = 40.

[0134] Furthermore, the preparation method includes the following steps:

[0135] Step I, synthesize acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol;

[0136] In Step I of the present invention, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:17:0.1:0.1. Under the condition of 90 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol, with the dropping time being 80 min. After the dropping is completed, raise the temperature to 140 °C and react for 8 h to obtain acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyne-1-yl]oxiran-2-yl]methanol.

[0137] Step II, synthesize ricinoleic acid polyether modified (3-carboxypropyl)trimethylammonium chloride;

[0138] In Step II of the present invention:

[0139] S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:0.1:17:9, and the relative molecular mass of the ricinoleic acid polyether is 1200 - 2000. Add ricinoleic acid and potassium hydroxide to the polymerization reaction kettle in sequence, displace the air with nitrogen 3 times, stir, and raise the temperature to 120 °C. After evacuating for 1 h, close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 160 °C and react for 3 h. Then cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, and cool down to 80 °C and evacuate to obtain the ricinoleic acid polyether.

[0140] In S2, the molar ratio of the polyether ricinoleate and (3 - carboxypropyl) trimethyl ammonium chloride is 1:2.4, and the mass of p - toluenesulfonic acid is 0.3% of the total mass of the polyether ricinoleate and (3 - carboxypropyl) trimethyl ammonium chloride. The polyether ricinoleate and (3 - carboxypropyl) trimethyl ammonium chloride are added in sequence, heated to 70 °C, stirred evenly, p - toluenesulfonic acid is slowly added, the vacuum is pumped, the temperature is raised to 140 °C, and the reaction is carried out for 8 h. Then the vacuum valve is closed to obtain the polyether ricinoleate - modified (3 - carboxypropyl) trimethyl ammonium chloride.

[0141] Step , dissolve 2 - methacryloyloxyethyl phosphorylcholine in deionized water, and sequentially add acrylamide and half of the dodecyl mercaptan, and stir evenly to prepare monomer solution A; dissolve the polyether ricinoleate - modified (3 - carboxypropyl) trimethyl ammonium chloride in deionized water, and sequentially add acrylic acid - modified [3 - [4 - [3 - (hydroxymethyl) oxiranyl] but - 1,3 - diynyl] oxiranyl] methanol and the other half of the dodecyl mercaptan, and stir evenly to prepare monomer solution B;

[0142] Step , under the protection of N2, slowly add monomer solution A and monomer solution B to the reaction equipment alternately, the addition time is 4 h, and at the same time, slowly drop - add the potassium persulfate solution to the reaction equipment at a dropping rate of 8 mL / min, control the reaction temperature at 80 °C, after the addition is completed, keep the temperature for another 5 h to obtain the phosphate - type quaternary ammonium salt polymer.

[0143] Furthermore, in the step , the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 7 wt% of the total amount of monomer solution A and monomer solution B.

[0144] Furthermore, the application of the phosphate - type quaternary ammonium salt polymer in personal care.

[0145] Comparative Example 1

[0146] A phosphate - type quaternary ammonium salt polymer, its preparation method and application, the preparation method and application are basically the same as those in Example 1, except that: 2 - methacryloyloxyethyl phosphorylcholine is not added.

[0147] Comparative Example 2

[0148] A phosphate - type quaternary ammonium salt polymer, its preparation method and application, the preparation method and application are basically the same as those in Example 1, except that: acrylic acid - modified [3 - [4 - [3 - (hydroxymethyl) oxiranyl] but - 1,3 - diynyl] oxiranyl] methanol is not added.

[0149] Comparative Example 3

[0150] A phosphate ester type quaternary ammonium salt polymer, its preparation method and application. The preparation method and application are basically the same as those in Example 1, except that: ricinoleic acid polyether modified (3-carboxypropyl) trimethyl ammonium chloride is not added.

[0151] Comparative Example 4

[0152] A commercially available shampoo with sodium lauryl polyether sulfate as the main component.

[0153] Comparative Example 5

[0154] A commercially available shampoo with sodium cocoyl isethionate as the main component.

[0155] Experimental results:

[0156] For the phosphate ester type quaternary ammonium salt polymers prepared in Examples 1-5 and Comparative Examples 1-3 of the present invention, shampoos are formulated according to the formula shown in Table 1 below:

[0157] The preparation method is as follows: First, mix the substances in Phase C evenly, then dissolve sodium lauryl polyether sulfate and cocamidopropyl betaine in deionized water, heat to 40°C, and stir evenly to form Phase A. Then add the phosphate ester type quaternary ammonium salt polymer in Phase B, and then add Phase C to obtain the shampoo.

[0158] Table 1 Shampoo formula

[0159]

[0160] 1. Combing performance test

[0161] A dynamic hair combing instrument Techno Hashimoto SK-7A is used to conduct a detailed test on the combability of the shampoos prepared from 5 examples and 5 comparative examples during each step of application, rinsing, wet hair, and dry hair.

[0162] The combing performance test method is as follows: Take 50 groups of hair bundles, randomly divide them into 10 groups and number them. There are 5 bundles each of the shampoos prepared from 5 examples and 5 comparative examples of the present invention. First, fix the hair bundles on the instrument device. Each hair bundle is first subjected to basic cleaning with 1 ml of 10% sodium lauryl polyether sulfate and combed 5 times; Use a syringe to suck 1.5 mL of the shampoos of 5 examples and 5 comparative examples of the present invention, apply them to the hair bundles, evenly apply the shampoo on both sides of the hair bundles with water, and comb 5 times, and comb 10 times while rinsing; Stop rinsing and continue to comb 5 times; Take down the hair bundles, place them in a constant temperature and humidity room to dry, and then place them on the dynamic combing instrument to analyze the combability of dry hair. The test data is saved and exported through software. Each hair bundle is tested 3 times, and the average value is taken. The combing performance test results are shown in Table 2 below.

[0163] Table 2 Results of Combing Property Test

[0164]

[0165] As can be seen from Table 2, the maximum combing work of the hair bundles treated with the shampoo prepared by using the preparation method of a phosphate quaternary ammonium salt polymer of the present invention is 0.02 - 0.06 J, which is less than that of the hair bundles treated with the shampoo mainly composed of commercially available sodium laureth sulfate and sodium cocoyl isethionate. The shampoo prepared by the present invention has the effect of improving the combing property of hair.

[0166] 2. Friction Force Test

[0167] The test method for friction force performance is as follows: Take 50 groups of hair bundles, randomly divide them into 10 groups and number them. Five hair bundles of each of the shampoos prepared from the 5 examples and 5 comparative examples of the present invention are taken. Each hair bundle is first subjected to basic cleaning with 1 ml of 10% sodium laureth sulfate; then 0.5 g of each shampoo is evenly applied to the hair bundle, left for 1 min, and then rinsed with clean water. After completion, the hair bundles are hung in a constant temperature and humidity environment of (26 ± 2)°C and (60 ± 10)% RH for drying and equilibration for 24 h. Then a mechanical meter is used to test the maximum friction force of the samples and take the average value. The test results of friction force performance are shown in Table 3 below.

[0168] Table 3 Test Results of Friction Force Performance

[0169]

[0170] As can be seen from Table 3, the maximum friction force of the hair bundles treated with the shampoo prepared by using the preparation method of a phosphate quaternary ammonium salt polymer of the present invention is 1.24 - 1.56 N, which is less than that of the hair bundles treated with the shampoo mainly composed of commercially available sodium laureth sulfate and sodium cocoyl isethionate. The shampoo prepared by the present invention has the effect of improving the smoothness of the hair surface.

[0171] 3. Foam Performance Test

[0172] The foam performance is evaluated by a DFA100 dynamic foam analyzer, including foam height, foam stability and foam structure analysis. First, the shampoos prepared from the 5 examples and 5 comparative examples of the present invention are prepared into a 5% mass fraction solution with deionized water, and then 50 mL of the test sample solution is sucked into a graduated cylinder with a syringe. The base bracket for fixing the graduated cylinder is inserted into the instrument for foam performance testing. Parameter settings: Temperature: (22 ± 1)°C; Rotation speed: 3000 r / min; Foaming time: Stir for 3 s and stop for 3 s, lasting for 30 cycles; Test time: 15 min. Each sample is tested three times. The test results of foam performance are shown in Table 4 below.

[0173] Table 4 Test Results of Foam Properties

[0174]

[0175] As can be seen from Table 4, the foaming height of the shampoo prepared by using the preparation method of a phosphate quaternary ammonium salt polymer of the present invention when formulated into a 5% by mass solution is 98 - 113 mm, which is higher than that of the shampoo mainly composed of commercially available sodium lauryl polyether sulfate and sodium cocoyl isethionate when formulated into a 5% by mass solution. The shampoo prepared by the present invention not only does not affect the anionic foaming performance, but also can increase the foam of the shampoo when used in combination with anionic surfactants.

[0176] 4. Sensory Evaluation Test

[0177] The sensory evaluation panel consists of 10 members who have received sensory evaluation training, aged 25 - 35 years old. This sensory evaluation panel conducts 4 evaluations on the shampoos prepared from 5 examples and 5 comparative examples of the present invention, and the specific contents are combability, softness, smoothness and ease of combing respectively, using a 10 - point scoring method, 1 - 10 points; all sensory evaluations are carried out in a constant temperature and humidity chamber. The test results of the sensory evaluation are shown in Table 5 below.

[0178] Table 5 Test Results of Sensory Evaluation

[0179]

[0180] As can be seen from Table 5, the combability, softness, smoothness and ease of combing of the shampoo prepared by using the preparation method of a phosphate quaternary ammonium salt polymer of the present invention are all 8 or 9, and the scores are higher than those of the shampoos mainly composed of commercially available sodium lauryl polyether sulfate and sodium cocoyl isethionate. The shampoo prepared by the present invention has excellent combability, softness, smoothness and ease of combing.

[0181] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above - mentioned embodiments. What is described in the above - mentioned embodiments and the specification is only the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims

1. A phosphate quaternary ammonium salt polymer, characterized in that, A compound comprising the following mass percentages: 10-20% of 2-methacryloyloxyethyl phosphorylcholine, 5-15% of acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, 15-25% of castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride, and 40-70% of acrylamide.

2. The quaternary ammonium salt polymer of the phosphate type according to claim 1, wherein The structural formulas of the 2-methacryloyloxyethyl phosphorylcholine, acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, and castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride are respectively: , and wherein, x + y = 20 - 40.

3. The preparation method of a phosphate quaternary ammonium salt polymer according to claim 1, characterized in that, The preparation method includes the following steps: Step I, synthesize acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol; Step II, synthesize castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride; Step , dissolve 2-methacryloyloxyethyl phosphorylcholine in deionized water, and successively add acrylamide and half of dodecyl mercaptan, and stir evenly to prepare monomer solution A; dissolve castor oil acid polyether modified 2,3-epoxypropyl trimethyl ammonium chloride in deionized water, and successively add acrylic acid modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diyneyl]oxiran-2-yl]methanol and the other half of dodecyl mercaptan, and stir evenly to prepare monomer solution B; Step , under the protection of N2, monomer solution A and monomer solution B are slowly added to the reaction equipment alternately, the addition time is 2 - 4 h, and at the same time, potassium persulfate solution is added dropwise to the reaction equipment at a dropping rate of 3 mL / min - 8 mL / min. The reaction temperature is controlled at 50 °C - 80 °C. After the addition is completed, keep warm for 2 - 5 h to obtain the phosphate quaternary ammonium salt polymer.

4. The preparation method of a phosphate quaternary ammonium salt polymer according to claim 3, characterized in that, The above-mentioned steps In the above, the potassium persulfate solution is a solution formed by dissolving potassium persulfate in deionized water; the total amount of the potassium persulfate solution is 3 wt% - 7 wt% of the total amount of monomer solution A and monomer solution B.

5. The preparation method of a phosphate quaternary ammonium salt polymer according to claim 4, characterized in that, The preparation method of the acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol includes the following steps: Under the condition of 70-90 °C, add the catalyst benzyltriethylammonium chloride and the inhibitor p-hydroxyanisole to acrylic acid, stir and mix evenly to obtain an acrylic acid mixture; dropwise add the acrylic acid mixture to [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, the dropping time is 40 min - 80 min, after the dropping is completed, raise the temperature to 120 °C - 140 °C, and react for 3 - 8 h to obtain acrylic acid-modified [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol.

6. According to the preparation method of a phosphate quaternary ammonium salt polymer as described in claim 5, the masses of [3-[4-[3-(hydroxymethyl)oxiran-2-yl]but-1,3-diynyl]oxiran-2-yl]methanol, acrylic acid, benzyltriethylammonium chloride, and p-hydroxyanisole are 19:(14 - 17):0.1:0.

1.

7. The preparation method of a phosphate quaternary ammonium salt polymer according to claim 6, characterized in that, The preparation method of the castor oil acid polyether-modified (3-carboxypropyl)trimethylammonium chloride includes the following steps: S1, sequentially add castor oil acid and potassium hydroxide to the polymerization reactor, displace the air with nitrogen 3 times, stir, and raise the temperature to 100 - 120 °C, evacuate for 1 h and then close the vacuum valve, slowly add 1 / 3 of ethylene oxide and 1 / 3 of propylene oxide, and at the same time raise the temperature to 140 - 160 °C, react for 3 h, cool down to 100 °C, add the remaining ethylene oxide and propylene oxide, react for 3 h, cool down to 80 °C, and evacuate to obtain castor oil acid polyether. S2. Sequentially add polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride, heat to 50 - 70 °C, stir evenly, slowly add p-toluenesulfonic acid, evacuate the air, heat up to 120 - 140 °C, react for 4 - 8 h, and then close the vacuum valve to obtain polyether ricinoleate modified (3-carboxypropyl) trimethyl ammonium chloride.

8. According to the preparation method of a phosphate quaternary ammonium salt polymer as described in claim 7, in S1, the mass ratio of ricinoleic acid, potassium hydroxide, ethylene oxide, and propylene oxide is 7:(0.06 - 0.1):(15 - 17):(6 - 9), and the relative molecular mass of the polyether ricinoleate is 1200 - 2000.

9. According to the preparation method of a phosphate quaternary ammonium salt polymer as described in claim 8, in S2, the molar ratio of polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride is 1:(2.2 - 2.4), and the mass of p-toluenesulfonic acid is 0.3% of the total mass of polyether ricinoleate and (3-carboxypropyl) trimethyl ammonium chloride.

10. Application of a phosphate quaternary ammonium salt polymer as described in claim 9 in personal care.

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