阅读说明：本技术 合成硅氧烷聚氨酯共聚物的制备方法 (Preparation method of synthetic siloxane polyurethane copolymer ) 是由 陈思贤 陈敬伦 陈盈珊 张腊梅 于 2021-07-22 设计创作，主要内容包括：本发明公开了一种合成硅氧烷聚氨酯共聚物的制备方法,涉及皮肤保护组合物领域,包括如下步骤：步骤一：将摩尔比为1：3.5～1：3.9的原硅酸酯与酸性水溶液进行水解及聚缩合反应得到含有烷氧基基团的聚硅氧树脂；步骤二：将摩尔比为1.1:1～1.5:1的二异氰酸酯与亲水性聚醚二元醇混合,搅拌,得到含有异氰酸酯基团的预聚物；步骤三：将得到的含有烷氧基基团的聚硅氧树脂与得到的含有异氰酸酯基团的预聚物按照摩尔比为1:0.5～1:1.5的配比混合,进行聚合反应,得到成膜聚合物；步骤四：将质量比5:100～10:100的成膜聚合物和溶剂混合,得到合成硅氧烷聚氨酯共聚物。按照本发明的方法制作的合成硅氧烷聚氨酯共聚物,可以在喷洒后形成具有良好防水性的保护膜,且喷洒后不易阻塞喷瓶的喷嘴。(The invention discloses a preparation method of a synthetic siloxane polyurethane copolymer, which relates to the field of skin protection compositions and comprises the following steps: the method comprises the following steps: mixing a mixture of 1: 3.5-1: 3.9 hydrolyzing and polycondensing the orthosilicate and the acidic aqueous solution to obtain a silicone resin containing alkoxy groups; step two: mixing diisocyanate and hydrophilic polyether diol in a molar ratio of 1.1: 1-1.5: 1, and stirring to obtain a prepolymer containing isocyanate groups; step three: mixing the obtained polysiloxane resin containing alkoxy groups and the obtained prepolymer containing isocyanate groups according to the molar ratio of 1: 0.5-1: 1.5, and carrying out polymerization reaction to obtain a film-forming polymer; step four: mixing the film-forming polymer and the solvent in a mass ratio of 5: 100-10: 100 to obtain the synthetic siloxane polyurethane copolymer. The synthetic siloxane polyurethane copolymer prepared by the method can form a protective film with good waterproofness after being sprayed, and the nozzle of a spray bottle is not easy to block after being sprayed.)

1. The preparation method of the synthetic siloxane polyurethane copolymer is characterized by comprising the following steps: the method comprises the following steps:

the method comprises the following steps: mixing a mixture of 1: 3.5-1: 3.9 hydrolyzing and polycondensing the orthosilicate and the acidic aqueous solution to obtain a silicone resin containing alkoxy groups;

step two: mixing diisocyanate and hydrophilic polyether diol in a molar ratio of 1.1: 1-1.5: 1, and stirring to obtain a prepolymer containing isocyanate groups;

step three: mixing the silicone resin containing alkoxy groups obtained in the step one with the prepolymer containing isocyanate groups obtained in the step two according to a molar ratio of 1: 0.5-1: 1.5, and carrying out polymerization reaction to obtain a film-forming polymer;

step four: mixing the film-forming polymer and the solvent in a mass ratio of 5: 100-10: 100 to obtain the synthetic siloxane polyurethane copolymer.

2. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: the pH value of the acidic aqueous solution is in the range of 3-5.

3. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: in the first step, the temperature range of the hydrolysis and polycondensation reaction of the orthosilicate and the acidic aqueous solution is 45-55 ℃, and the reaction time is 18-36 h.

4. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: in the second step, the temperature range of mixing the diisocyanate and the hydrophilic polyether glycol is 70-90 ℃, and the reaction time is 1-2 h.

5. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: in the third step, the temperature range of the mixture of the silicone resin and the prepolymer is 70-90 ℃, and the reaction time is 2-5 h.

6. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: the weight average molecular weight of the hydrophilic polyether glycol is 400-2,000 g/mol.

7. The method of preparing a synthetic silicone polyurethane copolymer of claim 1, wherein: the weight average molecular weight of the silicone resin obtained in the first step is 10,000-30,000 g/mol.

Technical Field

The invention relates to the field of skin protection compositions, and particularly relates to a preparation method of a synthetic siloxane polyurethane copolymer.

Background

Skin with a broken wound requires reduced external irritation (e.g., water or dirt) to facilitate healing, but also maintains good breathability and mobility of the area.

CN 109200333 a discloses a liquid skin protection composition which can be sprayed on the skin and form a non-irritating skin protection film. The liquid skin protection composition comprises a linear polymer dissolved in a solvent, the linear polymer having a polyphenylhydroxysiloxane structure.

However, the above liquid skin protective compositions tend to clog the nozzle of the spray bottle after spraying, and are still inconvenient to use. If the liquid skin protectant composition is contained in a pressurized spray bottle for spraying, the gas (e.g., gas) contained in the pressurized spray bottle may pose a risk in product transportation.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a preparation method of a synthetic siloxane polyurethane copolymer, which can form a protective film with good waterproofness after spraying and is not easy to block a nozzle after spraying.

The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the synthetic siloxane polyurethane copolymer comprises the following steps:

the method comprises the following steps: mixing a mixture of 1: 3.5-1: 3.9 hydrolyzing and polycondensing the orthosilicate and the acidic aqueous solution to obtain a silicone resin containing alkoxy groups;

step two: mixing diisocyanate and hydrophilic polyether diol in a molar ratio of 1.1: 1-1.5: 1, and stirring to obtain a prepolymer containing isocyanate groups;

step three: mixing the silicone resin containing alkoxy groups obtained in the step one with the prepolymer containing isocyanate groups obtained in the step two according to a molar ratio of 1: 0.5-1: 1.5, and carrying out polymerization reaction to obtain a film-forming polymer;

step four: mixing the film-forming polymer and the solvent in a mass ratio of 5: 100-10: 100 to obtain the synthetic siloxane polyurethane copolymer.

Further, the method comprises the following steps: the pH value of the acidic aqueous solution is in the range of 3-5.

Further, the method comprises the following steps: in the first step, the temperature range of the hydrolysis and polycondensation reaction of the orthosilicate and the acidic aqueous solution is 45-55 ℃, and the reaction time is 18-36 h.

Further, the method comprises the following steps: in the second step, the temperature range of mixing the diisocyanate and the hydrophilic polyether glycol is 70-90 ℃, and the reaction time is 1-2 h.

Further, the method comprises the following steps: in the third step, the temperature range of the mixture of the silicone resin and the prepolymer is 70-90 ℃, and the reaction time is 2-5 h.

Further, the method comprises the following steps: the weight average molecular weight of the hydrophilic polyether glycol is 400-2,000 g/mol.

Further, the method comprises the following steps: the weight average molecular weight of the silicone resin obtained in the first step is 10,000-30,000 g/mol.

The invention has the beneficial effects that: the synthetic siloxane polyurethane copolymer prepared by the method can form a protective film with good waterproofness after being sprayed, and the nozzle of a spray bottle is not easy to block after being sprayed.

Drawings

FIG. 1 is a diagram of the texture of the skin on the tape applied to the skin before spraying;

FIG. 2 is a diagram of the texture of the skin on the tape applied to the skin after spraying;

FIG. 3 is a view showing the state in which the toilet paper is permeated by water drops after spraying the liquid dressing E of the present embodiment;

FIG. 4 is a view showing the penetration of water droplets into the sanitary napkin after spraying the liquid dressing CE1 of comparative example 1;

FIG. 5 is a diagram showing the penetration of water droplets into a sanitary napkin after spraying the liquid dressing CE2 of comparative example 2;

Detailed Description

The invention is further described with reference to the following figures and detailed description.

Embodiments of the present application provide a method of preparing a synthetic silicone polyurethane copolymer, comprising the steps of:

the method comprises the following steps: mixing a mixture of 1: 3.5-1: 3.9 hydrolyzing and polycondensing the orthosilicate and the acidic aqueous solution to obtain a silicone resin containing alkoxy groups;

the orthosilicate may be tetraethylorthosilicate, tetramethylorthosilicate, or a combination thereof;

the acidic aqueous solution may be an aqueous acetic acid solution, an aqueous hydrochloric acid solution or an aqueous phosphoric acid solution.

Step two: mixing diisocyanate and hydrophilic polyether diol in a molar ratio of 1.1: 1-1.5: 1, and stirring to obtain a prepolymer containing isocyanate groups;

the diisocyanate may be Hexamethylene Diisocyanate (HDI), methylene dicyclohexyl diisocyanate (H12MDI, dicyclohexylmethane-4, 4' -diisocynate), isophorone diisocyanate (IPDI), or a combination thereof;

the hydrophilic polyether diol is polyethylene glycol (PEG)

Step three: mixing the silicone resin containing alkoxy groups obtained in the step one with the prepolymer containing isocyanate groups obtained in the step two according to a molar ratio of 1: 0.5-1: 1.5, and carrying out polymerization reaction to obtain a film-forming polymer;

step four: mixing the film-forming polymer and the solvent in a mass ratio of 5: 100-10: 100 to obtain the synthetic siloxane polyurethane copolymer.

The solvent is hexamethyldisilazane.

In addition to the above, the film-forming polymer does not contain an aromatic ring structure.

On the basis, the pH value of the acidic aqueous solution is in the range of 3-5.

On the basis, the temperature range of the hydrolysis and polycondensation reaction of the orthosilicate and the acidic aqueous solution in the first step is 45-55 ℃, and the reaction time is 18-36 h.

On the basis, the temperature range of mixing the diisocyanate and the hydrophilic polyether glycol in the second step is 70-90 ℃, and the reaction time is 1-2 h.

On the basis, the temperature range of the silicone resin and the prepolymer in the step three is 70-90 ℃, and the reaction time is 2-5 h.

On the basis, the weight average molecular weight of the hydrophilic polyether glycol is 400-2,000 g/mol.

On the basis, the weight average molecular weight of the hydrophilic polyether glycol is 500-1,000 g/mol.

On the basis, the weight average molecular weight of the silicone resin obtained in the step one is 10,000-30,000 g/mol.

The first embodiment is as follows:

the preparation method of the synthetic siloxane polyurethane copolymer comprises the following steps:

the method comprises the following steps: mixing tetraethyl orthosilicate (TEOS) and hydrochloric acid aqueous solution (pH value is 4-5) according to the weight ratio of TEOS: H2O is 1: 3.6, hydrolysis and polycondensation reaction at 50 ℃ for 24 hours, and then adding 0.1mol/l NaOH aqueous solution to neutralize to pH 7 to terminate the reaction, to obtain a silicone resin containing ethoxy groups and hydroxyl groups. In this example, the silicone resin had a weight average molecular weight of about 10,000 g/mol, and the silicone resin had a partially crosslinked network structure.

Step two: hexamethylene Diisocyanate (HDI) was reacted with polyethylene glycol PEG 1000 at a ratio of 1.3: 1, and reacting at 80 ℃ for 1h to obtain a prepolymer containing isocyanate groups.

Step three: mixing the silicone resin with the prepolymer in a ratio of 1:1 and carrying out polymerization reaction at 80 ℃ for 2 hours to obtain a film-forming polymer.

Step four: 5g of this film-forming polymer were dissolved in 100g of Hexamethyldisilazane (HMDS) to give liquid dressing E containing a silicone-polyurethane copolymer of the example

Example two:

the preparation method of the synthetic siloxane polyurethane copolymer comprises the following steps:

the method comprises the following steps: mixing tetramethylorthosilicate and an acetic acid aqueous solution (pH value is 4-5) in a ratio of 1: 3.8, hydrolysis and polycondensation reaction at 53 ℃ for 28 hours, and then 0.1mol/l NaOH aqueous solution is added to neutralize to pH 7 to terminate the reaction, so as to obtain the silicone resin containing ethoxy groups and hydroxyl groups. In this example, the silicone resin had a weight average molecular weight of about 15,000 g/mol, and the silicone resin had a partially crosslinked network structure.

Step two: methylene dicyclohexyl diisocyanate (H12MDI, dicyclohexylmethane-4, 4' -diisocyanate) was mixed with polyethylene glycol PEG 1000 at a ratio of 1.5:1, and reacting at 70 ℃ for 2 hours to obtain a prepolymer containing isocyanate groups.

Step three: mixing the silicone resin with the prepolymer in a ratio of 1:1.5, and carrying out polymerization reaction at 70 ℃ for 5 hours to obtain a film-forming polymer.

Step four: 10g of the film-forming polymer was dissolved in 100g of Hexamethyldisilazane (HMDS) to obtain the synthetic siloxane polyurethane copolymer of example.

Experiment:

comparative example 1

The liquid dressing CE1 of comparative example 1 was a SENSI-CARE protective skin spray commercially available from Convatec, Inc. (product number 420790).

Comparative example 2

The liquid dressing CE2 of comparative example 2 was sample 2 described in CN 109200333 a.

Comparative example 3

Liquid dressing CE3 of comparative example 3 was a Cavilon liquid dressing (model 3346N) commercially available from 3M company.

Observation by electron microscope

The liquid dressing E containing the silicone-polyurethane copolymer of the first example was placed in an air spray bottle, 0.3mL of the liquid dressing E was uniformly sprayed onto a specified area of 3cm × 3cm of the inner skin of the arm of the human body, after 10 seconds, the liquid dressing E was adhered to the skin surface of the specified area using a polypropylene tape, the tape was peeled off after being pressed and waited for 5 minutes, the tape was gold-plated for 1 minute with a gold plating machine, and the tape adhered to the skin before spraying and the tape adhered to the skin after spraying the liquid dressing E containing the silicone-polyurethane copolymer of the first example were observed with a low vacuum scanning electron microscope (LV-SEM, 9kV), as shown in fig. 1 and fig. 2, respectively.

And (4) conclusion: as can be seen from fig. 1 and 2, both the tape applied to the skin before spraying and the tape applied to the skin after spraying the liquid dressing E containing the silicone-polyurethane copolymer of the first embodiment have scaly skin texture, which indicates that the original air permeability of the human skin is not affected after spraying the liquid dressing E containing the silicone-polyurethane copolymer of the first embodiment.

Water resistance test

The liquid dressings E, CE1 and CE2 of the first example and comparative examples 1 to 2 were placed in 3 air spray bottles, pressed 6 times against 1 corresponding piece of toilet paper to uniformly spray and cover the 3 pieces of toilet paper, left to stand for 5min to ensure drying, and then dropped with a dropper on the spray position of the toilet paper (laid flat), and whether the toilet paper was penetrated by the water drops was observed, as shown in FIG. 3, FIG. 4, and FIG. 5, respectively.

And (4) conclusion:

the results of the water resistance test showed that, referring to fig. 3, the toilet paper after spraying the liquid dressing E containing the silicone-polyurethane copolymer of example one was completely not penetrated by water droplets, which remained water-beaded; referring to fig. 4, the toilet paper sprayed with the liquid dressing CE1 of comparative example 1 was significantly penetrated by water droplets, which completely penetrated the toilet paper; referring to fig. 5, the toilet paper after spraying the liquid dressing CE2 of comparative example 2 was slightly penetrated by water droplets, which remained water-like, but the toilet paper below (indicated by the arrows) was partially wet through.

Nozzle clogging test

The liquid dressings E, CE1 and CE2 of the first embodiment and the comparative examples 1 to 2 were placed in air spray bottles (including springs, suction tubes, aluminum bottle bodies, aluminum aerosol valves, plastic nozzles with 0.3 to 0.35mm in diameter and spray amount of about 0.1 to 0.12mL each time), pressed for 5 times respectively, placed for 2 weeks, continuously pressed again, and observed whether the nozzles can smoothly spray liquid, whether the nozzles will bounce off after being pressed, whether the spray range and the spray amount are uniform (without significant divergence), so as to evaluate the smooth degree of spraying.

And (4) conclusion:

the nozzle clogging test results showed that when the air bottle containing the liquid dressing E containing a silicone-polyurethane copolymer of example one was sprayed again, only about 1% of the air bottle was sprayed slightly unsmoothly, and the unsmoothly was immediately eliminated after the nozzle was wiped with alcohol cotton; when the air spray bottle containing the liquid dressing CE1 of comparative example 1 was sprayed again, about 67% of the air spray bottles were sprayed smoothly, and the unsmooth situation could not be eliminated immediately after the nozzle was wiped with alcohol cotton; when the air bottle containing the liquid dressing CE2 of comparative example 2 was sprayed again, about 97% of the air bottle was sprayed with a poor solution, and the poor solution could not be immediately eliminated even after the nozzle was wiped with alcohol cotton.

Test of air permeability

Selecting a spray head with a valve spraying amount of 50 μm, spraying the liquid dressing E in the embodiment with a spraying distance of 50 μm and the liquid dressing CE3 in the comparative example 3 on the collagen film, and controlling the spraying distance to be 8 cm;

the moisture penetration standard of the EN13726-2 dressing is utilized to carry out a test, in the process, a collagen film is clamped on a stainless steel container filled with water through a stainless steel clamp, after the device is ensured to be sealed (the clamp meets the requirement of the specification), the device is placed in an oven controlled by temperature and humidity for 24 hours (32 ℃ 10% RH), and then the measurement is carried out. Three groups consisting of two test groups and a control group (collagen film not sprayed with any product), 3 test samples per group.

The calculation method comprises the following steps: the difference in water volume in the stainless steel container was measured, and the amount of water loss in the other two groups was converted based on the amount of water solution reduced in the control group as 100% to compare the air permeability.

Experimental data: (amount of scattering)

Film sprayed with liquid dressing E	Film sprayed with liquid dressing CE3	Film of an uncoated product
			100±8％	90±15％	95±5％

Drying Rate test

Respectively and uniformly spraying 0.5mL of the liquid dressing E, CE3 of the above example and comparative example 3 on the skin of a human arm (pressed 5 times), wherein the spraying area is 3X3cm, the fixed distance is 10cm mL, and each sample is sprayed 5 times

The manner in which each judged dry was averaged with five data of visual non-reflection (with 3-person judgment) and toilet paper placement (2 tests).

Experimental data:

	this example (liquid dressing E)	Comparative example 3(CE3)
			Drying time	8±3s	20±5s

Residence time test

Respectively and uniformly spraying 0.5mL of the liquid dressing E, CE3 of the above example and comparative example 3 on the skin of the human arm (pressed 5 times), wherein the spraying area is 3X3cm, the fixed distance is 10cm mL,

the positions of 0000peak of the map measured after the initial spraying are used as the definite ratio and compared with 100% in each group, and then the position values are respectively observed according to 180s and 300s at different times to calculate the percentage of the reserve, and each group is tested for 3 times (N is 3).

Experimental data:

	after 180s	After 300s
			This embodiment (E)	95_±_10_％	85_±_5_％
Comparative example 3(CE3)	75_±11__％	_68_±_4_％

Wash test

Respectively and uniformly spraying 0.5mL of the liquid dressing E, CE3 of the above example and comparative example 3 on the skin of a human arm (5 times of pressing), spraying the liquid dressing on the skin of the human arm with an area of 3X3cm and a fixed distance of 10cm mL, and cleaning the liquid dressing 1 time, 2 times and 3 times by an infrared spectrophotometer and FTIR-ATR measurement;

the cleaning mode is that the Yibilian antibacterial hand washing cream is used for scrubbing both hands to wash out foams, the test part is scratched for 3 circles, then the foams are removed by clean water, and the test is carried out after the foams are dried. (N is 3)

Experimental data:

	after 1 time of cleaning	After 2 times of cleaning	After 3 times of cleaning
				E	85_±11__％	70__±5__％	63_±6__％
CE3	83_±_8_％	78_±_5_％	75_±_5_％

Sensory evaluation test

The liquid dressings E, CE3 of example and comparative example 3 were uniformly sprayed on the skin of human arms in an amount of 0.5mL (5 strokes), and the sprayed area was 3X3cm, and the fixed distance was 10cm mL, so that 20 panelists were given scores (minimum 1 point, maximum 6 points) for the degree of conformity with no unpleasant odor, low visibility, low feeling of existence, low stickiness, and smooth feeling, respectively, and the average results are shown in the following tables.

The present sensory test was carried out in the form of a questionnaire,

the subjects were asked to freely move for 5 minutes, and to feel a static posture and a foreign body sensation during movement.

Low stickiness the subjects were asked to feel whether the painted area was sticky or not when they were in contact with the skin.

Experimental data:

	has no unpleasant odor	Low visibility	Low sense of existence	Low stickiness	Smooth feeling
						E	5.5	4.65	4.15	5.0	4.8
CE3	1.8	3.9	1.9	1.8	2.15

In conclusion, the liquid dressing containing silicone-polyurethane copolymer of the present invention does not affect the original air permeability of skin, can form a protective film with good water resistance after spraying, and does not easily block the nozzle of the spray bottle after spraying, thereby achieving the purpose of the present invention.

The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.