CN104693774B - A kind of polyethyleneglycol diacrylate hydrogel with aromatic odor and preparation method thereof - Google Patents

Abstract

The invention relates to a polyethylene glycol diacrylate hydrogel with aromatic smell and a preparation method thereof. According to mass percentage, the polyethylene glycol diacrylate hydrogel raw material comprises: polyethylene glycol diacrylate 10.0- 40.0%, essence microcapsules 4.0‑6.0%, initiator 0.4‑0.6%, deionized water 53.4‑85.6%. Preparation: Dissolve polyethylene glycol diacrylate in deionized water, pass through N ₂ for a period of time, then add microcapsules embedded with essence, and obtain polyethylene glycol diacrylate with aromatic odor under the action of initiator Hydrogels. In the present invention, adding microcapsules not only plays the role of increasing fragrance, but also avoids the use of catalyst in the hydrogel preparation process, and simplifies the preparation process.

Description

A kind of polyethylene glycol diacrylate hydrogel with aromatic smell and its preparation method

technical field

The invention belongs to the field of hydrogel materials and preparation thereof, in particular to a polyethylene glycol diacrylate hydrogel with aromatic odor and a preparation method thereof.

Background technique

Polyethylene glycol is a polyether-type water-soluble polymer compound certified by the US Food and Drug Administration. Because the compound has the advantages of low toxicity, biocompatibility and no toxic and side effects in the living body, it is widely used in chemical industry, food, textile, medicine and other fields closely related to human body. In addition, the molecular weight of polyethylene glycol varies from several hundred to tens of thousands, so its application range is very wide. At the same time, the end of the polyethylene glycol molecular chain is a hydroxyl group. In industrial applications, it can be easily modified to obtain polyethylene glycol monomers with different functions. For example, the amino group is grafted on the polyethylene glycol molecule to make the reaction The activity is greatly improved, and the amide bond formed by the reaction with the carboxyl group is more stable than the ester bond formed by the reaction between the hydroxyl group and the carboxyl group.

Hydrogel is a multi-component system composed of a polymer with a three-dimensional network structure and water. Due to the existence of cross-linking, this multi-component system can absorb a large amount of water without dissolving in water, and it is a substance that exists widely in nature. Many parts of organisms are made of polymer hydrogels. Hydrogels with both liquid and solid forms have swelling properties, mechanical properties, permeability, and surface properties. These properties provide hydrogels with a wide range of application prospects in new medical devices, superabsorbent materials, and personal care. .

Essence microcapsules are micron-sized capsules with essence as the core material. Flavors are mainly composed of dozens of different components such as alcohols, anhydrides, esters, and ketones, which are highly volatile and highly hydrophilic. Microencapsulation of flavors 1. Overcome the influence of many external factors, such as changes in pH, pressure, and temperature on flavors; 2. The loss of flavors is suppressed and the aroma is kept intact, thereby improving the storage and use of flavors 3. It can achieve the effect of controlled release, which can make the product fragrance lasting and stable; 4. Improve the oxygen resistance, heat resistance and light resistance of the fragrance, and enhance its stability; 5. It can change the physical state of the fragrance so that Make it more widely used in industrial production.

Contents of the invention

The technical problem to be solved by the present invention is to provide a polyethylene glycol diacrylate hydrogel with an aromatic smell and a preparation method thereof. The preparation method of the present invention has mild conditions, simple and easy-to-control process, and the prepared polyethylene glycol Diacrylate hydrogel has high mechanical strength and mint flavor, and has certain medicinal value. The invention broadens the application space of the traditional hydrogel, and has a fragrant smell, which makes people feel comfortable, which just satisfies the pursuit trend of people's material needs.

A kind of polyethylene glycol diacrylate hydrogel with aromatic odor of the present invention, according to mass percentage, polyethylene glycol diacrylate hydrogel raw material comprises: polyethylene glycol diacrylate 10.0-40.0%, essence Microcapsule 4.0-6.0%, initiator 0.4-0.6%, deionized water 53.4-85.6%.

The essence microcapsule: a microcapsule in which essence is wrapped with polyurea as shell material.

The initiator is ammonium persulfate APS or potassium persulfate KPS.

A kind of preparation method of polyethylene glycol diacrylate hydrogel with aromatic smell of the present invention comprises:

(1) Add deionized water to the emulsifier aqueous solution, stir evenly to obtain the water phase; mix the diisocyanate and essence, and stir to obtain the oil phase; wherein the mass ratio of the emulsifier aqueous solution to the deionized water is 16.6-50.0:46.6- 80.0;

(2) Add the oil phase to the water phase, shear with a homogenizer to obtain an oil-in-water emulsion, then add diamine aqueous solution dropwise, stir at a constant temperature of 30-40°C for 20-30min, and heat up to 50-60°C , stirring at constant temperature for 1.5-2.5h to obtain essence microcapsules; wherein the mass ratio of diisocyanate MDI, essence, and diamine is 2.5-4.5:10.0-40.0:0.5-2.5;

(3) Mix polyethylene glycol diacrylate and deionized water, stir and mix to obtain a polyethylene glycol diacrylate solution, then add the essence microcapsules obtained in step (2), and stir in a nitrogen atmosphere for 1-3h , Add the initiator, 2-4h, namely polyethylene glycol diacrylate hydrogel.

The mass percent concentration of the emulsifier aqueous solution in the step (1) is 6%.

The diisocyanate in the step (1) is 4,4'-diphenylmethane diisocyanate MDI.

In the step (1), the emulsifier is a polymer (D-425) of alkylbenzene sulfonate and formaldehyde (Nanjing Jierun Technology Co., Ltd.), and the essence is peppermint oil.

In the step (2), the rotating speed of the homogenizer is 4000-10000rpm, and the shearing time is 3-5min.

The concentration of the diamine aqueous solution in the step (2) is 40 wt%, and the diamine is 1,6-hexanediamine HMDA.

Preparation of essence microcapsules: the oil phase is composed of diisocyanate and essence; the water phase is composed of emulsifier, diamine and deionized water; Under the action of shearing, an emulsion is formed, and at 55°C, diisocyanate and diamine polymerize at the oil-water interface of the formed emulsion droplets to form a polyurea shell, thereby encapsulating the fragrance in it to form microcapsules.

Beneficial effect

(1) The present invention uses polyethylene glycol as a raw material to prepare hydrogel, and the hydrogel prepared by using the compound has the advantages of low toxicity, biocompatibility and no toxic and side effects in vivo; in addition, polyethylene glycol The molecular weight of polyethylene glycol varies from several hundred to tens of thousands, so its application range is very wide. At the same time, the molecular chain end of polyethylene glycol is a hydroxyl group. In industrial applications, it can be easily modified to obtain polyethylene glycol monolayers with different functions. body, so many hydrogels with different structures and functions can be obtained;

(2) The essence microcapsules added by the present invention are mint oil microcapsules; mint oil is the composition after peppermint oil is debrained, and contains L-menthol, menthyl acetate and menthone etc. in its composition, and the addition of mint oil not only provides Aromatic smell, and simplify the preparation steps of polyethylene glycol hydrogel;

(3) The preparation method of the present invention has mild conditions, simple and easy-to-control process, and the prepared polyethylene glycol hydrogel has high mechanical strength and has mint flavor, and has certain medicinal value. The invention broadens the application space of the traditional hydrogel, and has a fragrant smell, which makes people feel comfortable, which just satisfies the pursuit trend of people's material needs.

Description of drawings

Fig. 1 is polyethylene glycol diacrylate hydrogel contrast figure, wherein a is comparative example 1, and b is embodiment 1;

Figure 2 is a gel comparison diagram of polyethylene glycol diacrylate, wherein a is Comparative Example 1, and b is Example 2.

detailed description

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Comparative example 1

(1) Mix 10.0g of polyethylene glycol diacrylate and 85.6g of deionized water, and stir until completely miscible;

(2) Add 0.4g APS to the above solution, and stir for 1-3h under _N2 environment;

(3) Add 0.4g Na ₂ S ₂ O ₄ to the above solution, and polyethylene glycol diacrylate hydrogel can be formed within 2-4 hours.

Example 1

(1) Preparation of essence microcapsules:

a preparation of water phase

Weigh 6.0g of the polymer (D-425) of emulsifier alkylbenzene sulfonate and formaldehyde into a beaker, add deionized water to 100g, and stir for 2 hours under the action of a magnetic stirrer to completely dissolve the emulsifier D-425 , be prepared into 6wt% emulsifier D-425 aqueous solution, and set aside. Add 16.6g of emulsifier D-425 aqueous solution into a 250ml beaker, then add 56.6g of deionized water, stir evenly to obtain the water phase;

Preparation of b oil phase

Add 3.2g of diisocyanate MDI into a 100ml beaker, then add 20g of mint oil, and stir until completely miscible to obtain an oil phase;

c emulsion formation

The oil phase was added rapidly to the water phase, forming an immiscible mixture. Under the action of a homogenizer at 6600 rpm, high-speed shearing for about 3 minutes forms an oil-in-water emulsion;

d Microcapsule formation

Add 3.6g of 40wt% 1,6-hexanediamine HMDA aqueous solution dropwise to the formed emulsion, stir magnetically at a constant temperature at 35°C for 30min, rapidly raise the temperature to 55°C, stir magnetically at a constant temperature for 2h, and obtain the fragrance microcapsule slurry ;

(2) Mix 10.0g of polyethylene glycol diacrylate and 85.6g of deionized water, and stir until completely miscible;

(3) Add 4.0 g of the essence microcapsules prepared in step (1) to the above solution, and stir for 1 to ₃ hours under N environment;

(4) Add 0.4g APS to the above solution, and polyethylene glycol diacrylate hydrogel can be formed within 2-4 hours.

Example 2

(1) Preparation of essence microcapsules:

a preparation of water phase

Weigh 6.0g of the polymer (D-425) of emulsifier alkylbenzene sulfonate and formaldehyde into a beaker, add deionized water to 100g, and stir for 2 hours under the action of a magnetic stirrer to completely dissolve the emulsifier D-425 , be prepared into 6wt% emulsifier D-425 aqueous solution, and set aside. Add 16.6g of emulsifier D-425 aqueous solution into a 250ml beaker, then add 36.6g of deionized water, stir evenly to obtain the water phase;

Preparation of b oil phase

Add 3.2g of diisocyanate MDI into a 100ml beaker, then add 40g of mint oil, and stir until completely miscible to obtain an oil phase;

c emulsion formation

The oil phase was added rapidly to the water phase, forming an immiscible mixture. Under the action of a homogenizer at 6600 rpm, high-speed shearing for about 3 minutes forms an oil-in-water emulsion;

d Microcapsule formation

Add 3.6g of 40wt% 1,6-hexanediamine HMDA aqueous solution dropwise to the formed emulsion, stir magnetically at a constant temperature at 35°C for 30min, rapidly raise the temperature to 55°C, stir magnetically at a constant temperature for 2h, and obtain the fragrance microcapsule slurry ;

(2) Mix 10.0g of polyethylene glycol diacrylate and 85.6g of deionized water, and stir until completely miscible;

(3) Add 4.0 g of the essence microcapsules prepared in step (1) to the above solution, and stir for 1 to ₃ hours under N environment;

(4) Add 0.4g APS to the above solution, and polyethylene glycol diacrylate hydrogel can be formed within 2-4 hours.

Claims (7)

1. a kind of polyethyleneglycol diacrylate hydrogel with aromatic odor, it is characterised in that：By mass percentage, poly- second Diol acrylate hydrogel raw material is：Polyethyleneglycol diacrylate 10.0-40.0%, essence microcapsule 4.0-6.0%, Initiator 0.4-0.6%, deionized water 53.4-85.6%；Wherein essence microcapsule：It is that core is wrapped by shell material essence of polyureas Cover；Initiator is ammonium persulfate APS or potassium peroxydisulfate KPS.

2. a kind of preparation method of the polyethyleneglycol diacrylate hydrogel as claimed in claim 1 with aromatic odor, Including：

(1) deionized water is added in emulsifier aqueous solution, stirred, obtain aqueous phase；Diisocyanate, essence are mixed, stirred Mix, obtain oil phase；Wherein the mass ratio of emulsifier aqueous solution and deionized water is 16.6-50.0:46.6-80.0；

(2) oil phase is added into aqueous phase, homogenizer shearing obtains emulsion oil-in-water, is then added dropwise to two amine aqueous solutions, Constant temperature stirs 20-30min under the conditions of 30-40 DEG C, is warming up to 50-60 DEG C, constant temperature stirring 1.5-2.5h obtains essence microcapsule； Wherein diisocyanate MDI, essence, the mass ratio of diamines are 2.5-4.5:10.0-40.0:0.5-2.5；

(3) polyethyleneglycol diacrylate and deionized water are mixed, stirs and evenly mixs, obtain polyethyleneglycol diacrylate molten Liquid, then adds step (2) gained essence microcapsule, 1-3h is stirred in nitrogen atmosphere, initiator is added, 2-4h is produced poly- Ethylene glycol diacrylate hydrogel.

3. a kind of preparation side of polyethyleneglycol diacrylate hydrogel with aromatic odor according to claim 2 Method, it is characterised in that：The mass percentage concentration of emulsifier aqueous solution is 6% in the step (1).

4. a kind of preparation side of polyethyleneglycol diacrylate hydrogel with aromatic odor according to claim 2 Method, it is characterised in that：Diisocyanate is 4,4 '-methyl diphenylene diisocyanate MDI in the step (1).

5. a kind of preparation side of polyethyleneglycol diacrylate hydrogel with aromatic odor according to claim 2 Method, it is characterised in that：Emulsifying agent is the polymer D-425 of alkylbenzenesulfonate and formaldehyde in the step (1), and essence is peppermint Vegetable oil.

6. a kind of preparation side of polyethyleneglycol diacrylate hydrogel with aromatic odor according to claim 2 Method, it is characterised in that：Homogenizer rotating speed is 4000-10000rpm in the step (2), and shear time is 3-5min.

7. a kind of preparation side of polyethyleneglycol diacrylate hydrogel with aromatic odor according to claim 2 Method, it is characterised in that：The concentration of two amine aqueous solutions is 40wt% in the step (2), and diamines is hexamethylene diamine HMDA.