CN114960277B

CN114960277B - Ampelopsis grossedentata extract, preparation method thereof and application thereof in waterproof and oil-proof agent

Info

Publication number: CN114960277B
Application number: CN202110755215.4A
Authority: CN
Inventors: 赵崇滔; 郑梓烁; 孙艳梅; 向华; 林木雄; 卞喻; 陈婉淳
Original assignee: Huizhou City Suihe Science & Technology Co ltd
Current assignee: Foshan Dingmao Technology Co ltd
Priority date: 2021-07-04
Filing date: 2021-07-04
Publication date: 2023-06-16
Anticipated expiration: 2041-07-04
Also published as: CN114960277A

Abstract

The invention discloses a vine tea extraction method, which adopts superfine crushed vine tea dry leaves, fully releases vine tea flavone therein, utilizes microwave-assisted heating to further destroy cell walls, releases more vine tea flavone, and then fully utilizes the solubility of vine tea flavone at different temperatures, the dissolution curve in vine tea flavone boiling water and the properties of vine tea Huang Tongre of high dissolution speed and low precipitation speed, and can obtain vine tea extract with the extraction rate of 80% and the purity of 95%. The extraction method adopts pure water extraction, has no addition, is safe, healthy and environment-friendly, and can extract and obtain the food-grade natural antibacterial agent. Meanwhile, the invention also discloses the vine tea extract prepared by the extraction method and a water-and-oil-proof agent containing the vine tea extract, and the water-and-oil-proof agent can prevent microbial pollution and has no health hidden trouble due to the fact that the vine tea extract is used as an antibacterial agent.

Description

Ampelopsis grossedentata extract, preparation method thereof and application thereof in waterproof and oil-proof agent

Technical Field

The invention relates to a vine tea extraction method and application of a vine tea extract obtained by extraction, in particular to a vine tea extraction method with higher extraction rate and purity and application of the vine tea extract obtained by extraction in a water and oil proofing agent.

Background

In the year 2020, the national development and reform commission and the ecological environment department jointly issue the most severe plastic regulations on history on opinion about further strengthening plastic pollution control, which points out that the consumption of disposable plastic products is further reduced, the replacement products are promoted, and the recycling and energy utilization ratio of plastic wastes is greatly improved. With the promotion of plastic limiting, domestic and international disposable plastic packaging articles, especially disposable plastic tableware will quickly come out of the market, and paper-based substitute products which can be repulped, recycled, safe and healthy will become the main stream of the market. The paper pulp fiber does not have water and oil resistance, the key point of replacing plastic with paper is to endow paper with water and oil resistance, and the key point is that the energized paper-based product has repulpability, so that the recycling of paper resources can be realized, and the ultimate goal of sustainable development is reached.

The current market viable solution is to solve this using two approaches:

first kind: the fluorine-containing oil-proofing agent is applied in the slurry during the preparation process. The fluorine atoms can form a compact thin layer with low surface energy, so that the interaction between fibers and liquid can be reduced, and the paper is endowed with good oil-proof performance. However, the current main fluorine-containing oil-proof agent C8-PFCs (containing 8 carbon perfluorocarbons) are toxicologically unsafe, such as bioaccumulation and potential system and developmental toxicity, so the substances gradually exit the market; while relatively safe short-chain C6-PFCs (containing 6 carbon perfluorocarbons) emerge, the toxicological data for C6-PFCs is still quite small and is not known to be safe. Therefore, fluorine-free oil-repellent agents have become a hot spot in the industry.

Second kind: a layer of water-proof and oil-proof agent is applied on the surface of the paper tableware. At present, PE is mainly used as a waterproof and oil-proof agent, but PE is difficult to separate from a paper base, and the prepared paper base substitute can only be buried or burnt, so that recycling is difficult to form; at present, the industry begins to try to use a new water-based fluorine-free coating as a water-proof and oil-proof agent, but the water-proof and oil-proof agent takes water as a solvent, is easy to cause microbial contamination in the storage process, is easy to generate peculiar smell after being coated on paper-based materials and is easy to be soaked in boiling water, and food is directly contacted after being manufactured into disposable tableware, so that the hidden danger of influencing the food safety is caused.

Conventional industrial paint antibacterial agents include Zinc Pyrithione (ZPT), 3-iodo-2-propargyl butyl carbamate (IPBC), 2-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one (DCOIT), and N-butyl-1, 2-benzisothiazolin-3-one (BBIT), which are used for surface sterilization and mildew prevention effects in buildings, equipment, etc. However, the water-proof and oil-proof agent is specially used on the surface of the paper-based material, the paper-based tableware which is directly contacted with food is prepared, and the selection of the antibacterial agent needs to be careful: it is necessary to consider whether the antibacterial agent migrates into food or is harmful to human health.

Vine tea is a plant with homology of medicine and food, and stem and leaf of vine tea is processed by a green tea-like manufacturing process, so that dry leaves with silver frost distributed on the surfaces can be obtained, and the silver frost is mainly flavonoid natural bactericide namely Dihydromyricetin (DMY). According to the growth part and picking time of fresh raw leaves, the DMY content in the vine tea dry leaf product is widely distributed, and most of the DMY content is 10-40%.

The currently reported DMY extraction methods mainly comprise recrystallization, resin adsorption, microwave extraction, column chromatography, high-speed countercurrent chromatography, supercritical fluid extraction and the like. The recrystallization method mainly utilizes the characteristic of DMY hot water dissolution and low-temperature precipitation, is simple and environment-friendly and easy to operate, but has low yield, and the yield of the product with 95 percent of high purity is less than 10 percent; the yield of the resin adsorption method can exceed 90 percent, but the purity is only about 80 percent; the microwave extraction method has high efficiency, but the yield is not high, and generally only about 30 percent; the column chromatography needs to use organic matters such as ethanol, toluene, ethyl acetate, methanol and the like, and has high safety requirement and high cost for large-scale production; the purity of the high-speed countercurrent chromatography product can reach 99 percent, the yield can reach 85 percent, but a large number of samples are difficult to obtain at one time, and the industrial popularization is impossible; the supercritical fluid extraction method has no pollution, but has low yield, large disposable equipment investment, high operation cost and difficult popularization. All the reported methods are based on a certain vine tea dry leaf raw material, a series of experiments are designed by an orthogonal method, and the optimal condition is selected, so that the actual situation that the DMY content in vine tea dry leaves is wide in distribution range cannot be considered, and the obtained optimal condition has large personalized difference, such as 20:1 optimal liquid-material ratio, 30:1 optimal liquid-material ratio and 40:1 optimal liquid-material ratio.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a vine tea flavone DMY extraction method under the guidance of theoretical research conclusion, which is applicable to vine tea dry leaves with different DMY contents, and has high yield and purity and is based on pure water solvent; meanwhile, the invention also provides the vine tea extract extracted by the extraction method and the application of the vine tea extract as an antibacterial agent in the waterproof and oilproof agent.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a vine tea extraction method, the method comprising the steps of:

(1) Crushing: superfine pulverizing dried vine tea leaves to obtain superfine vine tea powder;

(2) Premixing: pre-mixing the vine tea superfine powder with purified water to obtain thick slurry;

(3) Microwave auxiliary heating: heating the premixed thick slurry for 5-15 minutes under the microwave of 600-1000 w;

(4) Boiling and extracting: adding purified water into an extraction kettle, boiling, adding thick slurry heated by microwaves under high-speed stirring, and continuously keeping boiling and high-speed stirring for 3-5 minutes after the addition;

(5) And (5) filtering while hot: the mixed solution obtained in the step (4) is firstly filtered through a G3 sand core funnel under reduced pressure, and powder slag is filtered to obtain clear filtrate;

(6) Low temperature precipitation: naturally cooling the clear filtrate obtained in the step (5) to normal temperature, then placing the clear filtrate in low temperature for cold storage, aging overnight, crystallizing and separating out an off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY) initial product, filtering, washing with ice purified water, and drying to obtain light yellow powder;

(7) And (3) secondary extraction: concentrating the filtrate separated out of the primary product by rotary evaporation, and freeze-drying and collecting; adding half of pure water amount for the first extraction into an extraction kettle, carrying out microwave preheating on filter residues subjected to hot suction filtration, and then carrying out secondary extraction to obtain off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY);

(8) Three times of extraction: concentrating the filtrate after secondary extraction by rotary evaporation, and freeze-drying and collecting; adding half of pure water amount for the first extraction into an extraction kettle, carrying out microwave preheating on filter residues subjected to hot suction filtration, and then carrying out three times of extraction to obtain off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY);

(9) And (3) carrying out rotary evaporation and concentration on the filtrate after three times of extraction, then carrying out freeze-drying, combining the filtrate with the freeze-dried powder extracted in the previous two times, carrying out superfine grinding, testing the content of ampelopsis grossedentata flavone-Dihydromyricetin (DMY), calculating the boiling water dosage according to the content, and repeating the previous extraction process until the off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY) in the ampelopsis grossedentata dry leaves is obtained in a cumulative way.

In the ampelopsis grossedentata extraction method, superfine grinding is adopted in the step (1), so that ampelopsis grossedentata flavone-Dihydromyricetin (DMY) can be fully released from plant cells; the step (2) adopts a minimum amount of purified water to premix the superfine powder of the vine tea into thick slurry, which is beneficial to rapid dispersion during boiling extraction; in the step (3), when the premixed thick slurry is heated, the heating time is preferably 10 minutes; in the boiling extraction in the step (4), high-speed stirring is preferably mechanical stirring, and the speed is not lower than 5000 revolutions per minute.

As a preferred embodiment of the vine tea extraction method of the present invention, the superfine grinding in the step (1) is performed by using a 300 mesh screen as a standard; and (3) carrying out suction filtration while the filter liquor is hot in the step (5), and if a small amount of powder enters the filter liquor, adopting a G4 or even G5 sand core funnel to carry out suction filtration under reduced pressure to ensure that the filter liquor is clear.

As a preferred embodiment of the ampelopsis grossedentata extraction method, the yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (6) is not lower than 40%, and the purity is not lower than 95%; the accumulated yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (7) is not lower than 60%; the accumulated yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (8) is not lower than 70%.

Compared with the extraction method in the prior art, the vine tea extraction method disclosed by the invention mainly has the following differences:

(1) Superfine grinding: crushing the dry leaves, destroying cells, fully releasing DMY, and obtaining ultrafine powder smaller than 300 meshes;

(2) Microwave assistance: the microwave can not only preheat the superfine powder thick slurry, but also further destroy cell walls and release more DMY;

(3) The solubility of DMY at different temperatures is fully utilized:

at high temperature, accurately calculating the water-material ratio: firstly testing the DMY content of each batch of extracted vine tea, calculating the required pure water amount according to the solubility of the crude product of the flavone DMY of the boiled vine tea based on the tested content, ensuring the saturation of the DMY in the extracting solution, using as little water as possible, and reducing the energy consumption in the extracting process;

at low temperatures, this helps to ensure high yields: the DMY content in the saturated extracting solution is less than 5% of the DMY content in boiling water below ten ℃, and the high yield can be ensured by fully aging at the low temperature of 1-4 ℃;

(4) Fully utilizes the dissolution curve in DMY boiling water to improve the purity of the primary product: according to researches, more than 70% of DMY in vine tea can be rapidly dissolved into water 3-5 minutes before boiling extraction under sufficient stirring, and other components are dissolved out in more time, so that the purity of the primary product can be greatly improved by adopting ultra-short time extraction and ultra-high speed stirring;

(5) The method fully utilizes the property of high DMY thermosol speed and low precipitation speed, and obtains clear saturated extract by fractional filtration, thereby being beneficial to improving the purity of the primary product.

Secondly, the invention also provides a vine tea extract, which is extracted by adopting the extraction method.

Again, the present invention also provides a water and oil repellent agent having antibacterial effect, which contains the vine tea extract as described above.

As a preferred embodiment of the water-and oil-repellent agent of the present invention, the weight content of the ampelopsis grossedentata extract in the water-and oil-repellent agent is 0.6 to 1.4%. The vine tea extract has good antibacterial effect, and when the mass content of the vine tea extract in the water-proof and oil-proof agent is 0.6-1.4 per mill, the water-proof and oil-proof agent has obvious antibacterial effect.

As a preferred embodiment of the water-and oil-repellent agent of the present invention, the water-and oil-repellent agent further comprises a thermoplastic water-and oil-repellent acrylic resin and a thermoplastic reinforcing acrylic resin;

the thermoplastic waterproof and oil-proof acrylic resin contains waterproof monomers and oil-proof monomers; the waterproof monomer comprises an acrylic monomer and a styrene monomer; the oil-proof monomer is an acrylic ester monomer containing at least one of hydroxyl, amino and carboxyl;

the thermoplastic reinforced acrylic resin contains self-crosslinking groups.

The water-proof and oil-proof agent disclosed by the invention contains thermoplastic water-proof and oil-proof acrylic ester with water-proof and oil-proof effects besides the vine tea extract with antibacterial effects, wherein the thermoplastic water-proof and oil-proof acrylic ester contains a water-proof monomer and an oil-proof monomer, the water-proof monomer is generally selected from acrylic ester monomers and styrene monomers, and resin obtained by copolymerizing the acrylic ester monomers and the styrene monomers can provide good water resistance; the oil-proof monomer is generally selected from acrylic ester monomers containing hydroxyl, amino, carboxyl and other groups, and the resin obtained by copolymerizing the acrylic ester monomers has good oil-proof performance. Meanwhile, the waterproof and oilproof agent also comprises thermoplastic reinforced acrylic resin, the thermoplastic reinforced acrylic resin contains self-crosslinking groups, the self-crosslinking groups are generally selected from sodium acrylate and ammonium acrylate, the thermoplastic reinforced acrylic resin can improve the film forming property and the film strength of the coating, the adhesion fastness of the film on the surface of the paper material can also be enhanced through the interaction between the self-crosslinking groups and the paper material, the interaction can be relieved when the pH value is 10-11, the film can be easily and completely peeled off from the surface of the paper material (in order to verify whether the film of the waterproof and oilproof agent can be peeled off from the surface of the paper material or not, experiments are carried out by the inventor of the application, namely, the paper coating coated with the waterproof and oilproof agent can be easily and completely peeled off from the surface of the paper material under the deinking process condition of recycling waste paper, namely, the pH value is 10-11, and the waterproof and oilproof agent film can be separated from the paper material through a flotation process, so that the paper-based repulpability is realized.

As a preferred embodiment of the water and oil repellent agent of the present invention, the water repellent monomer contained in the thermoplastic water and oil repellent acrylic resin is selected from at least one of the following:

the oil-repellent monomer contained in the thermoplastic water-repellent and oil-repellent acrylic resin is selected from at least one of the following:

the self-crosslinking group is selected from at least one of the following:

as a preferred embodiment of the water and oil repellent agent of the present invention, the water and oil repellent agent comprises thermoplastic water and oil repellent acrylic resin and thermoplastic reinforcing acrylic resin in parts by weight, respectively: 65-75 parts of thermoplastic waterproof and oilproof acrylic resin and 15-25 parts of thermoplastic reinforced acrylic resin.

As a preferred embodiment of the water and oil repellent agent of the present invention, the water and oil repellent agent further comprises the following components in parts by weight: alcohol 2-8 parts and water 2-8 parts.

As a preferred embodiment of the water and oil repellent agent of the present invention, the water and oil repellent agent comprises the following components in parts by weight: 70 parts of thermoplastic water-proof and oil-proof acrylic resin, 20 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1 per mill of vine tea extract by mass.

The waterproof and oil-proof agent provided by the invention contains thermoplastic waterproof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin, adopts double acrylic resin, is scientifically compounded, can be used for forming a micron-sized coating on the surface of a paper material which is manufactured by a coating roller, and can be used for preparing various paper-based packages (including but not limited to disposable paper-based tableware) with waterproof and oil-proof requirements. The waterproof and oil-proof agent forms a compact film layer after a coating layer formed on the surface of a paper material is dried, has the properties of water resistance, oil resistance, temperature resistance, heat sealing and non-sticking rice, can be used for preliminarily replacing PE (polyethylene) film used for traditional disposable paper-based tableware such as paper cups, paper bowls and paper discs when being prepared into disposable paper-based tableware, reduces the use of PE, meets the requirement of government on plastic limiting, and can enter a pulping and papermaking stage together with other waste paper, the surface film layer of the recovered paper-based tableware can be completely peeled off from the surface of the paper material in a deinking process link, so that the paper material can enter a re-pulping stage, the recycling characteristics of the paper-based are fully utilized, and the development requirement of current circular economy is met. Provides a more environment-friendly disposable paper-based tableware solution for disposable plastic tableware. Meanwhile, the water-proof and oil-proof agent contains the vine tea extract, and food-grade vine tea flavone-Dihydromyricetin (DMY) in the vine tea extract is used as an antibacterial agent to be added into the water-proof and oil-proof agent, so that microbial pollution can be prevented, and health hidden danger can not be brought to the formula of the water-proof and oil-proof agent.

The waterproof and oil-proof agent adopts domestic acrylic resin, has lower cost, adopts two acrylic resins with different functions, scientifically compounds double acrylic resins, respectively provides waterproof and oil-proof effects, improves the film forming property of a coating, the strength of a film layer and the stripping effect of the film layer, adopts the acrylic resin with heat sealing property, can directly heat-seal and form paper materials with the waterproof and oil-proof requirements on the surface coated with the waterproof and oil-proof agent into various paper-based packages (including but not limited to disposable food packaging containers), does not contain fluorine, is nontoxic and tasteless.

The waterproof and oil-proof agent can achieve the following technical indexes:

(1) heat sealability: after the paper material with the surface layer coated with the water-proof and oil-proof agent is dried and solidified, the paper material can be directly manufactured into paper-based packaging containers (including but not limited to disposable food packaging containers such as paper cups, paper bowls, paper trays, paper boxes and paper bags) with the water-proof and oil-proof requirements according to the conventional process.

(2) Sensory requirements: the waterproof and oilproof paper-based packaging container prepared by the waterproof and oilproof agent has no peculiar smell after being filled with boiling water.

(3) Water and oil resistance requirements: condition 1: pouring the prepared mixture of tap water and edible oil with the mass ratio of 1:1 into a test container bag after boiling for 2 minutes, and placing the mixture in a 65 ℃ oven for 4 hours; condition 2: after the fries are contained, heating for 2 minutes in a microwave oven in a hot dish mode, and observing the outer surface of kraft paper of the whole container bag including a heat sealing position, wherein no water seepage and oil seepage phenomenon occur; the oil repellency rating is at least 6.

(4) Non-sticking rice: pouring hot meal into the prepared tableware, compacting, standing in a 50-DEG C oven for 4 hours, pouring, and keeping the rice grains on the inner surface only very little.

(5) Paper reslurried with the water-and oil-repellent agent of the present invention: after the paper with the surface layer coated with the waterproof and oil-proof agent is dried and solidified for 20 seconds by hot air blowing, the paper pulp can be manufactured into paper after cutting, beating, deinking and bleaching processes.

When the waterproof and oilproof agent is prepared, thermoplastic waterproof and oilproof acrylic resin and thermoplastic reinforced acrylic resin are uniformly mixed to obtain a resin mixture, and then the rest raw materials are added into the resin mixture, uniformly mixed and filtered to obtain the waterproof and oilproof agent.

Finally, the invention also provides application of the waterproof and oil-proof agent with the antibacterial effect in preparation of waterproof and oil-proof paper-based packages, wherein the waterproof and oil-proof agent is directly coated on the surface of a paper material which is manufactured, and then the waterproof and oil-proof paper-based packages are prepared by adopting the paper material; the waterproof and oil-proof paper-based package is a disposable paper-based container for food packaging, and the disposable paper-based container for food packaging comprises paper cups, paper bowls, paper trays, paper dishes, paper boxes and paper bags.

The waterproof and oil-proof agent is a water-based paint taking acrylic acid as main resin, adopts two different acrylic resins, is scientifically compounded, can be used for forming a micron-sized coating on the surface of a paper material manufactured by paper making through a coating roller, is a compact film layer after being dried, has the waterproof, oil-proof, temperature-resistant, heat-sealable, non-sticking, peelable performances, has no peculiar smell after hot water brewing, and can be used for preparing various paper-based packages with waterproof and oil-proof requirements. The coated paper material with the surface formed with the micron-sized coating layer after drying can be directly formed by heat sealing in the process of preparing the waterproof and oil-proof paper-based package, the prepared waterproof and oil-proof paper-based package has the waterproof, oil-proof and temperature-resistant effects, and the recovered waterproof and oil-proof paper-based package can enter a pulping and papermaking stage together with other waste paper, and the surface film layer can be completely peeled off from the surface of the paper material in a deinking process link, so that the paper material can enter a recycling stage.

In addition, the waterproof and oil-proof agent can be formed into a micron-sized coating layer by knife coating on the surface of the paper material manufactured by the coating roller, and the coating layer is a compact film layer after being dried, has the properties of waterproof, oil-proof, temperature-resistant, heat-sealable, non-sticking rice and strippable, has no peculiar smell when being soaked in hot water, the PE film coating can be used for preliminarily replacing the traditional disposable paper-based tableware such as paper cups, paper bowls and paper discs, so that the PE film coating is reduced, the government 'plastic limiting' requirement is met, the recycling characteristic of the paper base can be fully utilized, and a more environment-friendly disposable paper-based tableware solution is provided for the disposable plastic tableware.

When the waterproof and oil-proof agent is applied, the paper material with the surface layer coated with the waterproof and oil-proof agent is dried and solidified, and then can be directly manufactured into various paper-based packages (including but not limited to disposable paper-based tableware) with waterproof and oil-proof requirements according to a conventional process. After the disposable paper-based tableware prepared by the waterproof and oil-proof agent disclosed by the invention is filled with boiling water, no peculiar smell exists; after the prepared disposable paper-based tableware is filled with a mixture of tap water and edible oil in a ratio of 1:1, the disposable paper-based tableware is heated for 2 minutes in a microwave oven heating dish mode after being filled for 4 hours at 65 ℃, and the disposable paper-based tableware is water-proof and oil-proof (including a heat sealing position) and has an oil-proof grade of at least 6.

Compared with the prior art, the vine tea extraction method disclosed by the invention has the following main beneficial effects:

(1) The total extraction rate of the three times of extraction and superposition can reach 80 percent, and the purity can reach 95 percent;

(2) Pure water extraction, no addition, safety, health and environmental protection;

(3) The equipment and the process are simple, the cost is low, and the popularization is easy;

(4) The food-grade raw materials can provide food-grade natural antibacterial agents, and are water-based fluorine-free waterproof and oil-proof agents which are smoothly popularized and protected in food packaging.

The vine tea extract is obtained by adopting the vine tea extraction method disclosed by the invention, so that the extraction rate is higher, the purity of vine tea flavone-Dihydromyricetin (DMY) contained in the vine tea extract can reach 95%, and the pure water is adopted in the extraction method for extraction, so that no addition is caused, and the vine tea extract is safe, healthy and environment-friendly, and can be used as a raw material of a food-grade natural antibacterial agent. The water-proof and oil-proof agent is a water-based fluorine-free water-proof and oil-proof agent, and the vine tea extract is contained, so that microbial pollution can be prevented, a good antibacterial effect is achieved, and health risks are avoided.

Detailed Description

For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.

Example 1

An embodiment of the water and oil repellent agent of the present invention comprises the following components in parts by weight: 65 parts of thermoplastic waterproof and oilproof acrylic resin, 25 parts of thermoplastic reinforced acrylic resin, 4 parts of alcohol, 6 parts of water and 0.6 per mill of vine tea extract by mass. The waterproof and oil-proof agent of the embodiment is prepared by the following method: the water-proof and oil-proof agent is prepared by uniformly mixing thermoplastic water-proof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin (for example, uniformly stirring and mixing at the speed of 800 r/min) to obtain a resin mixture, adding alcohol and water into the resin mixture, uniformly mixing (for example, uniformly stirring and mixing at the speed of 400 r/min), filtering (for example, filtering by adopting a 200-mesh filter bag), and bottling.

In this embodiment, the vine tea extract is extracted by the following method:

(1) Crushing: superfine pulverizing Ampelopsis grossedentata dry leaves, and sieving with 300 mesh sieve to obtain ultra-fine powder;

(2) Premixing: pre-mixing the vine tea superfine powder with a minimum amount of purified water to obtain thick slurry;

(4) Boiling and extracting: adding purified water into an extraction kettle, boiling, adding thick slurry heated by microwaves under high-speed stirring (mechanical stirring is not less than 5000 revolutions per minute), and continuously keeping boiling and high-speed stirring for 3-5 minutes after the addition;

(5) And (5) filtering while hot: the mixed solution obtained in the step (4) is firstly filtered through a G3 sand core funnel under reduced pressure, and powder slag is filtered; if a small amount of powder enters the filtrate, a G4 or even G5 sand core funnel can be used for decompression and suction filtration to ensure that clear filtrate is obtained;

(6) Low temperature precipitation: naturally cooling the clear filtrate obtained in the step (5) to normal temperature, then placing the clear filtrate in low-temperature refrigeration (preferably 1-2 ℃) for aging overnight, and obtaining pale yellow powder after the offwhite ampelopsis grossedentata flavone-Dihydromyricetin (DMY) primary product is crystallized and separated out, filtering, washing with ice purified water and drying; weighing, the yield is 40%, and the purity is up to 95%;

(7) And (3) secondary extraction: concentrating the filtrate separated out of the primary product by rotary evaporation, and freeze-drying and collecting; adding half of pure water amount for the first extraction into an extraction kettle, carrying out microwave preheating on filter residues subjected to hot suction filtration, and then carrying out secondary extraction to obtain off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY), wherein the accumulated yield of the off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY) can reach 60%;

(8) Three times of extraction: concentrating the filtrate after secondary extraction by rotary evaporation, and freeze-drying and collecting; adding half of pure water amount for the first extraction into an extraction kettle, carrying out microwave preheating on filter residues subjected to hot suction filtration, and then carrying out three times of extraction to obtain off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY), wherein the accumulated yield of the off-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY) can reach 70%;

In this embodiment, the thermoplastic water-proof and oil-proof acrylic resin contains a water-proof monomer and an oil-proof monomer, and the water-proof monomer contains the following water-proof monomers:

the oil-proof monomer is as follows:

the thermoplastic reinforced acrylic resin contains self-crosslinking groups, wherein the self-crosslinking groups are as follows:

example 2

An embodiment of the water and oil repellent agent of the present invention comprises the following components in parts by weight: 75 parts of thermoplastic waterproof and oilproof acrylic resin, 15 parts of thermoplastic reinforced acrylic resin, 3 parts of alcohol, 7 parts of water and 0.8 per mill of vine tea extract by mass. The waterproof and oil-proof agent of the embodiment is prepared by the following method: the water-proof and oil-proof agent is prepared by uniformly mixing thermoplastic water-proof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin (for example, uniformly stirring and mixing at the speed of 800 r/min) to obtain a resin mixture, adding alcohol and water into the resin mixture, uniformly mixing (for example, uniformly stirring and mixing at the speed of 400 r/min), filtering (for example, filtering by adopting a 200-mesh filter bag), and bottling.

The preparation method of the vine tea extract in the embodiment is the same as that of the embodiment 1.

the oil-proof monomer is as follows:

example 3

An embodiment of the water and oil repellent agent of the present invention comprises the following components in parts by weight: 68 parts of thermoplastic waterproof and oilproof acrylic resin, 22 parts of thermoplastic reinforced acrylic resin, 8 parts of alcohol, 2 parts of water and 1.2 per mill of vine tea extract by mass. The waterproof and oil-proof agent of the embodiment is prepared by the following method: the water-proof and oil-proof agent is prepared by uniformly mixing thermoplastic water-proof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin (for example, uniformly stirring and mixing at the speed of 800 r/min) to obtain a resin mixture, adding alcohol and water into the resin mixture, uniformly mixing (for example, uniformly stirring and mixing at the speed of 400 r/min), filtering (for example, filtering by adopting a 200-mesh filter bag), and bottling.

the oil-proof monomer is as follows:

example 4

An embodiment of the water and oil repellent agent of the present invention comprises the following components in parts by weight: 70 parts of thermoplastic waterproof and oilproof acrylic resin, 20 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract. The waterproof and oil-proof agent of the embodiment is prepared by the following method: the water-proof and oil-proof agent is prepared by uniformly mixing thermoplastic water-proof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin (for example, uniformly stirring and mixing at the speed of 800 r/min) to obtain a resin mixture, adding alcohol and water into the resin mixture, uniformly mixing (for example, uniformly stirring and mixing at the speed of 400 r/min), filtering (for example, filtering by adopting a 200-mesh filter bag), and bottling.

the oil-proof monomer is as follows:

example 5

An embodiment of the water and oil repellent agent of the present invention comprises the following components in parts by weight: 72 parts of thermoplastic waterproof and oilproof acrylic resin, 18 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.4 per mill of vine tea extract by mass. The waterproof and oil-proof agent of the embodiment is prepared by the following method: the water-proof and oil-proof agent is prepared by uniformly mixing thermoplastic water-proof and oil-proof acrylic resin and thermoplastic reinforced acrylic resin (for example, uniformly stirring and mixing at the speed of 800 r/min) to obtain a resin mixture, adding alcohol and water into the resin mixture, uniformly mixing (for example, uniformly stirring and mixing at the speed of 400 r/min), filtering (for example, filtering by adopting a 200-mesh filter bag), and bottling.

the oil-proof monomer is as follows:

example 6

Effect test of the Water and oil repellent agent of the invention

In this example, test groups 1 to 5 were each made of the water-and oil-repellent agents described in examples 1 to 5, and control groups were each made of the following water-and oil-repellent agents:

the water and oil repellent agent of the control group 1 comprises the following components in parts by weight: 90 parts of thermoplastic waterproof and oilproof acrylic resin, 0 part of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract by mass content, wherein the selection and preparation methods of the components are the same as those of example 4;

the water and oil repellent agent of the control group 2 comprises the following components in parts by weight: 0 part of thermoplastic waterproof and oilproof acrylic resin, 90 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract by mass content, wherein the selection and preparation method of each component are the same as in example 4.

The water and oil repellent agent of the control group 3 comprises the following components in parts by weight: 45 parts of thermoplastic waterproof and oilproof acrylic resin, 45 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract by mass content, and the selection and preparation methods of the components are the same as in example 4.

The water and oil repellent agent of the control group 4 comprises the following components in parts by weight: 55 parts of thermoplastic waterproof and oilproof acrylic resin, 35 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract by mass content, wherein the selection and preparation method of each component are the same as in example 4.

The water and oil repellent agent of the control group 5 comprises the following components in parts by weight: 85 parts of thermoplastic waterproof and oilproof acrylic resin, 5 parts of thermoplastic reinforced acrylic resin, 5 parts of alcohol, 5 parts of water and 1.0 per mill of vine tea extract by mass content, and the selection and preparation methods of the components are the same as in example 4.

The waterproof and oilproof agents of the test group 1 to 5 and the control group 1 to 5 are respectively coated on the surface of the paper material manufactured by paper making through a coating roller to form a coating, and then the coating is directly heat-sealed and formed into the disposable paper bowl. The appearance of each group of waterproof and oil-proof agents is observed respectively, and the viscosity, the adhesive force, the anti-tackiness, the waterproof and oil-proof performance and the film layer peelability are tested and compared respectively for the disposable paper bowl prepared by each group, and the specific test method is as follows:

appearance: visual inspection;

viscosity: using a coating-4 cup and testing according to the requirements of the viscosity cup method in GB/T1723-1993;

adhesion force: the method comprises the steps of (1) tightly attaching 810 adhesive tapes of a 3M company to the surface of a gloss oil coating, discharging bubbles below the adhesive tapes by pressing the adhesive tapes with thumbs, fully attaching the adhesive tapes to the gloss oil, standing for 1 minute, rapidly pulling the adhesive tapes away by force, and looking at the dropping condition of the gloss oil, wherein the evaluation result is 1-5 grades, preferably 1 grade, completely not falling off, worst 5 grades and completely falling off;

anti-sticking: the paint film faces are overlapped, the paint film is separated after being pressed for 5 hours under the pressure of 39200Pa and the temperature of 60 ℃, and whether adhesion phenomenon exists during the separation is visually detected;

water and oil repellency: visually checking whether oil spots with water stains and oil stains penetrating out exist or not;

film peelability: under the conventional waste paper deinking process conditions (ph=10, temperature around 55 ℃), the water-and oil-repellent agent film layer can be completely peeled from the paper substrate.

The test results of each group are shown in table 1.

Table 1 results of Performance test of paper bowls prepared in groups

As can be seen from the test results in Table 1, the control group had leakage compared with the test group. From the above, it is clear that when only one of the thermoplastic water-and oil-repellent polyacrylic resin and the thermoplastic reinforced polyacrylic resin is contained in the present application, the obtained water-and oil-repellent agent cannot meet the performance requirement of disposable tableware; only when the two are scientifically compounded, and the weight ratio of the thermoplastic waterproof and oil-proof polyacrylic resin to the thermoplastic reinforced polyacrylic resin is 65-75 parts by weight and the weight ratio of the thermoplastic reinforced polyacrylic resin to the thermoplastic reinforced polyacrylic resin is 15-25 parts by weight, the waterproof and oil-proof effects can be achieved.

Example 7

The antibacterial effect test of the waterproof and oil-proof agent

In this example, test groups 1 to 5 were set, and the water and oil repellent formulations of test groups 1 to 5 are shown in Table 2.

Table 2 Water and oil repellent formulations of test groups 1 to 5

1. Antibacterial property of water-and oil-repellent agent itself

(1) Antibacterial property of water-proof and oil-proof agent emulsion

The testing method comprises the following steps: the antibacterial performance of the water-proof and oil-proof agents added with the ampelopsis grossedentata flavone with different concentrations is measured by adopting an oxford cup method. That is, in a single double-sided decontamination station under sterile conditions, the media was poured into sterile petri dishes, each dish was poured with about 15mL of agar media. After the medium had cooled and solidified, 200. Mu.L of a suspension of Staphylococcus aureus, escherichia coli and Salmonella paratyphi was taken out on a petri dish with a 200. Mu.L pipette, and the bacterial solution was uniformly coated with a coating rod. 4 oxford cups with the diameter of 6mm are placed on a culture dish, 200 mu L of physiological saline is respectively dripped into each oxford cup, and three antibacterial, waterproof and oil-proof agents with different vine tea flavone contents are tested in parallel for 3 samples. Then placing the culture dish in a biochemical incubator at the temperature of 37+/-1 ℃ for culturing for 24 hours, and observing and measuring the diameter of the inhibition zone. The test results are shown in table 3:

TABLE 3 antibacterial Water and oil repellent antibacterial Properties

(2) Antibacterial property research of waterproof and oil-proof coating (paper material as base material)

The testing method comprises the following steps:

negative control: 50mm by 50mm inner plates of sterile culture plates 90mm or 100mm in diameter;

blank control: is a paper material coated with a water-proof and oil-proof agent without an antibacterial component;

antibacterial coating sample: cutting the coated test paper into ten pieces of test paper with the size of 50mm multiplied by 50mm by using a paper material coated with water-proof and oil-proof agents containing different mass fractions of ampelopsis grossedentata flavone, sterilizing the test paper before the test, and suggesting to sterilize the test paper for 5min by using an ultraviolet sterilizing lamp in an ultra-clean workbench for later use.

And respectively dripping 0.4-0.5mL of test bacteria on the negative control sample, the blank control sample and 5 antibacterial paint samples. The sterilization cover films are clamped by a sterilization forceps and respectively covered on the 7 samples, the samples are paved and have no bubbles, bacteria are uniformly contacted with the samples, and the samples are placed in a sterilization plate for culturing for 24 hours under the conditions of (37+/-1) DEG C and relative humidity RH >90 percent. 3 replicates were run for each sample.

Taking out a sample for culturing for 24 hours, adding 20mL of washing solution respectively, repeatedly washing the sample and covering the membrane (preferably, washing the membrane by clamping with forceps), shaking the sample fully and uniformly, taking the washing solution, inoculating the washing solution into a nutrient agar medium (NA), culturing the sample for 24-48 hours at 37 ℃ and counting viable bacteria, and measuring the number of viable bacteria in the washing solution according to the method of GB 4789.2 "food sanitation microbiology test colony count determination".

Multiplying the result of the number of the viable bacteria determined above by 1000 to obtain the actual value of the recovered viable bacteria after each sample is cultured for 24 hours, so that the test result is ensured to meet the following requirements, otherwise, the test is invalid:

the values of 3 parallel viable bacteria of the same blank control sample are in accordance with (the highest logarithmic value-the lowest logarithmic value)/the average viable bacteria value logarithmic value is less than or equal to 0.3;

the actual recovery viable bacteria number of the negative control sample should be not less than 1.0X10 ⁵ cfu/tablet, and the actual recovery viable bacteria value of the blank control sample should be no less than 1.0X10% ⁴ cfu/tablet.

The antibacterial rate calculation formula is:

R(％)＝(B—C)/B×100％

wherein:

r-antibacterial ratio (%), the numerical value takes three significant digits;

b-average recovered bacteria count (cfu/tablet) after 24h of blank control;

c-average recovered bacteria count (cfu/tablet) after 24h of the antibacterial paint sample.

The test results are shown in Table 4.

(3) Test of mildew resistance of Water and oil resistant coating (paper as base material)

The testing method comprises the following steps:

negative control: 25mm x 25mm sterile filter paper;

antibacterial coating sample: the coated test paper is cut into ten pieces of test paper with the size of 50mm multiplied by 50mm by using a paper material coated with water-proof and oil-proof agents containing different mass fractions of ampelopsis grossedentata flavone, sterilization is carried out before the test, and the test paper is recommended to be washed by sterile water, and then is subjected to sterilization by irradiation of a sterilizing ultraviolet lamp for 5min for later use.

The negative control sample (sterile filter paper) was spread on the plating medium and the spore suspension was sprayed with a sprayer containing the freshly prepared mixed spore suspension, so that it was sprayed substantially uniformly over the medium and filter paper. After 7d incubation at 28℃and relative humidity above 90% RH, the filter paper should be significantly bacteria-grown, otherwise the test should be considered ineffective and the test should be repeated.

Meanwhile, a blank control sample and an antibacterial coating test board are respectively paved on the culture medium, and spore suspension is sprayed so that the spore suspension is fully and uniformly sprayed on the culture medium and the sample. 5 replicates were run for each sample. The samples are cultivated for 28 days under the conditions that the temperature is 28 ℃ and the relative humidity is more than 90%RH, and if the mould growth area of the samples is more than 10%, the experiment can be finished in advance.

The sample is taken out and is observed immediately, and the mould growth area of the blank control sample A is not less than 10%, otherwise, the blank control sample A cannot be used as the blank control sample of the test. Of the 5 replicates of each sample, 3 or more were rated as the long mold grade of that sample.

Sample mould rating:

stage I: i.e. no growth was observed under a microscope (magnification 50 times), i.e. no length of scale 0.

Stage II: i.e. grade 1 trace growth, i.e. macroscopic growth, but with a growth coverage of less than 10%.

Poor mold resistance: i.e. level 2, the growth coverage area is greater than 10%.

The test results are shown in Table 4.

(4) Antibacterial durability test (paper material as base material)

The testing method comprises the following steps:

1 ultraviolet lamp with the wavelength of 253.7nm and 30w is adopted, the ultraviolet lamp accords with GB 19258, the distance between an antibacterial paint test board and the ultraviolet lamp is 0.8-1.0 m, the irradiation is carried out for 100 hours, and the antibacterial durability of the test board after treatment is respectively carried out according to the antibacterial performance and the anti-mildew performance test method. The test results are shown in Table 4.

TABLE 4 antibacterial, water and oil repellent Properties of antibacterial, mildew-proof Agents

The antibacterial grade of the antibacterial, waterproof and oil-proof agent is grade II by combining the results. According to HG/T3950-2007, antibacterial paints are classified into two classes according to the degree of antibacterial effect: stage I and stage ii. The I grade is suitable for places with high requirements on antibacterial performance, and the II grade is suitable for places with requirements on antibacterial performance.

2. Application scenario

After the waterproof and oilproof agent disclosed in the embodiments 1 to 5 of the present invention is applied to the surface of paper and dried, the container is free from peculiar smell during brewing with boiling water.

Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A vine tea extraction method, which is characterized by comprising the following steps:

(4) Boiling and extracting: adding purified water into an extraction kettle, boiling, adding thick slurry heated by microwaves under high-speed stirring, and continuously keeping boiling and high-speed stirring for 3-5 minutes after the addition; the high-speed stirring is mechanical stirring, and the stirring speed is not lower than 5000 revolutions per minute;

(9) Concentrating the filtrate after three times of extraction by rotary evaporation, freeze-drying, combining the concentrated filtrate with the freeze-dried powder extracted in the previous two times, carrying out superfine grinding, testing the content of ampelopsis grossedentata flavone-Dihydromyricetin (DMY), calculating the boiling water dosage according to the content, and repeating the previous extraction process until the grey-white ampelopsis grossedentata flavone-Dihydromyricetin (DMY) in the ampelopsis grossedentata dry leaves is obtained in a cumulative way;

the yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (6) is not lower than 40%, and the purity is not lower than 95%; the accumulated yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (7) is not lower than 60%; the accumulated yield of ampelopsis grossedentata flavone-Dihydromyricetin (DMY) obtained in the step (8) is not lower than 70%.

2. The vine tea extraction method according to claim 1, wherein the superfine grinding in the step (1) is performed by taking a 300-mesh screen as a standard; and (3) carrying out suction filtration while the filter liquor is hot in the step (5), and if a small amount of powder enters the filter liquor, adopting a G4 or even G5 sand core funnel to carry out suction filtration under reduced pressure to ensure that the filter liquor is clear.

3. A vine tea extract, characterized in that the vine tea extract is extracted by the extraction method according to any one of claims 1-2.

4. A water and oil repellent agent comprising the tendril tea extract of claim 3.

5. The water-and oil-repellent agent according to claim 4, wherein the water-and oil-repellent agent comprises 0.6 to 1.4% by mass of the tendril tea extract.

6. The water and oil repellent agent according to claim 4 or 5, characterized in that the water and oil repellent agent further comprises a thermoplastic water and oil repellent acrylic resin and a thermoplastic reinforcing acrylic resin;

the thermoplastic reinforced acrylic resin contains self-crosslinking groups.

7. The water-and oil-repellent agent according to claim 6, wherein the water-repellent monomer contained in the thermoplastic water-and oil-repellent acrylic resin is at least one selected from the group consisting of:

；

；

the self-crosslinking group is selected from at least one of the following:

。

8. the water and oil repellent agent according to claim 6, wherein the thermoplastic water and oil repellent acrylic resin and the thermoplastic reinforcing acrylic resin contained in the water and oil repellent agent are each in parts by weight: 65-75 parts of thermoplastic waterproof and oilproof acrylic resin and 15-25 parts of thermoplastic reinforced acrylic resin.

9. The use of the water-and oil-repellent agent according to any one of claims 4 to 8 in the preparation of a water-and oil-repellent paper-based package, characterized in that the water-and oil-repellent agent is directly coated on the surface of a paper material manufactured by paper manufacture, and then the water-and oil-repellent paper-based package is prepared by using the paper material; the waterproof and oil-proof paper-based package is a disposable paper-based container for food packaging, and the disposable paper-based container for food packaging comprises paper cups, paper bowls, paper trays, paper dishes, paper boxes and paper bags.