CN113698522A - Environment-friendly fluorine-free waterproof and oilproof composition and preparation method thereof - Google Patents

Environment-friendly fluorine-free waterproof and oilproof composition and preparation method thereof Download PDF

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CN113698522A
CN113698522A CN202111078081.3A CN202111078081A CN113698522A CN 113698522 A CN113698522 A CN 113698522A CN 202111078081 A CN202111078081 A CN 202111078081A CN 113698522 A CN113698522 A CN 113698522A
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proof
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environment
oil
free water
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袁大想
吴健泳
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Shanghai Pu Xin Polymer Materials Co ltd
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Shanghai Pu Xin Polymer Materials Co ltd
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Abstract

The invention relates to the technical field of material preparation, in particular to an environment-friendly fluorine-free waterproof and oilproof composition and a preparation method thereof; according to the environment-friendly fluorine-free waterproof and oilproof composition, the hydrophilic monomer is introduced, and can be crosslinked with hydroxyl on the fiber and a functional group carried by a polymer after being shaped at high temperature to form functional group closure, so that the crosslinking density is increased, and the water and oil blocking resistance is further improved; meanwhile, the composition disclosed by the invention is free of fluorine, does not influence the health of human bodies and animals, and has the remarkable characteristics of safety and environmental protection.

Description

Environment-friendly fluorine-free waterproof and oilproof composition and preparation method thereof
Technical Field
The invention relates to the technical field of material preparation, in particular to an environment-friendly fluorine-free waterproof and oilproof composition and a preparation method thereof.
Background
The United states national environmental protection agency releases long-chain PFCs (containing perfluorooctyl, perfluorodecyl or perfluoroalkyl compounds or polymers containing higher carbon number) which have longer degradation period and stronger accumulation and migration, and seriously affect the health of animals and plants. There have been many companies working to develop a civil water and oil repellent surface treatment agent by using a perfluorohexyl fluorine-containing copolymer. However, the FDA regulates that the fluorine content of the surface of the inbound disposable paper tableware is required to be less than 800 ppm. At present, the products sold on the market can not meet the requirements of FDA under the condition of endowing the surfaces of the products with water-proof and oil-proof functions.
Patent CN112111221A proposes an oil-proof agent comprising silica sol, gamma glycidoxypropyltrimethoxysilane, sodium polyacrylate, silicone resin emulsion, etc. The water-repellent and oil-repellent composition with stable water property is prepared in a full water-based system without organic solvent, a coating formed by the water-repellent and oil-repellent composition has excellent water-repellent and oil-repellent characteristics, but a silicon coating of the composition has certain adhesiveness in the using process, so that the manufactured lunch box is easy to adhere and difficult to separate, and brings negative influence on the using experience of customers.
Patent CN201980050729 discloses an oil proofing agent for paper, the non-fluorine copolymer having: a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms; and an acrylic monomer having a hydrophilic group. The non-fluorine copolymer adopts the long-chain acrylic monomer with the carbon number of 7-40 as a waterproof and oilproof monomer, and the acrylic monomer with the long-chain hydrocarbon of 7-40 has strong oleophylic performance and is oilproof, so the oil-proof effect is 5-level, the effect of high-temperature-resistant oil is poorer, and the market demand can not be met far.
Disclosure of Invention
In order to solve the problems, the invention provides an environment-friendly fluorine-free waterproof and oilproof composition and a preparation method thereof, belonging to the technical field of material preparation.
An environment-friendly fluorine-free waterproof and oilproof composition and a preparation method thereof, the preparation method comprises the following steps according to the parts by weight:
under the protection of nitrogen, 50-150 parts of solvent, 25-50 parts of hard monomer, 15-25 parts of film forming monomer, 10-25 parts of hydrophilic monomer, 13-20 parts of cationic monomer and 0.5-1.2 parts of initiator are placed in a stirring container, heated to 50-75 ℃, fully stirred for 8-12 hours, and then added with 300-400 parts of emulsifier aqueous solution. The solvent is distilled off by a distillation method to obtain the environment-friendly fluorine-free water-proof oil-proof composition.
Further, the solvent is one or a combination of more of acetone, butanone, N-methyl pyrrolidone, ethyl acetate, isopropanol, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dipropylene glycol, tripropylene glycol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether;
further, the solvent is a composition optimized to be one or more of acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and tetraethylene glycol dimethyl ether;
further, the hard monomer is one or a composition of more of styrene, methyl styrene, cyclohexyl methacrylate, glycidyl methacrylate, isobornyl (meth) acrylate and methyl methacrylate;
further, the hard monomer is optimized to be one or a combination of more of methyl styrene, glycidyl methacrylate, isobornyl (meth) acrylate and methyl methacrylate;
further, the film-forming monomer is one or a combination of butyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate;
further, the hydrophilic monomer is one or a combination of more of 2-vinyl pyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate, methacrylic acid, acrylic acid, polyethylene glycol methacrylate, monomethyl ether polyethylene glycol methacrylate, (meth) acrylic acid modified cellulose and (meth) acrylic acid modified chitosan;
further, the hydrophilic monomer is optimized to be one or a composition of more of 2-vinyl pyrrolidone, hydroxyethyl acrylate, polyethylene glycol methacrylate, monomethyl ether polyethylene glycol methacrylate, (meth) acrylic acid modified cellulose and (meth) acrylic acid modified chitosan;
further, the cationic monomer is one or a combination of more of hydroxymethyl acrylamide, hydroxyethyl acrylamide, (meth) acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
further, the cationic monomer is optimized to be one or a combination of more of hydroxymethyl acrylamide, hydroxyethyl acrylamide and diethylaminoethyl (meth) acrylate;
further, the initiator is one or a combination of a plurality of azodiisobutyronitrile, dibenzoyl peroxide, azodiisobutyamidine hydrochloride, azodiisobutyronitrile dimethyl ester, azoisobutyryl cyano formamide, azodiisobutyamidine hydrochloride, azodiisoheptanonitrile and di-tert-butyl peroxide;
further, the initiator is optimized to be one or a combination of a plurality of azodiisobutyronitrile, azoisobutyryl cyano formamide, azodiisoheptanonitrile and di-tert-butyl peroxide;
further, the stirring speed is 60-120 r/min;
further, the emulsifier aqueous solution is selected from one or more of Polyacrylamide (PAM), Hydrolyzed Polyacrylamide (HPAM), polyvinylpyrrolidone (PVP) and C6-C22 alkyl trimethyl ammonium chloride;
further, the distillation temperature is 80-300 ℃.
The reaction mechanism equation is:
Figure RE-GDA0003307931310000031
the technical effects are as follows:
1. hydrophilic monomers are introduced, and the hydrophilic monomers can be crosslinked with hydroxyl groups on the fibers and functional groups carried by the polymers after high-temperature shaping to form functional group closure, increase crosslinking density and further improve the water and oil resistance.
2. The polymer has three groups of anion, nonionic and cation, thus increasing the binding capacity of different gradients of the polymer body and the cellulose, being beneficial to charge attraction between the polymer and improving the compactness of crosslinking between the polymer and the fiber.
3. The later addition of the aqueous emulsifier solution further increases the adhesion of the polymer to the fibers.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a styrene/butyl (meth) acrylate/2-vinylpyrrolidone/methylolacrylamide copolymer prepared in example 1.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
Under the protection of nitrogen, 50g of acetone, 25g of styrene, 15g of butyl (meth) acrylate, 10g of 2-vinyl pyrrolidone, 13g of hydroxymethyl acrylamide and 0.5g of azobisisobutyronitrile are placed in a stirring container, heated to 50 ℃, fully stirred for 8 hours at the stirring speed of 60r/min, and then 300g of Polyacrylamide (PAM) is added. The acetone is rectified to obtain solution by a distillation method, and the distillation temperature is 80 ℃, so that the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Example 2
Under the protection of nitrogen, 60g N, N-dimethylformamide, 30g of methyl styrene, 16g of ethyl (meth) acrylate, 12g of hydroxyethyl acrylate, 15g of hydroxyethyl acrylamide and 0.6g of azo-isobutyryl cyano formamide are placed in a stirring container, heated to 60 ℃, fully stirred for 9 hours at the stirring speed of 70r/min, and then 300g of Hydrolyzed Polyacrylamide (HPAM) is added. The N, N-dimethylformamide is rectified to obtain a solution by a distillation method, and the distillation temperature is 160 ℃, so that the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Example 3
80g N N-dimethylacetamide, 35g isobornyl (meth) acrylate, 18g propyl (meth) acrylate, 16g polyethylene glycol methacrylate, 18g diethylaminoethyl (meth) acrylate and 0.8g azobisisoheptonitrile were placed in a stirred vessel under nitrogen protection, heated to 65 ℃, stirred thoroughly for 9h at 80r/min, and 350g polyvinylpyrrolidone (PVP) was added. The N, N-dimethylacetamide is rectified to obtain a solution by a distillation method, the distillation temperature is 180 ℃, and the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Example 4
Under the protection of nitrogen, 100g of tetrahydrofuran, 40g of methyl methacrylate, 20g of butyl (meth) acrylate, 20g of acrylic acid, 18g of hydroxymethyl acrylamide and 1.0g of azobisisobutyramidine hydrochloride are put into a stirring container, heated to 60 ℃, fully stirred for 10 hours at the stirring speed of 90r/min, and then 350g C6 alkyl trimethyl ammonium chloride is added. The tetrahydrofuran is rectified out of the solution by a distillation method, the distillation temperature is 90 ℃, and the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Example 5
Under the protection of nitrogen, 120g of tetraethylene glycol dimethyl ether, 45g of cyclohexyl methacrylate, 23g of butyl (meth) acrylate, 23g of (meth) acrylic acid modified chitosan, 20g of hydroxyethyl acrylamide and 1.2g of azo isobutyryl cyano formamide are placed in a stirring container, heated to 75 ℃, fully stirred for 12 hours at the stirring speed of 100r/min, and then 400g of Polyacrylamide (PAM) is added. The solvent is rectified into the tetraethylene glycol dimethyl ether by a distillation method, the distillation temperature is 280 ℃, and the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Example 6
150g of ethanol, 50g of isobornyl (meth) acrylate, 25g of ethyl (meth) acrylate, 25g of (meth) acrylic acid modified cellulose, 20g of (meth) acryloyloxyethyltrimethyl ammonium chloride and 1.2g of azobisisoheptonitrile are placed in a stirring vessel under the protection of nitrogen, heated to 65 ℃, stirred sufficiently for 12 hours at a stirring speed of 120r/min, and then 400g of Hydrolyzed Polyacrylamide (HPAM) is added. The solution is distilled by the ethanol through a distillation method, and the distillation temperature is 100 ℃, so that the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Comparative example 1
50g of dipropylene glycol, 15g of (methyl) acrylic acid ethyl, 10g of 2-vinyl pyrrolidone, 13g of hydroxyethyl acrylamide and 0.5g of azo isobutyryl cyano formamide are put into a stirring container under the protection of nitrogen, heated to 75 ℃, fully stirred for 8 hours at the stirring speed of 120r/min, and then 300g of Polyacrylamide (PAM) is added. The acetone is rectified to obtain solution by a distillation method, and the distillation temperature is 300 ℃, so that the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
Comparative example 2
Under the protection of nitrogen, 150g of isopropanol, 50g of styrene, 25g of propyl (meth) acrylate, 20g of diethylaminoethyl (meth) acrylate and 1.2g of azoisobutylcyanoformamide are placed in a stirring vessel, heated to 65 ℃, stirred sufficiently for 12 hours at a stirring speed of 80r/min, and then 400g of polyvinylpyrrolidone (PVP) is added. The isopropanol is distilled out of the solution by a distillation method, and the distillation temperature is 120 ℃, so that the environment-friendly fluorine-free water-proof oil-proof composition is obtained.
EXAMPLES evaluation
The detection method comprises the following steps:
oil resistance (KIT method) was measured in accordance with TAPPIT-559 cm-02. The KIT test solution was prepared by mixing castor oil, toluene, and heptane at the ratios shown in table 1. 1 drop of the test solution shown in Table 1 was placed on paper, and the state of oil permeation was observed after 15 seconds. The highest point of the oil resistance given by the KIT test solution showing no permeation was regarded as the oil resistance. The higher the number of KIT test solution, the higher the oil resistance.
Figure RE-GDA0003307931310000061
Water resistance (Cobb value) was measured in accordance with JIS P8140. The weight (g) of water absorbed in 1 minute was measured using a 100 cm square paper supporting a height of 1 cm of water, and the value was converted to a weight per 1 m square (g/m)2)
Figure RE-GDA0003307931310000062
Figure RE-GDA0003307931310000071

Claims (15)

1. An environment-friendly fluorine-free waterproof and oilproof composition and a preparation method thereof, the preparation method comprises the following steps according to the parts by weight:
under the protection of nitrogen, 50-150 parts of solvent, 25-50 parts of hard monomer, 15-25 parts of film forming monomer, 10-25 parts of hydrophilic monomer, 13-20 parts of cationic monomer and 0.5-1.2 parts of initiator are placed in a stirring container, heated to 50-75 ℃, fully stirred for 8-12 hours, and then added with 300-400 parts of emulsifier aqueous solution. The solvent is distilled off by a distillation method to obtain the environment-friendly fluorine-free water-proof oil-proof composition.
2. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the solvent is one or a composition of more of acetone, butanone, N-methyl pyrrolidone, ethyl acetate, isopropanol, ethanol, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dipropylene glycol, tripropylene glycol, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
3. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 2, which is characterized in that: the solvent is one or a combination of acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran and tetraethylene glycol dimethyl ether.
4. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the hard monomer is one or a composition of more of styrene, methyl styrene, cyclohexyl methacrylate, glycidyl methacrylate, isobornyl (meth) acrylate and methyl methacrylate.
5. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 4, which is characterized in that: the hard monomer is one or a composition of a plurality of methyl styrene, glycidyl methacrylate, isobornyl (meth) acrylate and methyl methacrylate.
6. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the film-forming monomer is one or a combination of butyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate.
7. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the hydrophilic monomer is one or a combination of more of 2-vinyl pyrrolidone, hydroxyethyl acrylate, hydroxyethyl methacrylate, methacrylic acid, acrylic acid, polyethylene glycol methacrylate, monomethyl ether polyethylene glycol methacrylate, (methyl) acrylic acid modified cellulose and (methyl) acrylic acid modified chitosan.
8. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 7, which is characterized in that: the hydrophilic monomer is one or a combination of more of 2-vinyl pyrrolidone, hydroxyethyl acrylate, polyethylene glycol methacrylate, monomethyl ether polyethylene glycol methacrylate, (methyl) acrylic acid modified cellulose and (methyl) acrylic acid modified chitosan.
9. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the cationic monomer is one or a combination of more of hydroxymethyl acrylamide, hydroxyethyl acrylamide, (methyl) acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
10. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 9, which is characterized in that: the cationic monomer is one or a combination of more of hydroxymethyl acrylamide, hydroxyethyl acrylamide and diethylaminoethyl (meth) acrylate.
11. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the initiator is one or a combination of a plurality of azodiisobutyronitrile, dibenzoyl peroxide, azodiisobutyramidine hydrochloride, azodiisobutyronitrile dimethyl ester, azoisobutyryl formamide, azodiisobutymidine hydrochloride, azodiisoheptonitrile and di-tert-butyl peroxide.
12. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 11, which is characterized in that: the initiator is one or a composition of more of azodiisobutyronitrile, azoisobutyryl cyano formamide, azodiisoheptanonitrile and di-tert-butyl peroxide.
13. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the stirring speed is 60-120 r/min.
14. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the emulsifier aqueous solution is an acidic aqueous solution of one or a combination of more of Polyacrylamide (PAM), Hydrolyzed Polyacrylamide (HPAM), polyvinylpyrrolidone (PVP) and C6-C22 alkyl trimethyl ammonium chloride.
15. The environment-friendly fluorine-free water-proof and oil-proof composition as claimed in claim 1, which is characterized in that: the distillation temperature is 80-220 ℃.
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