CN114773523A - Water-based fluorine-containing waterproof and oil-proof agent for paper and preparation and application thereof - Google Patents

Water-based fluorine-containing waterproof and oil-proof agent for paper and preparation and application thereof Download PDF

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CN114773523A
CN114773523A CN202210350364.7A CN202210350364A CN114773523A CN 114773523 A CN114773523 A CN 114773523A CN 202210350364 A CN202210350364 A CN 202210350364A CN 114773523 A CN114773523 A CN 114773523A
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parts
monomer
fluorine
paper
oil
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张庆华
何波波
任勇源
任兰会
刘权
詹晓力
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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Zhejiang University ZJU
Quzhou Research Institute of Zhejiang University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a water-based fluorine-containing waterproof and oil-proof agent for paper and a preparation method thereof, wherein the water-based fluorine-containing waterproof and oil-proof agent is prepared from the following raw materials in parts by weight: the fluorine-containing copolymer comprises 50-80 parts of fluorine-containing monomer, 10-20 parts of organosilicon monomer, 1-10 parts of methyl methacrylate monomer, 1-10 parts of butyl methacrylate monomer, 1-10 parts of octadecyl acrylate monomer, 1-10 parts of diacetone acrylamide monomer, 5-25 parts of functional monomer, 1-5 parts of other monomers, 1-5 parts of soybean isoflavone glycoside, 100 parts of all monomers in total, 1-3 parts of initiator, 1-3 parts of chain transfer agent and 1-10 parts of protonic acid. The fluorine-containing copolymer introduces pure natural hydrophobic and oleophobic soybean isoflavone aglycone, so that the surface free energy of the treated paper on the surface of the paper can be obviously reduced, the waterproof and oilproof performance of the traditional water-based fluorine-containing acrylate copolymer can be better improved, the heat resistance and the chemical stability of the traditional water-based fluorine-containing acrylate copolymer can be improved, and the paper has higher waterproof and oilproof performance, tensile strength, tearing resistance, breaking resistance and the like so as to meet the performance requirements of various paper types.

Description

Water-based fluorine-containing waterproof and oil-proof agent for paper and preparation and application thereof
Technical Field
The invention relates to the technical field of water-proof and oil-proof treatment for paper, in particular to a water-based fluorine-containing water-proof and oil-proof agent for paper and a preparation method thereof.
Background
In general, a fluorine-containing oil-repellent agent used in the paper industry is composed of a perfluoroalkyl group which imparts extremely low surface tension to paper and a polar group which imparts solubility of the oil-repellent agent, the hydrophilic group of the oil-repellent agent being partially adsorbed or bonded to the surface of paper, and the trifluoromethyl group (-CF) at the terminal of the fluorocarbon chain3) The hydrophobic and oleophobic membrane is arranged outwards, so that the surface tension of the paper is reduced, and the paper cannot be wetted by oil.
The fluorine-containing acrylate copolymer has good waterproof and oilproof performance, thermal stability and antifouling performance. When the fluorine-containing acrylate copolymer is used as a sizing agent to perform surface sizing treatment on paper, a layer of film can be formed on the surface of the sized paper, and perfluorocarbon groups are directionally arranged outside the fiber surface of the paper, so that the surface of an adhesive film is prevented from contacting with air, and the surface free energy of the surface of the adhesive film is remarkably reduced, so that the softness, mechanical strength, air permeability and printing performance of the paper are not influenced while the water resistance of the paper is enhanced. Therefore, the fluorine-containing acrylate copolymer is one of the most promising surface sizing agents at present.
The use of organic fluorine compounds in the paper industry has been in history for decades, and fluorine compound-treated paper has been widely used in printing, industrial packaging, food packaging and articles for daily use abroad. The research in the field is relatively late in China, and because the preparation of the fluorine-containing acrylate monomer used for polymerization is relatively difficult, the fluorine-containing monomer and the polymer used in the domestic market mostly depend on import, so that the use of the fluorine-containing compound is limited. The fluorine-containing alkyl copolymer is widely applied as a waterproof and oil-proof agent, the waterproof and oil-proof performance of the fluorine-containing copolymer prepared on the market at present is improved compared with that of a micromolecular fluorine-containing compound, but the flash point of a system is too low due to the fact that a large amount of solvent is used in the preparation process of the fluorine-containing copolymer, and the problem of poor safety exists in the using process of the fluorine-containing copolymer. The soybean isoflavone is a secondary metabolite formed in the growth of soybeans, belongs to flavonoid compounds, and is mainly distributed in seed coats, hypocotyls and cotyledons of the soybeans. Free soybean isoflavone aglycone as a natural hydrophobic and oleophobic component can provide certain oleophobic effect, and belongs to bio-based materials which are harmless to human body. Silicones are polymers having alternating siloxane chain backbones with siloxane atoms bonded to organic groups on the silicon atoms. The silicon-oxygen bond energy is much larger than the carbon-carbon bond energy, and thus the siloxane has stronger heat resistance stability and weather resistance. The emulsion modified by the organic silicon has better performance, can prolong the service time when facing severe weather and extreme conditions, protects the property safety of people, and fully improves the application value of the current aqueous fluorine-containing acrylate products by the organic silicon modification.
Aiming at a series of problems of high preparation cost, low performance, poor safety and the like of the traditional fluorine-containing oil-proof agent in the current market, the patent discloses a novel water-based fluorine-containing water-proof and oil-proof agent for paper prepared by a brand-new method, compared with the common water-based fluorine-containing acrylate copolymer emulsion, organic silicon and soybean isoflavone are introduced to improve the performance and more remarkably reduce the surface free energy of the treated paper on the surface, the water-proof and oil-proof performance of the traditional water-based fluorine-containing acrylate copolymer can be better improved, meanwhile, the heat resistance and the chemical stability of the copolymer can be improved, so that the paper has higher water-proof and oil-proof performance, tensile strength, tearing resistance and breaking resistance and the like, and the performance requirements of various paper types can be met. Through the application of internal sizing and surface sizing, the prepared emulsion has the advantages of good oil-proof effect, small using amount, low price, good stability, high safety and the like, and has wide market prospect.
Disclosure of Invention
The invention provides a water-based fluorine-containing waterproof and oilproof agent for paper and a preparation method thereof, and the food packaging paper treated by the water-based fluorine-containing waterproof and oilproof agent has good waterproof and oilproof effects and excellent hot oil resistance.
The invention is realized by the following technical scheme:
a water-based fluorine-containing waterproof and oil-proof agent for paper and a preparation method thereof are characterized in that: the method is implemented according to the following steps:
step 1, respectively weighing the following raw materials in parts by weight:
50-80 parts (preferably 60-70 parts) of a fluorine-containing monomer (TEMAc-6), 10-20 parts (preferably 10-15 parts) of an organosilicon monomer, 1-10 parts (preferably 1-5 parts) of a methyl Methacrylate Monomer (MMA), 1-10 parts (preferably 1-5 parts) of a butyl methacrylate monomer (BA), 1-10 parts (preferably 1-5 parts) of an octadecyl acrylate monomer (SA), 1-10 parts (preferably 1-5 parts) of a diacetone acrylamide monomer (DAAM), 5-25 parts (preferably 10-15 parts) of a functional monomer, 1-5 parts (preferably 1-3 parts) of other monomers and 1-5 parts (preferably 1-3 parts) of soybean isoflavone glycoside;
step 2, placing the monomers weighed in the step 1 into a beaker, adding an organic solvent for mixing and preheating, heating and uniformly stirring, gradually dropwise adding 5-25 parts of functional monomers and 1-1.5 parts of an initiator, preserving heat and dispersing at a high speed for a period of time;
step 3, transferring 1/3-1/2 of the solution in the step 2 into a three-neck flask provided with a stirrer, a thermometer and a condenser, introducing nitrogen to remove oxygen, stirring, heating to the polymerization reaction temperature, and keeping the temperature;
step 4, dissolving the rest of the initiator and 1-5 parts of the chain transfer agent in the rest of the monomer solution, slowly dropping the mixture into the reaction solution in the step 3 through a constant-pressure dropping funnel, and reacting for a period of time until the reaction is finished;
step 5, adding 1-10 parts of protonic acid and 500 parts of 200-500 parts of deionized water after proper temperature reduction; meanwhile, under the action of reduced pressure, evaporating the organic solvent to obtain the water-based fluorine-containing copolymer emulsion for the food packaging paper.
The invention is also characterized in that:
the general formula of the fluorine-containing monomer can be shown as R3-A-OOCCR1＝CHR2: in the formula R3Represents a linear perfluoro-substituted alkyl group having 4 to 16 carbon atoms; a represents a cushion link having a-CH2CH2-、-CH2-、-SO2NHCH2CH2-and the like; r is1And R2Any of which is H and the other is H or an alkyl group having 1 to 4 carbon atoms.
The functional monomer is one or more of aminoethyl (meth) acrylate (DM), acryloyloxyethyltrimethyl ammonium chloride (DMC), acrylamide vinyl, hydroxybutyl vinyl ether (HBVE), Ethyl Vinyl Ether (EVE), cyclohexyl vinyl ether, hydroxyethyl allyl ether and the like.
The other monomer is any one or more than two of glycidyl acrylate, isooctyl acrylate and isobornyl acrylate.
The organosilicon monomer is one or more of vinyltrimethoxysilane, vinyltriethoxysilane or methylvinyldimethoxysilane.
The structural general formula of the soybean isoflavone aglycone is as follows:
Figure BDA0003579783230000031
wherein: r1H or OH, R2＝H、OCH3Or CH ═ CH2COCH3，R3＝H、COCH3、CH＝CH2COCH3Or COCH3COOH。
The initiator is selected from any one or more of peroxide (such as benzoyl peroxide and lauroyl peroxide) or azo compound (such as one or more of 2, 2-Azobisisobutyronitrile (AIBN), 4-azobis (4-cyanovaleric acid) and azodicarbonamide)
The chain transfer agent is one or more of alkyl mercaptan such as dodecyl mercaptan, lauryl mercaptan, octadecyl mercaptan or aminoethanethiol, mercaptoethanol and mercaptoacetic acid.
The protonic acid is one or more of phosphoric acid and acetic acid.
The organic solvent is one or more of acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol methyl ether, propylene glycol acetate, tetrahydrofuran, dioxan, acetonitrile, dimethylformamide, N-methyl-2-pyrrolidone, butyl lactone or dimethyl sulfoxide;
and the amount of the organic solvent is 80-120 parts and the amount of the water is 200-500 parts per 100 parts by mass of all the monomer mixture; preheating at 30-50 deg.C, dispersing for 15-20min, polymerizing at 55-70 deg.C, and maintaining for 10-12 h.
Compared with the common water-based fluorine-containing acrylate copolymer emulsion, the fluorine-containing copolymer is introduced with the pure natural hydrophobic and oleophobic soybean isoflavone aglycone, so that the surface free energy of the treated paper on the surface of the paper can be more remarkably reduced, the water and oil resistance of the traditional water-based fluorine-containing acrylate copolymer can be better improved, and the heat resistance and chemical stability of the traditional water-based fluorine-containing acrylate copolymer can be improved, so that the paper has higher water and oil resistance, tensile strength, tearing resistance, breaking resistance and the like, and the performance requirements of various paper types are met.
Due to the adoption of the technical scheme, the method has the following beneficial effects:
the invention relates to a water-based fluorine-containing waterproof and oil-proof agent for paper and a preparation method thereof, and aims at overcoming the defects in the prior art, an organic silicon modified water-based fluorine-containing acrylic emulsion is invented, and food packaging paper treated by the emulsion has ideal waterproof and oil-proof performance. The concrete beneficial effects are as follows:
(1) the water-based fluorine-containing copolymer emulsion for food packaging paper has excellent water and oil proofing effects, the maximum static contact angle of a paper product treated by the copolymer with water can reach 145.2 degrees, and the maximum static contact angle of the paper product treated by the copolymer with liquid paraffin can reach 126.3 degrees;
(2) the water-based fluorine-containing copolymer emulsion for food packaging paper has excellent water-proof and oil-proof effects, the optimal oil-proof effect reaches 10 grades, and the requirements of typical food packaging paper oil-proof application are exceeded.
(3) The water-based fluorine-containing copolymer emulsion for the food packaging paper has smaller particle size, the particle size is below 1 mu m, the particle size is distributed between 250-750nm, and the particle size is most concentrated at 450 nm;
(4) the water-based fluorine-containing copolymer emulsion for food packaging paper has good compatibility with cationized paper auxiliaries, and can well maintain the water-proof and oil-proof effects when used in combination;
(5) the water-based fluorine-containing water-and oil-repellent agent for paper of the present invention is excellent in hot oil resistance, and does not leak out when salad oil at 130 ℃ is injected into a container made of a paper product treated with the copolymer and kept at 130 ℃ for 30 minutes.
Detailed Description
Example 1
13g of perfluorohexylethyl methacrylate CH were weighed in order2＝C(CH3)COOCH2CH2C6F13(TEMAc-6),2.0g methyl vinyl dimethoxy silane (VMDMS), 0.6g vinyl soybean isoflavone (structure as above soybean isoflavone glycoside structural formula, wherein, R1＝OH,R2＝H,R3＝CHCOCH＝CH2) (ISO), 0.4g of Methyl Methacrylate (MMA), 0.6g of butyl methacrylate (BA), 0.8g of Stearyl Acrylate (SA) and 0.4g of diacetone acrylamide (DAAM) and 0.2g of Glycidyl Methacrylate (GMA) were placed in a 150mL flask, 20g of an organic solvent (acetone to isopropanol mass ratio 1: 1) heating to 50 deg.C and stirringUntil the solid is completely melted;
2.0g of methacryloyloxyethyl trimethyl ammonium chloride (DMC) and 0.1g of Azobisisobutyronitrile (AIBN) are weighed and slowly dripped into a beaker, and high-speed dispersion is carried out simultaneously, and the dispersion time is 20 min;
transferring 1/2 of the solution in the beaker into a three-neck flask with a stirrer, a thermometer and a condenser, introducing nitrogen to remove oxygen, stirring, heating to 65 ℃, and keeping the temperature for 30 min;
dissolving the rest 0.1g of Azobisisobutyronitrile (AIBN) and 0.2g of n-dodecyl mercaptan (L-SH) in the rest monomer solution, transferring the solution to a constant pressure dropping funnel, slowly dropping into a three-neck flask under the protection of nitrogen, and reacting for 12h at 65 ℃; after the reaction is finished, the reaction temperature is reduced to 45 ℃, 0.3g of acetic acid and 80g of deionized water are added, high-speed dispersion is carried out for 5min, and after the dispersion is finished, the organic solvent is evaporated out by heating under the condition that the vacuum degree is 0.01Mpa, so that the faint yellow clear water-based fluorine-containing copolymer emulsion for the food packaging paper is obtained.
Examples 2-11 were prepared using the same procedures (procedures and conditions) as in example 1, with the specific raw material formulations detailed in table 1: TABLE 1
Figure BDA0003579783230000051
Figure BDA0003579783230000061
Preparation and application of surface sizing liquid
Cationic starch and polyvinyl alcohol are commonly used as surface gelatinizing liquid in the market at present, and the preparation method comprises the following steps:
pasting cationic starch: adding 90.0g of water into the reactor, pouring 10.0g of cationic starch into the reactor, slowly stirring, heating to 95 ℃, and keeping the temperature and stirring for 0.5h to obtain 10% cationic starch pasting liquid.
Polyvinyl alcohol gelatinization: adding 95.0g of water into the reactor, adding 5.0g of polyvinyl alcohol into the reactor, stirring, heating to 90 ℃, and preserving heat for 0.5h to obtain 5% polyvinyl alcohol pasting liquid.
Preparation of surface sizing liquid: 10g of cationic starch and 5g of polyvinyl alcohol pasting liquid are poured into a reactor, 15g of the product of the invention example and 70g of deionized water are added, the temperature of the sizing liquid is kept at 60 ℃, and the mixture is stirred for 15min to obtain the surface sizing liquid with a certain concentration.
Surface sizing experiment, the quantitative ratio is (40 +/-0.5) g/m by adopting a manual coating pair2The unsized paper of (2.0 g/m) was surface sized2,The sized paper was dried in a glazing machine for 5min (120 ℃). And performing oil-proof performance detection on the obtained paper sample after constant temperature and humidity treatment for 24 hours.
Test method
(1) Stability test
Dispersion stability of fluorine-containing copolymer in water: the aqueous dispersion whose solid content was adjusted to 20 wt% was centrifuged for 5min in a centrifuge at a rotation speed of 3000rpm/min, and then the stability was judged by observing the amount of the precipitate: "good" means almost no precipitation; "general" means that there is a small amount of precipitation; "poor" means more precipitate.
(2) Oil repellency test
The Oil resistance was measured by the Oil Kit Test-TAPPI 557 International general Test method. Test oils were formulated with a series of different volume ratios of castor oil, toluene and n-heptane. The assay was rated on a total of 12 grades, with the lowest oil resistance rating at level 1 and the highest at level 12, the specific oil resistance rating and the volume ratio of the three materials shown in table 2. The test oil was applied to the sample at a height of about 1 inch and after the application of the test oil to the paper had been allowed to remain for 15 seconds, the excess liquid was removed with a piece of clean cotton or tissue paper and the wet condition was observed, and if the test oil did not leave any marks on the paper, the test oil rating was the oil resistance rating of the paper sample. Wherein the surface tension of 7-11 corresponding test oils is 0.0232/N.m-1、0.0228/N·m-1、0.0225/N·m-1、0.0224/N·m-1、0.0223/N·m-1。
TABLE 2 oil repellency test Standard solution
Figure BDA0003579783230000071
(3) Water resistance test
Bob (Cobb) assay. The method for measuring the water resistance in International Standard ISO 535 'test for Water absorption of paper and paperboard (Keblin method)' is used to measure the water resistance of paper sample, i.e. the water amount absorbed by the paper and paperboard in a unit area under a certain pressure and temperature for a specified time is measured in g/m2And (6) counting.
(4) Hot oil resistance test
The method for measuring the hot oil resistance comprises injecting 130 deg.C salad oil into pulp mold container, maintaining the temperature at 130 deg.C for 30min, and determining the penetration degree of salad oil from the container after 30min according to the following determination standards:
"good" means no leakage; "minor" means there is only a little leakage; "generally" means that there is a leak, but not a leak.
Examples 1 to 11 the test results are shown in Table 3 below
TABLE 3
Sample(s) Stability performance Water resistance Oil-proof performance Resistance to hot oil
Example 1 Good taste 30 11 Good taste
Example 2 Good taste 35 9 Good taste
Example 3 In general terms 37 10 Good taste
Example 4 Good taste 40 9 Small amount of
Example 5 In general terms 60 7 In general terms
Example 6 Good taste 42 8 Good taste
Example 7 Good taste 40 9 Good taste
Example 8 In general terms 50 8 In general terms
Example 9 In general terms 45 8 Small amount of
Example 10 In general 39 9 Good taste
Example 11 Good taste 44 8 Small amount of
Note: the waterproof performance unit is: g/m2。
Comparative example
Compared with the products which are commercially available and reported in patents at present, the product synthesized by the specification has better water and oil resistance and has the advantage of low cost. Through the application of internal sizing and surface sizing, the prepared emulsion has the advantages of good oil-proof effect, small using amount, low price, good stability, high safety and the like, and has wide market prospect.
Comparative example 1
The commercially available Kedrier 106 waterproof and oil-proof agent is purchased, the product is a cationic oil-proof agent, the effective solid content is 20%, the purchased product is used for preparing the surface sizing agent by adopting the process which is the same as the process of the invention, corresponding tests are carried out, and the test results are compared with the invention.
Comparative example 2
We bought commercially available TG5606 water and oil repellent agent, which is a cationic oil repellent agent with an effective solid content of 20%, prepared the surface sizing solution using the same process as the present invention, and performed corresponding tests, and the test results were compared with the present invention.
Comparative example 3
According to patent CN 103396510A, the solid content of the fluorine-containing oil-proof agent prepared by the method is 27.5%, but the price of reaction raw materials is high, and a large amount of organic solvent is used, so that the recovery is difficult and the environment is polluted. We prepared the surface sizing solution by the same process as the present invention and performed the corresponding test, and the test results were compared with the present invention.
Comparative example 4
The fluorine-containing oil-proof agent prepared by the method has the solid content of 27.5 percent according to the patent CN 102575435B, but the reaction raw materials are high in price, and a large amount of organic solvent is used, so that the recovery is difficult, and the environment is polluted. We prepared the surface sizing solution by the same process as the present invention and performed the corresponding test, and the test results were compared with the present invention.
Comparative example 5
The fluorine-containing oil-proofing agent is prepared according to the patent CN 1062577541A, the solid content of the fluorine-containing oil-proofing agent prepared by the method is 20.5%, the process is complicated, and the using amount of a solvent is large. We prepared the surface sizing solution by the same process as the present invention and performed the corresponding test, and the test results were compared with the present invention.
Comparative example 6
The fluorine-containing oil-proofing agent is prepared according to the patent CN 102762618A, the solid content of the fluorine-containing oil-proofing agent prepared by the method is 23.2%, but the reaction cost is high, and the synthesis process is complex. We prepared the surface sizing solution by the same process as the present invention and performed the corresponding test, and the test results were compared with the present invention.
Comparative examples 7-13 were prepared using the same procedures (procedures and conditions) as in example 1, and the specific raw material formulations are detailed in table 4:
Figure BDA0003579783230000091
Figure BDA0003579783230000101
the following are the performance and cost performance vs. ratio of the product of the invention (example 1) to the products reported in Kedrier 106, TG5606, patent CN 103396510A, patent CN 102575435B, patent CN 1062577541A, patent CN 102762618A and non-preferred comparative examples 7-13 currently on the market (preparation of surface sizing solutions and testing methods are as described above) in Table 5.
TABLE 5
Figure BDA0003579783230000102
Figure BDA0003579783230000111
Note: the waterproof performance unit is: g/m2The price unit is: yuan/kg.
From the comparison results, it can be seen that: the water-based fluorine-containing water-proof and oil-proof agent for paper prepared by the invention has water-proof and oil-proof performances obviously higher than those of other comparative examples, and has lower cost under the condition of keeping the same performances.

Claims (8)

1. The water-based fluorine-containing water-and-oil repellent agent for paper is characterized in that: the fluorine-containing copolymer comprises the following components in parts by weight: 50-80 parts (preferably 60-70 parts) of a fluorine-containing monomer (TEMAc-6), 10-20 parts (preferably 10-15 parts) of an organosilicon monomer, 1-10 parts (preferably 1-5 parts) of a methyl Methacrylate Monomer (MMA), 1-10 parts (preferably 1-5 parts) of a butyl methacrylate monomer (BA), 1-10 parts (preferably 1-5 parts) of an octadecyl acrylate monomer (SA), 1-10 parts (preferably 1-5 parts) of a diacetone acrylamide monomer (DAAM), 5-25 parts (preferably 10-15 parts) of a functional monomer, 1-5 parts (preferably 1-3 parts) of other monomers and 1-5 parts (preferably 1-3 parts) of soybean isoflavone glycoside; based on 100 parts of all the monomers, 1-3 parts (preferably 1-1.5 parts) of initiator, 1-3 parts (preferably 1-2 parts) of chain transfer agent and 1-10 parts (preferably 1-4 parts) of protonic acid are also contained in 100 parts of the monomers;
the functional monomer is any one or more than two of (aminoethyl methacrylate or) aminoethyl acrylate (DM), (methacryloyloxyethyl trimethyl ammonium chloride or) acryloyloxyethyl trimethyl ammonium chloride (DMC), (methacrylamide vinyl ether or) acrylamide vinyl ether, hydroxybutyl vinyl ether (HBVE), Ethyl Vinyl Ether (EVE), cyclohexyl vinyl ether and the like;
the other monomer is any one or more than two of glycidyl methacrylate, glycidyl acrylate, isooctyl acrylate and isobornyl acrylate.
2. The aqueous fluorine-containing water-and oil-repellent agent for paper as claimed in claim 1, characterized in that: the general formula of the fluorine-containing monomer can be shown as R3-A-OOCCR1＝CHR2(ii) a In the formula R3Represents a linear perfluoro substituted alkyl group having 4 to 16 carbon atoms; a represents a cushion link having a-CH2CH2-、-CH2-or-SO2NHCH2CH2-one or more than two of the same; r1And R2Any one of which is H, and the other is one or two of H or alkyl containing 1-4 carbon atoms.
3. The aqueous fluorine-containing water-and oil-repellent agent for paper according to claim 1, characterized in that: the organosilicon monomer is one or more of vinyltrimethoxysilane, vinyltriethoxysilane or methylvinyldimethoxysilane (VMDMS).
4. The aqueous fluorine-containing water-and oil-repellent agent for paper according to claim 1, characterized in that: the soybean isoflavone glycoside has the following structural general formula:
Figure FDA0003579783220000011
wherein: r1H or OH, R2＝H、OCH3Or CH ═ CH2COCH3，R3＝H、COCH3、CH＝CH2COCH3Or COCH3COOH。
5. The aqueous fluorine-containing water-and oil-repellent agent for paper according to claim 1, characterized in that: the initiator is selected from any one or more of peroxide (such as benzoyl peroxide and lauroyl peroxide) or azo compound (such as one or more of 2, 2-Azobisisobutyronitrile (AIBN), 4-azobis (4-cyanovaleric acid) and azodicarbonamide);
the chain transfer agent is one or more of alkyl mercaptan such as dodecyl mercaptan (L-SH), lauryl mercaptan, octadecyl mercaptan or aminoethanethiol, mercaptoethanol and mercaptoacetic acid;
the protonic acid is one or two of phosphoric acid and acetic acid.
6. A process for producing an aqueous fluorine-containing water-and oil-repellent agent for paper according to any one of claims 1 to 5, characterized in that: 50-80 parts of fluorine-containing monomer, 10-20 parts of organosilicon monomer, 1-10 parts of methyl methacrylate monomer, 1-10 parts of butyl methacrylate monomer, 1-10 parts of octadecyl acrylate monomer, 1-5 parts of soybean isoflavone glycoside and 1-5 parts of diacetone acrylamide monomer are dissolved in an organic solvent and preheated to 30-50 ℃, after uniform mixing, 5-25 parts of functional monomer and 1-3 parts of initiator are dripped in, shearing and dispersing are carried out, 1/3-1/2 of monomer mixed solution is transferred to a container after dispersing is finished, nitrogen is introduced for deoxygenation, stirring is carried out, the temperature is raised to the polymerization reaction temperature, and heat preservation is carried out; and dissolving the rest of initiator with required amount and 1-3 parts of chain transfer agent in the rest of monomer solution, dripping the initiator and the chain transfer agent into the heat-insulating reaction solution, reacting until the reaction is finished, cooling to room temperature, adding 1-10 parts of protonic acid and 500 parts of 200-one water, and evaporating the organic solvent under the action of 0.01-0.02Mpa of vacuum degree to obtain the water-based fluorine-containing copolymer emulsion for the food packaging paper.
7. The method of manufacturing according to claim 6, characterized in that: the organic solvent is any one or more than two of acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, propylene glycol methyl ether, propylene glycol acetate, tetrahydrofuran, dioxan, acetonitrile, dimethylformamide, N-methyl-2-pyrrolidone, butyl lactone or dimethyl sulfoxide; among them, any one or two or more of Methyl Ethyl Ketone (MEK), N-methyl-2-pyrrolidone, isopropyl alcohol, acetone, and a mixture thereof are preferable;
the dosage of the organic solvent is 80-120 parts and the water is 200-500 parts per 100 parts by mass of all the monomer mixture;
the polymerization reaction temperature is 55-70 ℃, and the time for keeping the temperature until the polymerization is completed is 10-12 h.
8. Use of an aqueous fluorine-containing water-and oil-repellent agent for paper according to any one of claims 1 to 5 for water-and oil-repellency of paper or paper products.
CN202210350364.7A 2022-04-02 2022-04-02 Water-based fluorine-containing waterproof and oil-proof agent for paper and preparation and application thereof Pending CN114773523A (en)

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CN114773523A true CN114773523A (en) 2022-07-22

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
樊能延: "《有机合成事典》", 北京理工大学出版社 *

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Application publication date: 20220722