CN112195682A - Waterproof and oilproof environment-friendly fluorine-free coating and preparation method thereof - Google Patents
Waterproof and oilproof environment-friendly fluorine-free coating and preparation method thereof Download PDFInfo
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- CN112195682A CN112195682A CN202011074419.3A CN202011074419A CN112195682A CN 112195682 A CN112195682 A CN 112195682A CN 202011074419 A CN202011074419 A CN 202011074419A CN 112195682 A CN112195682 A CN 112195682A
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- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 acrylic acid compound Chemical class 0.000 claims abstract description 52
- 239000003999 initiator Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920002472 Starch Polymers 0.000 claims description 23
- 229920001296 polysiloxane Polymers 0.000 claims description 23
- 239000008107 starch Substances 0.000 claims description 23
- 235000019698 starch Nutrition 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VHGQXSVGGOZFAO-UHFFFAOYSA-N 2-butyloctyl 2-methylprop-2-enoate Chemical compound CCCCCCC(CCCC)COC(=O)C(C)=C VHGQXSVGGOZFAO-UHFFFAOYSA-N 0.000 claims description 20
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 20
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 20
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 20
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 20
- 229940092650 2-butyloctyl methacrylate Drugs 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 3
- GDUZPNKSJOOIDA-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-yl 2-methylprop-2-enoate Chemical compound C1C(OC(=O)C(=C)C)CCC2OC21 GDUZPNKSJOOIDA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 108010073771 Soybean Proteins Proteins 0.000 claims description 3
- 239000005016 bacterial cellulose Substances 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000005871 repellent Substances 0.000 claims description 3
- 229940001941 soy protein Drugs 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims description 2
- 239000000123 paper Substances 0.000 abstract description 22
- 238000004806 packaging method and process Methods 0.000 abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 abstract description 12
- 239000011737 fluorine Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000004925 Acrylic resin Substances 0.000 abstract description 6
- 229920000178 Acrylic resin Polymers 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 235000013305 food Nutrition 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 4
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 244000246838 Falcataria moluccana Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003487 anti-permeability effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011084 greaseproof paper Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002939 oilproofing Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
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- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000021404 traditional food Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- D21H21/16—Sizing or water-repelling agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a waterproof and oilproof environment-friendly fluorine-free coating and a preparation method thereof. The coating comprises the following raw materials in parts by mass: 22-38% of acrylic acid compound, 4-8% of additive, 3-5% of first initiator, 1-3% of emulsifier, 6-10% of modifier, 15-22% of ethanol, 1-2% of second initiator and the balance of water. The invention adopts the modified acrylic resin technology to replace the traditional six-carbon fluorine waterproof and oilproof processing agent (such as Japanese Asahi glass AG-E081), does not contain fluorine, and improves the waterproof and oilproof effects of the coating; meanwhile, the paper packaging powder can be directly sprayed on the surface of paper packaging, and is not required to be added into paper pulp for molding by a mold, so that the paper packaging powder is green and environment-friendly, and is convenient in process and strong in practicability.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a waterproof and oilproof environment-friendly fluorine-free coating and a preparation method thereof.
Background
Packaging plays a very important role in the food industry, and the requirements for food packaging materials are getting stricter from both safety and aesthetic point of view, and the market share of the food packaging currently accounts for more than half of the packaging industry. In recent years, food enterprises pay more and more attention to the selection of product packaging materials. Food packaging materials are a wide variety of which plastic is a traditional packaging material, and which has a considerable market among the traditional food packaging market for its relatively lightweight, low cost and barrier properties.
However, since plastic has hidden danger to human health, and plastic is difficult to degrade in nature, causing serious pollution to the environment, the future food packaging field will gradually band this packaging material. In recent years, the importance of environmental protection has been called for by the global environmental protection organization, and there is a great development space for developing food packaging paper. The paper food package is the best substitute of non-degradable packaging materials such as plastics as a green and environment-friendly packaging material, and has very wide development prospect in the field of food packaging.
Grease-resistant paper, also known as greaseproof paper, refers to paper that prevents the absorption and penetration of grease. In recent years, a great deal of fluorine compounds with low surface tension are developed, and paper treated by methods such as internal sizing, paper surface sizing and the like has good oil-proof effect. At present, paper made of fluorine-containing materials is widely applied to printing and packaging materials. The surface energy of the fluorine-containing material is very low, and the low surface energy determines the hydrophobicity and oleophobicity, i.e. the surface wettability, of the surface. However, fluorine-containing materials have poor solubility, and the fluorine-containing compounds and other chemical substances are subjected to graft copolymerization to introduce other groups, so that the solubility of the fluorine-containing polymers and the compatibility with other resins can be improved. The waterproof and oil-proof agent can be made by utilizing the characteristic of fluorine materials, and the oil-proof paper made by the oil-proof agent through the methods of internal sizing, surface sizing and the like can not be wetted by water and oil, thereby having the water-resistant and oil-resistant performance.
Because of the wide application of fluorine-containing coatings in food contact materials, the safety problem has received social attention. The main factors affecting the safety of fluorine coatings are various additives required in the production process. Among them, the toxicity of perfluorinated compounds is a key factor affecting the safety of fluorine coatings, and includes perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and salts thereof. PFOA, PFOS and their salts have many toxicities, such as harming reproductive system and immune system, interfering gene expression, affecting late development of fetus, etc. If PFOA and PFOS in the food contact material migrate into the food, it will harm the health of the person. The development of fluorine-free water-proof oil-proof impervious materials is an urgent problem to be solved in the paper base material industry.
Disclosure of Invention
According to the waterproof and oil-proof environment-friendly fluorine-free coating and the preparation method thereof, the traditional six-carbon fluorine-containing waterproof and oil-proof processing agent (such as Japanese Asahi glass AG-E081) is replaced by the modified acrylic resin technology, and the waterproof and oil-proof effects of the coating are improved while the coating does not contain fluorine; meanwhile, the paper packaging powder can be directly sprayed on the surface of paper packaging, and is not required to be added into paper pulp for molding by a mold, so that the paper packaging powder is green and environment-friendly, and is convenient in process and strong in practicability.
The invention provides a waterproof and oilproof environment-friendly fluorine-free coating, which comprises the following raw materials in percentage by mass: 22-38% of acrylic acid compound, 4-8% of additive, 3-5% of first initiator, 1-3% of emulsifier, 6-10% of modifier, 15-22% of ethanol, 1-2% of second initiator and the balance of water.
In a preferred embodiment, the acrylic compound is at least one selected from the group consisting of 2, 3-dihydroxypropyl acrylate, 2-butyloctyl methacrylate, 2, 3-epoxypropyl acrylate, 4- (2-oxiranylmethoxy) butyl acrylate, and 3, 4-epoxycyclohexyl methacrylate.
In a preferred embodiment, the acrylic compound is 4- (2-oxiranylmethoxy) butyl acrylate and 2-butyloctylmethacrylate, the weight ratio of 4- (2-oxiranylmethoxy) butyl acrylate to 2-butyloctylmethacrylate being 1: (0.6-0.8).
In a preferred embodiment, the modifier is a polysiloxane derivative.
In a preferred embodiment, the polysiloxane derivative is an amino group-containing polysiloxane.
In a preferred embodiment, the additive comprises at least one of polyvinyl alcohol, soy protein, bacterial cellulose, glycerol, etherified starch, hydroxypropyl methylcellulose.
In a preferred embodiment, the additives are etherified starch and hydroxypropyl methylcellulose.
In a preferred embodiment, the weight ratio of the etherified starch and hydroxypropyl methylcellulose is (1-2.5): 1.
in a preferred embodiment, the emulsifier is hydrogenated castor oil polyoxyethylene ether.
The invention provides a preparation method of a waterproof and oilproof environment-friendly fluorine-free coating, which comprises the following specific preparation steps:
s1, pouring water into a reaction kettle, and preheating to 70-80 ℃;
s2, adding a first initiator and an acrylic acid compound into a reaction kettle, and stirring for 5min at a speed of 60-120 r/min;
s3, adding a modifier, an additive and an emulsifier into the reaction kettle, keeping the temperature at 70-80 ℃, and stirring and reacting at the speed of 100-240r/min for 1-4 h;
s4, adding a second initiator into the reaction kettle, and stirring at the speed of 60-120r/min for 10-15 min;
s5, adding ethanol into the reaction kettle, and stirring at the speed of 100-;
s6, cooling to 20-37 ℃ to obtain the coating.
Has the advantages that:
the waterproof and oilproof environment-friendly fluorine-free coating prepared by the invention has the advantages of toughness, high strength, strong ageing resistance, wide applicable temperature range and strong adaptability to base layer shrinkage, deformation and cracking. Meanwhile, the paint has strong adhesive force and good extensibility, can achieve the effects of water resistance, oil resistance and impermeability for a long time, is particularly suitable for packaging boxes of perishable articles or storage of special articles in a high-humidity environment, and can also be applied to the fields of printing, decoration and the like. The product adopts modified acrylic resin technology to replace the traditional six-carbon fluorine series waterproof and oilproof processing agent (such as AG-E081), does not contain fluorine, and improves the waterproof and oilproof effects of the coating; meanwhile, the invention can be directly sprayed on the surface of paper packaging, does not need to be added into paper pulp for mold forming, is environment-friendly, has convenient process and wide application prospect.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will be further understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "including," and/or "containing," when used in this specification means that the recited composition, step, method, article, or device is present, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or devices. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present application, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, the present invention provides, in a first aspect, an environmentally friendly fluorine-free coating material that is water and oil repellent. The coating comprises the following raw materials in parts by mass: 22-38% of acrylic acid compound, 4-8% of additive, 3-5% of first initiator, 1-3% of emulsifier, 6-10% of modifier, 15-22% of ethanol, 1-2% of second initiator and the balance of water.
In some preferred embodiments, the acrylic compound is selected from at least one of 2, 3-dihydroxypropyl acrylate, 2-butyloctyl methacrylate, 2, 3-epoxypropyl acrylate, 4- (2-oxiranylmethoxy) butyl acrylate, 3, 4-epoxycyclohexyl methacrylate.
Further preferably, the acrylic compound is 4- (2-oxiranylmethoxy) butyl acrylate and 2-butyloctylmethacrylate, and the weight ratio of 4- (2-oxiranylmethoxy) butyl acrylate to 2-butyloctylmethacrylate is 1: (0.6-0.8). 4- (2-Oxiranylmethoxy) butyl acrylate has a CAS number of 119692-59-0 and 2-butyloctyl methacrylate has a CAS number of 10097-26-4.
The invention discovers that when the acrylic compounds are 4- (2-ethylene oxide methoxyl) butyl acrylate and 2-butyl octyl methacrylate, the prepared coating has excellent waterproof and oil-resistant performance when being coated on a paper-based package. The reason is probably that the acrylic resin containing epoxy groups has higher activity, can be crosslinked with polysiloxane containing amino groups, and further generates free radical copolymerization with 2-butyl octyl methacrylate to synthesize modified acrylic resin with low surface tension, thereby improving the waterproof and oil-resistant performance of the package. It has also been found that when the weight ratio of 4- (2-oxiranylmethoxy) butyl acrylate to 2-butyloctyl methacrylate is 1: (0.6-0.8), the elongation at break of the film formed from the resulting coating is optimum. The reason is probably that the specific amount of the 2-butyl octyl methacrylate optimizes the network structure of the amino-containing polysiloxane, enhances the cross-linking capability of polymer molecular chains while improving the polymerization reaction activity, and thus enhances the film-forming flexibility of the coating.
In some preferred embodiments, the modifying agent is a polysiloxane derivative.
In some preferred embodiments, the polysiloxane derivative is an amino-containing polysiloxane.
Further preferably, the amino group-containing polysiloxane has an ammonia value of 0.4 to 1 mmol/L.
The invention discovers that when the ammonia value of the amino-containing polysiloxane is 0.4-1mmol/L, the prepared coating not only has water-proof and oil-proof properties, but also improves the film-forming speed of the coating. The reason is supposed to be that the introduction of the amino enhances the affinity of the etherified starch with the paper pulp, so that the binding capacity of positive charges carried by the etherified starch in surface sizing and negative charges carried by fibers on the surface of the paper shell is enhanced, and the gaps among the fibers are further reduced, thereby promoting the coating to form a compact film on the surface of the paper.
In some preferred embodiments, the additive comprises at least one of polyvinyl alcohol, soy protein, bacterial cellulose, glycerol, etherified starch, hydroxypropyl methylcellulose.
In some preferred embodiments, the additives are etherified starch and hydroxypropyl methylcellulose.
In some preferred embodiments, the weight ratio of the etherified starch and hydroxypropyl methylcellulose is (1-2.5): 1. the etherified starch may be commercially available, for example, new chemical company, Inc. of Qinyang, model number YLS-2; the hydroxypropyl methylcellulose may be commercially available, for example from sigma aldrich trade, inc, under CAS number 9004-65-3.
The invention discovers that when the additive is etherified starch and hydroxypropyl methyl cellulose, the weight ratio of the etherified starch to the hydroxypropyl methyl cellulose is (1-2.5): 1, the prepared coating has the water-proof and oil-proof performance, and the brightness and smoothness of a formed film of the coating are improved. The introduction of the amino active group enables the prepared coating to have the water-proof and oil-proof characteristics, but active hydrogen in the amino easily forms a chromophore, so that the coating is easy to yellow after the film is formed. The present inventors have unexpectedly found that the addition of specific amounts of etherified starch and hydroxypropyl methylcellulose suppresses the yellowing problem of the coating after film formation, and hypothesize that the etherified starch and hydroxypropyl methylcellulose act synergistically with amino-containing polysiloxane to improve the film forming effect of the acrylic resin.
In some preferred embodiments, the weight ratio of acrylic compound to modifier is (3-5): 1.
the invention discovers that when the weight ratio of the acrylic compound to the modifier is (3-5): 1, the prepared coating has the best permeation resistance after film forming, and the smoothness and the mechanical property of the film formed by the coating are better. The reason is guessed that the network structure of molecular chains in the system is optimized by adding the polysiloxane, so that chain growth and crosslinking reaction are more stable, the structural regularity of the molecular chains of the polymer is improved, the uniformity and the dispersibility of the additive in the proportion are further improved, the problem that the etherified starch is easy to flocculate is solved, the synergistic effect of the etherified starch, the hydroxypropyl methyl cellulose and the polysiloxane containing amino groups is promoted, and the smoothness and the elongation at break of a film formed by the coating are improved.
In some preferred embodiments, the emulsifier is hydrogenated castor oil polyoxyethylene ether. Hydrogenated castor oil polyoxyethylene ether is commercially available, for example, as model HEL-40 from Iavailable Chemicals Inc.
In some preferred embodiments, the first initiator and the second initiator are both Ammonium Persulfate (APS). APS is commercially available, for example from Sigma Aldrich trade, Inc. under CAS number 7727-54-0.
The invention provides a preparation method of a waterproof and oilproof environment-friendly fluorine-free coating, which comprises the following specific preparation steps:
s1, pouring water into a reaction kettle, and preheating to 70-80 ℃;
s2, adding a first initiator and an acrylic acid compound into a reaction kettle, and stirring for 5min at a speed of 60-120 r/min;
s3, adding a modifier, an additive and an emulsifier into the reaction kettle, keeping the temperature at 70-80 ℃, and stirring and reacting at the speed of 100-240r/min for 1-4 h;
s4, adding a second initiator into the reaction kettle, and stirring at the speed of 60-120r/min for 10-15 min;
s5, adding ethanol into the reaction kettle, and stirring at the speed of 100-;
s6, cooling to 20-37 ℃ to obtain the coating.
The invention surprisingly finds that the coating prepared by adding the initiator in batches in the manner has the advantages of quick film forming, good water and oil proofing effects and flexible and glossy film forming. The reason is presumably that the subsequent addition of APS in the system promotes the free radical copolymerization reaction of the 4- (2-ethylene oxide methoxyl) butyl acrylate and the amino-containing polysiloxane crosslinked product with the ammonia value of 0.4-1mmol/L and 2-butyl octyl methacrylate, improves the compatibility among polymers, modifiers and additives in the system, leads all components to be more fully synergistic, and further reduces the surface tension of acrylic polymers in the system, thereby improving the anti-permeability capability, flexibility and glossiness of the coating film.
Examples
Example 1.
The waterproof and oilproof environment-friendly fluorine-free coating comprises the following raw materials in parts by mass: 32% of acrylic acid compound, 5% of additive, 5% of first initiator, 2% of emulsifier, 8% of modifier, 20% of ethanol, 1% of second initiator and the balance of water.
The acrylic compound is 4- (2-ethylene oxide methoxyl) butyl acrylate and 2-butyl octyl methacrylate, and the weight ratio of the 4- (2-ethylene oxide methoxyl) butyl acrylate to the 2-butyl octyl methacrylate is 1: 0.6.
the modifier is amino-containing polysiloxane, the ammonia value of the amino-containing polysiloxane is 0.6mmol/L, and the amino-containing polysiloxane is purchased from Honghou chemical industry Co., Ltd. in Guangzhou, and the type of the amino-containing polysiloxane is OFX-8468.
The additive is etherified starch and hydroxypropyl methyl cellulose, and the weight ratio of the etherified starch to the hydroxypropyl methyl cellulose is 2: 1. the etherified starch is purchased from a new chemical company, Inc. in Qinyang city, and the model is YLS-2; hydroxypropyl methylcellulose is purchased from sigma aldrich trade, inc, under CAS number 9004-65-3.
The emulsifier is hydrogenated castor oil polyoxyethylene ether, the hydrogenated castor oil polyoxyethylene ether is purchased from chemical optimization limited company, and the model is HEL-40.
The first initiator and the second initiator are each Ammonium Persulfate (APS), which is purchased from Sigma Aldrich trade, Inc. under CAS number 7727-54-0.
The preparation method of the coating comprises the following specific steps:
s1, pouring water into a reaction kettle, and preheating to 75 ℃;
s2, adding a first initiator and an acrylic compound into a reaction kettle, and stirring at the speed of 60r/min for 5 min;
s3, adding a modifier, an additive and an emulsifier into the reaction kettle, keeping the temperature at 75 ℃, and stirring and reacting for 4 hours at the speed of 120 r/min;
s4, adding a second initiator into the reaction kettle, and stirring at the speed of 60r/min for 10 min;
s5, adding ethanol into the reaction kettle, and stirring at the speed of 100r/min for 1 h;
s6, cooling to 37 ℃ to obtain the coating.
Example 2.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. The difference is that the amino group-containing polysiloxane has an ammonia value of 0.4mmol/L, and is available from Batai chemical Co., Ltd, Guangzhou under the model number BT-6179.
Example 3.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. The difference is that the weight ratio of the 4- (2-ethylene oxide methoxyl) butyl acrylate to the 2-butyl octyl methacrylate is 1: 0.8.
example 4.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. The different points are that the weight ratio of the etherified starch to the hydroxypropyl methyl cellulose is 1: 1.
comparative example 1.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. The difference is that the modifier is 201 dimethyl silicone oil, and the 201 dimethyl silicone oil is purchased from Qingdao Zhongbao silicon material science and technology limited company with the model number of 201-20.
Comparative example 2.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. Except that no additives were added.
Comparative example 3.
The specific implementation mode of the waterproof and oil-proof environment-friendly fluorine-free coating is the same as that of example 1. The difference is that the mass fraction of the first initiator added is 6% and the second initiator is not added (i.e. the initiator is not added in 2 portions).
Performance test method
Surface tension:
the surface tension of the coating was determined with reference to GB/T22237/2008.
Film forming time:
the same amounts as those obtained in examples 1-2 and comparative examples 1-4 were applied to clean glass sheets and dried at a temperature of 100 ℃ to obtain film samples, and the film formation time was recorded.
Elongation at break:
the elongation at break of the film sample is tested by an LLY-06E type electronic single fiber strength tester, the tensile speed is set to be 20mm/min during the test, the clamping distance is set to be 10mm, each sample is tested for 20 times, and the result is averaged.
Oil resistance rating:
the paper can be divided into different Oil-proof grades according to the difference of Oil-proof capability, and the Oil-proof grade Test adopts the international universal standard detection method of Oil Kit Test-T559 cm-12. The oil resistance rating is 12 at the highest and 1 at the lowest, and the higher the rating of the oil-proof paper is, the higher the oil resistance of the paper is.
Results of Performance testing
| Surface tension N/m | Film formation time s | Elongation at break% | Oil repellency rating | |
| Example 1 | 0.020 | 49.6 | 367 | 7 |
| Example 2 | 0.024 | 54.8 | 353 | 6 |
| Example 3 | 0.022 | 52.9 | 314 | 6 |
| Example 4 | 0.021 | 53.1 | 335 | 6 |
| Comparative example 1 | 0.029 | 65.7 | 286 | 5 |
| Comparative example 2 | 0.031 | 67.3 | 245 | 3 |
| Comparative example 3 | 0.027 | 59.2 | 292 | 4 |
As is clear from the results of comparative examples 1 to 4 and comparative examples 1 to 3, when the acrylic compound is used in a weight ratio of 1: when the 4- (2-ethylene oxide methoxyl) butyl acrylate and the 2-butyl octyl methacrylate (0.6-0.8) are used, the surface tension of the formed film of the coating can be reduced by the synergistic effect of the etherified starch and the hydroxypropyl methyl cellulose, and the water-proof and oil-proof effects of the coating can be further improved. And when the amino-containing polysiloxane with the ammonia value of 0.4-1mmol/L is selected to modify the acrylic compound, the waterproof and oilproof performance of the coating can be improved, and the film forming time of the coating is also obviously prolonged. Meanwhile, the invention discovers that the addition of the initiator for 2 times can promote the compatibility among the components, thereby improving the mechanical property, the film forming time and the water and oil resistance of the coating.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The waterproof and oilproof environment-friendly fluorine-free coating is characterized by comprising the following raw materials in parts by mass: 22-38% of acrylic acid compound, 4-8% of additive, 3-5% of first initiator, 1-3% of emulsifier, 6-10% of modifier, 15-22% of ethanol, 1-2% of second initiator and the balance of water.
2. The environmentally friendly fluorine-free water and oil repellent coating according to claim 1, wherein the acrylic compound is at least one selected from the group consisting of 2, 3-dihydroxypropyl acrylate, 2-butyloctyl methacrylate, 2, 3-epoxypropyl acrylate, 4- (2-oxiranylmethoxy) butyl acrylate, and 3, 4-epoxycyclohexyl methacrylate.
3. The environment-friendly fluorine-free paint capable of preventing water and oil according to claim 2, characterized in that the acrylic compound is 4- (2-ethylene oxide methoxyl) butyl acrylate and 2-butyl octyl methacrylate, the weight ratio of the 4- (2-ethylene oxide methoxyl) butyl acrylate to the 2-butyl octyl methacrylate is 1: (0.6-0.8).
4. The environmentally friendly fluorine-free coating material for preventing water and oil according to claim 1, wherein the modifier is a polysiloxane derivative.
5. The environmentally friendly fluorine-free paint for preventing water and oil according to claim 4, wherein the polysiloxane derivative is polysiloxane containing amino.
6. The environment-friendly fluorine-free paint with water and oil resistance as claimed in claim 1, wherein the additive comprises at least one of polyvinyl alcohol, soy protein, bacterial cellulose, glycerol, etherified starch and hydroxypropyl methyl cellulose.
7. The environment-friendly fluorine-free paint capable of preventing water and oil according to claim 6, characterized in that the additive is etherified starch and hydroxypropyl methyl cellulose.
8. The waterproof and oilproof environment-friendly fluorine-free coating as claimed in claim 7, wherein the weight ratio of the etherified starch and the hydroxypropyl methyl cellulose is (1-2.5): 1.
9. the environment-friendly fluorine-free paint with water and oil resistance as claimed in claim 1, wherein the emulsifier is hydrogenated castor oil polyoxyethylene ether.
10. The preparation method of the water-and oil-repellent environment-friendly fluorine-free coating according to any one of claims 1 to 9, which is characterized by comprising the following specific preparation steps:
s1, pouring water into a reaction kettle, and preheating to 70-80 ℃;
s2, adding a first initiator and an acrylic acid compound into a reaction kettle, and stirring for 5min at a speed of 60-120 r/min;
s3, adding a modifier, an additive and an emulsifier into the reaction kettle, keeping the temperature at 70-80 ℃, and stirring and reacting at the speed of 100-240r/min for 1-4 h;
s4, adding a second initiator into the reaction kettle, and stirring at the speed of 60-120r/min for 10-15 min;
s5, adding ethanol into the reaction kettle, and stirring at the speed of 100-;
s6, cooling to 20-37 ℃ to obtain the coating.
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