CN115058918A - Fluorine-free oil-proof agent and application thereof in paper pulp molding - Google Patents
Fluorine-free oil-proof agent and application thereof in paper pulp molding Download PDFInfo
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- CN115058918A CN115058918A CN202210933333.4A CN202210933333A CN115058918A CN 115058918 A CN115058918 A CN 115058918A CN 202210933333 A CN202210933333 A CN 202210933333A CN 115058918 A CN115058918 A CN 115058918A
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- 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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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention discloses a fluorine-free oil-proofing agent, which comprises a component A: acrylic acid or methacrylic acid; and (B) component: having the general formula CH 2 An acrylic ester monomer of ═ CX-C (═ O) -O-Y, in the general formula, X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atoms, and Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms; and (3) component C: an epoxy-based silane coupling agent; and (3) component D: alpha, omega-dihydroxy polydimethylsiloxane; and (3) component E: dimethyl diethyl siloxane; and (3) component F: a crosslinking agent; a component G: an emulsifier; a component H: a V50 initiator; a component I: deionized water. Its advantages are no fluorine contained in oil-proof agent, good oil-proof performance, and high effect on preventing oilThe paper pulp molded product prepared from the paper pulp of the fluorine-free oil-proof agent has good oil-proof property.
Description
Technical Field
The invention relates to the technical field of oil-proof agent preparation, in particular to a fluorine-free oil-proof agent and application thereof in paper pulp molding.
Background
With the rapid development of social economy and the continuous acceleration of life rhythm, people consume more and more fast food, so that the demand of disposable tableware (lunch boxes, bowls, plates and cups) is rapidly increased, and with the implementation of 'plastic restriction' in China, the share of plastic products in the traditional food packaging market is continuously reduced, and the demand of green and environment-friendly paper pulp molded products is increasingly increased. The pulp molding product takes recyclable and completely biodegradable plant fiber as a raw material, no waste water and waste gas are discharged in the production, and the pulp molding product is a real green environment-friendly packaging material.
The paper pulp molding product is a packaging paper product which is made by using primary plant fibers or waste paper regenerated fibers as main raw materials and utilizing the papermaking technology through processes of mold molding, hot-pressing drying and the like and has a certain geometric cavity structure and buffering capacity. The paper product can be completely recycled, the waste can be naturally degraded, and meanwhile, the paper product has good buffering performance, is a typical green environment-friendly packaging product, and is widely applied to the field of packaging as a main substitute of foamed plastic. The paper pulp molding product mainly comprises three main components of cellulose, hemicellulose and lignin, and has the defects of easy water absorption, high air permeability, poor oil resistance and the like due to certain pores, so that the barrier property of the paper pulp molding product is influenced.
At present, aiming at the oil-proof treatment of paper materials internationally, two modes are mainly adopted: (1) the fluorine-containing oil-proof agent is prepared by coating a film made of polyethylene, polypropylene, polyvinyl chloride and other traditional plastic packaging materials on a paper surface (2) and adopting fluorocarbon to prepare the fluorine-containing oil-proof agent, mainly contains a perfluoroalkyl group monomer with 6-16 carbon atoms, and a nonpolar end of the fluorine-containing oil-proof agent has a fluorine-containing branched chain with extremely low surface energy, and a polar group with positive charge is adsorbed on pulp fibers with negative charge, so that an oil-repellent layer with extremely low surface energy is formed on the fiber surface, and the material has a very good oil-proof effect, wherein the longer the chain of the carbon atom in the perfluoroalkyl group is, the better the water-proof and oil-proof performance is. However, as the environmental awareness of various countries is continuously enhanced, the disadvantages of plastic film materials and fluorine-containing chemicals begin to appear, firstly, the plastic film is a plastic film, and because the plastic film is difficult to degrade in the nature or degrades very slowly, the plastic film can cause great pollution to human environment, and fluorine-containing oil-proof chemicals can generate toxic and harmful substances in the production process and can not be biodegraded, so that soil and human health safety can be polluted, therefore, the development of a novel oil-proof agent which is non-toxic and environment-friendly is urgently needed, and the problems and the defects existing in the oil-proof aspect in the field of the current pulp molding products are solved.
Disclosure of Invention
The invention aims to make up the defects and discloses a fluorine-free oil-proof agent and application thereof in paper pulp molding to the society.
The technical scheme of the invention is realized as follows:
a fluorine-free oil-repellent agent comprises
And (2) component A: acrylic acid or methacrylic acid;
and (B) component: having the formula CH 2 One or more acrylate monomers of ═ CX-C (═ O) -O-Y, in the general formula, X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atoms, Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms;
and (3) component C: an epoxy-based silane coupling agent;
and (3) component D: alpha, omega-dihydroxy polydimethylsiloxane;
and (3) component E: dimethyl diethyl siloxane;
and (3) component F: a crosslinking agent;
a component G: an emulsifier;
a component H: a V50 initiator;
a component I: deionized water.
As the improvement, the component B is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
As an improvement, the epoxy silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
As an improvement, the crosslinking agent is glycidyl methacrylate.
As an improvement, the emulsifier is prepared by compounding an anionic emulsifier A-51 and a nonionic emulsifier AEO-9 according to the mass ratio of 1: 3.
As an improvement, the sum of the weight of the component A and the component B accounts for 30-50 wt% of the total weight of the oil-proofing agent.
As an improvement, the fluorine-free oil-proof agent also comprises one or more auxiliary agents of aqueous liquid medium, surfactant, rheological agent, dispersant, preservative, delustering agent and pH regulator.
A preparation method of a fluorine-free oil-proofing agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethylsiloxane are subjected to high-speed stirring at 1000r/min under the catalysis of tin isooctanoate according to the molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the using amount of a catalytic substance is 8-20 wt% of reactants;
step two, preparing an acrylate copolymer: copolymerizing acrylic acid or methacrylic acid and the component B under the reaction of a cross-linking agent to generate an acrylate copolymerization emulsion, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylate copolymer;
adding V50 initiator into polysiloxane and acrylate copolymer according to the molar ratio of 1:1 under the action of epoxy silane coupling agent, and fully oscillating and stirring to obtain siloxane-acrylate copolymer emulsion;
placing the siloxane-acrylate copolymer emulsion into a reaction kettle under the condition of mixing an emulsifier and deionized water, stirring and dissolving, adding 1mol of siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of emulsifier and 0.4mol of aqueous solution of a V50 initiator; reacting for 30min to obtain seed emulsion, reacting for 15min, heating to 82 deg.C, reacting for 90min at constant temperature, naturally cooling, and filtering to obtain the oil-proofing agent.
The glass transition temperature of the fluorine-free oil-proof agent is-30-40 ℃, and the weight average molecular weight of the fluorine-free oil-proof agent is 20-60 ten thousand.
The application of the fluorine-free oil-proof agent is used in pulp molding.
Compared with the prior art, the invention has the advantages that:
the oil-proof agent of the invention does not contain fluorine, the production process is non-toxic and harmless, has good oil-proof performance, and can be used in containers for containing food, the preparation method is simple, the source of raw materials is wide, the paper pulp molding product prepared by the paper pulp added with the fluorine-free oil-proof agent has good oil-proof performance, and after testing, the paper pulp after the fluorine-free oil-proof agent is dripped, and the oil-proof function of the molded paper product after dehydration, wet pressing and dry pressing can not permeate at 70 ℃.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
All percentages, parts, ratios, etc., are by weight unless otherwise indicated; additional instructions include, but are not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
The invention is described in further detail below:
a fluorine-free oil-repellent agent comprises
And (2) component A: acrylic acid or methacrylic acid;
and (B) component: having the general formula CH 2 One or more acrylate monomers of ═ CX-C (═ O) -O-Y, in the general formula, X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atoms, Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms;
and (3) component C: an epoxy-based silane coupling agent;
and (3) component D: alpha, omega-dihydroxy polydimethylsiloxane;
and (4) component E: dimethyl diethyl siloxane;
and (3) component F: a crosslinking agent;
a component G: an emulsifier;
a component H: a V50 initiator;
a component I: deionized water.
Component A is preferably acrylic acid.
The component B is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
And (3) component C: the epoxy silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, and the component F: the cross-linking agent is glycidyl methacrylate.
A component G: the emulsifier is prepared by compounding an anionic emulsifier A-51 and a nonionic emulsifier AEO-9 according to the mass ratio of 1: 3.
The sum of the weight of the component A and the component B accounts for 30-50 wt% of the total weight of the oil-proofing agent.
The fluorine-free oil-proof agent also comprises one or more auxiliary agents of aqueous liquid medium, surfactant, rheological agent, dispersant, preservative, delustering agent and pH regulator.
A preparation method of a fluorine-free oil-proof agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethylsiloxane are subjected to high-speed stirring at 1000r/min under the catalysis of tin isooctanoate according to the molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the using amount of a catalytic substance is 8-20 wt% of reactants;
step two, preparing an acrylate copolymer: copolymerizing acrylic acid or methacrylic acid and the component B under the reaction of a cross-linking agent to generate an acrylate copolymerization emulsion, and stirring the mixed solution (mixing the acrylic acid or the methacrylic acid, the component B and the cross-linking agent) at a high speed of 1000r/min for pre-emulsification for 30min to obtain a stable acrylate copolymer;
adding V50 initiator into polysiloxane and acrylate copolymer according to the molar ratio of 1:1 under the action of epoxy silane coupling agent, and fully oscillating and stirring to obtain siloxane-acrylate copolymer emulsion;
placing the siloxane-acrylate copolymer emulsion into a reaction kettle under the condition of mixing an emulsifier and deionized water, stirring and dissolving, adding 1mol of siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of emulsifier and 0.4mol of aqueous solution of a V50 initiator; reacting for 30min to obtain seed emulsion, reacting for 15min, heating to 82 deg.C, reacting for 90min at constant temperature, naturally cooling, and filtering to obtain the oil-proofing agent.
The glass transition temperature of the fluorine-free oil-proof agent is-30-40 ℃, and the weight average molecular weight of the fluorine-free oil-proof agent is 20-60 ten thousand.
The application of the fluorine-free oil-proof agent is used in pulp molding.
The following is further illustrated by specific examples:
example 1
A fluorine-free oil-repellent agent comprises
Component A: acrylic acid, 6 parts by weight;
and (B) component: 18 parts by weight of methyl methacrylate;
hydroxyethyl acrylate (hydrophilic monomer), 18 parts by weight;
and (3) component C: epoxy silane coupling agent: 2 parts by weight of 3- (2, 3-glycidoxy) propyltrimethoxysilane (A-187);
and (3) component D: 20 parts of alpha, omega-dihydroxy polydimethylsiloxane;
and (3) component E: 20 parts by weight of dimethyl diethyl siloxane;
and (3) component F: a crosslinking agent: 5 parts by weight of glycidyl methacrylate;
a component G: 6 parts of emulsifier;
a component H: v50 initiator (azobisisobutyramidine hydrochloride), 0.4 parts by weight;
a component I: 170 parts of deionized water;
1 part by weight of tin isooctanoate serving as a catalyst.
The preparation method of the acrylic acid comprises the following steps: propylene, water vapor and air pass through a catalyst bed layer of the reactor according to the mixing molar ratio of 6.5:11.7:10, and gas phase oxidation is carried out at the temperature of 310-; propylene is oxidized in the first section catalyst bed layer of the reactor to generate acrolein, and then the acrolein is cooled through a heat exchanger and enters the second section catalyst bed layer of the reactor to be further oxidized at the oxidation temperature of 275-310 ℃ to generate acrylic acid.
The preparation method of the fluorine-free oil-proofing agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethylsiloxane are subjected to high-speed stirring at 1000r/min under the catalysis of tin isooctanoate according to the molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the using amount of a catalytic substance is 8-20 wt% of reactants;
step two, preparing an acrylate copolymer: copolymerizing acrylic acid, methyl methacrylate and hydroxyethyl acrylate in a molar ratio of 1:3:3 under the reaction of a cross-linking agent to generate an acrylate copolymerization emulsion, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylate copolymer;
step three, adding V50 initiator under the action of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane (A-187) coupling agent according to the molar ratio of 1:1 into polysiloxane and acrylate copolymer, and fully oscillating and stirring to prepare siloxane-acrylate copolymer emulsion;
step four, placing the siloxane-acrylate copolymer emulsion into a reaction kettle under the condition of mixing emulsifier and deionized water, stirring and dissolving, adding the siloxane-acrylate copolymer emulsion and deionized water, stirring and heating to 72 ℃, and adding emulsifier and V50 initiator aqueous solution; reacting for 30min to obtain seed emulsion, reacting for 15min, heating to 82 deg.C, reacting for 90min at constant temperature, naturally cooling, and filtering to obtain the oil-proofing agent.
The oil-proof agent is added into paper pulp for preparing the paper pulp molded product, and the paper pulp molded product is tested to improve the oil-proof performance, and the oil-proof function of the molded paper product can not penetrate at 70 ℃ after the paper pulp is dehydrated, wet-pressed and dry-pressed. The oil-proof agent in the application does not contain fluorine, so that the oil-proof agent can be used in a container for containing food.
The prepared oil-proof agent is added into paper pulp for preparing a paper pulp molding product, and 3 percent (3 percent of the mass of the pulp) of a water-proof auxiliary agent (modified acrylic resin type water-proof agent can be adopted) is added, and the water-proof and oil-proof performance of the prepared paper pulp molding product is improved through tests; it can prevent 100 deg.C hot water from leaking and can prevent oil from leaking when its temp is up to 70 deg.C.
Example 2
This example provides a fluorine-free oil repellent, which is prepared from the same raw materials, weight parts, and preparation method as in example 1, except that in the first step of this example, when preparing polydimethylsiloxane, α, ω -dihydroxypolydimethylsiloxane and dimethyldiethylsiloxane were prepared in a molar ratio of 1: 0.5.
Example 3
This example provides a fluorine-free oil repellent, which is prepared from the same raw materials, in parts by weight, and in a similar manner as in example 1 except that in the case of polydimethylsiloxane preparation in the first step of this example, α, ω -dihydroxypolydimethylsiloxane and dimethyldiethylsiloxane were prepared in a molar ratio of 1: 2.
Example 4
This example provides a fluorine-free oil repellent, which is prepared from the same raw materials, weight parts and preparation method as those in example 1, except that diacrylic acid, methyl methacrylate and hydroxyethyl acrylate were prepared in a molar ratio of 1:1: 1.
Example 5
This example provides a fluorine-free oil-repellent agent, which is prepared from the same raw materials, weight parts, and preparation method as those in example 1, except that the trisiloxane and the acrylate copolymer in the step of this example are sufficiently shaken and stirred at a molar ratio of 1:2 to obtain a siloxane-acrylate copolymer emulsion.
Example 6
This example provides a fluorine-free oil-repellent agent, which is prepared from the same raw materials, weight parts, and preparation method as those in example 1, except that the trisiloxane and the acrylate copolymer in the step of this example are sufficiently shaken and stirred at a molar ratio of 3:1 to obtain a siloxane-acrylate copolymer emulsion.
Comparative example 1
This example provides a fluorine-free oil-repellent agent, which is prepared from the same raw materials in parts by weight and in a similar manner as in example 1 except that the acrylic acid ester copolymer was not graft-copolymerized with linear polydimethylsiloxane in the pulp molding process of this example.
Comparative example 2
This example provides a fluorine-free oil-repellent agent, which was prepared substantially in the same manner as in example 1 except that the silicone-acrylate copolymer emulsion and soft water were thoroughly mixed in step four.
Comparative example 3
This example provides a fluorine-free oil-repellent agent, which is prepared from the same raw materials, in parts by weight, and in a similar manner to example 1, except that 0.05mol of a retention aid, polyacrylamide, was added to the oil-repellent agent slurry.
And (3) oil resistance testing:
sample preparation:
1. the pulp is not added, namely the primary pulp,
2. 3 percent of waterproof auxiliary agent is added into the paper pulp,
3. the paper pulp was charged with the fluorine-free oil-repellent agents of examples 1 to 11, and 3% of the water-repellent auxiliary.
The above three types of pulp were molded into paper-plastic bowls for testing. Hot oil permeability test: and (3) testing the sample, namely bending the sample into a bowl shape, placing the bowl shape on a flat plate lined with filter paper, pouring hot oil at the temperature of 70 +/-0.5 ℃ into the sample, standing for 30min, observing whether the sample is deformed and whether the back of the sample has oil marks, and judging whether the mechanical strength of the pulp molding sample meets the requirements of GB/T36787-2018.
And (4) hot water prevention test: and (3) testing the sample, bending the sample into a bowl shape, pouring hot water with the temperature of 100 +/-0.5 ℃ into the sample, standing for 2 hours, and observing whether the back of the sample leaks water or not.
| Sample(s) | Hot water at 100 deg.C | Oil resistance at 70 DEG C |
| Virgin pulp | Leakage of fluid | Leakage of fluid |
| Virgin pulp and 3% waterproof auxiliary agent | Leakage-proof | Leakage of fluid |
| Virgin pulp + example 1+3% waterproof auxiliary agent | Leakage-proof | Leakage-proof |
| Virgin pulp + example 2+3% waterproof auxiliary agent | Leakage-proof | Leakage-proof |
| Virgin stock + example 3+3% waterproof auxiliary | Leakage-proof | Leakage-proof |
| Virgin pulp + example 4+3% waterproof auxiliary | Leakage-proof | Leakage-proof |
| Virgin pulp + example 5+3% waterproof aid | Leakage-proof | Leakage-proof |
| Virgin pulp + example 6+3% waterproof auxiliary agent | Leakage-proof | Leakage-proof |
| Raw stock + comparative example 1+3% waterproof auxiliary agent | Leakage-proof | Leakage of fluid |
| Raw stock + comparative example 2+3% waterproof auxiliary agent | Leakage-proof | Partial point of infiltration |
| Raw stock and comparative example 3+3% waterproof auxiliary agent | Leakage-proof | Leakage-proof |
As can be seen from the examples 1 to 4, the alpha, omega-dihydroxy polydimethylsiloxane fully reacts with the dimethyl diethylsiloxane, and a functional group is introduced to the end of the siloxane to generate a copolymer with an acrylate polymer, so that the characteristics of polysiloxane are introduced into the acrylate organic polymer to achieve a good oil-proof effect; as can be seen from the comparison of the examples 5 and 6 and the comparative example 1, the siloxane and the acrylate copolymer are fully reacted, the crosslinking density of the siloxane-acrylate is improved, and the oil resistance of the siloxane-acrylate is enhanced; as can be seen from the comparison between example 1 and comparative example 2, the impurities in the water are increased, and the oil-proof performance of the oil-proof agent is reduced; as can be seen from comparative example 3, the addition of the retention aid acrylamide did not affect the oil-repellent properties.
While the preferred embodiments of the present invention have been illustrated, various changes and modifications may be made by one skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A fluorine-free oil-proof agent is characterized in that: comprises that
And (2) component A: acrylic acid or methacrylic acid;
and (B) component: having the general formula CH 2 One or more acrylate monomers of ═ CX-C (═ O) -O-Y, in the general formula, X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atoms, Y is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted cyclic hydrocarbon group having 3 to 10 carbon atoms;
and (3) component C: an epoxy-based silane coupling agent;
and (3) component D: alpha, omega-dihydroxy polydimethylsiloxane;
and (3) component E: dimethyl diethyl siloxane;
and (3) component F: a crosslinking agent;
a component G: an emulsifier;
a component H: a V50 initiator;
a component I: deionized water.
2. The fluorine-free oil-repellent agent according to claim 1, wherein: the component B is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, hydroxyethyl acrylate, butyl methacrylate and 2-ethylhexyl methacrylate.
3. The fluorine-free oil-repellent agent according to claim 1, wherein: the epoxy silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
4. The fluorine-free oil-repellent agent according to claim 1, wherein: the cross-linking agent is glycidyl methacrylate.
5. The fluorine-free oil-repellent agent according to claim 1, wherein: the emulsifier is prepared by compounding an anionic emulsifier A-51 and a nonionic emulsifier AEO-9 according to the mass ratio of 1: 3.
6. The fluorine-free oil-repellent agent according to claim 1, wherein: the sum of the weight of the component A and the component B accounts for 30-50 wt% of the total weight of the oil-proofing agent.
7. The fluorine-free oil-repellent agent according to claim 1, which comprises: the fluorine-free oil-proof agent also comprises one or more auxiliary agents of aqueous liquid medium, surfactant, rheological agent, dispersant, preservative, delustering agent and pH regulator.
8. The process for producing a fluorine-free oil-repellent agent according to claim 1, which comprises: the method comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxy polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethylsiloxane are subjected to high-speed stirring at 1000r/min under the catalysis of tin isooctanoate according to the molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the using amount of a catalytic substance is 8-20 wt% of reactants;
step two, preparing an acrylate copolymer: copolymerizing acrylic acid or methacrylic acid and the component B under the reaction of a cross-linking agent to generate an acrylate copolymerization emulsion, stirring the mixed solution at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylate copolymer;
adding V50 initiator into polysiloxane and acrylate copolymer according to the molar ratio of 1:1 under the action of epoxy silane coupling agent, and fully oscillating and stirring to obtain siloxane-acrylate copolymer emulsion;
placing the siloxane-acrylate copolymer emulsion into a reaction kettle under the condition of mixing an emulsifier and deionized water, stirring and dissolving, adding 1mol of siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of emulsifier and 0.4mol of aqueous solution of a V50 initiator; reacting for 30min to obtain seed emulsion, reacting for 15min, heating to 82 deg.C, reacting for 90min at constant temperature, naturally cooling, and filtering to obtain the oil-proofing agent.
9. The method for producing a fluorine-free oil-repellent agent according to claim 8, characterized in that: the glass transition temperature of the fluorine-free oil-proof agent is-30-40 ℃, and the weight average molecular weight of the fluorine-free oil-proof agent is 20-60 ten thousand.
10. Use of a fluorine-free oil-repellent agent according to any one of claims 1 to 7, characterized in that: the fluorine-free oil-proof agent is used in pulp molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210933333.4A CN115058918B (en) | 2022-08-04 | 2022-08-04 | Fluorine-free oil-proof agent and application thereof in pulp molding |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210933333.4A CN115058918B (en) | 2022-08-04 | 2022-08-04 | Fluorine-free oil-proof agent and application thereof in pulp molding |
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| Publication Number | Publication Date |
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| CN115058918A true CN115058918A (en) | 2022-09-16 |
| CN115058918B CN115058918B (en) | 2023-07-28 |
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| CN115928490A (en) * | 2022-12-31 | 2023-04-07 | 浙江九本环保技术有限公司 | Fluorine-free oil-proof agent for paper-based material and application thereof |
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