CN115058918B - Fluorine-free oil-proof agent and application thereof in pulp molding - Google Patents
Fluorine-free oil-proof agent and application thereof in pulp molding Download PDFInfo
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- CN115058918B CN115058918B CN202210933333.4A CN202210933333A CN115058918B CN 115058918 B CN115058918 B CN 115058918B CN 202210933333 A CN202210933333 A CN 202210933333A CN 115058918 B CN115058918 B CN 115058918B
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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-proof agent, which comprises the following components: acrylic acid or methacrylic acid; component B: having the general formula CH 2 An acrylic acid ester monomer of =cx-C (=o) -O-Y, wherein X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atom, 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; component C: an epoxy silane coupling agent; component D: alpha, omega-dihydroxy polydimethylsiloxane; component E: dimethyl diethyl siloxane; component F: a cross-linking agent; component G: an emulsifying agent; component H: a V50 initiator; component I: deionized water. The fluorine-free oil-proofing agent has the advantages that the fluorine-free oil-proofing agent does not contain fluorine, can be used in a container for containing food, has good oil-proofing performance, and a pulp molding product prepared from the paper pulp added with the fluorine-free oil-proofing agent has good oil proofing performance.
Description
Technical Field
The invention relates to the technical field of preparation of oil-proofing agents, in particular to a fluorine-free oil-proofing agent and application thereof in pulp molding.
Background
With the rapid development of social economy and the continuous acceleration of life rhythm, people consume fast food more and more, so that the demand of disposable tableware (lunch boxes, bowls, dishes and cups) is rapidly increased, 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 pulp molding products is increasingly increased. The pulp molding product takes recyclable and completely biodegradable plant fiber as a raw material, and no waste water and waste gas are discharged in production, so that the pulp molding product is a famous and real green environment-friendly packaging material.
The pulp molding product is a packaging paper product which is made from primary plant fiber or waste paper regenerated fiber as a main raw material by using a papermaking technology through processes such as mold molding, hot press drying and the like and has a certain geometric cavity structure and buffer capacity. The paper products can be fully recycled, the waste can be naturally degraded, and the paper products have good buffering performance, are typical green environment-friendly packaging products, and are widely applied to the packaging field as main substitutes of foaming plastics. The 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, thereby influencing the barrier property of the pulp molding product.
At present, the oil-proof treatment of paper materials mainly adopts two modes: (1) The film is made of polyethylene, polypropylene, polyvinyl chloride and other traditional plastic packaging materials and coated on the paper surface (2) to prepare the fluorine-containing oil-proof agent by adopting fluorocarbon, wherein the fluorine-containing oil-proof agent mainly comprises perfluoroalkyl monomers with 6-16 carbon atoms, the nonpolar end of the fluorine-containing oil-proof agent is provided with an extremely low surface energy fluorine-containing branched chain, the fluorine-containing branched chain is adsorbed on negatively charged pulp fibers through positively charged polar groups of the fluorine-containing branched chain, and an extremely low surface energy oil-proof layer is formed on the surfaces of the fibers, so that the material has an extremely good oil-proof effect, wherein the longer the chain of the carbon atoms in the perfluoroalkyl group is, the better the water-proof and oil-proof performance is. However, with the continuous enhancement of environmental awareness of various countries, the defects of plastic film materials and fluorine-containing chemicals begin to appear, and the plastic film is firstly adopted, so that the plastic film is difficult to degrade in nature or is extremely slow to degrade, and can cause great pollution to human environment, and fluorine-containing oil-proof chemicals can generate toxic and harmful substances in the production process and cannot be biodegraded, so that soil and human health and safety can be polluted, therefore, the development of a novel non-toxic and environment-friendly oil-proof agent is needed, and the problems and defects in the oil proofing aspect of the field of the current pulp molding products are solved.
Disclosure of Invention
The invention aims to remedy the defects and discloses a fluorine-free oil-proofing agent and application thereof in pulp molding to society.
The technical scheme of the invention is realized as follows:
a fluorine-free oil-repellent agent comprising
Component A: acrylic acid or methacrylic acid;
component B: having the general formula CH 2 ＝CX-C(＝O) -one or more acrylate monomers of the general formula O-Y, wherein X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms or a halogen atom other than fluorine atom, 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;
component C: an epoxy silane coupling agent;
component D: alpha, omega-dihydroxy polydimethylsiloxane;
component E: dimethyl diethyl siloxane;
component F: a cross-linking agent;
component G: an emulsifying agent;
component H: a V50 initiator;
component I: deionized water.
As an 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-glycidoxy) propyl trimethoxy silane.
As an improvement, the cross-linking 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 a mass ratio of 1:3.
As an improvement, the sum of the weight of the component A and the weight of 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 an aqueous liquid medium, a surfactant, a rheological agent, a dispersing agent, a preservative, a matting agent and a pH regulator.
The preparation method of the fluorine-free oil-proof agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxyl polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethyl siloxane are stirred at a high speed of 1000r/min under the catalysis of tin isooctanoate according to a molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the catalyst dosage is 8-20wt% of reactants;
step two, preparing an acrylic ester copolymer: copolymerizing acrylic acid or methacrylic acid and a component B under the reaction of a cross-linking agent to generate acrylic ester copolymer emulsion, stirring the mixed solution at a high speed at a rotating speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylic ester copolymer;
step three, adding a V50 initiator into the polysiloxane and acrylic ester copolymer according to a molar ratio of 1:1 under the action of an epoxy silane coupling agent, and fully oscillating and stirring to prepare a siloxane-acrylic ester copolymer emulsion;
step four, placing the siloxane-acrylate copolymer emulsion in a reaction kettle for stirring and dissolving under the condition that an emulsifier and deionized water are mixed together, adding 1mol of the siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of the emulsifier and 0.4mol of a V50 initiator aqueous solution; after reacting for 30min, obtaining seed emulsion, reacting for 15min, heating to 82 ℃, reacting for 90min at constant temperature, naturally cooling and filtering to obtain the oil-proof 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-proofing agent is that the fluorine-free oil-proofing 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, has no toxicity and harm in the production process, has good oil-proof performance, can be used in a container for containing food, has simple preparation method and wide raw material sources, and the pulp molding product prepared by adding the paper pulp of the fluorine-free oil-proof agent has good oil-proof performance, and the paper pulp after dripping the fluorine-free oil-proof agent is tested, and has the oil-proof function reaching 70 ℃ and is impermeable after being dehydrated, wet pressed and dry pressed into the molded paper product.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
All percentages, parts, ratios, etc., are by weight unless otherwise specified; the other specification includes, but is not limited to, "wt%" means weight percent, "mol%" means mole percent, "vol%" means volume percent.
The present invention is described in further detail below:
a fluorine-free oil-repellent agent comprising
Component A: acrylic acid or methacrylic acid;
component B: having the general formula CH 2 One or more acrylate monomers of the formula =cx-C (=o) -O-Y, wherein X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atom, 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;
component C: an epoxy silane coupling agent;
component D: alpha, omega-dihydroxy polydimethylsiloxane;
component E: dimethyl diethyl siloxane;
component F: a cross-linking agent;
component G: an emulsifying agent;
component H: a V50 initiator;
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.
Component C: the epoxy silane coupling agent is 3- (2, 3-glycidoxy) propyl trimethoxy silane, and the component F: the cross-linking agent is glycidyl methacrylate.
Component G: the emulsifier is prepared by compounding an anionic emulsifier A-51 and a nonionic emulsifier AEO-9 according to a mass ratio of 1:3.
The sum of the weight of the component A and the weight of 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 an aqueous liquid medium, a surfactant, a rheological agent, a dispersing agent, a preservative, a delustrant and a pH regulator.
The preparation method of the fluorine-free oil-proof agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxyl polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethyl siloxane are stirred at a high speed of 1000r/min under the catalysis of tin isooctanoate according to a molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the catalyst dosage is 8-20wt% of reactants;
step two, preparing an acrylic ester copolymer: copolymerizing acrylic acid or methacrylic acid and a component B under the reaction of a cross-linking agent to generate acrylic ester copolymer emulsion, stirring a mixed solution (the acrylic acid or methacrylic acid, the component B and the cross-linking agent are mixed) at a high speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylic ester copolymer;
step three, adding a V50 initiator into the polysiloxane and acrylic ester copolymer according to a molar ratio of 1:1 under the action of an epoxy silane coupling agent, and fully oscillating and stirring to prepare a siloxane-acrylic ester copolymer emulsion;
step four, placing the siloxane-acrylate copolymer emulsion in a reaction kettle for stirring and dissolving under the condition that an emulsifier and deionized water are mixed together, adding 1mol of the siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of the emulsifier and 0.4mol of a V50 initiator aqueous solution; after reacting for 30min, obtaining seed emulsion, reacting for 15min, heating to 82 ℃, reacting for 90min at constant temperature, naturally cooling and filtering to obtain the oil-proof 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-proofing agent is that the fluorine-free oil-proofing agent is used in pulp molding.
The following is further illustrated by specific examples:
example 1
A fluorine-free oil-repellent agent comprising
Component A: acrylic acid, 6 parts by weight;
component B: 18 parts by weight of methyl methacrylate;
hydroxy ethyl acrylate (hydrophilic monomer), 18 parts by weight;
component C: epoxy group silane coupling agent: 2 parts by weight of 3- (2, 3-glycidoxy) propyltrimethoxysilane (A-187);
component D: 20 parts by weight of alpha, omega-dihydroxy polydimethylsiloxane;
component E: dimethyl diethyl siloxane, 20 parts by weight;
component F: crosslinking agent: glycidyl methacrylate, 5 parts by weight;
component G: 6 parts by weight of an emulsifier;
component H: v50 initiator (azobisisobutyrimidine hydrochloride), 0.4 parts by weight;
component I: 170 parts of deionized water;
1 part by weight of catalyst tin isooctanoate.
The preparation method of the acrylic acid comprises the following steps: propylene, water vapor and air pass through a catalyst bed layer of a reactor according to a mixed mole ratio of 6.5:11.7:10, and are subjected to gas-phase oxidation at a temperature of 310-340 ℃; propylene is oxidized in a first section of catalyst bed layer of the reactor to generate acrolein, then the acrolein is cooled by a heat exchanger, and enters a second section of 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-proof agent comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxyl polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethyl siloxane are stirred at a high speed of 1000r/min under the catalysis of tin isooctanoate according to a molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the catalyst dosage is 8-20wt% of reactants;
step two, preparing an acrylic ester copolymer: copolymerizing acrylic acid, methyl methacrylate and hydroxyethyl acrylate according to a molar ratio of 1:3:3 under the reaction of a cross-linking agent to generate an acrylic ester copolymer emulsion, stirring the mixed solution at a high speed at a rotating speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylic ester copolymer;
step three, adding a V50 initiator into the polysiloxane and acrylate copolymer according to a molar ratio of 1:1 under the action of a 3- (2, 3-glycidoxy) propyl trimethoxy silane (A-187) coupling agent, and fully oscillating and stirring to obtain a siloxane-acrylate copolymer emulsion;
step four, placing the siloxane-acrylate copolymer emulsion in a reaction kettle for stirring and dissolving under the condition that an emulsifier and deionized water are mixed together, adding the siloxane-acrylate copolymer emulsion and deionized water, stirring and heating to 72 ℃, and adding an emulsifier and a V50 initiator aqueous solution; after reacting for 30min, obtaining seed emulsion, reacting for 15min, heating to 82 ℃, reacting for 90min at constant temperature, naturally cooling and filtering to obtain the oil-proof agent.
The oil-proof agent is added into paper pulp for preparing paper pulp molding products, and the prepared paper pulp molding products are tested to improve the oil-proof performance, and the oil-proof performance of the paper pulp after dripping fluorine-free oil-proof agent reaches 70 ℃ and is impermeable through the formed paper products after dehydration, wet pressing and dry pressing. Since the oil repellent agent in the present application does not contain fluorine, it can be used in a container for holding food.
The oil-proof agent prepared by the method is added into paper pulp for preparing paper pulp molding products, and then 3 percent (3 percent of the mass of the pulp) of waterproof auxiliary agent (modified acrylic resin waterproof agent can be adopted) is added, and the prepared paper pulp molding products have improved waterproof and oil-proof performance through tests; it can prevent leakage of hot water at 100deg.C and oil at 70deg.C.
Example 2
The present example provides a fluorine-free oil repellent agent, which is substantially the same as in example 1 in terms of raw materials, parts by weight, and preparation methods, except that in the preparation of polydimethylsiloxane in step one of the present example, alpha, omega-dihydroxy polydimethylsiloxane and dimethyl diethyl siloxane were prepared in a molar ratio of 1:0.5.
Example 3
This example provides a fluorine-free oil repellent agent, which is substantially the same as in example 1 in terms of raw materials, parts by weight and preparation method, except that in the preparation of polydimethylsiloxane in step one of this example, alpha, omega-dihydroxy polydimethylsiloxane and dimethyl diethyl siloxane were prepared in a molar ratio of 1:2.
Example 4
The raw materials, parts by weight and the preparation method of the fluorine-free oil-proofing agent are basically the same as those of the embodiment 1, and the difference is that the step of the embodiment is that the diacrylic acid, the methyl methacrylate and the hydroxyethyl acrylate are prepared according to the molar ratio of 1:1:1.
Example 5
The raw materials, parts by weight and the preparation method of the fluorine-free oil-proofing agent are basically the same as those of the embodiment 1, and the difference is that the siloxane-acrylate copolymer emulsion is prepared by fully oscillating and stirring the polysiloxane and the acrylate copolymer according to the molar ratio of 1:2 in the step III of the embodiment.
Example 6
The raw materials, parts by weight and the preparation method of the fluorine-free oil-proofing agent are basically the same as those of the embodiment 1, and the difference is that the siloxane-acrylate copolymer emulsion is prepared by fully oscillating and stirring the polysiloxane and the acrylate copolymer according to the molar ratio of 3:1 in the step III of the embodiment.
Comparative example 1
This example provides a fluorine-free oil repellent agent which is substantially the same as in example 1 in terms of the raw materials, parts by weight and preparation method, except that the acrylic ester copolymer in the pulp molding of this example is not graft copolymerized with the linear polydimethylsiloxane.
Comparative example 2
This example provides a fluorine-free oil repellent agent which is substantially the same as in example 1 in terms of raw materials, parts by weight thereof, and preparation method, except that the silicone-acrylate copolymer emulsion and soft water are thoroughly mixed in the fourth step.
Comparative example 3
This example provides a fluorine-free oil repellent agent, which is basically the same as in example 1 in terms of raw materials, parts by weight and preparation method, except that 0.05mol of a retention aid polyacrylamide is added when the oil repellent agent is added to the oil repellent agent slurry.
Oil repellency test:
sample:
1. the pulp is not added, namely raw pulp,
2. 3 percent of waterproof auxiliary agent is added into the paper pulp,
3. the fluorine-free oil-proofing agent of examples 1-11 and 3% of water-proofing auxiliary agent are added into the paper pulp.
The three types of slurries were made into paper-plastic bowls by pulp molding for testing. Hot oil permeability test: the method comprises the steps of testing a sample, bending the sample into a bowl shape, placing the bowl shape on a flat plate lined with filter paper, pouring hot oil at 70+/-0.5 ℃ into the sample, standing for 30min, observing whether the sample is deformed or not and whether oil printing appears on the back of the sample, and judging whether the mechanical strength of the pulp molding sample meets the requirements of GB/T36787-2018.
And (3) hot water prevention test: and (3) testing the sample, bending the sample into a bowl shape, pouring hot water at 100+/-0.5 ℃ into the sample, standing for 2 hours, and observing whether water leaks at the back of the sample.
| Sample of | Prevent hot water at 100 DEG C | Oil resistance at 70 DEG C |
| Raw pulp | Leakage of | Leakage of |
| Primary pulp +3% waterproof auxiliary agent | Leakless | Leakage of |
| Original pulp + example 1+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + example 2+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + example 3+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + example 4+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + example 5+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + example 6+3% waterproof auxiliary | Leakless | Leakless |
| Original pulp + comparative example 1+3% waterproof auxiliary agent | Leakless | Leakage of |
| Original pulp + comparative example 2+3% waterproof auxiliary agent | Leakless | Partial penetration point |
| Original pulp + comparative example 3+3% waterproof auxiliary agent | Leakless | Leakless |
It can be seen from examples 1 to 4 that the alpha, omega-dihydroxy polydimethylsiloxane fully reacts with the dimethyl diethyl siloxane, and functional groups are introduced at the tail end of the siloxane to form a copolymer with the acrylic ester polymer, so that the characteristics of polysiloxane are introduced into the acrylic ester organic polymer, and a better oil-proof effect is achieved; as can be seen from the comparison of example 5, example 6 and comparative example 1, the siloxane and the acrylate copolymer are fully reacted, so that the crosslinking density of the siloxane-acrylate is improved, and the oil-proof performance of the siloxane-acrylate is enhanced; as can be seen from the comparison of example 1 and comparative example 2, the impurities in the water are increased, and the oil-proofing performance of the oil-proofing agent is reduced; as can be seen from comparative example 3, the addition of the retention aid acrylamide does not affect the oil repellency.
While the preferred embodiments of the present invention have been illustrated, various changes and modifications can be made by one of ordinary skill in the art without departing from the scope of the invention.
Claims (8)
1. A fluorine-free oil-proofing agent is characterized in that: comprising
Component A: acrylic acid or methacrylic acid;
component B: having the general formula CH 2 One or more acrylate monomers of the formula =cx-C (=o) -O-Y, wherein X is a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom other than fluorine atom, 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;
component C: an epoxy silane coupling agent;
component D: alpha, omega-dihydroxy polydimethylsiloxane;
component E: dimethyl diethyl siloxane;
component F: the crosslinking agent is glycidyl methacrylate;
component G: an emulsifying agent;
component H: a V50 initiator;
component I: deionized water;
the sum of the weight of the component A and the weight of the component B accounts for 30-50 wt% of the total weight of the oil-proofing agent.
2. A fluorine-free oil repellent agent according to claim 1, characterized in that: 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. A fluorine-free oil repellent agent according to claim 1, characterized in that: the epoxy silane coupling agent is 3- (2, 3-epoxypropoxy) propyl trimethoxy silane.
4. A fluorine-free oil repellent agent according to claim 1, characterized in that: the emulsifier is prepared by compounding an anionic emulsifier A-51 and a nonionic emulsifier AEO-9 according to a mass ratio of 1:3.
5. A fluorine-free oil repellent agent according to claim 1, characterized in that: the fluorine-free oil-proof agent also comprises one or more auxiliary agents of an aqueous liquid medium, a surfactant, a rheological agent, a dispersing agent, a preservative, a delustrant and a pH regulator.
6. The method for producing a fluorine-free oil repellent agent according to claim 1, characterized by: the method comprises the following steps:
step one, polysiloxane preparation: alpha, omega-dihydroxyl polydimethylsiloxane with the polymerization degree of 80 and dimethyl diethyl siloxane are stirred at a high speed of 1000r/min under the catalysis of tin isooctanoate according to a molar ratio of 1:1, and are condensed to prepare linear polydimethylsiloxane, wherein the catalyst dosage is 8-20wt% of reactants;
step two, preparing an acrylic ester copolymer: copolymerizing acrylic acid or methacrylic acid and a component B under the reaction of a cross-linking agent to generate acrylic ester copolymer emulsion, stirring the mixed solution at a high speed at a rotating speed of 1000r/min, and pre-emulsifying for 30min to obtain a stable acrylic ester copolymer;
step three, adding a V50 initiator into the polysiloxane and acrylic ester copolymer according to a molar ratio of 1:1 under the action of an epoxy silane coupling agent, and fully oscillating and stirring to prepare a siloxane-acrylic ester copolymer emulsion;
step four, placing the siloxane-acrylate copolymer emulsion in a reaction kettle for stirring and dissolving under the condition that an emulsifier and deionized water are mixed together, adding 1mol of the siloxane-acrylate copolymer emulsion and 1.5mol of deionized water, stirring and heating to 72 ℃, and adding 0.15mol of the emulsifier and 0.4mol of a V50 initiator aqueous solution; after reacting for 30min, obtaining seed emulsion, reacting for 15min, heating to 82 ℃, reacting for 90min at constant temperature, naturally cooling and filtering to obtain the oil-proof agent.
7. The method for producing a fluorine-free oil repellent agent according to claim 6, 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.
8. Use of a fluorine-free oil repellent according to any of claims 1 to 5, characterized in that: the fluorine-free oil-proofing agent is used in pulp molding, and the oil-proofing agent is added into pulp for preparing pulp molding products to prepare the pulp molding products.
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| 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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| CN115058918B true CN115058918B (en) | 2023-07-28 |
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