CN109988525B - Archive mildew-proof insect-expelling adhesive - Google Patents
Archive mildew-proof insect-expelling adhesive Download PDFInfo
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- CN109988525B CN109988525B CN201910172044.5A CN201910172044A CN109988525B CN 109988525 B CN109988525 B CN 109988525B CN 201910172044 A CN201910172044 A CN 201910172044A CN 109988525 B CN109988525 B CN 109988525B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a mildew-proof insect-repelling adhesive for files. The archive mildew-proof insect-repellent adhesive comprises a p-aminobenzene sulfonic acid terpinyl ester compound serving as an active ingredient, wherein the p-aminobenzene sulfonic acid terpinyl ester compound is prepared by taking p-aminobenzene sulfonic acid and terpineol as raw materials and performing acid-alcohol esterification reaction under the catalysis of an acidic catalyst. The file mildew-proof insect-repelling adhesive is specially used for binding and repairing files, prevents the files from mildewing and breeding insect pests, and has excellent mechanical properties.
Description
The technical field is as follows:
the invention relates to the technical field of mildew prevention and insect repelling, in particular to a mildew-proof insect-repelling adhesive for files.
Background art:
in southern areas of China, the climate is warm and humid, so that archives are easy to mildew and insect pests are easy to breed. According to one investigation in 90 years, 93% county-level archives in the south of China have insect pests and mildew phenomena to different degrees, even some archives are sore and have hundreds of holes, and the whole roll, bundle and box of archives are swallowed into the abdomen by termites and are frightened; some files go moldy, mildewed and even become paper bricks, which makes people feel painful. Therefore, the insect-repelling and mildew-proof work of the files becomes an important link of the file protection work. At present, most of the archives are applied and convenient to use, namely, the mothball (naphthalene) and the camphor essence block have certain effects on preventing mildew and expelling insects, but the mothball (naphthalene) and the camphor have strong volatility and bad smell, have stimulation effect on human bodies after being contacted for a long time, and are not beneficial to the health of archive workers. Therefore, the search for an ideal method for preventing mold and repelling insects has been a subject of constant search. From ancient times to present, a plurality of mildew-proof insect-repelling methods exist, wherein a mildew-proof insect-repelling adhesive is used in binding and mounting of files, and the method is one of the methods.
Some relevant reports on the mildew-proof adhesive are reported at home and abroad. The research on high-efficiency mildew-proof polysulfide sealant is reported by Irish British musical instrument and the like, and 3 kinds of mildew-proof agents of thiazoles, organic metal complexes and imidazoles are selected to be applied to the polysulfide sealant, so that the polysulfide mildew-proof sealant with good mildew-proof effect is prepared. ZL200510045295.5 discloses a single-component mildew-proof flame-retardant organic silicon mechanical sealant, and a mildew-proof flame-retardant organic silicon mechanical glass adhesive is prepared by adding a mildew inhibitor into an organic silicon sealant. ZL200810130693.0 discloses a nanometer mildew-proof neutral silicone sealant, the effective mildew-proof agent component of which is nanometer silver particles, and the nanometer silver particles have the defects of high cost, easy color change and weak mildew inhibition effect. CN102485823A discloses a mildewcide silicone sealant, and the mildewcide used in this application is 2n acyl isothiazolinone and Benzisothiazolinone (BIT). ZL201210067831.1 discloses a method for producing a hollow glass mildew-proof silicone sealant, wherein no mildew-proof component is added in the production process, the hollow glass mildew-proof silicone sealant is claimed to never go moldy in a humid place, but the actual operation is not necessarily the same, siloxane organic matters contained in the components can easily become nutrient substances for the growth of microorganisms in a proper environment with proper temperature and humidity, and active nano calcium carbonate contained in the components has almost no inhibitory effect on the microorganisms. ZL201310055983.4 discloses an antibacterial and mildewproof silicone adhesive and a preparation method thereof, wherein an antibacterial agent used in the adhesive is a cubic zirconium phosphate silver-loaded compound, and the component belongs to a silver antibacterial agent which has excellent bacterial inhibition and killing effects but weak mould inhibition effects and has the risk of silver yellowing and discoloration in the using process.
At present, researches on mildew resistance of adhesives mostly focus on the fields of airplanes, ships, electronics, machinery and the like, and the adhesives are only specially used for mildew resistance, and special adhesive products for mildew resistance and insect repelling of archives are rarely reported.
The invention content is as follows:
the invention aims to provide a file mildew-proof insect-expelling adhesive which is specially used for binding and mounting files, prevents the files from mildewing and breeding insect pests and has excellent mechanical properties.
The invention aims to provide a p-aminobenzene sulfonic acid terpinyl ester compound, which is prepared by taking p-aminobenzene sulfonic acid and terpinyl as raw materials and carrying out acid-alcohol esterification reaction under the catalysis of an acid catalyst.
Regarding Sulfanilic acid (Sulfanilic acid), the sodium salt of Sulfanilic acid is sodium sulfanilate, sulfur S is contained in a chemical structure, S enters thalli and mainly acts on an electron transfer process between cytochrome b and cytochrome c, and electrons are captured in an oxidation-reduction system, so that normal oxidation-reduction of the thalli is interfered, and bacteria are killed. On the other hand, the integral structure of the sodium sulfanilate is similar to that of the p-aminobenzoic acid, the p-aminobenzoic acid synthesizes folic acid with the help of dihydrofolate synthetase in thalli, and the folic acid has the function of promoting protein synthesis, so the sodium sulfanilate and the p-aminobenzoic acid compete for an enzyme system, the synthesis of the folic acid is prevented, the formation of the protein is further influenced, and the growth and the propagation of the thalli are prevented.
Regarding Terpineol (Terpineol), Terpineol has a repellent effect not only against Aedes albopictus (Aedes albopictus), but also significantly against tea tree pest Empoasca vitis (Empoasca vitis), and also against adult pleurotus ostreatus (Lycoriella pleuroti). The terpineol is obtained by hydration reaction of turpentine, and is prepared by generating terpineol hydrate from pinene which is a main component in the turpentine, dehydrating to obtain crude terpineol, and fractionating. The turpentine is oleoresin of pine needle family tree. The natural oil-containing resin (resin turpentine) is yellowish opaque block, and has viscosity when heated, and the distillate is turpentine.
According to the antibacterial action of sulfanilic acid and the insect repelling action of terpineol, the synergistic prodrug is designed and synthesized by comprehensively utilizing the design principle of the prodrug and the basic design principle of the structure combination principle to synthesize the sulfanilic acid terpilester compound, so that the adhesive with the antibacterial, mildewproof and insect repelling effects is obtained. The synthesis of the sulfanilic acid terpinyl ester compound adopts a one-step simplified synthesis route, and has the advantages of simple method, mild reaction conditions and simple and easy operation.
Preferably, the sulfanilic acid terpinyl ester compound is prepared by the following steps: under the anhydrous condition, adding sulfanilic acid and terpineol into a reaction container, stirring uniformly at normal temperature, adding an acidic catalyst while stirring, stirring for reacting for 2-4 h to obtain a mixed solution, extracting the mixed solution by using an organic solvent to obtain an extracting solution, washing and filtering the extracting solution, and evaporating the filtrate to dryness to obtain the sulfanilic acid terpineol compound.
Preferably, the acidic catalyst is selected from one or more of concentrated sulfuric acid, hydrofluoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, metal trifluoromethanesulfonate or supported trifluoromethanesulfonate, heteropolyacid, acidic zeolite, perfluoro resin and ionic liquid.
Taking concentrated sulfuric acid as an example of an acidic catalyst, the sulfanilic acid terpinyl ester compound is prepared by the following steps: under the anhydrous condition, adding sulfanilic acid and terpineol into a reaction container, uniformly stirring at normal temperature, then dropwise adding concentrated sulfuric acid while stirring, stirring and reacting for 2-4 h to obtain a mixed solution, extracting the mixed solution for a plurality of times by using ethyl acetate, combining the obtained extracting solutions to obtain an ethyl acetate extracting solution, washing the ethyl acetate extracting solution by using a sodium bicarbonate solution with the mass fraction of 25%, filtering, and evaporating the filtrate to dryness to obtain the sulfanilic acid terpineol compound.
The chemical reaction equation of the sulfanilic acid pine oil ester compound by using concentrated sulfuric acid as a catalyst is as follows:
the invention also aims to provide the file mildew-proof insect-repellent adhesive which comprises the p-aminobenzene sulfonic acid terpinyl ester compound as an active ingredient.
Preferably, the mildew-proof insect-repelling adhesive is mildew-proof insect-repelling white latex, mildew-proof insect-repelling glass cement or mildew-proof insect-repelling solvent cement.
The mildew-proof insect-repellent white latex comprises the following components in parts by weight: 15-75 parts of sulfanilate, 2-8 parts of polyvinyl alcohol, 0-1 part of thickener, 20-75 parts of water and 1-3 parts of emulsifier.
Further preferably, the mildew-proof insect-repellent white latex comprises the following components in parts by mass: 45 parts of sulfanilate, 5 parts of polyvinyl alcohol, 1 part of thickening agent, 48 parts of water and 1 part of emulsifying agent.
More preferably, the thickener is sodium carboxymethylcellulose, and the emulsifier is octyl (or nonyl) phenol polyoxyethylene (10) ether.
The mildew-proof insect-repellent glass cement comprises the following components in parts by mass: 15-50 parts of p-aminobenzene sulfonic acid terpinyl ester, 30-50 parts of alpha, omega-dihydroxy polydimethylsiloxane, 3-20 parts of plasticizer, 1-5 parts of coupling agent, 9-16 parts of filler and 0.05-1 part of catalyst.
Preferably, the mildew-proof insect-repellent glass cement comprises the following components in parts by mass: 15 parts of sulfanilate, 50 parts of basic glue alpha, omega-dihydroxy polydimethylsiloxane, 20 parts of plasticizer, 5 parts of coupling agent, 9.95 parts of filler and 0.05 part of catalyst.
Further preferably, the plasticizer is polydimethylsiloxane, the coupling agent is gamma- (methacryloyloxy) propyl trimethoxy silane, the filler is fumed silica and calcium carbonate, and the catalyst is dibutyltin dilaurate.
The mildew-proof insect-repellent solvent adhesive comprises the following components in parts by weight: 15-90 parts of p-aminobenzene sulfonic acid terpinyl ester and 10-85 parts of ethyl acetate.
Preferably, the mildew-proof insect-repellent solvent adhesive comprises the following components in parts by mass: 50 parts of p-aminobenzene sulfonic acid terpinyl ester and 50 parts of ethyl acetate.
The invention has the beneficial effects that:
(1) the synergistic effect of the sulfanilic acid and the terpineol is that the mildew-proof effect of the sulfanilic acid terpineol compound is obviously better than that of the sulfanilic acid, and the insect-repellent effect of the sulfanilic acid terpineol compound is obviously better than that of the terpineol;
(2) the mildew-proof insect-expelling adhesive provided by the invention can prevent files from mildewing and breeding insect pests, and has excellent mechanical properties.
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1:
under the anhydrous condition, 15.20g of sulfanilic acid and 13.36g of terpineol are sequentially added into a three-neck flask, the materials are uniformly stirred under the normal temperature condition, then 4.24g of concentrated sulfuric acid is dropwise added while stirring, the stirring reaction is carried out for 2 hours to obtain a mixed solution, 90mL of ethyl acetate is used for extracting the mixed solution for 3 times and 30mL each time, 3 times of extracting solutions are combined, sodium bicarbonate eluting solution with the mass fraction of 25% is used for eluting, the filtering is carried out, the obtained filtrate is evaporated to dryness, and 13.48g of the sulfanilic acid terpineol is obtained.
The yield of the p-aminobenzene sulfonic acid terpinyl ester is 50.30%, the p-aminobenzene sulfonic acid terpinyl ester has light lilac taste, the color of the p-aminobenzene sulfonic acid terpinyl ester is light yellow viscous liquid, and the compound is easily soluble in organic solvents such as ethyl acetate and the like and is insoluble in water.
Example 2:
under the anhydrous condition, 21.28g of sulfanilic acid and 13.36g of terpineol are sequentially added into a three-neck flask, the materials are uniformly stirred under the normal temperature condition, then 4.24g of concentrated sulfuric acid is dropwise added while stirring, the stirring reaction is carried out for 4 hours to obtain a mixed solution, 90mL of ethyl acetate is used for extracting the mixed solution for 3 times and 30mL each time, 3 times of extracting solutions are combined, sodium bicarbonate eluting solution with the mass fraction of 25% is used for eluting, the filtering is carried out, the obtained filtrate is evaporated to dryness, and 14.52g of the terpineol sulfanilate is obtained.
The yield of the p-aminobenzene sulfonic acid terpinyl ester is 54.18%, the p-aminobenzene sulfonic acid terpinyl ester has light lilac taste and light yellow viscous liquid, and the compound is easily soluble in organic solvents such as ethyl acetate and the like and is insoluble in water.
Example 3:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as mildew-proof insect-repellent glue to prepare mildew-proof insect-repellent white latex.
The mildew-proof insect-repellent white latex comprises the following components in parts by weight: mildew-proof insect-repelling glue: 45 parts of p-aminobenzene sulfonic acid terpinyl ester; water-based adhesive: 5 parts of polyvinyl alcohol (PVA-1799); thickening agent: 1 part of sodium carboxymethylcellulose (CMC-FH9) and 48 parts of purified water; emulsifier: 1 part of octyl (or nonyl) phenol polyoxyethylene (10) ether (OP-10).
The preparation method of the mildew-proof insect-repellent white latex comprises the following steps:
a: firstly, heating to 95 ℃ by a water bath heating method, stirring and dissolving polyvinyl alcohol (PVA-1799) and purified water;
b: then adding the mildew-proof insect-repellent glue, the emulsifier and the thickener in sequence, stirring for 3h, naturally cooling to room temperature, and taking out of the pot to obtain the white latex (mildew-proof insect-repellent white latex) containing the sulfanilic acid terpinyl.
Example 4:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as mildew-proof insect-repellent glue to prepare mildew-proof insect-repellent white latex.
The mildew-proof insect-repellent white latex comprises the following components in parts by weight: mildew-proof insect-repelling glue: 15 parts of p-aminobenzene sulfonic acid terpinyl ester; water-based adhesive: 8 parts of polyvinyl alcohol (PVA-1799); thickening agent: 1 part of sodium carboxymethylcellulose (CMC-FH9) and 75 parts of purified water; emulsifier: 1 part of octyl (or nonyl) phenol polyoxyethylene (10) ether (OP-10).
The preparation method of the mildew-proof insect-repellent white latex comprises the following steps:
a: firstly, heating to 90 ℃ by a water bath heating method, stirring and dissolving polyvinyl alcohol (PVA-1799) and purified water;
b: then adding the mildew-proof insect-repellent glue, the emulsifier and the thickener in sequence, stirring for 3h, naturally cooling to room temperature, and taking out of the pot to obtain the white latex (mildew-proof insect-repellent white latex) containing the sulfanilic acid terpinyl.
Example 5:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as mildew-proof insect-repellent glue to prepare mildew-proof insect-repellent white latex.
The mildew-proof insect-repellent white latex comprises the following components in parts by weight: mildew-proof insect-repelling glue: 75 parts of terpinyl sulfanilate; water-based adhesive: 2 parts of polyvinyl alcohol (PVA-1799); 20 parts of purified water; emulsifier: 3 portions of octyl (or nonyl) phenol polyoxyethylene (10) ether (OP-10).
The preparation method of the mildew-proof insect-repellent white latex comprises the following steps:
a: firstly, heating to 100 ℃ by a water bath heating method, stirring and dissolving polyvinyl alcohol (PVA-1799) and purified water;
b: then sequentially adding the mildew-proof insect-repellent glue and the emulsifier, stirring for 3h, naturally cooling to room temperature, and taking out of the pot to obtain the white latex (mildew-proof insect-repellent white latex) containing the p-aminobenzenesulfonic acid terpinyl ester.
The mildew-proof insect-repellent white latex prepared in the embodiments 3 to 5 can be used for bonding hardboards, wood boards, plastic products, common paper and the like.
Example 6:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as the mildew-proof insect-repellent glue to prepare the mildew-proof insect-repellent glass glue.
The mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following components in parts by mass: mildew-proof insect-repelling glue: 15 parts of p-aminobenzene sulfonic acid terpinyl ester; base glue: 50 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue); plasticizer: 20 parts of polydimethylsiloxane; coupling agent: 5 parts of gamma- (methacryloyloxy) propyltrimethoxysilane (KH-570); filling: 1 part of fumed silica and 8.95 parts of calcium carbonate; catalyst: 0.05 part of dibutyltin dilaurate.
The preparation method of the mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following steps:
a: firstly, putting the basic glue, the plasticizer and the mildew-proof insect repellent glue into a multifunctional stirrer according to the proportion, and stirring for 20min in vacuum at 100 ℃;
b: then adding the filler and continuing stirring for 45min, then adding the catalyst and the coupling agent, and stirring for 45min in vacuum at 125 ℃;
c: and finally, cooling to 35 ℃, extruding the material, sealing and packaging to obtain the silicone adhesive (mildew-proof insect-repellent glass adhesive) containing the p-aminobenzene sulfonic acid terpinyl.
Example 7:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as the mildew-proof insect-repellent glue to prepare the mildew-proof insect-repellent glass glue.
The mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following components in parts by mass: mildew-proof insect-repelling glue: 50 parts of p-aminobenzene sulfonic acid terpinyl ester; base glue: 30 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue); plasticizer: 3 parts of polydimethylsiloxane; coupling agent: 1 part of gamma- (methacryloyloxy) propyl trimethoxy silane (KH-570); filling: 5 parts of fumed silica and 10 parts of calcium carbonate; catalyst: 1 part of dibutyltin dilaurate.
The preparation method of the mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following steps:
a: firstly, putting the basic adhesive, the plasticizer and the mildew-proof insect repellent adhesive into a multifunctional stirrer according to a ratio, and stirring for 30min in vacuum at 80 ℃;
b: then adding filler and continuing stirring for 30min, then adding catalyst and coupling agent, and stirring for 60min under vacuum at 100 ℃;
c: and finally, cooling to 30 ℃, extruding the material, sealing and packaging to obtain the silicone adhesive (mildew-proof insect-repellent glass adhesive) containing the p-aminobenzene sulfonic acid terpinyl.
Example 8:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as the mildew-proof insect-repellent glue to prepare the mildew-proof insect-repellent glass glue.
The mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following components in parts by mass: mildew-proof insect-repelling glue: 30 parts of p-aminobenzene sulfonic acid terpinyl ester; base glue: 40 parts of alpha, omega-dihydroxy polydimethylsiloxane (107 glue); plasticizer: 10 parts of polydimethylsiloxane; coupling agent: 3 parts of gamma- (methacryloyloxy) propyltrimethoxysilane (KH-570); filling: 1 part of fumed silica and 15 parts of calcium carbonate; catalyst: 1 part of dibutyltin dilaurate.
The preparation method of the mildew-proof insect-repellent silicone adhesive (glass adhesive) comprises the following steps:
a: firstly, putting the base rubber, the plasticizer and the mildew-proof insect repellent rubber into a multifunctional stirrer according to a ratio, and stirring for 15min in vacuum at 120 ℃;
b: then adding the filler and continuing stirring for 60min, then adding the catalyst and the coupling agent, and stirring for 30min under vacuum at 150 ℃;
c: and finally, cooling to 40 ℃, pressing the materials out, sealing and packaging to obtain the silicone adhesive (mildew-proof insect-repellent glass adhesive) containing the p-aminobenzene sulfonic acid terpinyl ester.
The mildew-proof insect-repellent silicone adhesive (glass adhesive) prepared in examples 6 to 8 can be used for bonding metal, glass, wood, ceramic, plastic and the like.
Example 9:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as a mildewproof insect repellent glue to prepare a mildewproof insect repellent solvent glue.
The mildew-proof insect-repelling solvent adhesive comprises the following components in parts by mass: 50 parts of p-aminobenzene sulfonic acid terpinyl ester, solvent: 50 parts of ethyl acetate.
The preparation method of the mildew-proof insect-repellent solvent adhesive comprises the following steps: directly stirring and mixing 50 parts by mass of p-aminobenzene sulfonic acid terpinyl ester and 50 parts by mass of ethyl acetate to obtain the mildew-proof insect-repellent solvent adhesive.
Example 10:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as a mildewproof insect repellent glue to prepare a mildewproof insect repellent solvent glue.
The mildew-proof insect-repelling solvent adhesive comprises the following components in parts by mass: 15 parts of p-aminobenzene sulfonic acid terpinyl ester, solvent: 85 parts of ethyl acetate.
The preparation method of the mildew-proof insect-repellent solvent adhesive comprises the following steps: directly stirring and mixing 15 parts by mass of p-aminobenzene sulfonic acid terpinyl ester and 85 parts by mass of ethyl acetate to obtain the mildew-proof insect-repellent solvent adhesive.
Example 11:
the p-aminobenzenesulfonic acid terpinyl ester prepared in example 1 is used as a mildewproof insect repellent glue to prepare a mildewproof insect repellent solvent glue.
The mildew-proof insect-repelling solvent adhesive comprises the following components in parts by mass: 90 parts of p-aminobenzene sulfonic acid terpinyl ester, solvent: and 10 parts of ethyl acetate.
The preparation method of the mildew-proof insect-repellent solvent adhesive comprises the following steps: directly stirring and mixing 90 parts by mass of p-aminobenzene sulfonic acid terpinyl ester and 10 parts by mass of ethyl acetate to obtain the mildew-proof insect-repellent solvent adhesive.
The mildew-proof insect-repellent solvent adhesive prepared in the embodiment 9-11 can be used for bonding wood boards and plastic products. The performance of the mildew and insect repellent solvent glue was tested and the results of example 9 were as follows: bond curing time (30 ℃): <120min, peel strength: 110N/(2.5cm), initial viscosity (25 ℃ C.): 9890 mPas.
Test example 12:
by referring to the determination and evaluation of the conditions for controlling wood mold and blue-stain bacteria of the mildew preventive specified in the national standard GB/T18261-2000 test method for controlling wood mold and blue-stain bacteria of the mildew preventive, the pine wood sample is treated by the p-aminobenzene sulfonic acid terpinyl ester prepared in the example 1, and the mildew prevention effect is evaluated.
After the sample was inoculated and cultured for 4 weeks, the infected area and degree of blue discoloration of the test bacteria were examined. Inoculating a mould sample, and only checking the mould degree of the surface of the sample; the samples inoculated with the blue-changing bacteria were cleaved in the direction of the grain at the center line of the thickness of the sample, except for recording the degree of infection on the surface, and the degree of blue-changing in the interior of the sample was examined. The damage values are graded according to Table 1, the lower the damage value, the greater the efficacy. The average damage value of a sample treated with a certain chemical is determined as the limit concentration of the chemical to a certain test bacterium, which is determined by inoculating the test bacterium with the chemical, and culturing for 1 week, and the damage value of the sample is shown in Table 1.
TABLE 1 value of damage to test specimen
| Value of damage | Test bacteria infection area and blue change degree |
| 0 | No hypha on the surface of the sample, and normal internal and external colors |
| 1 | Infected area of sample surface<1/4, normal internal color |
| 2 | The infected area on the surface of the sample is 1/4-1/2, and the internal color is normal |
| 3 | The surface infection area of the sample is 1/2-3/4, or the internal blue change area<1/10 |
| 4 | Infected area of sample surface>3/4, or internal blue-changing area>1/10 |
The control efficacy (control effect) was calculated by the following formula:
the test results are shown in table 2, and table 2 shows the results of the mold-proofing test, as shown in table 2.
TABLE 2 mildew proof laboratory test results (4 weeks)
The control efficacy against mold is expressed as the arithmetic mean of the control efficacy against 3 molds. The control efficacy against cyanobacteria is expressed as the control efficacy against coccobacillus cacao.
As can be seen from the table 2, the sulfanilic acid terpinyl ester has obvious mildew-proof effect, the mildew-proof limit concentration is 15%, and when the concentration of the sulfanilic acid terpinyl ester is more than or equal to 15%, the mildew-proof effect meets the requirements of the international standard GB/T18261-2000.
Test example 13:
the mildewproof efficacy of the pine wood samples was evaluated by treating the pine wood samples with example 10 (15% by mass of p-aminobenzenesulfonic acid terpinyl ester) and 15% by mass of p-aminobenzenesulfonic acid according to the same test method as in test example 12, and the test results are shown in table 3, and table 3 is the mildewproof test results, as shown in table 3.
TABLE 3 mildew proof laboratory test results (4 weeks)
The control efficacy against mold is expressed as the arithmetic mean of the control efficacy against 3 molds. The control efficacy against cyanobacteria is expressed as the control efficacy against coccobacillus cacao. Different lower case letters, indicating a significant difference at P < 0.05.
As can be seen from table 3, both the sulfanilic acid terpinyl ester with a mass fraction of 15% and the sulfanilic acid with a mass fraction of 15% have the mildew-proof effect, and the mildew-proof effect of the sulfanilic acid terpinyl ester (example 10) is remarkably superior to the mildew-proof effect of the sulfanilic acid (P < 0.05), which indicates that the sulfanilic acid and the terpineol have the synergistic effect.
Test example 14:
referring to the conditions for evaluating the termite-resistant performance of the preservative-treated material specified in the national standard GB/T18260-2015 laboratory test method for toxicity of wood preservatives to termites, the pine wood sample is respectively treated with the sulfanilic acid terpinyl adhesive (white latex, silicone adhesive and solvent adhesive), the acquired adhesive, the acquired glass cement and the terpineol with the mass fraction of 50% prepared in example 3, example 6 and example 9, and the termite-resistant effect of the pine wood sample is evaluated.
The mass loss rate was calculated using the following formula:
the results of the insect resistance test are shown in Table 4, as shown in Table 4.
TABLE 4 insect resistance laboratory test results (4 weeks)
The data in the table are mean mass ± standard deviation (n ═ 5); different lower case letters, indicating a significant difference at P < 0.05.
The results in table 4 show that the mass loss rates of examples 3, 6 and 9 containing the sulfanilic acid terpinyl ester component are all significantly lower than those of the market product of the strong glue, the natural glass glue and the blank control (P is less than 0.05) which do not contain the sulfanilic acid terpinyl ester component, and the adhesive containing the sulfanilic acid terpinyl ester has extremely obvious non-preference and extremely obvious insect resistance to the ivory. Compared with the blank control, the difference between the super glue and the return glass glue is not significant (P is less than 0.05). Example 9 (50% by mass of P-aminobenzene sulfonic acid terpinyl ester) compared with 50% by mass of terpineol, the effect of resisting the taiwan lactotermite is remarkably different (P is less than 0.05), and the insect repellent effect of the P-aminobenzene sulfonic acid terpinyl ester with the same concentration is remarkably superior to that of the terpineol, which shows that the P-aminobenzene sulfonic acid and the terpineol have synergistic effect.
When the experiment is carried out, the death of the taiwan lactotermite is not observed, and after the experiment is finished, the survival rate of each treated taiwan lactotermite is over 95 percent and has no difference with the control, so that the sulfanilic acid terpinyl ester has no insecticidal activity to the taiwan opal termites.
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The p-aminobenzene sulfonic acid terpinyl ester compound is characterized in that the p-aminobenzene sulfonic acid terpinyl ester compound is obtained by taking p-aminobenzene sulfonic acid and terpinyl alcohol as raw materials and carrying out acid-alcohol esterification reaction under the catalysis of an acid catalyst.
2. The sulfanilic acid terpinyl ester compound of claim 1, wherein the acidic catalyst is selected from one or more of concentrated sulfuric acid, hydrofluoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, metal trifluoromethanesulfonate or supported trifluoromethanesulfonate, heteropoly acid, and acidic zeolite.
3. The terpinyl sulfanilate compound of claim 2, prepared by the steps of: under the anhydrous condition, adding sulfanilic acid and terpineol into a reaction container, stirring uniformly at normal temperature, then adding concentrated sulfuric acid while stirring, stirring and reacting for 2-4 h to obtain a mixed solution, extracting the mixed solution by using an organic solvent to obtain an extracting solution, washing and filtering the extracting solution, and evaporating the filtrate to dryness to obtain the sulfanilic acid terpineol compound.
4. An archival mildew-resistant insect-repellent adhesive comprising the p-aminobenzenesulfonic acid terpinyl ester compound of claim 1 as an active ingredient.
5. The mildewproof and anthelmintic adhesive for files of claim 4, wherein the mildewproof and anthelmintic adhesive is mildewproof and anthelmintic white latex, mildewproof and anthelmintic glass cement or mildewproof and anthelmintic solvent cement.
6. The mildewproof and insect-repellent adhesive for files as claimed in claim 5, wherein the mildewproof and insect-repellent white latex comprises the following components in parts by weight: 15-75 parts of sulfanilate, 2-8 parts of polyvinyl alcohol, 0-1 part of thickener, 20-75 parts of water and 1-3 parts of emulsifier.
7. An archival mildew and insect repellent adhesive as claimed in claim 6, wherein the thickener is sodium carboxymethylcellulose and the emulsifier is OP-10.
8. The mildewproof and insect-repellent adhesive for files as claimed in claim 5, wherein the mildewproof and insect-repellent glass cement comprises the following components in parts by weight: 15-50 parts of p-aminobenzene sulfonic acid terpinyl ester, 30-50 parts of alpha, omega-dihydroxy polydimethylsiloxane, 3-20 parts of plasticizer, 1-5 parts of coupling agent, 9-16 parts of filler and 0.05-1 part of catalyst.
9. The archival, mold-proof, insect-repellent adhesive of claim 8, wherein the plasticizer is polydimethylsiloxane, the coupling agent is gamma- (methacryloyloxy) propyl trimethoxysilane, the filler is fumed silica and calcium carbonate, and the catalyst is dibutyltin dilaurate.
10. The mildewproof and insect-repellent adhesive for files as claimed in claim 5, wherein the mildewproof and insect-repellent solvent adhesive comprises the following components in parts by weight: 15-90 parts of p-aminobenzene sulfonic acid terpinyl ester and 10-85 parts of ethyl acetate.
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