CN116536022A - Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof - Google Patents

Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof Download PDF

Info

Publication number
CN116536022A
CN116536022A CN202310643085.4A CN202310643085A CN116536022A CN 116536022 A CN116536022 A CN 116536022A CN 202310643085 A CN202310643085 A CN 202310643085A CN 116536022 A CN116536022 A CN 116536022A
Authority
CN
China
Prior art keywords
adhesive
mass
voc
acid
stirring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202310643085.4A
Other languages
Chinese (zh)
Other versions
CN116536022B (en
Inventor
朱国虎
刘丽君
陶荣鹅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Anyi New Material Co ltd
Original Assignee
Zhejiang Anyi New Material Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Anyi New Material Co ltd filed Critical Zhejiang Anyi New Material Co ltd
Priority to CN202310643085.4A priority Critical patent/CN116536022B/en
Publication of CN116536022A publication Critical patent/CN116536022A/en
Application granted granted Critical
Publication of CN116536022B publication Critical patent/CN116536022B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses an adhesive for low VOC paper and a preparation method thereof, wherein a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate are reacted to form a prepolymer, corn starch is reacted with aspartic acid to esterify carboxyl on aspartic acid and hydroxyl on corn starch to prepare modified starch, the modified starch is reacted with the prepolymer of polyurethane to react amino on the modified starch with isocyanate groups on polyurethane, triethylamine is used for salifying carboxyl, so that the stability of the adhesive is better, the addition of starch increases the cohesiveness of the adhesive, the adhesive molecules are aqueous molecules, no organic solvent is needed, the volatilization of VOC is reduced, the side chain of the modified monomer contains a polyacrylate structure and the acrylate chain segment contains a large amount of polyphenol structure, the cohesiveness of the adhesive can be improved, and simultaneously, the benzoxazine and the organosilicon chain segment of the main chain increase the crosslinking density and the mechanical property of the adhesive.

Description

Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof
Technical Field
The invention relates to the technical field of adhesive preparation, in particular to an adhesive for low-VOC (volatile organic compound) paper and a preparation method thereof.
Background
The adhesive is a substance which can bond two or more parts or materials together through the synergistic action of interfacial adhesion, cohesive force and the like. Natural adhesives are difficult to collect and therefore cannot be used by humans: most of the synthetic adhesives adopt high molecular polymers as main materials of the adhesives, a great deal of manpower and material resources are consumed, and because of using organic solvents, human beings, organisms and the environment are injured to a certain extent, and the requirements of environmental protection are not met. To solve these problems, water-based adhesives have received attention from numerous researchers. The water-based adhesive has good underwater adhesion performance and underwater operability, so that the water-based adhesive is widely applied to the fields of biomedicine and the like. However, the problems of limited types of synthetic materials, complex synthetic method, difficult degradation, poor biocompatibility and the like of the current water-based adhesives still remain the main development bottleneck in the field. Therefore, development and research of new materials to prepare easily degradable, low-toxicity water-based adhesives are urgent demands for development of the current society.
Disclosure of Invention
The invention aims to provide an adhesive for low-VOC paper and a preparation method thereof, which solve the problems that the adhesive for paper has general adhesive effect and VOC can be released when an organic solvent is needed at present.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the adhesive for the low-VOC paper specifically comprises the following steps:
step S1: uniformly mixing a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and DMF (dimethyl formamide), stirring at a rotating speed of 150-200r/min and a temperature of 80-85 ℃, adding isophorone diisocyanate, and reacting for 2-3h to obtain a prepolymer;
step S2: dissolving corn starch in deionized water, stirring at a rotating speed of 200-300r/min and a temperature of 50-60 ℃, adding aspartic acid and p-toluenesulfonic acid, heating to 95-98 ℃, reacting for 3-5h, and distilling to remove deionized water to obtain modified starch;
step S3: dispersing modified starch in deionized water, adding a prepolymer, stirring for 1-1.5h at the rotation speed of 150-200r/min and the temperature of 80-85 ℃, cooling to 40-45 ℃, adding triethylamine, and stirring for 20-30min at the rotation speed of 1000-1200r/min to obtain the adhesive for the low-VOC paper.
Further, the molar ratio of the modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate in the step S1 is 5:10:8:3:30.
Further, the amount of aspartic acid in the step S2 is 8-10% of the mass of the corn starch, and the amount of p-toluenesulfonic acid is 5% of the mass of the aspartic acid.
Further, the mass ratio of the modified starch to the deionized water in the step S3 is 1:2-3, the molar ratio of the hydroxyl groups on the modified starch to the amino groups on the prepolymer is 1:1, and the molar ratio of the triethylamine to the carboxyl groups on the prepolymer is 1.2:1.
Further, the modified monomer is prepared by the following steps:
step A1: uniformly mixing paraformaldehyde, toluene and chloroform, stirring at the rotation speed of 200-300r/min and the temperature of 50-60 ℃, adding 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, stirring for 10-15min, adding catechol, heating to 92-95 ℃, reacting for 6-8h to obtain an intermediate 1, mixing the intermediate 1, a sodium hydroxide solution and epichlorohydrin at the rotation speed of 200-300r/min and the temperature of 50-60 ℃, and stirring for 5-7h to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 2, allyl alcohol and trifluoromethanesulfonic acid, reacting for 8-10 hours at the rotation speed of 200-300r/min and the temperature of 70-80 ℃ to obtain an intermediate 3, mixing the allyl alcohol, gallic acid, p-toluenesulfonic acid and toluene, and reacting for 3-5 hours at the rotation speed of 200-300r/min and the temperature of 110-120 ℃ to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 3, the intermediate 4, butyl acrylate, isooctyl acrylate and toluene to obtain monomer liquid, taking one third volume of the monomer liquid, adding the monomer liquid into a reaction kettle, stirring and adding ammonium persulfate under the condition of the rotating speed of 150-200r/min and the temperature of 60-65 ℃, heating to 77-80 ℃ after the addition is finished, carrying out reaction for 30-40min, adding the rest monomer liquid, continuing to react for 1-1.5h, regulating the pH value to be neutral, and removing toluene to obtain the modified monomer.
Further, the ratio of the amount of paraformaldehyde, toluene, chloroform, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane to catechol in the step A1 was 0.53 g/60 mL/30 mL/2.53 g/0.77 g, the ratio of the amount of intermediate 1, sodium hydroxide and epichlorohydrin was 1 g/50 mL/5 mL, and the concentration of the sodium hydroxide solution was 0.1mol/L.
Further, the molar ratio of the intermediate 2 to the allyl alcohol in the step A2 is 1:2, the amount of the trifluoromethanesulfonic acid is 3-3.5% of the sum of the mass of the intermediate 1 and the mass of the dodecanol, the molar ratio of the allyl alcohol to the mass of the gallic acid is 1:1, and the amount of the p-toluenesulfonic acid is 3-5% of the sum of the mass of the allyl alcohol and the mass of the gallic acid.
Further, the mass ratio of the intermediate 3 to the intermediate 4 to the butyl acrylate to the isooctyl acrylate in the step A3 is 3.5:12.3:23.8:15.6, and the dosage of the ammonium persulfate is 0.3-0.5% of the sum of the mass of the intermediate 3 to the intermediate 4 to the mass of the butyl acrylate to the mass of the isooctyl acrylate.
The invention has the beneficial effects that: the adhesive for the low VOC paper prepared by the invention is characterized in that modified monomers, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate are reacted to form a prepolymer, corn starch is reacted with aspartic acid to esterify carboxyl groups on aspartic acid and hydroxyl groups on corn starch to prepare modified starch, the modified starch is reacted with the prepolymer of polyurethane to react amino groups on the modified starch with isocyanate groups on polyurethane, triethylamine is used to form salt with carboxyl groups to ensure that the stability of the adhesive is better, the addition of the starch increases the cohesiveness of the adhesive, the adhesive molecules are aqueous molecules, organic solvents are not required, the volatilization of VOC is reduced, the modified monomers are reacted with 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, paraformaldehyde and catechol to form a benzoxazine structure to prepare an intermediate 1, the intermediate 1 is reacted with epoxy chloropropane in an alkaline environment to react with phenolic hydroxyl groups on the intermediate 1, the intermediate 2 is closed-loop in the alkaline environment to form a salt with carboxyl group on the polyurethane, the adhesive molecules are not required to use organic solvents, the volatilization of VOC is reduced, the modified monomers are reacted with 1, the intermediate 3-tetramethyl disiloxane, the paraformaldehyde and catechol are reacted with the hydroxyl groups on the intermediate 2 to prepare allyl acrylate, the intermediate 2 is polymerized to prepare the acrylic acid, the intermediate 2, the acrylic acid is prepared into a modified allyl acrylate, the intermediate has a modified structure, and the hydroxyl structure is prepared with the intermediate 4, and the acrylic acid is prepared with the intermediate has a high hydroxyl structure, and the modified structure is prepared with the acrylic acid, and has a high formaldehyde structure, and a high formaldehyde structure is prepared with the acrylic acid chain is prepared with a high-modified acrylic acid chain, and has a high formaldehyde structure, at the same time, the benzoxazine and the organosilicon chain segment of the main chain increase the crosslinking density of the adhesive and the mechanical property of the adhesive.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the adhesive for the low-VOC paper specifically comprises the following steps:
step S1: uniformly mixing a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and DMF (dimethyl formamide), stirring at a rotating speed of 150r/min and a temperature of 80 ℃, adding isophorone diisocyanate, and reacting for 2 hours to obtain a prepolymer;
step S2: dissolving corn starch in deionized water, stirring and adding aspartic acid and p-toluenesulfonic acid under the condition that the rotating speed is 200r/min and the temperature is 50 ℃, heating to 95 ℃, reacting for 3 hours, and distilling to remove deionized water to obtain modified starch;
step S3: dispersing modified starch in deionized water, adding a prepolymer, stirring for 1-1.5h at the rotation speed of 150r/min and the temperature of 80 ℃, cooling to 40 ℃, adding triethylamine, and stirring for 20min at the rotation speed of 1000r/min to obtain the adhesive for the low-VOC paper.
The molar ratio of the modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate in the step S1 is 5:10:8:3:30.
The dosage of the aspartic acid in the step S2 is 8% of the mass of the corn starch, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the aspartic acid.
The mass ratio of the modified starch to the deionized water in the step S3 is 1:2, the molar ratio of the hydroxyl groups on the modified starch to the amino groups on the prepolymer is 1:1, and the molar ratio of the triethylamine to the carboxyl groups on the prepolymer is 1.2:1.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing paraformaldehyde, toluene and chloroform, stirring at a rotating speed of 200r/min and a temperature of 50 ℃, adding 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, stirring for 10min, adding catechol, heating to 92 ℃, reacting for 6h to obtain an intermediate 1, mixing the intermediate 1, a sodium hydroxide solution and epichlorohydrin at a rotating speed of 200r/min and a temperature of 50 ℃, and stirring for 5h to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 2, allyl alcohol and trifluoromethanesulfonic acid, reacting for 8 hours at the rotation speed of 200r/min and the temperature of 70 ℃ to obtain an intermediate 3, mixing the allyl alcohol, gallic acid, p-toluenesulfonic acid and toluene, and reacting for 3 hours at the rotation speed of 200r/min and the temperature of 110 ℃ to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 3, the intermediate 4, butyl acrylate, isooctyl acrylate and toluene to obtain monomer liquid, adding one third volume of the monomer liquid into a reaction kettle, stirring and adding ammonium persulfate under the condition of the rotating speed of 150r/min and the temperature of 60 ℃, heating to 77 ℃ after the addition is finished, carrying out reaction for 30min, adding the rest of the monomer liquid, continuing to react for 1h, regulating the pH value to be neutral, and removing toluene to obtain the modified monomer.
The dosage ratio of paraformaldehyde, toluene, chloroform, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane and catechol in the step A1 is 0.53g:60mL:30mL:2.53g:0.77g, the dosage ratio of the intermediate 1, sodium hydroxide and epichlorohydrin is 1g:50mL:5mL, and the concentration of the sodium hydroxide solution is 0.1mol/L.
The mol ratio of the intermediate 2 to the allyl alcohol in the step A2 is 1:2, the using amount of the trifluoromethyl sulfonic acid is 3% of the sum of the mass of the intermediate 1 and the mass of the dodecanol, the mol ratio of the allyl alcohol to the mass of the gallic acid is 1:1, and the using amount of the p-toluenesulfonic acid is 3% of the sum of the mass of the allyl alcohol and the mass of the gallic acid.
The mass ratio of the intermediate 3 to the intermediate 4 to the butyl acrylate to the isooctyl acrylate in the step A3 is 3.5:12.3:23.8:15.6, and the dosage of the ammonium persulfate is 0.3 percent of the sum of the mass of the intermediate 3 to the mass of the intermediate 4 to the mass of the butyl acrylate to the mass of the isooctyl acrylate.
Example 2
The preparation method of the adhesive for the low-VOC paper specifically comprises the following steps:
step S1: uniformly mixing a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and DMF (dimethyl formamide), stirring at a rotating speed of 150r/min and a temperature of 83 ℃, adding isophorone diisocyanate, and reacting for 2.5 hours to obtain a prepolymer;
step S2: dissolving corn starch in deionized water, stirring and adding aspartic acid and p-toluenesulfonic acid under the condition that the rotating speed is 200r/min and the temperature is 55 ℃, heating to 96 ℃, reacting for 4 hours, and distilling to remove deionized water to obtain modified starch;
step S3: dispersing modified starch in deionized water, adding a prepolymer, stirring for 1.3 hours at the rotation speed of 200r/min and the temperature of 83 ℃, cooling to 43 ℃, adding triethylamine, and stirring for 25 minutes at the rotation speed of 1000r/min to obtain the adhesive for the low-VOC paper.
The molar ratio of the modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate in the step S1 is 5:10:8:3:30.
The dosage of the aspartic acid in the step S2 is 9% of the mass of the corn starch, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the aspartic acid.
The mass ratio of the modified starch to the deionized water in the step S3 is 1:2.5, the molar ratio of the hydroxyl group on the modified starch to the amino group on the prepolymer is 1:1, and the molar ratio of the triethylamine to the carboxyl group on the prepolymer is 1.2:1.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing paraformaldehyde, toluene and chloroform, stirring at a rotation speed of 200r/min and a temperature of 55 ℃, adding 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, stirring for 13min, adding catechol, heating to 93 ℃, reacting for 7h to obtain an intermediate 1, mixing the intermediate 1, a sodium hydroxide solution and epichlorohydrin at a rotation speed of 200r/min and a temperature of 55 ℃, and stirring for 6h to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 2, allyl alcohol and trifluoromethanesulfonic acid, reacting for 9 hours at the rotation speed of 200r/min and the temperature of 75 ℃ to obtain an intermediate 3, mixing the allyl alcohol, gallic acid, p-toluenesulfonic acid and toluene, and reacting for 4 hours at the rotation speed of 300r/min and the temperature of 115 ℃ to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 3, the intermediate 4, butyl acrylate, isooctyl acrylate and toluene to obtain monomer liquid, adding one third volume of the monomer liquid into a reaction kettle, stirring and adding ammonium persulfate under the condition of the rotating speed of 150r/min and the temperature of 63 ℃, heating to 78 ℃ after the addition is finished, carrying out reaction for 35min, adding the rest of the monomer liquid, continuing to react for 1.3h, adjusting the pH value to be neutral, and removing toluene to obtain the modified monomer.
The dosage ratio of paraformaldehyde, toluene, chloroform, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane and catechol in the step A1 is 0.53g:60mL:30mL:2.53g:0.77g, the dosage ratio of the intermediate 1, sodium hydroxide and epichlorohydrin is 1g:50mL:5mL, and the concentration of the sodium hydroxide solution is 0.1mol/L.
The mol ratio of the intermediate 2 to the allyl alcohol in the step A2 is 1:2, the using amount of the trifluoromethyl sulfonic acid is 3.3 percent of the sum of the mass of the intermediate 1 and the mass of the dodecanol, the mol ratio of the allyl alcohol to the mass of the gallic acid is 1:1, and the using amount of the p-toluenesulfonic acid is 4 percent of the sum of the mass of the allyl alcohol and the mass of the gallic acid.
The mass ratio of the intermediate 3 to the intermediate 4 to the butyl acrylate to the isooctyl acrylate in the step A3 is 3.5:12.3:23.8:15.6, and the dosage of the ammonium persulfate is 0.4 percent of the sum of the mass of the intermediate 3 to the mass of the intermediate 4 to the mass of the butyl acrylate to the mass of the isooctyl acrylate.
Example 3
The preparation method of the adhesive for the low-VOC paper specifically comprises the following steps:
step S1: uniformly mixing a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and DMF (dimethyl formamide), stirring at a rotating speed of 200r/min and a temperature of 85 ℃, adding isophorone diisocyanate, and reacting for 3 hours to obtain a prepolymer;
step S2: dissolving corn starch in deionized water, stirring at a rotating speed of 300r/min and a temperature of 60 ℃, adding aspartic acid and p-toluenesulfonic acid, heating to 98 ℃, reacting for 5 hours, and distilling to remove deionized water to obtain modified starch;
step S3: dispersing modified starch in deionized water, adding a prepolymer, stirring for 1.5 hours at the speed of 200r/min and the temperature of 85 ℃, cooling to 45 ℃, adding triethylamine, and stirring for 30 minutes at the speed of 1200r/min to obtain the adhesive for the low-VOC paper.
The molar ratio of the modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate in the step S1 is 5:10:8:3:30.
The dosage of the aspartic acid in the step S2 is 10% of the mass of the corn starch, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the aspartic acid.
The mass ratio of the modified starch to the deionized water in the step S3 is 1:3, the molar ratio of the hydroxyl groups on the modified starch to the amino groups on the prepolymer is 1:1, and the molar ratio of the triethylamine to the carboxyl groups on the prepolymer is 1.2:1.
The modified monomer is prepared by the following steps:
step A1: uniformly mixing paraformaldehyde, toluene and chloroform, stirring at a rotation speed of 300r/min and a temperature of 60 ℃, adding 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, stirring for 15min, adding catechol, heating to 95 ℃, reacting for 8h to obtain an intermediate 1, mixing the intermediate 1, a sodium hydroxide solution and epichlorohydrin at a rotation speed of 300r/min and a temperature of 60 ℃, and stirring for 7h to obtain an intermediate 2;
step A2: uniformly mixing the intermediate 2, allyl alcohol and trifluoromethanesulfonic acid, reacting for 10 hours at the rotation speed of 300r/min and the temperature of 80 ℃ to obtain an intermediate 3, mixing the allyl alcohol, gallic acid, p-toluenesulfonic acid and toluene, and reacting for 5 hours at the rotation speed of 300r/min and the temperature of 120 ℃ to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 3, the intermediate 4, butyl acrylate, isooctyl acrylate and toluene to obtain monomer liquid, adding one third volume of the monomer liquid into a reaction kettle, stirring and adding ammonium persulfate under the condition of the rotating speed of 200r/min and the temperature of 65 ℃, heating to 80 ℃ after the addition is finished, carrying out reaction for 40min, adding the rest of the monomer liquid, continuing to react for 1.5h, regulating the pH value to be neutral, and removing toluene to obtain the modified monomer.
The dosage ratio of paraformaldehyde, toluene, chloroform, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane and catechol in the step A1 is 0.53g:60mL:30mL:2.53g:0.77g, the dosage ratio of the intermediate 1, sodium hydroxide and epichlorohydrin is 1g:50mL:5mL, and the concentration of the sodium hydroxide solution is 0.1mol/L.
The mol ratio of the intermediate 2 to the allyl alcohol in the step A2 is 1:2, the using amount of the trifluoromethyl sulfonic acid is 3.5 percent of the sum of the mass of the intermediate 1 and the mass of the dodecanol, the mol ratio of the allyl alcohol to the gallic acid is 1:1, and the using amount of the p-toluenesulfonic acid is 5 percent of the sum of the mass of the allyl alcohol and the mass of the gallic acid.
The mass ratio of the intermediate 3 to the intermediate 4 to the butyl acrylate to the isooctyl acrylate in the step A3 is 3.5:12.3:23.8:15.6, and the dosage of the ammonium persulfate is 0.5 percent of the sum of the mass of the intermediate 3 to the mass of the intermediate 4 to the mass of the butyl acrylate to the mass of the isooctyl acrylate.
Comparative example 1
This comparative example was identical to example 1 except that no modifying monomer was added.
Comparative example 2
This comparative example is modified with corn starch monomer as compared to example 1, with the remainder of the procedure being the same.
The adhesive coating films prepared in examples 1-3 and comparative examples 1-2 were adhered to the surface of a wood board, and then tested for tensile shear force according to the standard of GB/T7124-2008, adhesion area was 25 mm. Times.12.5 mm, sample holder separation speed was 25mm/min, peel angle 180℃and adhesion area was 25 mm. Times.100 mm, and tensile rate was 50mm/min according to the standard of GB/T532-2008, and the test results are shown in the following table.
As is clear from the above table, the tensile shear force of the present application is 1.301-1.352MPa, and the peeling force is 2.103-2.135N/mm, which shows that the present invention has a good bonding effect.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (9)

1. The preparation method of the adhesive for the low VOC paper is characterized by comprising the following steps: the method specifically comprises the following steps:
step S1: mixing and stirring a modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and DMF (dimethyl formamide), adding isophorone diisocyanate, and reacting to obtain a prepolymer;
step S2: dissolving corn starch in deionized water, stirring, adding aspartic acid and p-toluenesulfonic acid, heating for reaction, and distilling to remove deionized water to obtain modified starch;
step S3: dispersing modified starch in deionized water, adding a prepolymer, stirring, cooling, adding triethylamine, and stirring to obtain the low-VOC adhesive for paper.
2. The method for preparing the adhesive for low-VOC paper according to claim 1, characterized in that: the molar ratio of the modified monomer, 1, 4-butanediol, polyethylene glycol-1000, dimethylolpropionic acid and isophorone diisocyanate in the step S1 is 5:10:8:3:30.
3. The method for preparing the adhesive for low-VOC paper according to claim 1, characterized in that: the dosage of the aspartic acid in the step S2 is 8-10% of the mass of the corn starch, and the dosage of the p-toluenesulfonic acid is 5% of the mass of the aspartic acid.
4. The method for preparing the adhesive for low-VOC paper according to claim 1, characterized in that: the mass ratio of the modified starch to the deionized water in the step S3 is 1:2-3, the molar ratio of the hydroxyl on the modified starch to the amino on the prepolymer is 1:1, and the molar ratio of the triethylamine to the carboxyl on the prepolymer is 1.2:1.
5. The method for preparing the adhesive for low-VOC paper according to claim 1, characterized in that: the modified monomer is prepared by the following steps:
step A1: mixing and stirring paraformaldehyde, toluene and chloroform, adding 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, stirring, adding catechol, heating for reaction to obtain an intermediate 1, mixing and stirring the intermediate 1, a sodium hydroxide solution and epichlorohydrin to obtain an intermediate 2;
step A2: mixing and reacting the intermediate 2, allyl alcohol and trifluoromethanesulfonic acid to obtain an intermediate 3, and mixing and reacting allyl alcohol, gallic acid, p-toluenesulfonic acid and toluene to obtain an intermediate 4;
step A3: uniformly mixing the intermediate 3, the intermediate 4, butyl acrylate, isooctyl acrylate and toluene to obtain monomer liquid, adding one third of the volume of the monomer liquid into a reaction kettle, stirring, adding ammonium persulfate, heating to react after the addition, adding the rest of the monomer liquid, continuing to react, regulating the pH to be neutral, and removing toluene to obtain the modified monomer.
6. The method for preparing the adhesive for low-VOC paper according to claim 5, wherein the method comprises the following steps: the dosage ratio of paraformaldehyde, toluene, chloroform, 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane and catechol in the step A1 is 0.53g:60mL:30mL:2.53g:0.77g, the dosage ratio of the intermediate 1, sodium hydroxide and epichlorohydrin is 1g:50mL:5mL, and the concentration of the sodium hydroxide solution is 0.1mol/L.
7. The method for preparing the adhesive for low-VOC paper according to claim 5, wherein the method comprises the following steps: the mol ratio of the intermediate 2 to the allyl alcohol in the step A2 is 1:2, the dosage of the trifluoromethanesulfonic acid is 3-3.5% of the sum of the mass of the intermediate 1 and the mass of the dodecanol, the mol ratio of the allyl alcohol to the mass of the gallic acid is 1:1, and the dosage of the p-toluenesulfonic acid is 3-5% of the sum of the mass of the allyl alcohol and the mass of the gallic acid.
8. The method for preparing the adhesive for low-VOC paper according to claim 5, wherein the method comprises the following steps: the mass ratio of the intermediate 3 to the intermediate 4 to the butyl acrylate to the isooctyl acrylate in the step A3 is 3.5:12.3:23.8:15.6, and the dosage of the ammonium persulfate is 0.3-0.5% of the sum of the mass of the intermediate 3 to the mass of the intermediate 4 to the mass of the butyl acrylate to the mass of the isooctyl acrylate.
9. The low VOC is gluing agent for paper, its characterized in that: the preparation method according to any one of claims 1-8.
CN202310643085.4A 2023-06-01 2023-06-01 Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof Active CN116536022B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310643085.4A CN116536022B (en) 2023-06-01 2023-06-01 Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310643085.4A CN116536022B (en) 2023-06-01 2023-06-01 Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof

Publications (2)

Publication Number Publication Date
CN116536022A true CN116536022A (en) 2023-08-04
CN116536022B CN116536022B (en) 2024-04-16

Family

ID=87456072

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310643085.4A Active CN116536022B (en) 2023-06-01 2023-06-01 Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116536022B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101215451A (en) * 2007-12-26 2008-07-09 华南农业大学 Starch-base adhesive and preparation method thereof
US20100285309A1 (en) * 2007-09-21 2010-11-11 Henkel Ag & Co. Kgaa Primer compositions for adhesive bonding systems and coatings
DE102016210898A1 (en) * 2016-06-17 2017-12-21 Tesa Se Biodegradable pressure-sensitive adhesive
CN114736650A (en) * 2022-05-17 2022-07-12 烟台信友新材料有限公司 Low-shrinkage high-weatherability UV-thermal dual-curing adhesive and preparation method thereof
CN115260970A (en) * 2022-09-28 2022-11-01 江苏斯瑞达材料技术股份有限公司 Acrylic acid composite glue with good weather resistance and humidity resistance and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100285309A1 (en) * 2007-09-21 2010-11-11 Henkel Ag & Co. Kgaa Primer compositions for adhesive bonding systems and coatings
CN101215451A (en) * 2007-12-26 2008-07-09 华南农业大学 Starch-base adhesive and preparation method thereof
DE102016210898A1 (en) * 2016-06-17 2017-12-21 Tesa Se Biodegradable pressure-sensitive adhesive
CN114736650A (en) * 2022-05-17 2022-07-12 烟台信友新材料有限公司 Low-shrinkage high-weatherability UV-thermal dual-curing adhesive and preparation method thereof
CN115260970A (en) * 2022-09-28 2022-11-01 江苏斯瑞达材料技术股份有限公司 Acrylic acid composite glue with good weather resistance and humidity resistance and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李娜等: "开环聚合型酚醛类树脂苯并恶嗪树脂的研究进展", 《中北大学学报》, vol. 25, no. 5, 30 October 2004 (2004-10-30), pages 363 - 367 *
陈妍等: "不同添加量的氨基酸辅助干热处理对玉米淀粉理化和消化性质的影响", 《粮油食品科技》, vol. 30, no. 5, 21 September 2022 (2022-09-21), pages 123 - 129 *

Also Published As

Publication number Publication date
CN116536022B (en) 2024-04-16

Similar Documents

Publication Publication Date Title
KR100485626B1 (en) Adhesive Composition for Polarizing Plates and Polarizing Plates
AU700073B2 (en) Poly(beta -hydroxyorganoate) pressure sensitive adhesive compositions
JPH10316930A (en) Carbodiimide crosslinking agent, its production and coating material
EP2723787B1 (en) Pressure-sensitive adhesives with onium-epoxy crosslinking system
US4994538A (en) Siliconized emulsion based pressure-sensitive adhesives
JPH07502548A (en) Improvements in repulpable pressure-sensitive adhesive compositions
CN109943264B (en) High-strength wet-adhesion bionic adhesive material and method and application thereof
EP1858999B8 (en) Pressure sensitive adhesive composition as well as a method of applying it and a method for the preparation thereof
CN116536022B (en) Adhesive for low-VOC (volatile organic compound) paper and preparation method thereof
CN115260929B (en) Hydrophobic self-adhesive cellulose-based transparent adhesive tape and synthetic method thereof
NO307973B1 (en) Water-soluble or water-dispersible, pressure-sensitive adhesive mixture and pressure-sensitive adhesive tape
CN114605962B (en) Water-resistant flexible packaging adhesive taking hydrolyzed collagen and oxidized starch as basic raw materials, and preparation method and application thereof
CN115197366A (en) Bio-based acrylic pressure-sensitive adhesive and processing technology thereof
CN115785862A (en) Bio-based anti-warping acrylic pressure-sensitive adhesive and preparation method thereof
JPH01178568A (en) Pressure-sensitive adhesive
Li et al. Development and characterization of pressure-sensitive adhesives from dimer acid and epoxides
JP3194383B2 (en) One-part pressure-sensitive adhesive composition
JP2022122842A (en) Adhesion structure and method for manufacturing the same, adherend set, adherend, and activated alkyne group-containing polymer
CN118406458B (en) Solvent-free single-component polyurethane adhesive for woodworking building materials and application method thereof
CN113549414B (en) Preparation method of environment-friendly nano-cellulose crosslinked dopa adhesive
CN118325547B (en) Adhesive coated on surface of film and preparation method thereof
CN109721676B (en) Emulsion type acrylate adhesive and preparation method thereof
JP3347190B2 (en) Functional acrylic adhesive
CN115991852A (en) Bio-based polyacrylate material and preparation method and application thereof
CN118085770A (en) Preparation method of all-hydrophobic polymer adhesive based on hydrophobic eutectic solvent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Zhu Guohu

Inventor after: Liu Lijun

Inventor after: Tao Ronge

Inventor before: Zhu Guohu

Inventor before: Liu Lijun

Inventor before: Tao Ronge