CN110564311B - Preparation method of impact-resistant low-whitening instant adhesive - Google Patents

Preparation method of impact-resistant low-whitening instant adhesive Download PDF

Info

Publication number
CN110564311B
CN110564311B CN201910874776.9A CN201910874776A CN110564311B CN 110564311 B CN110564311 B CN 110564311B CN 201910874776 A CN201910874776 A CN 201910874776A CN 110564311 B CN110564311 B CN 110564311B
Authority
CN
China
Prior art keywords
butadiene
acrylate
copolymer modified
acrylate copolymer
alpha
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.)
Active
Application number
CN201910874776.9A
Other languages
Chinese (zh)
Other versions
CN110564311A (en
Inventor
林闪光
叶善明
金艳
应磊
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 Paifeite New Material Technology Co ltd
Original Assignee
Zhejiang Paifeite New Material Technology 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 Paifeite New Material Technology Co ltd filed Critical Zhejiang Paifeite New Material Technology Co ltd
Priority to CN201910874776.9A priority Critical patent/CN110564311B/en
Publication of CN110564311A publication Critical patent/CN110564311A/en
Application granted granted Critical
Publication of CN110564311B publication Critical patent/CN110564311B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a preparation method of an impact-resistant low-whitening instant adhesive, which comprises the following steps: s1: copolymerizing a functional monomer mainly comprising alpha-ethyl cyanoacrylate, a butadiene gas monomer and a sulfonic acid monomer to obtain a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer; s2: obtaining purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by means of reduced pressure distillation, precipitation separation and supercritical separation; s3: and uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive. The instant adhesive has the advantages of high curing speed, high bonding strength and simple and convenient operation; at the same time, has excellent impact resistance and low whitening performance.

Description

Preparation method of impact-resistant low-whitening instant adhesive
Technical Field
The invention relates to the technical field of instant adhesive, in particular to a preparation method of impact-resistant low-whitening instant adhesive.
Background
The main component of the instant adhesive is alpha-cyanoacrylate adhesive, which is a single-component, low-viscosity, transparent, normal-temperature fast curing adhesive. The adhesive has wide adhesive surface and good adhesive capacity to most materials, and is one of important room temperature curing adhesives. The glue formed by the single alpha-cyanoacrylate monomer has the disadvantages of over-high reaction speed, high brittleness and poor impact resistance, and is mostly used for temporary bonding.
In addition, in the construction process of the traditional instant adhesive, due to the volatility of the alpha-cyanoacrylate adhesive monomer, a layer of white fog is easily formed on the surface of the adhesive through a crosslinking reaction, which causes serious influence on the construction, and how to reduce the whitening rate of the instant adhesive and ensure that the product after gluing and curing does not generate the whitening phenomenon is a long-term problem which troubles technicians in the field.
Disclosure of Invention
In view of the defects of the prior art, the invention provides a preparation method of an impact-resistant low-whitening instant adhesive, which aims to solve the technical problems that the traditional instant adhesive is poor in impact resistance and easy to generate a whitening phenomenon, and thus the using effect of the instant adhesive is improved.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a preparation method of an impact-resistant low-whitening instant adhesive comprises the following steps:
s1: preparation of butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: adding a functional monomer mainly containing alpha-ethyl cyanoacrylate and a solvent into a reaction kettle, introducing butadiene gas for polymerization reaction under the protection of inert atmosphere, introducing sulfonic monomers for copolymerization, slowly dropwise adding acrylate monomers in the solvent for polymerization in the reaction process, and adding a polymerization inhibitor to terminate the reaction after dropwise adding is finished to prepare a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s2: purifying the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: removing high-boiling-point organic compounds contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer prepared in the step S1 and unreacted monomers, solvents and other small molecular substances contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by a reduced pressure distillation mode, performing precipitation separation in acetone, introducing supercritical carbon dioxide, and slowly releasing pressure to separate out residual unreacted monomers and other organic small molecular substances to obtain the purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
step S2, the prepolymer and the low molecular compound are effectively separated by reduced pressure distillation, precipitation separation and supercritical separation to obtain a purified prepolymer, thereby reducing the phenomenon that the instant adhesive is aggravated by low molecular organic matters which do not participate in the reaction but are easy to volatilize in the instant adhesive;
s3: preparing the instant adhesive: and (4) uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer obtained in the step (S2) and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive.
According to the instant adhesive, a jelly is formed through a polymerization reaction of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer and an alpha-n-butyl cyanoacrylate monomer, so that the impact resistance of the instant adhesive is improved, and the whitening rate of the instant adhesive is reduced.
In the step S3 of preparing the instant adhesive, inorganic nano-fillers and/or stabilizers are also added.
The inorganic nano filler is nano calcium carbonate or nano titanium dioxide and is used for enhancing the strength of the instant adhesive.
The stabilizer is prepared from the following components in percentage by mass of 1: 1, 3, 5-di-tert-butylphenol and polyvinylpyrrolidone, which are used for improving the stability of the instant adhesive, prolonging the storage life of the instant adhesive and improving the durability of the instant adhesive.
Further, in step S1, the weight ratio of the comonomers in the butadiene/acrylate copolymer modified α -cyanoethyl acrylate prepolymer is: 5-15% of functional monomer, 40-60% of butadiene monomer, 5-15% of sulfonic acid monomer and 30-50% of acrylate monomer.
Further, in step S1, the sulfonic acid-based monomer is at least one selected from the group consisting of sodium 4-vinylphenylmethanesulfonate, vinylsulfonic acid, sodium methallyl sulfonate, sodium 3-prop-2-enyloxypropane-1-sulfonate, and sodium 2-methylpropan-2-ene-1-sulfonate.
Further, in step S1, the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, butyl methacrylate, lauryl acrylate, octadecyl acrylate, butyl acrylate, isooctyl acrylate, octyl acrylate, and tridecyl acrylate.
Further, in step S1, the solvent is imidazole-based silicon-containing ionic liquid.
Further, in step S1, the polymerization inhibitor is prepared by mixing the components in a mass ratio of 5-15: 1 hydroquinone and sulfur dioxide.
Further, in step S1, the polymerization inhibitor is added in an amount of 0.01 to 0.5wt% based on the total weight of all the comonomers.
Further, in step S3, the mass ratio of the butadiene/acrylate copolymer modified α -ethyl cyanoacrylate prepolymer to α -n-butyl cyanoacrylate is 3-18: 82 to 97.
The invention has the beneficial effects that:
according to the instant adhesive, the copolymer obtained through the polymerization reaction of the butadiene monomer and the acrylate monomer has good flexibility, and the impact resistance of the instant adhesive is improved. By introducing the sulfonic functional group, the vapor pressure of the raw material components of the instant adhesive is reduced due to the anion acid radical characteristics of the sulfonic group, so that the occurrence rate of the whitening phenomenon of the instant adhesive is reduced; meanwhile, due to the hydrophilicity of the sulfonic acid group, the instant adhesive is more suitable for being contacted with a substrate to form a compact adhesive layer, so that the using effect and the service life of the instant adhesive are improved.
The instant adhesive has the advantages of high curing speed, high bonding strength, simple and convenient operation and suitability for scenes without white residues in a joint area.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the impact-resistant low-whitening instant adhesive comprises the following steps:
s1: preparation of butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: adding a functional monomer mainly containing alpha-ethyl cyanoacrylate and a solvent into a reaction kettle, introducing butadiene gas for polymerization reaction under the protection of inert atmosphere, introducing sulfonic monomers for copolymerization, slowly dropwise adding acrylate monomers in the solvent for polymerization in the reaction process, and adding a polymerization inhibitor to terminate the reaction after dropwise adding is finished to prepare a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer; the weight ratio of the comonomers of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 10% of functional monomer, 50% of butadiene monomer, 10% of sulfonic acid monomer and 30% of acrylate monomer; the sulfonic acid monomer is 4-vinyl benzene methane sulfonic acid sodium salt; the acrylic ester monomer is prepared from the following components in a molar ratio of 1: 1, methyl acrylate and tridecyl acrylate; the polymerization inhibitor comprises the following components in percentage by mass: 1, hydroquinone and sulfur dioxide; the addition amount of the polymerization inhibitor is 0.2wt% of the total weight of all comonomers;
s2: purifying the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: removing high-boiling-point organic compounds contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer prepared in the step S1 and unreacted monomers, solvents and other small molecular substances contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by a reduced pressure distillation mode, performing precipitation separation in acetone, introducing supercritical carbon dioxide, and slowly releasing pressure to separate out residual unreacted monomers and other organic small molecular substances to obtain the purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s3: preparing the instant adhesive: and (4) uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer obtained in the step (S2) and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive. The mass ratio of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer to alpha-n-butyl cyanoacrylate is 9: 91.
example 2
The preparation method of the impact-resistant low-whitening instant adhesive comprises the following steps:
s1: preparation of butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: adding a functional monomer mainly containing alpha-ethyl cyanoacrylate and a solvent into a reaction kettle, introducing butadiene gas for polymerization reaction under the protection of inert atmosphere, introducing sulfonic monomers for copolymerization, slowly dropwise adding acrylate monomers in the solvent for polymerization in the reaction process, and adding a polymerization inhibitor to terminate the reaction after dropwise adding is finished to prepare a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer; the weight ratio of the comonomers of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 5% of functional monomer, 40% of butadiene monomer, 5% of sulfonic acid monomer and 50% of acrylate monomer; the sulfonic acid monomer is prepared from the following components in a molar ratio of 1: 1 of vinylsulfonic acid and 2-methylpropane-2-ene-1-sodium sulfonate; the molar ratio of the acrylate monomers is 2: 1 of ethyl acrylate and butyl methacrylate; the polymerization inhibitor comprises the following components in percentage by mass: 1, hydroquinone and sulfur dioxide; the addition amount of the polymerization inhibitor is 0.05wt% of the total weight of all the comonomers;
s2: purifying the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: removing high-boiling-point organic compounds contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer prepared in the step S1 and unreacted monomers, solvents and other small molecular substances contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by a reduced pressure distillation mode, performing precipitation separation in acetone, introducing supercritical carbon dioxide, and slowly releasing pressure to separate out residual unreacted monomers and other organic small molecular substances to obtain the purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s3: preparing the instant adhesive: and (4) uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer obtained in the step (S2) and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive. The mass ratio of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer to alpha-n-butyl cyanoacrylate is 3: 97.
example 3
The preparation method of the impact-resistant low-whitening instant adhesive comprises the following steps:
s1: preparation of butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: adding a functional monomer mainly containing alpha-ethyl cyanoacrylate and a solvent into a reaction kettle, introducing butadiene gas for polymerization reaction under the protection of inert atmosphere, introducing sulfonic monomers for copolymerization, slowly dropwise adding acrylate monomers in the solvent for polymerization in the reaction process, and adding a polymerization inhibitor to terminate the reaction after dropwise adding is finished to prepare a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer; the weight ratio of the comonomers of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 15% of functional monomer, 40% of butadiene monomer, 15% of sulfonic acid monomer and 30% of acrylate monomer; the sulfonic acid monomer is sodium methallyl sulfonate; the acrylate monomer is isooctyl acrylate; the polymerization inhibitor comprises the following components in percentage by mass: 1, hydroquinone and sulfur dioxide; the addition amount of the polymerization inhibitor is 0.3wt% of the total weight of all comonomers;
s2: purifying the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: removing high-boiling-point organic compounds contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer prepared in the step S1 and unreacted monomers, solvents and other small molecular substances contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by a reduced pressure distillation mode, performing precipitation separation in acetone, introducing supercritical carbon dioxide, and slowly releasing pressure to separate out residual unreacted monomers and other organic small molecular substances to obtain the purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s3: preparing the instant adhesive: and (4) uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer obtained in the step (S2) and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive. The mass ratio of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer to alpha-n-butyl cyanoacrylate is 18: 82.
example 4
The preparation method of the impact-resistant low-whitening instant adhesive of the embodiment is basically similar to that of the embodiment 1, and the main difference is that in step S1, the weight ratio of the comonomers of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 8% of functional monomer, 52% of butadiene monomer, 10% of sulfonic acid monomer and 30% of acrylate monomer; the sulfonic acid monomer is 3-propyl-2-enoyloxypropane-1-sodium sulfonate; the molar ratio of the acrylate monomers is 2: 1, methyl acrylate and octadecyl acrylate; the polymerization inhibitor comprises the following components in percentage by mass: 1, hydroquinone and sulfur dioxide; the polymerization inhibitor was added in an amount of 0.15wt% based on the total weight of all comonomers.
In step S3, the mass ratio of the butadiene/acrylate copolymer modified α -ethyl cyanoacrylate prepolymer to α -n-butyl cyanoacrylate is 5: 94.
in the step S3 of preparing the instant adhesive, nano calcium carbonate accounting for 1wt% of the instant adhesive is also added.
Example 5
The preparation method of the impact-resistant low-whitening instant adhesive of the embodiment is basically similar to that of the embodiment 1, and the main difference is that in step S1, the weight ratio of the comonomers of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 12% of functional monomer, 45% of butadiene monomer, 8% of sulfonic acid monomer and 35% of acrylate monomer; the sulfonic acid monomer is 2-methylpropane-2-alkene-1-sodium sulfonate; the acrylate monomer is lauryl acrylate; the polymerization inhibitor comprises the following components in percentage by mass of 12: 1, hydroquinone and sulfur dioxide; the addition amount of the polymerization inhibitor is 0.1wt% of the total weight of all comonomers;
in step S3, the mass ratio of the butadiene/acrylate copolymer modified α -ethyl cyanoacrylate prepolymer to α -n-butyl cyanoacrylate is 14: 85 parts by weight;
in the step S3 of preparing the instant adhesive, a stabilizer accounting for 1wt% of the mass of the instant adhesive is also added.
The stabilizer is prepared from the following components in percentage by mass of 1: 1 of 3, 5-di-tert-butylphenol and polyvinylpyrrolidone.
Comparative example 1
The preparation method of the impact-resistant low-whitening flash adhesive of the comparative example is substantially similar to that of example 1, and mainly differs in that no sulfonic acid-based monomer is introduced to participate in copolymerization in step S1.
Comparative example 2
The preparation method of the impact-resistant low-whitening instant adhesive of the comparative example is basically similar to that of example 1, and mainly differs in that in step S1, no acrylate monomer is added dropwise in the reaction process to carry out polymerization reaction in the solvent.
Comparative example 3
The preparation method of the impact-resistant low-whitening instant adhesive of the comparative example is basically similar to that of example 1, and is mainly different in that the purification process of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer in the step S2 is omitted.
The performance of the instant adhesive prepared in examples 1-5 and comparative examples 1-3 was tested, and the performance results are shown in table 1:
adhesion and bond strength testing: fixing a steel sheet with the diameter of 30mm on a cylindrical clamp of a universal testing machine, coating 3mg of instant adhesive between the front surfaces of the two steel sheets, pulling the two steel sheets back and forth and bonding for 10 times, compacting for 10min by using 20N force to enable the bonding surfaces of the two steel sheets to be uniformly and tightly contacted, pulling the steel sheets apart at the speed of 1mm/min, measuring the bonding force and the bonding strength of the instant adhesive, and repeating five times to obtain an average value.
And (3) testing the impact resistance: a free falling impact stripping test device is adopted, a pair of steel sheets are glued by instant adhesive to form a T-shaped impact stripping sample, and under the specified condition, impact force is applied to the non-glued end of the sample, so that the sample is stripped along the glue line. The impact resistance of the instant adhesive was evaluated by measuring the peel length of the test specimens.
TABLE 1
Adhesive force, kN Adhesive strength, MPa Impact resistance, mm Whitening Curing speed, s
Example 1 2.3 11.6 19 Low whitening 8
Example 2 2.5 10.2 23 Low whitening 5
Example 3 2.3 12.2 16 No whitening 15
Example 4 2.4 10.6 21 Low whitening 7
Example 5 2.3 11.8 17 No whitening 14
Comparative example 1 2.2 12.1 20 Severe whitening 6
Comparative example 2 2.1 9.5 25 Low whitening 8
Comparative example 3 2.2 7.3 19 Severe whitening 8
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.

Claims (8)

1. The preparation method of the impact-resistant low-whitening instant adhesive is characterized by comprising the following steps of:
s1: preparation of butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: adding a functional monomer mainly containing alpha-ethyl cyanoacrylate and a solvent into a reaction kettle, introducing butadiene gas for polymerization reaction under the protection of inert atmosphere, introducing sulfonic monomers for copolymerization, slowly dropwise adding acrylate monomers in the solvent for polymerization in the reaction process, and adding a polymerization inhibitor to terminate the reaction after dropwise adding is finished to prepare a butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s2: purifying the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer: removing high-boiling-point organic compounds contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer prepared in the step S1 and unreacted monomers, solvents and other small molecular substances contained in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer by a reduced pressure distillation mode, performing precipitation separation in acetone, introducing supercritical carbon dioxide, and slowly releasing pressure to separate out residual unreacted monomers and other organic small molecular substances to obtain the purified butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer;
s3: preparing the instant adhesive: and (4) uniformly stirring and mixing the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer obtained in the step (S2) and alpha-n-butyl cyanoacrylate to obtain the impact-resistant low-whitening instant adhesive.
2. The method for preparing the impact-resistant low-whitening instant adhesive according to claim 1, wherein in step S1, the weight ratio of the comonomers in the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer is as follows: 5-15% of functional monomer, 40-60% of butadiene monomer, 5-15% of sulfonic acid monomer and 30-50% of acrylate monomer.
3. The method of claim 1, wherein in step S1, the sulfonic acid monomer is at least one of sodium 4-vinylphenylmethane sulfonate, vinyl sulfonic acid, sodium methallyl sulfonate, and sodium 3-prop-2-enoyloxypropane-1-sulfonate.
4. The method of claim 1, wherein in step S1, the acrylate monomer is at least one of methyl acrylate, ethyl acrylate, butyl methacrylate, lauryl acrylate, stearyl acrylate, butyl acrylate, isooctyl acrylate, octyl acrylate, and tridecyl acrylate.
5. The method of claim 1, wherein in step S1, the solvent is an imidazole-based silicon-containing ionic liquid.
6. The method for preparing the impact-resistant low-whitening flash adhesive according to claim 1, wherein in the step S1, the polymerization inhibitor is prepared from the following components in a mass ratio of 5-15: 1 hydroquinone and sulfur dioxide.
7. The method of claim 1, wherein the polymerization inhibitor is added in an amount of 0.01 to 0.5wt% based on the total weight of all the comonomers in step S1.
8. The preparation method of the impact-resistant low-whitening instant adhesive according to claim 1, wherein in step S3, the mass ratio of the butadiene/acrylate copolymer modified alpha-ethyl cyanoacrylate prepolymer to the alpha-n-butyl cyanoacrylate is 3-18: 82 to 97.
CN201910874776.9A 2019-09-17 2019-09-17 Preparation method of impact-resistant low-whitening instant adhesive Active CN110564311B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910874776.9A CN110564311B (en) 2019-09-17 2019-09-17 Preparation method of impact-resistant low-whitening instant adhesive

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910874776.9A CN110564311B (en) 2019-09-17 2019-09-17 Preparation method of impact-resistant low-whitening instant adhesive

Publications (2)

Publication Number Publication Date
CN110564311A CN110564311A (en) 2019-12-13
CN110564311B true CN110564311B (en) 2021-06-08

Family

ID=68780503

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910874776.9A Active CN110564311B (en) 2019-09-17 2019-09-17 Preparation method of impact-resistant low-whitening instant adhesive

Country Status (1)

Country Link
CN (1) CN110564311B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285710B (en) * 2023-03-07 2023-10-10 永一胶粘(中山)有限公司 Instantaneous adhesive and preparation method and application thereof
CN116870236A (en) * 2023-05-16 2023-10-13 帝斯博(常州)医疗用品股份有限公司 Surgical hemostatic adhesive and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1138614A (en) * 1995-03-23 1996-12-25 株式会社三键 Cyanoacrylate adhesive composition
CN101967354A (en) * 2010-09-15 2011-02-09 北京天山新材料技术股份有限公司 Low whitening alpha-cyanoacrylate adhesive
CN104130607A (en) * 2013-05-03 2014-11-05 精磁科技股份有限公司 Antifogging coating, antifogging base material and method for producing antifogging base material
CN104708875A (en) * 2013-12-13 2015-06-17 精磁科技股份有限公司 Antifog heat insulating film
CN105315902A (en) * 2014-07-28 2016-02-10 孙志红 Preparation and application method for instant adhesive used for hair extension
CN108463525A (en) * 2015-11-06 2018-08-28 汉高知识产权控股有限责任公司 Cyanoacrylate compositions
CN108587484A (en) * 2018-03-28 2018-09-28 广州慧谷工程材料有限公司 A kind of optical film adhesive for being bonded entirely and its preparation method and application and based on its optical film
CN109021843A (en) * 2018-06-07 2018-12-18 得力集团有限公司 Low albefaction instant glue of a kind of impact resistance and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040131827A1 (en) * 2003-01-06 2004-07-08 Loctite (R&D) Limited Toughened cyanoacrylate compositions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1138614A (en) * 1995-03-23 1996-12-25 株式会社三键 Cyanoacrylate adhesive composition
CN101967354A (en) * 2010-09-15 2011-02-09 北京天山新材料技术股份有限公司 Low whitening alpha-cyanoacrylate adhesive
CN104130607A (en) * 2013-05-03 2014-11-05 精磁科技股份有限公司 Antifogging coating, antifogging base material and method for producing antifogging base material
CN104708875A (en) * 2013-12-13 2015-06-17 精磁科技股份有限公司 Antifog heat insulating film
CN105315902A (en) * 2014-07-28 2016-02-10 孙志红 Preparation and application method for instant adhesive used for hair extension
CN108463525A (en) * 2015-11-06 2018-08-28 汉高知识产权控股有限责任公司 Cyanoacrylate compositions
CN108587484A (en) * 2018-03-28 2018-09-28 广州慧谷工程材料有限公司 A kind of optical film adhesive for being bonded entirely and its preparation method and application and based on its optical film
CN109021843A (en) * 2018-06-07 2018-12-18 得力集团有限公司 Low albefaction instant glue of a kind of impact resistance and preparation method thereof

Also Published As

Publication number Publication date
CN110564311A (en) 2019-12-13

Similar Documents

Publication Publication Date Title
JP4603781B2 (en) Polymer, aqueous dispersion of said polymer, adhesive and pressure sensitive adhesive containing the same, use of pressure sensitive adhesive and adhesive product
CN110564311B (en) Preparation method of impact-resistant low-whitening instant adhesive
SE407584B (en) WATER DISPERGABLE PRESSURE ADHESIVE ADHESIVE COMPOSITION CONTAINING A COPY OF AN ACRYLIC ACID ESTER AND AN ALKANOLAMINE PARTIALLY NEUTRALIZED VINYL CARBOXYLIC ACID AND METHOD OF PREPARING
JP2665744B2 (en) Curable acrylic / fumar-based pressure-sensitive adhesive
JP2009126934A (en) Aqueous pressure-sensitive adhesive composition and utilization thereof
JP3888647B2 (en) Repulpable contact adhesive
JP2008540742A (en) Wet and dry tacky adhesives, articles and methods
ATE319753T1 (en) ACRYLATE COPOLYMERS AND ADHESIVE ADHESIVES AVAILABLE THEREOF FOR BONDING LOW-ENERGY SURFACES
JP2558142B2 (en) Pressure sensitive adhesive
CN108795340B (en) Solvent type acrylate pressure-sensitive adhesive with high molecular weight and high conversion rate, and preparation method and application thereof
CN110591569B (en) Environment-friendly low-whitening instant adhesive
JPH04114079A (en) Pressure-sensitive adhesive composition
CN109762486A (en) A kind of pressure-sensitive adhesive making flexible PVC electrical adhesive tape and its processing method
JPS6020982A (en) Remover composition for adhesive
CN117327230A (en) Polyisobutylene grafted acrylate copolymer, adhesive and pressure-sensitive adhesive tape
JPH03292379A (en) Pressure-sensitive adhesive tape or sheet
JPWO2023074468A5 (en)
JPS6386777A (en) Aqueous pressure-sensitive adhesive
JPS594610A (en) Synthetic latex for adhesives
JPH03217478A (en) Adhesive for electrostatic flocking
JPH0345676A (en) Resin composition for pressure-sensitive adhesive
JP3475451B2 (en) Resin for adhesive
JPH03265678A (en) Water-base pressure-sensitive adhesive composition
JPS58113277A (en) Phosphoric acid group-containing emulsion-type pressure- sensitive adhesive
CN116688215A (en) Gel-like adhesive and application method thereof

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