CN115627124B - Low-whitening impact-resistant quick-drying adhesive composition and preparation method thereof - Google Patents

Low-whitening impact-resistant quick-drying adhesive composition and preparation method thereof Download PDF

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CN115627124B
CN115627124B CN202211376765.6A CN202211376765A CN115627124B CN 115627124 B CN115627124 B CN 115627124B CN 202211376765 A CN202211376765 A CN 202211376765A CN 115627124 B CN115627124 B CN 115627124B
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cyanoacrylate
whitening
alpha
impact
parts
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CN115627124A (en
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李洪宇
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Shanghai Lansheng New Material Technology Co ltd
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    • 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

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  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a low-whitening impact-resistant quick-drying adhesive composition and a preparation method thereof; the composition comprises the following components in parts by weight: 40-80 parts of small molecular weight alpha-cyanoacrylate; 10-50 parts of large molecular weight alpha-cyanoacrylate; 5-15 parts of rubber. The invention prepares the low-whitening impact-resistant quick-drying adhesive by reasonably blending the proportion of small molecular weight alpha-cyanoacrylate and large molecular weight alpha-cyanoacrylate in a formula, adding a certain amount of high molecular weight rubber at the same time and adopting a specific process. Solves the technical problems of poor shock resistance and easy occurrence of whitening phenomenon of the traditional quick-drying adhesive, thereby remarkably improving the use effect of the quick-drying adhesive.

Description

Low-whitening impact-resistant quick-drying adhesive composition and preparation method thereof
Technical Field
The invention relates to a quick-drying adhesive, in particular to a low-whitening impact-resistant quick-drying adhesive composition and a preparation method thereof.
Background
The main component of the quick-drying adhesive is alpha-cyanoacrylate adhesive, which is a single-component, low-viscosity, transparent and normal-temperature curing adhesive. The adhesive material has wide range and extremely high curing speed, has good adhesive property for most metals, plastics, rubber and inorganic nonmetallic materials, and is one of important room-temperature curing adhesive types. The adhesive formed by pure alpha-cyanoacrylate monomer has the advantages of over-high reaction speed, large brittleness and poor shock resistance, and can not be used for structural bonding.
In addition, in the sizing operation process of the traditional quick-drying adhesive, due to the volatility of the alpha-cyanoacrylate adhesive monomer, a layer of white fog is easily formed on the adhesive surface by crosslinking reaction, the attractiveness of adhered articles or adhered parts is seriously reduced, the whitening rate of the quick-drying adhesive is reduced, the product after the adhesive is coated and cured does not generate whitening phenomenon, and the quick-drying adhesive is a long-term problem puzzling to the person skilled in the art.
In the prior method for solving the problems, a butadiene/acrylic ester copolymer modified alpha-ethyl cyanoacrylate prepolymer is prepared through polymerization reaction, and the prepolymer and the alpha-n-butyl cyanoacrylate are uniformly stirred and mixed according to a certain proportion to obtain the impact-resistant low-whitening instant adhesive. However, the raw materials required by the prepolymer synthesis are more in operation steps of the synthesis process and the purification process, and the requirements on the operation accuracy of equipment and personnel are higher, and particularly, the purification process needs to be subjected to three continuous processes of reduced pressure distillation, precipitation separation and supercritical separation, so that the purity of the produced prepolymer is not high, and the corresponding obtained impact-resistant low-whitening quick-drying adhesive is unstable.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-whitening impact-resistant quick-drying adhesive composition and a preparation method thereof. The invention reasonably prepares the low-whitening impact-resistant quick-drying adhesive with stable performance by reasonably blending the proportion of the small molecular weight alpha-cyanoacrylate and the large molecular weight alpha-cyanoacrylate in the formula and simultaneously adding a certain amount of high molecular weight rubber and adopting a continuous stirring dispersion process.
The invention aims at realizing the following technical scheme:
the invention provides a low-whitening impact-resistant quick-drying adhesive composition, which comprises the following components in parts by weight:
40-80 parts of small molecular weight alpha-cyanoacrylate;
10-50 parts of large molecular weight alpha-cyanoacrylate;
5-15 parts of rubber.
In one embodiment, the small molecular weight α -cyanoacrylate is selected from the group consisting of: one or more of methyl alpha-cyanoacrylate, ethyl alpha-cyanoacrylate, propyl alpha-cyanoacrylate, isopropyl alpha-cyanoacrylate and allyl alpha-cyanoacrylate.
In one embodiment, the high molecular weight α -cyanoacrylate is selected from the group consisting of: one or more of butyl-alpha-cyanoacrylate, isobutyl-alpha-cyanoacrylate, amyl-alpha-cyanoacrylate, isoamyl-alpha-cyanoacrylate, octyl-alpha-cyanoacrylate, isooctyl-alpha-cyanoacrylate, methoxyethyl-alpha-cyanoacrylate, methoxypropyl-alpha-cyanoacrylate and ethoxyethyl-alpha-cyanoacrylate.
In one embodiment, the mass ratio of the small molecular weight α -cyanoacrylate to the large molecular weight α -cyanoacrylate is from 1:1 to 8:1. Too high or too low a ratio can affect the toughening effect because the solubility of the rubber in the large molecular weight alpha-cyanoacrylate is significantly less than the solubility in the small molecular weight alpha-cyanoacrylate, while the inner toughening effect of the large molecular weight alpha-cyanoacrylate is much higher than the outer toughening effect of the rubber, too high a ratio can result in a significant decrease in the amount of added rubber, and too low a ratio can result in a significant decrease in the inner toughening effect, all of which can cause a decrease in the overall toughening effect.
In one embodiment, the rubber is selected from: one or more of nitrile rubber, chloroprene rubber, acrylate rubber, core-shell structure type copolymer rubber and polyurethane rubber.
The invention also provides a preparation method of the low-whitening impact-resistant quick-drying adhesive composition, which comprises the following steps:
s1, preparing a prefabricated material: uniformly mixing small-molecular-weight alpha-cyanoacrylate and large-molecular-weight alpha-cyanoacrylate to obtain a prefabricated material;
s2, adding rubber into the prefabricated material, stirring and dispersing until the solution is uniform and has no particles, and obtaining the quick-drying rubber composition.
In one embodiment, the time of stirring and dispersing is 4 hours or more, preferably 4 to 6 hours.
In one embodiment, the stirring is for a period of 3 to 6 hours. The dispersion rate is 600-1800RPM. In some embodiments, the agitation is at 20RPM and the dispersion is at 1000RPM.
Compared with the prior art, the invention has the following beneficial effects:
1) By adding the alpha-cyanoacrylate with large molecular weight and the rubber with high molecular weight into the alpha-cyanoacrylate with small molecular weight, the volatility of the quick-drying adhesive is reduced, and the whitening problem of the quick-drying adhesive is reduced.
2) The alpha-cyanoacrylate with large molecular weight has an inner toughening effect, the rubber with high molecular weight has a remarkable outer toughening effect, and the impact resistance of the quick-drying adhesive is improved by adding the two toughening agents.
3) The product prepared by the method is low-whitening impact-resistant quick-drying adhesive, and solves the technical problems of poor impact resistance and easy occurrence of whitening phenomenon of the traditional quick-drying adhesive, thereby remarkably improving the use effect of the quick-drying adhesive.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Example 1
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
80 parts of component 1 alpha-ethyl cyanoacrylate;
10 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3, 15 parts of acrylate rubber.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1500RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 20KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: low whitening.
Example 2
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
40 parts of component 1 alpha-ethyl cyanoacrylate;
40 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3, 5 parts of acrylate rubber.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1000RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 15KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: low whitening.
Example 3
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
60 parts of component 1 alpha-ethyl cyanoacrylate;
30 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3 nitrile rubber 10 parts.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1000RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 18KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: low whitening.
Comparative example 1
The quick-drying adhesive comprises the following components in parts by weight:
60 parts of component 1 alpha-ethyl cyanoacrylate;
component 2α -ethoxyethyl cyanoacrylate 30 parts.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1000RPM, and the time is more than 4H;
step three, the preparation of the quick-drying adhesive is completed: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 6KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: whitening is severe.
Comparative example 2
The quick-drying adhesive comprises the following components in parts by weight:
60 parts of component 1 alpha-ethyl cyanoacrylate;
component 2 alpha-butyl cyanoacrylate 30 parts.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1000RPM, and the time is more than 4H;
step three, the preparation of the quick-drying adhesive is completed: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 5KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: whitening is severe.
Comparative example 3
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
80 parts of component 1 alpha-ethyl cyanoacrylate;
component 3, 15 parts of acrylate rubber.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding component 1 to a vessel;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1500RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 9KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: whitening is severe.
Comparative example 4
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
100 parts of component 1 alpha-ethyl cyanoacrylate;
10 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3, 15 parts of acrylate rubber.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1500RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 8KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: whitening is severe.
Comparative example 5
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
80 parts of component 1 alpha-ethyl cyanoacrylate;
90 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3, 5 parts of acrylate rubber.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1500RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 11KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: low whitening.
Comparative example 6
The formula of the low-whitening impact-resistant quick-drying adhesive comprises the following components in parts by weight:
80 parts of component 1 alpha-ethyl cyanoacrylate;
10 parts of component 2 alpha-ethoxyethyl cyanoacrylate;
component 3 core-shell structured copolymer rubber MX154 (KANEKA, japan) 5 parts.
The manufacturing process comprises the following steps:
step one, preparing a prefabricated material: adding the component 1 and the component 2 into a container, and uniformly mixing;
step two, adding a component 3;
step three, dissolving component 3: starting a stirrer and a disperser, wherein the stirring speed is 20RPM, the dispersing speed is 1500RPM, and the time is more than 4H;
and step four, manufacturing the low-whitening impact-resistant quick-drying adhesive: and (5) sampling and observing, wherein the solution is uniform, no particles exist, and the glue preparation is completed.
The glue was tested as follows:
impact strength: 11KJ/M 2 (impact Property test according to GB/T1043.1-2008/ISO 179-1:2000)
Whitening condition: whitening is severe.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the invention.

Claims (5)

1. The low-whitening impact-resistant quick-drying adhesive composition is characterized by comprising the following components in parts by weight:
40-80 parts of small molecular weight alpha-cyanoacrylate,
10-50 parts of large molecular weight alpha-cyanoacrylate,
5-15 parts of rubber;
the small molecular weight alpha-cyanoacrylate is alpha-cyanoacrylate, and the large molecular weight alpha-cyanoacrylate is alpha-cyanoacrylate ethoxyethyl;
the mass ratio of the small molecular weight alpha-cyanoacrylate to the large molecular weight alpha-cyanoacrylate is 1:1-8:1;
the rubber is selected from: one or more of nitrile rubber, chloroprene rubber, acrylic rubber and polyurethane rubber.
2. A method of preparing a low whitening impact resistant quick setting adhesive composition according to claim 1, said method comprising the steps of:
s1, preparing a prefabricated material: uniformly mixing small-molecular-weight alpha-cyanoacrylate and large-molecular-weight alpha-cyanoacrylate to obtain a prefabricated material;
s2, adding rubber into the prefabricated material, stirring and dispersing until the solution is uniform and has no particles, and obtaining the quick-drying rubber composition.
3. The method for preparing a low whitening impact-resistant quick setting adhesive composition as claimed in claim 2, wherein the time of stirring and dispersing is 3 to 6 hours.
4. The method of preparing a low whitening impact resistant quick setting adhesive composition as claimed in claim 2, wherein the stirring rate is 15 to 30RPM.
5. The method of preparing a low whitening impact resistant quick setting adhesive composition as claimed in claim 2, wherein the dispersion rate is 600 to 1800RPM.
CN202211376765.6A 2022-11-04 2022-11-04 Low-whitening impact-resistant quick-drying adhesive composition and preparation method thereof Active CN115627124B (en)

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CN116376336B (en) * 2023-05-10 2024-04-19 浙江久而久化学有限公司 Rubber modified instant adhesive and preparation method thereof

Citations (3)

* 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
CN104927680A (en) * 2014-03-17 2015-09-23 宁波百仕高联合工业有限公司 Fast-curing instant glue and preparation method thereof
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6660327B2 (en) * 2001-12-28 2003-12-09 Mattel, Inc. Process of applying a cyanoadhesive composition

Patent Citations (3)

* 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
CN104927680A (en) * 2014-03-17 2015-09-23 宁波百仕高联合工业有限公司 Fast-curing instant glue and preparation method thereof
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

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