CN113429893A - Nonpolar rubber and plastic material surface treatment agent and surface treatment method - Google Patents
Nonpolar rubber and plastic material surface treatment agent and surface treatment method Download PDFInfo
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- CN113429893A CN113429893A CN202110832830.0A CN202110832830A CN113429893A CN 113429893 A CN113429893 A CN 113429893A CN 202110832830 A CN202110832830 A CN 202110832830A CN 113429893 A CN113429893 A CN 113429893A
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- component
- surface treatment
- rubber
- plastic material
- treating agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
-
- 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
-
- 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
- C09J2407/00—Presence of natural rubber
- C09J2407/008—Presence of natural rubber in the pretreated surface to be joined
-
- 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
- C09J2409/00—Presence of diene rubber
- C09J2409/008—Presence of diene rubber in the pretreated surface to be joined
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/008—Presence of polyolefin in the pretreated surface to be joined
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/16—Presence of ethen-propene or ethene-propene-diene copolymers
- C09J2423/168—Presence of ethen-propene or ethene-propene-diene copolymers in the pretreated surface to be joined
Abstract
The invention discloses a nonpolar rubber and plastic material surface treating agent and a surface treating method, the surface treating agent comprises A, B bi-component, A component is polyisocyanate, B component is diamine, A, B component is prepared according to the mass ratio of 1: 0.1 to 1. The surface treating agent has the capability of rapid penetration and rapid reaction, so that the treated surface and the inside of the penetration form an integrated network structure, and the surface property of the treated material is improved. The surface treating agent has simple treatment process and easy operation, and is particularly suitable for large-scale mobile construction (such as shipbuilding industry).
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a surface treatment agent and a surface treatment method for a nonpolar rubber plastic material, and particularly relates to a surface treatment method and a surface treatment agent for strengthening the combination of polyurethane urea and the nonpolar rubber plastic material.
Background
The polyurethane, polyurea and polyurethane urea have various varieties, wide raw material selection range and excellent comprehensive performance, and are widely used as adhesives, pouring adhesives, sealants and the like in various fields. The bonding interface of the materials is metal, ceramic, cement, wood and high polymer materials such as glass fiber reinforced plastic, various coatings, polyolefin cables, various rubbers and the like.
However, the problems often encountered during the use process are that the bonding force is insufficient when the material is combined with some nonpolar materials such as polyolefin cables and styrene-butadiene rubber, and the bonding and sealing of the material on test pieces in some special occasions such as cable sealing, underwater facility bonding and sealing, long-term dynamic vibration environment and long-term alternating temperature (low temperature) environment are limited.
Disclosure of Invention
The invention aims to provide a brand-new scheme for modifying the surface property of a nonpolar material aiming at the problems of weak interface bonding force and limited application of polyurethane (urea) and some nonpolar materials.
The traditional surface treatment is mostly by surface polarization treatment such as plasma treatment, surface polarity transition such as coupling agent treatment, etc. The surface layer and the treating agent permeating the shallow surface layer are quickly reacted to form a semi-interpenetrating network structure, and the surface layer is linked by the anchor chain, so that the surface property of the non-polar material is improved, and the interface binding force is greatly improved.
The purpose of the invention is realized by the following modes:
a surface treating agent for a non-polar rubber-plastic material comprises A, B double components, wherein the component A is polyisocyanate, the component B is diamine, and the component A, B is prepared from the following components in a mass ratio of 1: 0.1 to 1. Preferably, A, B components are prepared in a mass ratio of 1: 0.3 to 0.5. The nonpolar rubber plastic material is natural rubber, styrene butadiene rubber, ethylene propylene rubber or butyl rubber. The surface of the non-polar rubber plastic material may preferably be the surface of a polyolefin cable or the surface of styrene butadiene rubber.
Preferably, the polyisocyanate is HDI trimer or TDI trimer, and the diamine is MOCA (3,3 '-dichloro-4, 4' -diaminodiphenylmethane), DETDDA (diethyltoluenediamine) or DMTDA (dimethylthiotoluenediamine).
Preferably, the diluent is added to the component B to make the concentration of the diluted component B be 15-25%, and most preferably, the concentration of the diluted component B be 20%. The diluent used may be acetone, butanone, toluene or ethyl acetate. The selected diluent has good solubility with diamine and better swelling property with non-polar rubber plastic materials.
The treating agent has a structure similar to that of polyurethane (urea), has moderate molecular weight, can ensure rapid permeation, has high reaction speed (within minutes), and can quickly form a network.
The surface treatment method by using the surface treating agent is to spray or scrape the surface treating agent at the temperature of more than 0 ℃ and the relative humidity of the environment of less than 90 percent, and the surface treating agent is preferably used under the conditions of the environmental temperature of 0-35 ℃ and the relative humidity of 65-90 percent. Under the conditions of high temperature and high humidity with the temperature of 35 ℃ and the humidity of 90 percent, the invention can still obviously improve the interface bonding force and is particularly suitable for being used under the condition of severe environment.
After the surface treatment, the polyurethane urea sealant can be adopted for bonding or sealing for 0.5h-7 d.
The invention relates to a surface treating agent for reinforcing the combination of polyurethane (urea) and non-polar rubber and plastic materials, which has a structure similar to that of a main body material of the polyurethane urea. The invention uses a simple process to treat the surface of the nonpolar material by the surface treating agent, so that the interface binding force is greatly improved, the use of the test piece under the alternating fatigue environment is adapted, and the durability is improved.
Compared with the prior art, the invention has the beneficial effects that: the surface treating agent has the capability of rapid penetration and rapid reaction, so that an integrated net structure is formed between the treated surface and the penetrated interior, and the surface property of the treated material is improved; the method has simple treatment process and easy operation, can still obviously improve the interface bonding force under the condition of high humidity, and is particularly suitable for large-scale mobile construction (such as shipbuilding industry).
The specific implementation mode is as follows:
the invention is further illustrated by the following specific examples:
the surface treatment agent of the following examples comprises A, B two components, wherein the A component is HDI trimer or TDI trimer, and the B component mainly comprises MOCA, DETDDA or DMTDA.
Preparation of the surface treating agent: preparing the component B into a diamine solution with the concentration of 15-25% (the solvent is acetone or butanone or ethyl acetate); the component A and a diamine solution with the concentration of 15-25% are mixed according to the mass ratio in the table 1-table 3.
Surface treatment operation steps:
(1) cleaning the surface of the treated material: wiping the surface with a uric acid-ethyl acetate solution or a uric acid-acetone solution to remove dirt;
(2) placing operation after treatment: spraying or brushing the surface treating agent on the treated surface in a certain temperature and humidity environment, and bonding or sealing by adopting a polyurethane urea system sealant 0.5h-7d after the surface treatment.
Specific examples 1 to 16 and comparative examples 1 to 7 are shown in tables 1 to 3:
in example 2, the component A is HDI trimer, the component B is butanone solution with MOCA concentration of 20%, and the mass ratio of the component A to the component B is 1: 2; standing for 0.5h after treatment;
in example 3, the component A was HDI trimer, the component B was 20% concentration butanone solution, and the mass ratio of the two was 1: 2; placing for 7d after treatment;
in example 4, the component A was HDI trimer, and the component B was an ethyl acetate solution with a DETDA concentration of 15%; the mass ratio of the two is 1: 2; standing for 0.5h after treatment;
example 5, component A was HDI trimer and component B was a 25% DMTDA solution in ethyl acetate; the mass ratio of the two is 1: 2; standing for 0.5h after treatment;
in comparative example 1, the A component was HDI trimer, and the B component was an ethyl acetate solution of DMTDA concentration of 25%; the mass ratio of the two is 1: 7; after treatment, the mixture is left for 0.5 h.
In comparative example 1, the component A was HDI trimer, and the component B was an ethyl acetate solution of DMTDA in a mass ratio of 1: 7; standing for 0.5h after treatment, and carrying out the other steps by 1-5;
in examples 6 and 7, the component A is HDI trimer, the component B is butanone solution with MOCA concentration of 20%, and the mass ratio of the component A to the component B is 1: 2; standing for 0.5h after treatment;
in example 8 and example 9, the component A was HDI trimer, and the component B was 20% MOCA solution in butanone in a mass ratio of 1: 2; standing for 7h after treatment;
in example 10, the component A was HDI trimer, and the component B was an ethyl acetate solution with a DETDA concentration of 20%; the mass ratio of the two is 1: 2; standing for 0.5h after treatment;
in example 11, the A component was HDI trimer and the B component was an ethyl acetate solution of DMTDA concentration 20%; the mass ratio of the two is 1: 2; standing for 0.5h after treatment;
in comparative examples 2 and 3, the component A is epoxy resin, the component B is polyamide, and the mass ratio of the component A to the component B is 1: 2; standing for 0.5h after treatment; the rest of the procedure was the same as in examples 6 to 11;
in examples 13 to 14, the component A was an HDI trimer, and the component B was a 20% MOCA butanone solution in a mass ratio of 1: 2; standing for 0.5h after treatment;
in examples 15 to 16, the component A was an HDI trimer, and the component B was a 20% MOCA butanone solution in a mass ratio of 1: 2; standing for 7h after treatment;
in comparative examples 4 and 5, the component A was an epoxy resin and the component B was a polyamide; the mass ratio of the two is 1: 2; standing for 0.5h after treatment; the rest of the procedure was the same as in examples 12 to 16;
in comparative example 6 and comparative example 7, the component A was HDI trimer, the component B was 20% of butanone solution with MOCA concentration in a mass ratio of 1:0.6, and the mixture was left for 0.5h after treatment; the remaining steps were as in examples 12-16.
The following are examples 1 to 16, and the specific conditions and results are shown in tables 1 to 3.
TABLE 1 styrene butadiene rubber Strength test
TABLE 2 styrene butadiene rubber Strength test
TABLE 3 polyolefin Strength test
Note: the 'adhesive shear strength' test method refers to the national standard GB/T13936-2014
"Peel Strength" test method refer to national Standard GB/T2791-1995
Claims (10)
1. The nonpolar rubber and plastic material surface treating agent is characterized by comprising A, B double components, wherein the component A is polyisocyanate, the component B is diamine, and the component A, B is prepared according to the mass ratio of 1: 0.1 to 1.
2. The non-polar rubber-plastic material surface treating agent according to claim 1, wherein the A, B component is prepared in a mass ratio of 1: 0.3 to 0.5.
3. The surface treatment agent for non-polar rubber-plastic materials according to claim 1, wherein the polyisocyanate is HDI trimer or TDI trimer.
4. The non-polar rubber-plastic material surface treating agent according to claim 1, wherein the diamine is MOCA, DETDA or DMTDA.
5. The surface treating agent for non-polar rubber-plastic material as claimed in claim 1, wherein the concentration of the diluted component B is 15-25% by adding the diluent.
6. The surface treatment agent according to claim 5, wherein the component B is diluted with a diluent to a concentration of 20%.
7. The surface treatment agent for non-polar rubber-plastic material as claimed in claim 5, wherein the diluent is acetone, methyl ethyl ketone, toluene or ethyl acetate.
8. The surface treatment method by using the nonpolar rubber and plastic material surface treatment agent of claim 1, characterized in that the surface treatment agent is sprayed or blade-coated at an ambient temperature of more than 0 ℃ and a relative humidity of less than 90%.
9. The method for surface treatment by the non-polar rubber-plastic material surface treatment agent according to claim 8, wherein the ambient temperature is 0-35 ℃ and the relative humidity is 65-90%.
10. The surface treatment method using the surface treatment agent as claimed in claim 8, wherein the nonpolar rubber-plastic material is natural rubber, styrene-butadiene rubber, ethylene-propylene rubber, or butyl rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110832830.0A CN113429893A (en) | 2021-07-22 | 2021-07-22 | Nonpolar rubber and plastic material surface treatment agent and surface treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110832830.0A CN113429893A (en) | 2021-07-22 | 2021-07-22 | Nonpolar rubber and plastic material surface treatment agent and surface treatment method |
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| Publication Number | Publication Date |
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| CN113429893A true CN113429893A (en) | 2021-09-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110832830.0A Pending CN113429893A (en) | 2021-07-22 | 2021-07-22 | Nonpolar rubber and plastic material surface treatment agent and surface treatment method |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4004050A (en) * | 1974-08-26 | 1977-01-18 | The Goodyear Tire & Rubber Company | Two-part primer system for FRP bonding |
| US4443519A (en) * | 1983-02-04 | 1984-04-17 | Monsanto Company | Bonded plastic structures |
| US5232531A (en) * | 1991-08-19 | 1993-08-03 | Ashland Oil, Inc. | Adhesive for bonding epdm rubber roofing membrane and bonding method employing same |
| US20020091222A1 (en) * | 2000-08-03 | 2002-07-11 | Nathalie Viegas | Adhesive for rubber compositions, process for its preparation and articles comprising this adhesive |
| JP2005046686A (en) * | 2003-07-31 | 2005-02-24 | Canon Inc | Method for forming polyurea film |
| CN101378765A (en) * | 2005-11-22 | 2009-03-04 | Rmi聚合体公司 | Hydrophobic elastomeric polymer chemistry device for inhibiting the growth of onychomycosis and urushiol-induced allergic contact dermatitis |
| CN102675584A (en) * | 2011-03-08 | 2012-09-19 | 北京市大禹王防水工程集团有限公司 | Polyurethane base coat special for spraying polyurea on concrete base face and preparation method and application of polyurethane base coat |
| CN107548322A (en) * | 2015-05-06 | 2018-01-05 | 巴斯夫涂料有限公司 | The method that multilayer paint system is prepared on plastic basis material |
| CN111386323A (en) * | 2017-11-22 | 2020-07-07 | 科思创德国股份有限公司 | System for applying base coats and bonding floor coverings |
-
2021
- 2021-07-22 CN CN202110832830.0A patent/CN113429893A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4004050A (en) * | 1974-08-26 | 1977-01-18 | The Goodyear Tire & Rubber Company | Two-part primer system for FRP bonding |
| US4443519A (en) * | 1983-02-04 | 1984-04-17 | Monsanto Company | Bonded plastic structures |
| US5232531A (en) * | 1991-08-19 | 1993-08-03 | Ashland Oil, Inc. | Adhesive for bonding epdm rubber roofing membrane and bonding method employing same |
| US20020091222A1 (en) * | 2000-08-03 | 2002-07-11 | Nathalie Viegas | Adhesive for rubber compositions, process for its preparation and articles comprising this adhesive |
| JP2005046686A (en) * | 2003-07-31 | 2005-02-24 | Canon Inc | Method for forming polyurea film |
| CN101378765A (en) * | 2005-11-22 | 2009-03-04 | Rmi聚合体公司 | Hydrophobic elastomeric polymer chemistry device for inhibiting the growth of onychomycosis and urushiol-induced allergic contact dermatitis |
| CN102675584A (en) * | 2011-03-08 | 2012-09-19 | 北京市大禹王防水工程集团有限公司 | Polyurethane base coat special for spraying polyurea on concrete base face and preparation method and application of polyurethane base coat |
| CN107548322A (en) * | 2015-05-06 | 2018-01-05 | 巴斯夫涂料有限公司 | The method that multilayer paint system is prepared on plastic basis material |
| CN111386323A (en) * | 2017-11-22 | 2020-07-07 | 科思创德国股份有限公司 | System for applying base coats and bonding floor coverings |
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Application publication date: 20210924 |
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