CN109266270A - A kind of adhesive and preparation method and application - Google Patents
A kind of adhesive and preparation method and application Download PDFInfo
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- CN109266270A CN109266270A CN201710581898.XA CN201710581898A CN109266270A CN 109266270 A CN109266270 A CN 109266270A CN 201710581898 A CN201710581898 A CN 201710581898A CN 109266270 A CN109266270 A CN 109266270A
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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
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/504—Additional features of adhesives in the form of films or foils characterized by process specific features process of pretreatment for improving adhesion of rubber on metallic surfaces
Abstract
The present invention provides a kind of adhesive and preparation method and application.Adhesive of the invention, the component including following parts by weight: 20-30 parts of carboxylated nitrile rubber；20-30 parts of butadiene-styrene-vinyl pyridine rubber；80-100 parts of resorcinol-formaldehyde resin；150-400 parts of toluene；2-4 parts of (methyl) acryloxypropyl trialkoxy silane；2-4 parts of glycidol the third oxygen propyl group trialkoxy silane；1-4 parts of carbon black；10-30 parts of nano aluminium oxide.Adhesive of the invention has good thermal conductivity and heat resistance, so as to effectively improve the service life of rubber.
Description
Technical field
The present invention relates to a kind of adhesives, and in particular to a kind of adhesive and preparation method and application.
Background technique
With the rapid development of rubber industry, rubber composite material is widely used.Rubber composite material is in rubber
It is compounded with a variety of different framework materials in gum base materials and increases material, to meet certain purposes or service performance.It obtains
High performance rubber composite material, other than selecting suitable framework material, the quality of adhesive be also rubber composite material at
The key of function.Adhesive for use product under severe conditions when remain that framework material is integrated with rubber, thus
The effect for preferably playing framework material extends the service life of rubber product to improve the quality of rubber product.
With rubber composite product type increase and the expansion of application field, the requirement to adhering technique are more and more severe
It carves.Currently, the bonding of rubber and metal relies primarily on heat cure adhesive, a variety of rubber and various metals can be suitable for
Bonding.However, rubber is by alternate stress effect and outside after using conventional heat cure adhesive bonding rubber and metal
When portion's high temperature action, the heat inside rubber can not transmit heat dissipation in time, to can accelerate the aging of rubber, for high temperature item
The stator rubber used under part is especially prominent.Therefore, expect a kind of adhesive with thermal conductive resin and heat resistance.
Summary of the invention
The present invention provides a kind of adhesive and preparation method and application, which has good thermal conductivity and heat-resisting
Property, so as to effectively improve the service life of rubber.
The present invention provides a kind of adhesive, the component including following parts by weight:
20-30 parts of carboxylated nitrile rubber；
20-30 parts of butadiene-styrene-vinyl pyridine rubber；
80-100 parts of resorcinol-formaldehyde resin；
150-400 parts of toluene；
2-4 parts of (methyl) acryloxypropyl trialkoxy silane；
2-4 parts of glycidol the third oxygen propyl group trialkoxy silane；
1-4 parts of carbon black；
10-30 parts of nano aluminium oxide.
In the present invention, carboxylated nitrile rubber (i.e. carboxy nitrile rubber, abbreviation XNBR) is that by butadiene, acrylonitrile and have
Machine acid (such as acrylic acid) ternary polymerization forms；The introducing of carboxyl increases the polarity of rubber, increases between phenolic resin
Compatibility, and make rubber that there is high-intensitive and good cementability and resistance to ag(e)ing, improve wearability, the tearing of rubber
Intensity and oil resistivity.In concrete scheme of the invention, the mass content of acrylonitrile can be 30- in the carboxylated nitrile rubber
40%, Mooney viscosity can be 40-75.
In the present invention, butadiene-styrene-vinyl pyridine rubber is the terpolymer of vinylpyridine, butadiene and styrene, pyridine groups
Introducing increase the polarity of rubber, be conducive to improve metal and the direct adhesive force of rubber；In concrete scheme of the invention
In, the mass content of styrene can be 18-20% in the butadiene-styrene-vinyl pyridine rubber, and the mass content of vinylpyridine can be
13-15%, Mooney viscosity can be 40-75.
In concrete scheme of the invention, the softening point of the resorcinol-formaldehyde resin can be 80-110 DEG C；Have
The resorcinol-formaldehyde resin of the softening point range can increase the adhesive property of adhesive.
In concrete scheme of the invention, (methyl) the acryloxypropyl trialkoxy silane is selected from acryloyl-oxy third
Base trimethoxy silane, acryloxypropyl triethoxysilane, acryloxypropyl tripropoxy silane, methacryloxypropyl
In propyl trimethoxy silicane, methacryloxypropyl triethoxysilane and methacryloxypropyl tripropoxy silane
At least one.Above-mentioned specific (methyl) acryloxypropyl trialkoxy silane can significantly increase rubber and glue to substrate
Knot property.
Further, the partial size of the nano aluminium oxide can be 20-80nm, and specific surface area can be 20-200m2/g。
Above-mentioned specific nano aluminium oxide is added in adhesive, can make rubber that there is thermal conduction characteristic, while can be improved rubber
Heat resistance.
The present invention also provides the preparation methods of above-mentioned adhesive, include the following steps:
1) by 20-30 parts of carboxylated nitrile rubber, 20-30 parts of butadiene-styrene-vinyl pyridine rubber, 80-100 parts of resorcinol-formaldehyde resin and
150-400 parts of toluene are uniformly mixed, and obtain the first mixture；
2) by 2-4 parts of (methyl) acryloxypropyl trialkoxy silane, glycidol the third oxygen propyl group trialkoxy silane
2-4 parts, 1-4 parts of carbon black and 10-30 parts of nano aluminium oxide are uniformly mixed, and obtain the second mixture；
3) first mixture and second mixture are uniformly mixed, obtain described adhesive.
The present invention also provides application of the above-mentioned adhesive on metal and rubber adhesion.
The present invention also provides a kind of adhesive bonding methods, include the following steps:
On metal base by the coating of any of the above-described described adhesive, the first vulcanization is then carried out, on metal base shape
At coating；
Rubber is placed on the coating, the second vulcanization is then carried out, rubber composite material is made.
Further, the temperature of first vulcanization is 150-160 DEG C, time 5-10min；The temperature of second vulcanization
Degree is 150-160 DEG C, time 20-30min.
Implementation of the invention, at least has the advantage that
1, the thermal coefficient of adhesive of the invention is 0.85-1.15W/mK, and the resistance to boiling water time is 640-720h,
Bonding metal can in time pass out the heat inside rubber with when rubber, it is therefore prevented that rubber aging at high temperature, from
And effectively improve the service life of rubber.
2, the adhesion strength of adhesive of the invention is 0.72-0.95MPa, can ensure that rubber and metal are not easy to take off
From.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Technical solution in inventive embodiments is clearly and completely described, it is clear that described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
The adhesive of the present embodiment is grouped as by the group of following parts by weight:
20 parts of carboxylated nitrile rubber；
20 parts of butadiene-styrene-vinyl pyridine rubber；
80 parts of resorcinol-formaldehyde resin；
150 parts of toluene；
2 parts of acryloxypropyl trimethoxy silane；
2 parts of trialkoxy silane of the third oxygen propyl group of glycidol；
1 part of carbon black；
10 parts of nano aluminium oxide；
Wherein, the mass content of acrylonitrile is 30% in carboxylated nitrile rubber, Mooney viscosity 40；Benzene in butadiene-styrene-vinyl pyridine rubber
The mass content of ethylene is 18%, and the mass content of vinylpyridine is 13%, Mooney viscosity 40；Resorcinol-formaldehyde tree
The softening point of rouge is 80 DEG C；Nano aluminium oxide is White crystal powder, partial size 20nm, specific surface area 200m2/g；Carbon black is
High-carbon black pigment.
The step of preparing above-mentioned adhesive are as follows:
1) by 20 parts of carboxylated nitrile rubber, 20 parts of butadiene-styrene-vinyl pyridine rubber, 80 parts of resorcinol-formaldehyde resin and 150 parts of toluene
It is uniformly mixed, obtains the first mixture；
2) by 2 parts of acryloxypropyl trimethoxy silane, 2 parts of the third oxygen propyl group of glycidol trialkoxy silane, carbon black 1
Part is uniformly mixed with 10 parts of nano aluminium oxide, obtains the second mixture；
3) above-mentioned first mixture and the second mixture are mixed, stirs evenly at room temperature, above-mentioned adhesive is made.
Embodiment 2
The adhesive of the present embodiment is grouped as by the group of following parts by weight:
30 parts of carboxylated nitrile rubber；
30 parts of butadiene-styrene-vinyl pyridine rubber；
100 parts of resorcinol-formaldehyde resin；
400 parts of toluene；
4 parts of methacryloxypropyl triethoxysilane；
4 parts of trialkoxy silane of the third oxygen propyl group of glycidol；
4 parts of carbon black；
30 parts of nano aluminium oxide；
Wherein, the mass content of acrylonitrile is 40% in carboxylated nitrile rubber, Mooney viscosity 75；Benzene in butadiene-styrene-vinyl pyridine rubber
The mass content of ethylene is 20%, and the mass content of vinylpyridine is 15%, Mooney viscosity 75；Resorcinol-formaldehyde tree
The softening point of rouge is 110 DEG C；Nano aluminium oxide is White crystal powder, partial size 80nm, specific surface area 20m2/g；Carbon black is
High-carbon black pigment.
The step of preparing above-mentioned adhesive are as follows:
1) by 30 parts of carboxylated nitrile rubber, 30 parts of butadiene-styrene-vinyl pyridine rubber, 100 parts of resorcinol-formaldehyde resin and 400 parts of toluene
It is uniformly mixed, obtains the first mixture；
2) by 4 parts of methacryloxypropyl triethoxysilane, 4 parts of the third oxygen propyl group of glycidol trialkoxy silane,
4 parts and 30 parts of nano aluminium oxide of carbon black are uniformly mixed, and obtain the second mixture；
3) above-mentioned first mixture and the second mixture are mixed, stirs evenly at room temperature, above-mentioned adhesive is made.
Embodiment 3
The adhesive of the present embodiment is grouped as by the group of following parts by weight:
25 parts of carboxylated nitrile rubber；
25 parts of butadiene-styrene-vinyl pyridine rubber；
90 parts of resorcinol-formaldehyde resin；
300 parts of toluene；
3 parts of methyl allyl acyloxypropyl trimethoxysilane；
3 parts of trialkoxy silane of the third oxygen propyl group of glycidol；
3 parts of carbon black；
20 parts of nano aluminium oxide；
Wherein, the mass content of acrylonitrile is 35% in carboxylated nitrile rubber, Mooney viscosity 60；Benzene in butadiene-styrene-vinyl pyridine rubber
The mass content of ethylene is 19%, and the mass content of vinylpyridine is 14%, Mooney viscosity 60；Resorcinol-formaldehyde tree
The softening point of rouge is 100 DEG C；Nano aluminium oxide is White crystal powder, partial size 50nm, specific surface area 110m2/g；Carbon black
For high-carbon black pigment.
The step of preparing above-mentioned adhesive are as follows:
1) by 25 parts of carboxylated nitrile rubber, 25 parts of butadiene-styrene-vinyl pyridine rubber, 90 parts of resorcinol-formaldehyde resin and 300 parts of toluene
It is uniformly mixed, obtains the first mixture；
2) by 3 parts of methyl allyl acyloxypropyl trimethoxysilane, 3 parts of the third oxygen propyl group of glycidol trialkoxy silane,
3 parts and 20 parts of nano aluminium oxide of carbon black are uniformly mixed, and obtain the second mixture；
3) above-mentioned first mixture and the second mixture are mixed, stirs evenly at room temperature, above-mentioned adhesive is made.
Embodiment 4
The adhesive of the present embodiment is grouped as by the group of following parts by weight:
30 parts of carboxylated nitrile rubber；
30 parts of butadiene-styrene-vinyl pyridine rubber；
100 parts of resorcinol-formaldehyde resin；
400 parts of toluene；
4 parts of methacryloxypropyl triethoxysilane
4 parts of trialkoxy silane of the third oxygen propyl group of glycidol；
4 parts of carbon black；
30 parts of nano aluminium oxide；
Wherein, the mass content of acrylonitrile is 37% in carboxylated nitrile rubber, Mooney viscosity 55；Benzene in butadiene-styrene-vinyl pyridine rubber
The mass content of ethylene is 19%, and the mass content of vinylpyridine is 15%, Mooney viscosity 70；Resorcinol-formaldehyde tree
The softening point of rouge is 90 DEG C；Nano aluminium oxide is White crystal powder, partial size 60nm, specific surface area 150m2/g；Carbon black is
High-carbon black pigment.
The step of preparing above-mentioned adhesive are as follows:
1) by 30 parts of carboxylated nitrile rubber, 30 parts of butadiene-styrene-vinyl pyridine rubber, 100 parts of resorcinol-formaldehyde resin and 400 parts of toluene
It is uniformly mixed, obtains the first mixture；
2) by 4 parts of methacryloxypropyl triethoxysilane, 4 parts of the third oxygen propyl group of glycidol trialkoxy silane,
4 parts and 30 parts of nano aluminium oxide of carbon black are uniformly mixed, and obtain the second mixture；
3) above-mentioned first mixture and the second mixture are mixed, stirs evenly at room temperature, above-mentioned adhesive is made.
The application effect of each adhesive of table 1
| Adhesive | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Thermal coefficient (W/mK) | 0.85 | 1.132 | 0.942 | 0.896 |
| Adhesion strength (MPa) | 0.72 | 0.95 | 0.87 | 0.81 |
| Resistance to boiling water time (h) | 640 | 720 | 700 | 680 |
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of adhesive, which is characterized in that the component including following parts by weight:
20-30 parts of carboxylated nitrile rubber；
20-30 parts of butadiene-styrene-vinyl pyridine rubber；
80-100 parts of resorcinol-formaldehyde resin；
150-400 parts of toluene；
2-4 parts of (methyl) acryloxypropyl trialkoxy silane；
2-4 parts of glycidol the third oxygen propyl group trialkoxy silane；
1-4 parts of carbon black；
10-30 parts of nano aluminium oxide.
2. adhesive according to claim 1, which is characterized in that the mass content of acrylonitrile in the carboxylated nitrile rubber
For 30-40%, Mooney viscosity 40-75.
3. adhesive according to claim 1, which is characterized in that the mass content of styrene is in the butadiene-styrene-vinyl pyridine rubber
18-20%, the mass content of vinylpyridine are 13-15%, Mooney viscosity 40-75.
4. adhesive according to claim 1, which is characterized in that the softening point of the resorcinol-formaldehyde resin is 80-
110℃。
5. adhesive according to claim 1, which is characterized in that (methyl) the acryloxypropyl trialkoxy silane
Selected from acryloxypropyl trimethoxy silane, acryloxypropyl triethoxysilane, acryloxypropyl tripropoxy silicon
Alkane, methyl allyl acyloxypropyl trimethoxysilane, methacryloxypropyl triethoxysilane and methacryloxypropyl third
At least one of base tripropoxy silane.
6. adhesive according to claim 1, which is characterized in that the partial size of the nano aluminium oxide is 20-80nm, compares table
Area is 20-200m2/g。
7. the preparation method of any described adhesive of claim 1 to 6, which comprises the steps of:
1) by 20-30 parts of carboxylated nitrile rubber, 20-30 parts of butadiene-styrene-vinyl pyridine rubber, 80-100 parts of resorcinol-formaldehyde resin and toluene
150-400 parts are uniformly mixed, and obtain the first mixture；
2) by 2-4 parts of (methyl) acryloxypropyl trialkoxy silane, glycidol the third oxygen propyl group trialkoxy silane 2-4
Part, 1-4 parts of carbon black and 10-30 parts of nano aluminium oxide are uniformly mixed, and obtain the second mixture；
3) first mixture and second mixture are uniformly mixed, obtain described adhesive.
8. application of any described adhesive of claim 1 to 6 on metal and rubber adhesion.
9. a kind of adhesive bonding method, which comprises the steps of:
On metal base by any described adhesive coating of claim 1 to 6, the first vulcanization is then carried out, in metal base
Upper formation coating；
Rubber is placed on the coating, the second vulcanization is then carried out, rubber composite material is made.
10. adhesive bonding method according to claim 9, which is characterized in that the temperature of first vulcanization is 150-160 DEG C,
Time is 5-10min；The temperature of second vulcanization is 150-160 DEG C, time 20-30min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110862592A (en) * | 2019-11-28 | 2020-03-06 | 北京石油化工学院 | Alumina/carboxylic butyronitrile composite material and preparation method thereof |
| CN110982156A (en) * | 2019-12-24 | 2020-04-10 | 海隆石油产品技术服务（上海）有限公司 | Easily-bonded high-filling polyolefin sheet material and preparation method and application thereof |
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