CN106752981A - A kind of environment-friendly modified adhesive and preparation method thereof - Google Patents
A kind of environment-friendly modified adhesive and preparation method thereof Download PDFInfo
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- CN106752981A CN106752981A CN201611109282.4A CN201611109282A CN106752981A CN 106752981 A CN106752981 A CN 106752981A CN 201611109282 A CN201611109282 A CN 201611109282A CN 106752981 A CN106752981 A CN 106752981A
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- Prior art keywords
- environment
- rubber
- friendly modified
- mass parts
- modified adhesive
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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
- C09J4/00—Adhesives 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
- C09J4/06—Organic 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to preparation technology and the material composition of a kind of environment-friendly modified adhesive, with the unsaturated carboxylic acids such as acrylic acid or other there is the polymerisable monomer of second functional group, metal oxide etc. can be with the material of above-mentioned monomer reaction, in the presence of the initiators such as peroxide, reaction modifying is carried out to natural rubber Polymer material, a kind of new type rubber metal-to-metal adhesive is prepared；The present invention prepare environment-friendly modified adhesive have the advantages that bonding strength it is high, bonding scope it is wide, adhesion process is easy, prepare, using pollution-free.
Description
Technical field
The present invention relates to a kind of adhesive, specifically, it is related to a kind of environment-friendly modified adhesive and its preparation side
Method.
Background technology
Rubber binds with metal, is capable of the high resiliency of comprehensive rubber and the high-modulus of metal；High performance rubber-metal is answered
Component, can be used for vehicle, ship, machine-building and aerospace field.
For the rubber-metal composite article such as traditional rubber absorbers, skeleton sealing element, the bonding of metalwork and rubber
It is many to bind method using indirect.But the method has complex manufacturing, efficiency low, environmental pollution is serious, and bonding strength is not
The shortcomings of stabilization.
Directly vulcanization adhesion process can partly avoid disadvantages mentioned above, such as be widely used in radial tire undertread sizing material
Bonding system --- resorcinol/methylene donor/white carbon system, and cobalt salt.But resorcinol is in high-temperature mixing
When can distil, the methylene donor containing free formaldehyde in mixing and is applied and also polluted the environment in tire.For cobalt
, there are three shortcomings in salt.One is the poor dispersion in sizing material, if local content is excessive, can cause the generation of cuprous sulfide
Speed is accelerated, and the resinification extent of reaction is too deep, crosslink density is excessive, and the cement properties of sizing material are influenceed on the contrary.Two is cobalt salt
A kind of pro-oxidant, it can promote it is aging, accelerate cuprous sulfide layer degraded and cause bonding strength to decline.Three is cobalt salt price
It is higher, and price is very unstable.
In recent years, the slaine of acrylic or methacrylic acid is used for rubber-metal adhesion promoters, and the auxiliary agent belongs to
Method tackifier is directly binded, it is easy to use, but cement properties still have much room for improvement.
The content of the invention
The purpose of the present invention is to prepare a kind of environment-friendly modified adhesive for rubber-metal bonding.Use propylene
Acid or the unsaturated carboxylic acid such as methacrylic acid, to containing zinc oxide metal oxides such as (or) magnesia, peroxide (such as peroxide
Change the initiator such as diisopropylbenzene (DIPB)) and other rubber often carry out reaction in-situ with the natural rubber (or synthetic rubber) of compounding ingredient and change
Property, prepare a kind of free from extraneous odour, easy to store, outward appearance it is nondistinctive with common elastomeric compound mixing glue-type binder, or further with
The mixing of benzene series, ketone system, petroleum, ester series solvent or mixed solvent, prepares rubber cement type binder.Mixing glue-type binder, can
For directly vulcanizing adhesion process；Rubber cement type binder, can be used for indirect method adhesion process.Acrylates prepared by the present invention changes
Property rubber-type binder there is bonding strength high, bonding scope wide (can be used for the bonding of various metals and various rubber), bonding
Technique easy (directly bonding can obtain bonding strength high without carry out blasting treatment to metal), preparation, using pollution-free etc.
Advantage.
The present invention adopts the following technical scheme that realization：A kind of environment-friendly modified adhesive, it is characterised in that it presses matter
The formula for measuring part is as follows：Unsaturated carboxylic acid or other there are the polymerisable monomer 40-900 mass parts of second functional group, metal oxygen
Compound or hydroxide etc. can with above-mentioned unsaturated carboxylic acid or other have second functional group polymerisable monomer react thing
The initiator 1-3 mass parts such as matter 15-30 mass parts, peroxide, rubber or other mass parts of macromolecular material 150, foaming agent
1-3 mass parts, acetic acid 0.1-0.5 mass parts, saccharin 1-5 mass parts.
Preferably, described unsaturated carboxylic acid includes acrylic or methacrylic acid, and can be with metal oxide or hydrogen
The polymerisable monomer with second functional group of oxide reaction.
Preferably, can with unsaturated carboxylic acid or other have second functional group polymerisable monomer react material include oxygen
Change the hydroxide such as the metal oxides such as zinc, magnesia, aluminum oxide, magnesium hydroxide, aluminium hydroxide.
Preferably, the initiator such as described peroxide includes cumyl peroxide, benzoyl peroxide.
Preferably, the rubber for being used or other macromolecular materials include natural rubber, synthetic rubber, thermoplastic elastomer (TPE)
Polymer material and all performed polymers, monomer, latex, the rubber cement that can be polymerized.
The invention also discloses the preparation technology of above-mentioned environment-friendly modified adhesive, using method (1) or (2), (1)
First by elastomeric polymeric material and metal oxide, peroxide, the mixing of other compounding ingredients, then reacted with unsaturated carboxylic acid,
Adhesive is obtained；(2) above-mentioned formula materials arbitrarily arranged in pairs or groups, mixed, and static state at various temperatures is parked or is molded, and
The processes such as dynamic mechanically processing, are obtained adhesive.
Preferably, obtained adhesive is mixing glue-type adhesive or rubber cement type adhesive.
Preferably, mixing glue-type binder includes sheet, graininess or strip.
Preferably, the solvent that rubber cement type binder is used includes benzene series, ketone system, petroleum, ester system equal solvent and its mixes
Bonding solvent.
Reaction principle of the invention is：Acrylic acid, methacrylic acid (or other unsaturated carboxylic acids) are aoxidized with metal is contained
After thing, the rubber mix of peroxide, (methyl) acrylates, polymethylacrylic acid, poly- methyl can be generated at a certain temperature
Acrylates, and reacted with rubber molecular chain in the vulcanization of rubber, while firm adsorption is formed with metal, so that
Rubber is sticked together with metal, and the presence of foaming agent, acetic acid and saccharin helps to improve the performance of adhesive.
Environment-friendly modified adhesive prepared by the present invention has advantages below：1st, bonding strength is high, better than other cities
Sell binder or tackifier；2nd, bonding scope is wide：Can be used for the bonding of various metals and various rubber.3rd, adhesion process is easy：
Can be used for directly vulcanization bonding, it can also be used to which indirect method is binded.Directly bonding is strong without that can obtain bonding high to abrasive blasting
Degree.4th, prepare, using pollution-free：Closed production, waste gas recovery are carried out during preparation, it is substantially pollution-free；All monomers have been when using
It is aggregated, non-volatile gas.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
By 150kg synthetic rubber, with 15kg magnesia, 3kg cumyl peroxides, 1kg foaming agents, 0.1kg acetic acid,
1kg saccharin, is kneaded uniform by two-roll mill；
Above-mentioned elastomeric compound is processed into graininess or other shapes, is then mixed uniformly with 40kg acrylic acid；
Above-mentioned material is placed in closed container, is parked at 50-90 DEG C 24 hours, it is anti-to acrylic acid and magnesia etc.
Should be complete；
Above-mentioned material is dried into (80 DEG C, 24-36 hours) or vacuum drying (80 DEG C, 10 hours), elastomeric compound is removed
Middle possible remaining acrylic acid is simultaneously reclaimed；
Above-mentioned material is uniform in the enterprising one-step melting of two-roll mill, and process slabbing, graininess, strip etc., i.e.,
Can be used to rubber be binded with the direct vulcanization of metal.
The mixed solvent that above-mentioned material 100kg and toluene 20kg, ethyl acetate 80kg, 120# gasoline 100kg are constituted is entered
Row stirring, is well mixed, and is made rubber cement, can be used for metal surface gluing, then carries out vulcanization bonding with rubber.
Mixing glue-type binder and rubber cement type binder manufactured in the present embodiment, for synthetic rubber and non-surface treated
Aluminium, 45# steel, stainless steel bonding, failure mode is synthetic rubber main body destruction.
Embodiment 2
By 150kg synthetic rubber, with 15kg magnesia, 3kg cumyl peroxides, 1kg foaming agents, 0.1kg acetic acid,
1kg saccharin, is kneaded uniform by the equipment such as two-roll mill or banbury, screw extruder；
Then in the equipment such as mill, to being added in above-mentioned material, the mixing of 60kg acrylic acid is uniform, and by above-mentioned mixing
Glue is processed into graininess, strip or other small size shapes；
Above-mentioned material is placed in closed container, is parked at 50-90 DEG C 24 hours, it is anti-to acrylic acid and magnesia etc.
Should be complete；
Above-mentioned material is dried into (80 DEG C, 24-36 hours) or vacuum drying (80 DEG C, 10 hours), elastomeric compound is removed
Middle possible remaining acrylic acid is simultaneously reclaimed；
Above-mentioned material is uniform in the enterprising one-step melting of two-roll mill, and process slabbing, graininess, strip etc., i.e.,
Can be used to rubber be binded with the direct vulcanization of metal.
The mixed solvent that above-mentioned material 100kg and toluene 20kg, ethyl acetate 80kg, 120# gasoline 100kg are constituted is entered
Row stirring, is well mixed, and is made rubber cement, can be used for metal surface gluing, then carries out vulcanization bonding with rubber.
Mixing glue-type binder and rubber cement type binder manufactured in the present embodiment, for synthetic rubber and non-surface treated
Aluminium, 45# steel, stainless steel bonding, failure mode is synthetic rubber main body destruction.
Embodiment 3
By 150kg synthetic rubber, with 15kg magnesia, 3kg cumyl peroxides, 1kg foaming agents, 0.1kg acetic acid,
1kg saccharin, is kneaded uniformly, and above-mentioned elastomeric compound is processed into by the equipment such as two-roll mill or banbury, screw extruder
Graininess, strip or other small size shapes；
Above-mentioned material 100kg and 80kg acrylic acid and toluene 20kg, ethyl acetate 150kg, 120# gasoline 90kg are stirred
Mix to dissolving；
Above-mentioned material is placed in closed container, is stirred 48 hours at 70 DEG C, to the reaction such as acrylic acid and magnesia
Completely；Can be used for metal surface gluing, then carry out vulcanization bonding with rubber.Rubber cement type binder manufactured in the present embodiment, uses
In natural rubber and not surface treated aluminium, 45# steel, stainless steel bonding, failure mode is synthetic rubber main body destruction.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of environment-friendly modified adhesive, it is characterised in that the formula that it presses mass parts is as follows：Unsaturated carboxylic acid or its
It has the polymerisable monomer 40-900 mass parts of second functional group, and metal oxide or hydroxide etc. can be with above-mentioned insatiable hungers
With carboxylic acid or other there are the material 15-30 mass parts that the polymerisable monomer of second functional group reacts, the initiator such as peroxide
1-3 mass parts, rubber or other mass parts of macromolecular material 150, foaming agent 5-10 mass parts, acetic acid 0.1-0.5 mass parts, sugar
Smart 1-5 mass parts.
2. environment-friendly modified adhesive according to claim 1, it is characterised in that described unsaturated carboxylic acid includes
Acrylic or methacrylic acid, and the polymerizable list with second functional group that can be reacted with metal oxide or hydroxide
Body.
3. environment-friendly modified adhesive according to claim 1, it is characterised in that：Can with unsaturated carboxylic acid or other
The material of the polymerisable monomer reaction with the second functional group metal oxide, hydrogen-oxygen such as including zinc oxide, magnesia, aluminum oxide
Change the hydroxide such as magnesium, aluminium hydroxide.
4. environment-friendly modified adhesive according to claim 1, it is characterised in that：Described peroxide etc. triggers
Agent includes cumyl peroxide, benzoyl peroxide.
5. environment-friendly modified adhesive according to claim 1, it is characterised in that：The rubber for being used or other height
Molecular material includes natural rubber, synthetic rubber, thermoplastic elastomer (TPE) Polymer material and all performed polymers, can be polymerized
Monomer, latex, rubber cement.
6. the preparation technology of environment-friendly modified adhesive according to claim 1, it is characterised in that：Using method
Or (2) (1)
(1) first by elastomeric polymeric material and metal oxide, peroxide, the mixing of other compounding ingredients, then with unsaturated carboxylic
Acid reaction, is obtained adhesive；
(2) above-mentioned formula materials arbitrarily arranged in pairs or groups, mixed, and static state at various temperatures is parked or is molded, and dynamic machine
The processes such as tool processing, are obtained adhesive.
7. the preparation technology of environment-friendly modified adhesive according to claim 6, it is characterised in that：Obtained bonding
Agent is mixing glue-type adhesive or rubber cement type adhesive.
8. the preparation technology of environment-friendly modified adhesive according to claim 7, it is characterised in that：Mixing glue-type is sticked
Mixture includes sheet, graininess or strip.
9. the preparation technology of environment-friendly modified adhesive according to claim 7, it is characterised in that：Rubber cement type binds
The solvent that agent is used includes benzene series, ketone system, petroleum, ester system equal solvent and its mixed solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611109282.4A CN106752981A (en) | 2016-12-06 | 2016-12-06 | A kind of environment-friendly modified adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611109282.4A CN106752981A (en) | 2016-12-06 | 2016-12-06 | A kind of environment-friendly modified adhesive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106752981A true CN106752981A (en) | 2017-05-31 |
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ID=58878304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611109282.4A Pending CN106752981A (en) | 2016-12-06 | 2016-12-06 | A kind of environment-friendly modified adhesive and preparation method thereof |
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| Country | Link |
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| CN (1) | CN106752981A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289597A (en) * | 2013-06-26 | 2013-09-11 | 青岛科技大学 | Environment-friendly (methyl) acrylate modified rubber type adhesive and preparation process thereof |
-
2016
- 2016-12-06 CN CN201611109282.4A patent/CN106752981A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289597A (en) * | 2013-06-26 | 2013-09-11 | 青岛科技大学 | Environment-friendly (methyl) acrylate modified rubber type adhesive and preparation process thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李红强: "《胶黏原理、技术及应用》", 31 January 2014, 华南理工大学出版社 * |
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Application publication date: 20170531 |