CN108192060A - Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof - Google Patents
Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof Download PDFInfo
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- CN108192060A CN108192060A CN201711399237.1A CN201711399237A CN108192060A CN 108192060 A CN108192060 A CN 108192060A CN 201711399237 A CN201711399237 A CN 201711399237A CN 108192060 A CN108192060 A CN 108192060A
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- resorcinol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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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
- C09J161/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C09J161/04, C09J161/18 and C09J161/20
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- General Chemical & Material Sciences (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to rubber chemicals technical fields, and in particular to a kind of multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof, and resorcinol is added to molten-bath, and styrene and alkadienes, insulation reaction is added dropwise in heating melting into molten-bath respectively；Reaction product is transferred to condensation kettle, and formaldehyde is added dropwise into condensation kettle, after reaction, lye is added to carry out neutralization pH value=7；Air-distillation, vacuum distillation are carried out, catalyst is added in and adds in azole compounds, etherification reaction of leaveing neutralizes.Multicomponent provided by the invention is modified green syt high-performance rubber adhesive and preparation method thereof, product resorcinol formaldehyde resin GLR 20 have the characteristics that bond properties is strong, free phenol content is low, non-hygroscopic not smoke, and the 20 S Product Levels of B of advanced U.S. INDSPEC companies production in the world are reached, especially in tensile strength, the physical properties such as tearing toughness, H extraction forces are superior to the 20 S products of B in the U.S..
Description
Technical field
The invention belongs to rubber chemicals technical fields, and in particular to a kind of multicomponent is modified green syt high-performance rubber and glues
Mixture and preparation method thereof.
Background technology
In rubber industry, rubber and framework material（Steel wire, fibrous material）Bonding it is particularly significant, it is viscous between them
Heshui puts down the performance and used life for directly influencing rubber.M- first-white direct binding system（HRH binding systems）It is
Rubber and fiber（Steel wire）Wait framework materials bonding main adhesive system, be by methylene donor (such as：Hexa methoxy first
Base melamine, HMMM), methylene receptor（Such as：Resorcinol monomer or resin type resorcinol）With three groups of white carbon composition
Divide binding system.It is main in the past to use resorcinol monomer as methylene receptor, but resorcinol is being kneaded high temperature
Lower can distil and release toxic irritative gas（Smoke）, it had both polluted environment or had influenced the health of worker, moreover, because
Its sublimation problem causes metering inaccurate, has an adverse effect to the performance of product.It is largely ground for this purpose, research staff has done
Study carefully development, attempted the compounding for including resorcinol and stearic acid etc., resorcinol reacts spanning tree with formaldehyde or acetaldehyde
The methods of fat, has developed various resorcinol formaldehyde resins（RF resins）.Due to excessive resorcinol participate in reaction and
The structural instability of resorcinol, formaldehyde binary polycondensation product, can cause the content of free phenol in product to increase, a large amount of free phenols
Presence, still environment and human body are polluted and endangered.Meanwhile it is because having hygroscopicity, therefore it is easy to caking cohesion, it causes
Dispensing is difficult or even damages automatic batching system.
The fast development of automobile industry and the attention increasingly of environmental protection propose Rubber Chemicals Industries higher want
It asks, the technology upgrading of the rubber chemicals in China is extremely urgent, and " high-performance high added value, cleans, pre-dispersed type " is must
Right development trend, there is an urgent need to realize environmentally protective, dynamical novel for the direct binding system-HRH binding systems of rubber
Resorcinol formaldehyde resin binder（Methylene receptor）Production domesticization.
Invention content
For above-mentioned technical problem, the present invention provide a kind of multicomponent be modified green syt high-performance rubber adhesive and its
Preparation method.
Specific technical solution is：
Multicomponent is modified green syt high-performance rubber adhesive, and gained is prepared by following methods：
（1）Resorcinol is first added to molten-bath, heating melting, temperature adds in catalyst, start stirring at 125-135 DEG C；
（2）Styrene and alkadienes is added dropwise into molten-bath respectively, temperature is controlled between 125-135 DEG C, and time control is 60
~120 minutes, after being added dropwise, keep 125-138 DEG C of temperature, insulation reaction 1 hour；
（3）Reaction product is transferred to condensation kettle, and formaldehyde is added dropwise into condensation kettle, and temperature is controlled between 130-95 DEG C, time control
System was at 60~120 minutes；
（4）After reaction, lye is added to carry out neutralization pH value=7；
（5）Reaction system heats up, and carries out air-distillation, and temperature starts to be evaporated under reduced pressure at 155-165 DEG C；Vacuum during vacuum distillation
In >=0.08Mpa, temperature is 165 ± 10 DEG C for degree control；
（6）It adds in catalyst and adds in azole compounds, etherification reaction of leaveing neutralizes；
（7）Softening point is surveyed in sampling, is controlled between 99~109 DEG C, vacuum time should be extended by being such as not achieved 99 DEG C.
Further, the dosage of each raw material is according to mass fraction：Resorcinol 900, styrene 265, alkadienes 265,
37% formaldehyde 370 of mass concentration, azole compounds 55.
Multicomponent provided by the invention is modified green syt high-performance rubber adhesive and preparation method thereof, product between
Resorcinol formaldehyde resin GLR-20 has the characteristics that bond properties is strong, free phenol content is low, non-hygroscopic not smoke.It is not only comprehensive
Can be better than resorcinol monomer or compound resorcinol formaldehyde resin, and solve content of free aldehyde height, moisture absorption and smoke
The shortcomings of, and reached the B-20-S Product Levels of advanced U.S. INDSPEC companies production in the world, especially stretching by force
The physical properties such as degree, tearing toughness, H extraction forces are superior to the B-20-S products in the U.S..With Environmental protection and clearly
Clean production puts more effort, the market so that traditional common resorcinol class product will gradually fade out, this is just green work
Skill, high-performance kind rubber cement GLR-20 provide vast market prospect.
Specific embodiment
It is described in conjunction with the embodiments the specific technical solution of the present invention.
（1）Resorcinol is first added to molten-bath, heating melting, temperature adds in catalyst, start at 125-135 DEG C
Stirring；
（2）Styrene and alkadienes is added dropwise into molten-bath respectively, temperature is controlled between 125-135 DEG C, and time control is 60
~120 minutes, after being added dropwise, keep 125-138 DEG C of temperature, insulation reaction 1 hour；
（3）Reaction product is transferred to condensation kettle, and formaldehyde is added dropwise into condensation kettle, and temperature is controlled between 130-95 DEG C, time control
System was at 60~120 minutes；
（4）After reaction, lye is added to carry out neutralization pH value=7；
（5）Reaction system heats up, and carries out air-distillation, and temperature starts to be evaporated under reduced pressure at 155-165 DEG C；Vacuum during vacuum distillation
In >=0.08Mpa, temperature is 165 ± 10 DEG C for degree control；
（6）It adds in catalyst and adds in azole compounds, etherification reaction of leaveing neutralizes；
（7）Softening point is surveyed in sampling, is controlled between 99~109 DEG C, vacuum time should be extended by being such as not achieved 99 DEG C.
The dosage of each raw material is according to mass fraction：Resorcinol 900, styrene 265, alkadienes 265, mass concentration
37% formaldehyde 370, azole compounds 55.
The technical indicator of products therefrom：
Appearance：Brownish black graininess；
Softening point（Ring and ball method）：99~109 DEG C；
Heating loss：≤0.6%；
Free resorcinol：≤4.5%；
Initial steel wire extraction force：≥1300N.
The multicomponent is modified green syt high-performance rubber adhesive and is mainly used in rubber tyre industry, improves rubber compound
Viscosity between composite bed improves processing performance and improves product quality.
Since the high-effective viscosity of product acts on, traditional manual painting sizing process can be eliminated, realizes the large, medium and small wheel in China
The linkage and automation of calendering-severing-fitting-moulding process of tire factory improve technological level and labor capacity.
Using styrene（Or derivative）Part aralkyl glycosylation reaction is carried out to resorcinol, greatly reduces free isophthalic
The content of diphenol (between 3-5%), hence it is evident that less than the free resorcinol content 8% of common resorcinol formaldehyde resin, overcome
The smoke pollution of resorcinol, loss of weight problem；And hydrophobic group is introduced in product structure（Styryl）, it is not easy to it inhales
Moisture is received, between heating loss 0.2-0.4%, and the heating loss of general methylene receptor adhesive will be far above 1%, solution
It has determined the moisture absorption agglomeration problems of resorcinol, therefore will not generate that charging is difficult and damage automatic blending in the application link of product
Phenomena such as system.
Preferably use methyl cyclopentadiene（Or other alkadienes）Part alkylation reaction modification, production are carried out to resorcinol
It at least compared with phenylethene modified resorcinol acceptor is applied alone, is effectively improved containing diene structure modified body in product structure
Intermiscibility between rubber, significantly improves the binding force between rubber material and steel cord, steel wire extraction force and adhesion strength
Etc. indexs show and can improve more than 10%；In addition, gained resin structure is reasonable, it is fine using rear stability.
In technical process, effectively modification of the control to 2,4,6 three reflecting points of resorcinol is sufficiently reserved methylene
Ability to accept carries out the modified skill of novelty of partial ethers reaction using the phenolic hydroxyl group position to resorcinol with azole compounds
Art further eliminates free resorcinol, can be reduced between 0-3%, even without the free resorcinol of detection；
And using the azole compounds of etherified response function group, high molecular polymer will not be formed in etherification procedure,
Contain azoles heterocycle structure in the molecular structure, the bonding force of resin is stronger.
Claims (2)
1. multicomponent is modified green syt high-performance rubber adhesive, which is characterized in for preparing gained by following methods：
（1）Resorcinol is first added to molten-bath, heating melting, temperature adds in catalyst, start stirring at 125-135 DEG C；
（2）Styrene and alkadienes is added dropwise into molten-bath respectively, temperature is controlled between 125-135 DEG C, and time control is 60
~120 minutes, after being added dropwise, keep 125-138 DEG C of temperature, insulation reaction 1 hour；
（3）Reaction product is transferred to condensation kettle, and formaldehyde is added dropwise into condensation kettle, and temperature is controlled between 130-95 DEG C, time control
System was at 60~120 minutes；
（4）After reaction, lye is added to carry out neutralization pH value=7；
（5）Reaction system heats up, and carries out air-distillation, and temperature starts to be evaporated under reduced pressure at 155-165 DEG C；Vacuum during vacuum distillation
In >=0.08Mpa, temperature is 165 ± 10 DEG C for degree control；
（6）It adds in catalyst and adds in azole compounds, etherification reaction of leaveing neutralizes；
（7）Softening point is surveyed in sampling, is controlled between 99~109 DEG C, vacuum time should be extended by being such as not achieved 99 DEG C.
2. multicomponent according to claim 1 is modified green syt high-performance rubber adhesive, it is characterised in that：Each raw material
Dosage be according to mass fraction：Resorcinol 900, styrene 265, alkadienes 265,37% formaldehyde 370 of mass concentration, azole
Compound 55.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399237.1A CN108192060A (en) | 2017-12-22 | 2017-12-22 | Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711399237.1A CN108192060A (en) | 2017-12-22 | 2017-12-22 | Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof |
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| CN108192060A true CN108192060A (en) | 2018-06-22 |
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| CN201711399237.1A Pending CN108192060A (en) | 2017-12-22 | 2017-12-22 | Multicomponent is modified green syt high-performance rubber adhesive and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791241A (en) * | 2019-09-19 | 2020-02-14 | 江苏国立化工科技有限公司 | Preparation method of resorcinol adhesive with high adhesion for tires |
| CN116376468A (en) * | 2023-04-11 | 2023-07-04 | 江苏国立化工科技有限公司 | Optimized production process and equipment of resorcinol rubber adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338014A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Resorcin phenolic resins |
| CN101338028A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Method for preparing resorcinol resins |
| CN103113541A (en) * | 2012-12-19 | 2013-05-22 | 山东沾化奥仕化学有限公司 | Resorcinol aldehyde resin formed by modification of olefin and aromatic hydrocarbon and production process thereof |
| CN103183799A (en) * | 2011-12-30 | 2013-07-03 | 江苏国立化工科技有限公司 | Alkyl phenolic resin rubber tackifier and preparation method |
-
2017
- 2017-12-22 CN CN201711399237.1A patent/CN108192060A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338014A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Resorcin phenolic resins |
| CN101338028A (en) * | 2007-09-21 | 2009-01-07 | 江苏国立化工科技有限公司 | Method for preparing resorcinol resins |
| CN103183799A (en) * | 2011-12-30 | 2013-07-03 | 江苏国立化工科技有限公司 | Alkyl phenolic resin rubber tackifier and preparation method |
| CN103113541A (en) * | 2012-12-19 | 2013-05-22 | 山东沾化奥仕化学有限公司 | Resorcinol aldehyde resin formed by modification of olefin and aromatic hydrocarbon and production process thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791241A (en) * | 2019-09-19 | 2020-02-14 | 江苏国立化工科技有限公司 | Preparation method of resorcinol adhesive with high adhesion for tires |
| CN116376468A (en) * | 2023-04-11 | 2023-07-04 | 江苏国立化工科技有限公司 | Optimized production process and equipment of resorcinol rubber adhesive |
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Application publication date: 20180622 |