CN107090099A - A kind of preparation method of rubber protective materials - Google Patents
A kind of preparation method of rubber protective materials Download PDFInfo
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- CN107090099A CN107090099A CN201710447099.3A CN201710447099A CN107090099A CN 107090099 A CN107090099 A CN 107090099A CN 201710447099 A CN201710447099 A CN 201710447099A CN 107090099 A CN107090099 A CN 107090099A
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- tpa
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- terephthalic acid
- stirred continuously
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
Abstract
The present invention relates to a kind of preparation method of rubber protective materials.The main points of preparation method are：（1）Antioxidant MB is dissolved in sodium hydroxide, 2 mercaptobenzimidazole sodium salt solutions are obtained；（2）Terephthalic acid (TPA) is dissolved in sodium hydroxide, terephthalic acid (TPA) sodium salt solution is obtained；（3）By step（1）With（2）Sodium salt solution mixing, obtain mixed liquor；（4）It is stirred continuously down, pre-configured liquor zinci chloridi is added into step（3）In obtained mixed liquor, continue 30 ~ 120min of stirring reaction under 100 ~ 600r/min rotating speed, centrifuge, dry, produce target product.The product that the present invention is obtained has moderate cost, is difficult bloom, influences the characteristics of small, barrier propterty is excellent to elastomeric compound vulcanization characteristics, simultaneously, moreover it is possible to improve the processing characteristics of rubber.
Description
Technical field
Product prepared by the present invention is applied to rubber compounding, and in particular to a kind of rubber that variable valency metal can be prevented to be catalyzed aging
The preparation method of glue protective materials.
Background technology
Rubber and its product during processing, storage and use, can occur because of the comprehensive function of internal and external factor cracking,
The symptoms of aging such as tacky, hardening, softening, efflorescence, discoloration, mildew, finally lose use value.More important aging action
Have：Deterioration by oxidation, heat ageing, ozone aging, fatigue aging, photocatalysis aging and the catalysis aging of 3 heavy metal ion.
Mainly there be the source of heavy metal particles in rubber：（1）It is mixed into rubber and other raw material；（2）Rubber
It is mixed into process；（3）What product was mixed into use.So-called heavy metal ion catalysis aging refers to that copper, iron etc. become
Valence metal ion constitutes redox system in rubber, and they play catalyst in the oxidation reaction, accelerates rubber
Oxidation reaction speed.Thus, need to add metallic passivator in rubber compounding, it is insoluble by complexing or formation
Product suppresses the catalytic action of heavy metal ion.
Antioxidant MB（2-mercaptobenzimidazole）The accelerated ageing effect of poisonous metal particle can effectively be suppressed, meanwhile, it is right
Thermo-oxidative ageing, Weather also have protective action, are a kind of non-pollutings, can be widely used in light, gorgeous color rubber
The age resistor of medium protective benefitses.But, there is price height, solubility little Yi blooms, influence lacking for elastomeric compound vulcanization characteristics in it
Point.
The purpose of the present invention is antioxidant MB to be improved there is provided a kind of moderate cost, be difficult bloom, to elastomeric compound sulphur
Changing characteristic influences less rubber protective materials.
The content of the invention
It is an object of the invention to provide a kind of preparation method of rubber protective materials.The protection material prepared using this method
Material has moderate cost, is difficult bloom, influences the characteristics of small, barrier propterty is excellent to elastomeric compound vulcanization characteristics, simultaneously, moreover it is possible to change
The processing characteristics of kind rubber.
To achieve the above object, the present invention is achieved through the following technical solutions：A kind of rubber protective materials of the present invention
Preparation method, comprise the following steps：
（1）In the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 3% ~ 5% sodium hydroxide solution, treats age resistor
After MB is completely dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
（2）In the case where being stirred continuously, stoichiometrically terephthalic acid (TPA) is added the sodium hydroxide solution that concentration is 1% ~ 10% by relation
In, after terephthalic acid (TPA) is completely dissolved, the activated carbon for accounting for that solution quality percentage composition is 0.3% is added, stirring 15min makes it
It is dispersed then to filter in the solution, obtain the para-phthalic sodium clarified solution through decolouring；
（3）In the case where being stirred continuously, by step（1）With（2）Obtained sodium salt solution is well mixed, and obtains mixed liquor；
（4）It is stirred continuously down, pre-configured liquor zinci chloridi is added into step（3）In obtained mixed liquor, 100 ~
Continue 30 ~ 120min of stirring reaction under 600r/min rotating speed, centrifuge, dry, produce target product.
Further, in step（2）In, terephthalic acid (TPA) is by Waste Polyester through hydrolysis, alcoholysis, acidolysis, alkaline hydrolysis or alcohol alkali
The techniques such as composite degradation are obtained.
In step（4）In, the concentration of liquor zinci chloridi is preferably 40% ~ 60%.
Beneficial effect：The terephthalic acid (TPA) that the present invention is reclaimed using Waste Polyester prepares rubber protective materials, cost of material
It is cheap so that target product price is low compared with antioxidant MB by 20% or so.The introducing of terephthalic acid (TPA) zinc, not only right in target product
Heavy metal particles have good complexing, and stabilizing heavy metal ion lifts the effect of anti-Metal toxicity；And terephthaldehyde
Sour zinc can react with polydiene generates salt cross-bond, improves the defect that antioxidant MB easily migrates bloom.In addition,
The protective materials is because of the introducing of metal salt of terephthalic acid, moreover it is possible to improve the processing characteristics of sizing material, and to elastomeric compound vulcanization characteristics
Substantially without influence.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment., can according to following embodiments
To more fully understand the present invention.Embodiment is not defined to the scope of the present invention.
Embodiment 1
（1）In the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 3% sodium hydroxide solution, treats that antioxidant MB is complete
After fully dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
（2）In the case where being stirred continuously, stoichiometrically terephthalic acid (TPA) is added concentration in 1% sodium hydroxide solution, to treat by relation
After terephthalic acid (TPA) is completely dissolved, the activated carbon for accounting for that solution quality percentage composition is 0.3% is added, stirring 15min makes it uniformly divide
Dissipate in the solution, then filter, obtain the para-phthalic sodium clarified solution through decolouring；
（3）In the case where being stirred continuously, by step（1）With（2）Obtained sodium salt solution is well mixed, and obtains mixed liquor；
（4）It is stirred continuously down, pre-configured mass percent is added into step for 40% liquor zinci chloridi（3）Obtain
In mixed liquor, continue stirring reaction 30min under 100r/min rotating speed, centrifuge, dry, produce target product.
Further, in step（2）In, terephthalic acid (TPA) is by Waste Polyester through hydrolysis, alcoholysis, acidolysis, alkaline hydrolysis or alcohol alkali
The techniques such as composite degradation are obtained.
Embodiment 2
The difference of embodiment 2 and embodiment 1 is：
In step（1）In, in the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 5% sodium hydroxide solution, treats
After antioxidant MB is completely dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
In step（2）In, in the case where being stirred continuously, stoichiometrically terephthalic acid (TPA) is added the hydroxide that concentration is 10% by relation
In sodium solution, after terephthalic acid (TPA) is completely dissolved, the activated carbon for accounting for that solution quality percentage composition is 0.3%, stirring are added
15min makes its dispersed in the solution, then filters, and obtains the para-phthalic sodium clarified solution through decolouring；
In step（4）In, it is stirred continuously down, pre-configured mass percent is added into step for 60% liquor zinci chloridi
（3）In obtained mixed liquor, continue stirring reaction 120min under 600r/min rotating speed, centrifuge, dry, produce target
Product.
Embodiment 3
The difference of embodiment 3 and embodiment 1 is：
In step（1）In, in the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 4% sodium hydroxide solution, treats
After antioxidant MB is completely dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
In step（2）In, in the case where being stirred continuously, stoichiometrically terephthalic acid (TPA) is added the sodium hydroxide that concentration is 5% by relation
In solution, after terephthalic acid (TPA) is completely dissolved, the activated carbon for accounting for that solution quality percentage composition is 0.3% is added, 15min is stirred
Make its dispersed in the solution, then filter, obtain the para-phthalic sodium clarified solution through decolouring；
In step（4）In, it is stirred continuously down, pre-configured mass percent is added into step for 50% liquor zinci chloridi（3）
In obtained mixed liquor, continue stirring reaction 90min under 400r/min rotating speed, centrifuge, dry, produce target product.
Comparative example 1
（1）In the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 3% sodium hydroxide solution, treats that antioxidant MB is complete
After fully dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
（2）It is stirred continuously down, pre-configured mass percent is added into step for 40% liquor zinci chloridi（1）Obtain
In sodium salt solution, continue stirring reaction 30min under 100r/min rotating speed, centrifuge, dry, produce target product.
Experiment 1
Different types of age resistor is applied in tire tread formula, formula used is：NR 100, stearic acid 2, zinc oxide
4th, sulphur 1.2, NOBS 1.6, N220 45, white carbon 8, Si69 0.8, aromatic naphtha 5, protection wax 2, age resistor（Change product
Kind：Zinc salt of 2 mercaptobenzimidazole and antioxidant MB prepared by the age resistor of the preparation of embodiment 1, comparative example 1）1.5；Above-mentioned
On the basis of formula, then extra addition accounts for the copper of mix quality fraction 0.005%.
In two-roll mill, first natural rubber is plasticated, various auxiliary agents are then added, elastomeric compound, Ran Hou is obtained
Vulcanized at 151 DEG C by sulfurizing time, obtain vulcanizing rubber.Tested by national standard, gained performance is as shown in table 1.
Table 1
The data of analytical table 1 can be seen that：（1）Processing characteristics compares：Rubber materials are often with ML sides reflection elastomeric compound processing characteristics
Quality, numerical value is smaller, illustrates that processing characteristics is better；By comparing 4 ML numerical value, protective materials prepared by embodiment 1 changes
It has been apt to the processing characteristics of elastomeric compound；（2）The comparison of vulcanization characteristics：2, formula 3 and MH, T for being formulated 4 will be formulated10、T90With formula 1
Compare, it is known that 2-mercaptobenzimidazole is converted into after zinc salt of 2 mercaptobenzimidazole, the influence to elastomeric compound vulcanization characteristics subtracts
Small, novel protective material prepared by embodiment 1 is on elastomeric compound vulcanization characteristics substantially without influence；（3）Preventing heavy metal particle-catalytic is old
The comparison of change：Before and after the aging tensile strength, elongation change situation and aging coefficient relatively from the point of view of, it is prepared by embodiment 1
Novel protective material have more excellent anti-Metal toxicity effect.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, the present invention
Claimed scope is by appended claims, specification and its equivalent thereof.
Claims (3)
1. a kind of preparation method of rubber protective materials, it is characterised in that comprise the following steps：
（1）In the case where being stirred continuously, stoichiometrically relation adds antioxidant MB in 3% ~ 5% sodium hydroxide solution, treats age resistor
After MB is completely dissolved, 2-mercaptobenzimidazole sodium salt solution is obtained；
（2）In the case where being stirred continuously, stoichiometrically terephthalic acid (TPA) is added the sodium hydroxide solution that concentration is 1% ~ 10% by relation
In, after terephthalic acid (TPA) is completely dissolved, the activated carbon for accounting for that solution quality percentage composition is 0.3% is added, stirring 15min makes it
It is dispersed then to filter in the solution, obtain the para-phthalic sodium clarified solution through decolouring；
（3）In the case where being stirred continuously, by step（1）With（2）Obtained sodium salt solution is well mixed, and obtains mixed liquor；
（4）It is stirred continuously down, pre-configured liquor zinci chloridi is added into step（3）In obtained mixed liquor, 100 ~
Continue 30 ~ 120min of stirring reaction under 600r/min rotating speed, centrifuge, dry, produce target product.
2. the preparation method of rubber protective materials as claimed in claim 1, it is characterised in that terephthalic acid (TPA) is by Waste Polyester
Obtained through techniques such as hydrolysis, alcoholysis, acidolysis, alkaline hydrolysis or alcohol alkali composite degradations.
3. the preparation method of rubber protective materials as claimed in claim 1, it is characterised in that in step（4）In, zinc chloride
The concentration of solution is preferably 40% ~ 60%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710447099.3A CN107090099B (en) | 2017-06-14 | 2017-06-14 | A kind of preparation method of rubber protective materials |
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| CN107090099A true CN107090099A (en) | 2017-08-25 |
| CN107090099B CN107090099B (en) | 2019-03-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922638A (en) * | 2019-12-23 | 2020-03-27 | 常州市五洲环保科技有限公司 | Method for preparing protective material for rubber by recycling textile white mud |
| CN111286080A (en) * | 2020-04-24 | 2020-06-16 | 常州市五洲化工有限公司 | Protective material special for polar rubber and preparation method thereof |
| CN111393665A (en) * | 2020-05-04 | 2020-07-10 | 常州市五好新材料科技有限公司 | Preparation method and application of calcium metal organic framework material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686871A (en) * | 2005-04-23 | 2005-10-26 | 陈一鸣 | Method for preparing antiager from wastewater of alkali weight reduction |
| CN104829879A (en) * | 2015-05-09 | 2015-08-12 | 江苏爱特恩东台新材料科技有限公司 | Method for preparing multifunctional rubber assistant by recycling alkali-weight-reduction processing discharged liquor |
| CN105111064A (en) * | 2015-07-20 | 2015-12-02 | 浙江大学 | Method and device for recovery of terephthalic acid from polyester alkali decrement wastewater |
-
2017
- 2017-06-14 CN CN201710447099.3A patent/CN107090099B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1686871A (en) * | 2005-04-23 | 2005-10-26 | 陈一鸣 | Method for preparing antiager from wastewater of alkali weight reduction |
| CN104829879A (en) * | 2015-05-09 | 2015-08-12 | 江苏爱特恩东台新材料科技有限公司 | Method for preparing multifunctional rubber assistant by recycling alkali-weight-reduction processing discharged liquor |
| CN105111064A (en) * | 2015-07-20 | 2015-12-02 | 浙江大学 | Method and device for recovery of terephthalic acid from polyester alkali decrement wastewater |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922638A (en) * | 2019-12-23 | 2020-03-27 | 常州市五洲环保科技有限公司 | Method for preparing protective material for rubber by recycling textile white mud |
| CN111286080A (en) * | 2020-04-24 | 2020-06-16 | 常州市五洲化工有限公司 | Protective material special for polar rubber and preparation method thereof |
| CN111393665A (en) * | 2020-05-04 | 2020-07-10 | 常州市五好新材料科技有限公司 | Preparation method and application of calcium metal organic framework material |
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| CN107090099B (en) | 2019-03-19 |
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