CN105085981B - A kind of rubber adhesion promotor and its preparation method and application - Google Patents
A kind of rubber adhesion promotor and its preparation method and application Download PDFInfo
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- CN105085981B CN105085981B CN201410201617.XA CN201410201617A CN105085981B CN 105085981 B CN105085981 B CN 105085981B CN 201410201617 A CN201410201617 A CN 201410201617A CN 105085981 B CN105085981 B CN 105085981B
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Abstract
The invention discloses the Multifunctional rubber adhesion promotor shown in a kind of formula (I), the content 15%~25% of its metal ion included, resorcinol content is 0%~9%.The invention also discloses the preparation method of the Multifunctional rubber adhesion promotor and its application in rubber.Adhesion promotor of the present invention has methylene receptor and promoter for binding cobalt salt function simultaneously in the bonding of rubber and framework material, and consumption reduction, efficiency is improved.
Description
Technical field
The present invention relates to the synthesis field of multi-functional adhesion promotor, and in particular to a kind of rubber adhesion promotor and its
Preparation method and application.
Background technology
It is usually resorcinol or resorcinol resin that current rubber industry, which is used for rubber and the material of framework material bonding,
With the system such as m- first-cobalt of the organic acid cobalt such as new cobalt decanoate or cobalt naphthenate composition or m- first-white-cobalt.Due to isophthalic two
Phenol easily distils, and often discharges a large amount of poisonous volatile matters into air in use, harm is brought to environment and workers ' health.Isophthalic
Although two phenol resin reduce the vapour pressure of resorcinol, are difficult distillation, but the production of resins technical difficulty is larger, has to equipment
Certain to require, cost is higher.The use of rubber industry cobalt salt is transitioned into organic acid cobalt, traditional organic acid cobalt from inorganic cobalt
Salt refers to more in conventional technical patent, for example：Chinese patent CN200310105264.5 proposes straight using organic acid
Connect the technique for preparing cobalt salt with basic cobaltous carbonate reaction.Chinese patent CN201110189532.0 puts forward using tall oil, firmly
The method that the fatty acid mixeds such as resin acid prepare cobalt salt with cobalt hydroxide reaction.Chinese patent CN200710013046.7 proposes one
Plant the method that cobalt salt compound is prepared with cobalt hydroxide reaction using capric acid, mixing valeric acid, mixing second propionic acid etc..Chinese patent
CN201110145768.4 is proposed prepares promoter for binding cobalt salt with cobalt salt solution metathesis reaction using organic acid is saponified
Method.Chinese patent CN200910235112.4 is proposed using floating oil fatty acid as the side of Material synthesis ready denier oil acid cobalt
Method.United States Patent (USP) US5021522 describes a kind of synthetic method of modified resorcinol formaldehyde resin.Chinese patent
CN1726254A proposes a kind of synthetic method of the resorcinol formaldehyde resin of phenol or modified by alkyl phenol.Above invention is
There is the preparation of single performance material for synthesis organic acid cobalt or resorcinol resin etc..It can only be embodied in rubber applications
Simple function.
The content of the invention
The present invention overcomes the deficiencies in the prior art, and there is provided a kind of new rubber adhesion promotor, its structure such as formula (I)
It is shown,
In formula (I), R is Co salt, Ni salt, Zn salt etc..
Rubber adhesion promotor of the present invention, the content 15%~25% of its metal ion included, resorcinol content
For 0%~9%.
Rubber of the present invention is Co salt, Ni salt or Zn salt with metal ion described in adhesion promotor, it is preferable that the gold
Category ion is Co.Rubber of the present invention adhesion promotor has double resorcinol type structures, while having resorcinol resin
The adhesion promotion function of methylene receptor and metal salt.Wherein, the metal salt includes cobalt salt, nickel salt, zinc salt etc..It is preferred that
Ground, cobalt salt refers to the one or more therein such as cobalt acetate, cobaltous sulfate, cobalt chloride cobalt.
Rubber of the present invention is a kind of bisphenol type metal salt, i.e. resorcinol type metal salt with adhesion promotor, in use
Do not distil, no blooming, and there is the dual-use function of adhesion promotion and methylene receptor simultaneously.In the adhesion promotor, two
The presence of valency metal (including divalence cobalt etc.) can promote the generation of transition zone on the framework materials such as all-steel cord, be used for well
The bonding of rubber and framework material.The presence of resorcinol type structure may also serve as methylene receptor, improve rubber
Crosslink density, with rubber formation interpenetrating networks, the bonding force of enhancing rubber and framework material.So as to play existing two kinds of raw materials
Some double effectses, substitute resorcinol and its resin and organic acid cobalt salt, reduce raw material dosage, reduce cost.
Present invention also offers the preparation method of rubber adhesion promotor, comprise the following steps：
Step (1)：The reaction generation resorcinol list phenates such as raw material resorcinol and sodium methoxide, caustic alcohol, potassium acetate；
Step (2)：Foregoing resorcinol list phenates continues to react with metal salt, prepares the rubber bonding and promotees
Enter agent.The metal salt includes metal organic salt or metal inorganic salt.The metal refers to divalent metal, including cobalt, nickel, zinc
Deng.
In one specific embodiment, raw material resorcinol reacts with sodium methoxide, and the process of preparation method of the present invention is：Between
Benzenediol reacts in a solvent with sodium methoxide obtains resorcinol list phenates, and the product continues to react in a solvent with cobalt salt to obtain
The precipitation of target product, washing is dried to neutrality and obtains the product.Its reaction equation is：
Wherein, R is Co salt, Ni salt, Zn salt.
In step (1), metal inorganic salt includes lead acetate, cobalt carbonate, cobaltous sulfate, zinc chloride.Preferably, metal inorganic
Salt is acetate.Preferably, metal salt is cobalt salt.Cobalt salt refers to that cobalt acetate, cobaltous sulfate, cobalt chloride etc. are therein a kind of or many
Kind.
In step (1), the mol ratio of raw material resorcinol and sodium methoxide, caustic alcohol or potassium acetate etc. is 1: 1~1: 1.1.
In step (1), solvent is the one or more therein such as methanol, ethanol, toluene, dimethylbenzene, DMF.
In step (1), pH=7~9 of reaction system；Reaction temperature is 70~110 degrees Celsius.
In step (2), the mol ratio of intermediate product resorcinol list phenates and metal salt is 2: 1~5: 1.Preferably, in
Between product resorcinol list phenates and cobalt salt mol ratio be 2: 1~3: 1.
In step (2), reaction temperature is 80~150 degrees Celsius.
Present invention also offers another synthetic route of the preparation method of formula (I) rubber adhesion promotor, including it is following
Step：
Wherein, R is Co salt, Ni salt, Zn salt etc..
Wherein, metal salt includes lead acetate, cobalt carbonate, cobaltous sulfate, zinc chloride.Preferably, metal inorganic salt is acetate.
Preferably, metal salt is cobalt salt.Cobalt salt refers to the one or more therein such as cobalt acetate, cobaltous sulfate, cobalt chloride.
Present invention also offers the intermediate product benzenediol list phenates shown in a kind of formula (II),
In formula (II), R is Na ions, K ions etc..
Present invention also offers application of the Multifunctional rubber adhesion promotor in rubber product is prepared shown in formula (I).
Adhesion promotor of the present invention has methylene receptor and promoter for binding cobalt salt simultaneously in the bonding of rubber and framework material
Function, so as to realize consumption reduction, efficiency is improved.
Raw material resorcinol is generated with one or more reactions in oxide, hydroxide, acylate in the present invention
Single phenates, then generates a kind of mixture of double resorcinol type cobalt salts of specific structure or both by metathesis reaction.With
Prior art is compared, and distillation, no blooming are difficult in use of the invention.Reduce consumption, improve efficiency, reduce it is unknown because
The influence of element.In prior art rubber industry, for rubber and framework material bond be typically resorcinol-formaldehyde resin with
M- first-cobalt system of cobalt salt composition, but above-mentioned substance only has simple function in use.And resorcinol proposed by the present invention
The synthetic method of type metal salt, the material prepared can be while have methylene to connect in the bonding of rubber and framework material
Acceptor and promoter for binding cobalt salt function, so as to substitute original m- first-cobalt system.
Brief description of the drawings
The synthetic route schematic diagram of Fig. 1 preparation methods of the present invention.
Another synthetic route schematic diagram of Fig. 2 preparation methods of the present invention.
Embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection domain.The process of the implementation present invention,
Condition, reagent, experimental method etc., are the universal knowledege and common knowledge of this area in addition to the following content specially referred to,
Content is not particularly limited in the present invention.
Embodiment 1：
110 grams of resorcinols are added in the 500mL four-hole boiling flasks for having nitrogen to protect, 300 grams of absolute methanol is warming up to 70
Degree is entirely molten to start stirring, and 27 grams of sodium methoxides are slowly added to.Flowed back 10 minutes after adding, stratification filters off solvent and washed extremely
PH=6.5~7.Plus 200 grams of anhydrous tetrahydro furan is warming up to 100 degree, the 140 grams of anhydrous cobaltous sulfates pulverized are slow added into, plus
It is kept stirring for after complete 30 minutes, normal pressure sloughs solvent to 120 degree of beginning vacuum distillations.Residue is dried in vacuo, in nitrogen protection
Under be cooled to room temperature, obtain 151.9 grams of reddish brown powder.Identified, product is red-brown powder, has phenyl ring through infrared test
Characteristic absorption peak (1500cm-1,1600cm-1) and phenolic hydroxyl group characteristic absorption peak (3200cm-1) are present.Through elementary analysis, C：
51.0%, H：3.3%, Co：The chemical constitution of 20.1%, the i.e. product：
Embodiment 2：
55 grams of resorcinols, 100 grams of anhydrous tetrahydro furan, heating are added in the 500mL four-hole boiling flasks for having nitrogen to protect
Stirring is started, 25 grams of potassium acetate is slowly added to, continues to react 30 minutes, adjustment pH=6.5~7 are stood.The intermediate product with
62.5 grams of nickel acetates continue to react, and after largely being separated out to salt, suction filtration is simultaneously washed three times with absolute methanol.Vacuum drying 0.5 hour,
Room temperature is cooled under nitrogen protection, about 75 grams of product is obtained.Identified, product is grey powder, has phenyl ring feature through infrared test
Absworption peak (1500cm-1,1600cm-1) and phenolic hydroxyl group characteristic absorption peak (3200cm-1) are present.Through elementary analysis, C：
51.9%, H：3.5%, Co：The chemical constitution of 21.1%, the i.e. product：
Embodiment 3：
55 grams of resorcinols, absolute ethyl alcohol 100mL are added in the 500mL four-hole boiling flasks for having nitrogen to protect.Start stirring
Be warming up to 70 degree it is entirely molten, be slowly added to the 60 grams of cobalt acetates pulverized.Kept for 0.5 hour after adding.Add concentrated ammonia liquor 300mL, 80
Degree is kept for 5 hours, and filtering precipitation is washed with ethanol to neutrality, and room temperature is gradually cooling under nitrogen protection, 73 grams of product is obtained.Through
Identification, product is red-brown powder, has phenyl ring characteristic absorption peak (1500cm-1,1600cm-1) and phenolic hydroxyl group special through infrared test
Absworption peak (3200cm-1) is levied to exist.Through elementary analysis, C：51.0%, H：3.3%, Co：The chemistry knot of 21.0%, the i.e. product
Structure：
Embodiment 4：
55 grams of resorcinols, absolute ethyl alcohol 100mL are added in the 500mL four-hole boiling flasks for having nitrogen to protect.Start stirring
Be warming up to 70 degree it is entirely molten, be slowly added to the 46 grams of zinc acetates pulverized.Kept for 0.5 hour after adding.Add concentrated ammonia liquor 300mL, 80
Degree is kept for 5 hours, and filtering precipitation is washed with ethanol to neutrality, and room temperature is gradually cooling under nitrogen protection, 77.3 grams of product is obtained.
Identified, product is grey powder, has phenyl ring characteristic absorption peak (1500cm-1,1600cm-1) and phenolic hydroxyl group special through infrared test
Absworption peak (3200cm-1) is levied to exist.Through elementary analysis, C：50.1%, H：3.5%, Co：The chemistry knot of 20.3%, the i.e. product
Structure：
Embodiment 5
Using the product of embodiment 1~4, according to table 1 below, 100 parts of natural rubber, N32655 parts, zinc oxide etc. other
Material is begun to pratise certain time after sequentially adding on the machine of beginning to pratise, and formula 1 uses CN20.5%0.5 parts, 3 parts of resorcinol, formula 2
~5 use synthetic sample respectively.Prepare rubber testing formula 1~5.
The rubber testing formula of table 1
The hot air aging (100 DEG C of 24h) of detection formula 1~5, as a result as shown in table 2 below.
The performance difference percentage (%) of table 2
| Detection project | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| 10% is fixed secondary | 100 | 104 | 110 | 106 | 95 |
| 30% is fixed secondary | 100 | 99 | 105 | 104 | 97 |
| 50% is fixed secondary | 100 | 98 | 100 | 105 | 103 |
| 100% is fixed secondary | 100 | 98 | 98 | 105 | 109 |
| Breaking strength | 100 | 105 | 96 | 98 | 99 |
| Pull apart Zhongchang rate | 100 | 106 | 100 | 105 | 97 |
| Hardness | 100 | 103 | 101 | 100 | 108 |
Table 2 illustrates that using standard recipe 1 as calculating benchmark synthetic product has certain performance to match somebody with somebody compared with standard respectively after adding
The test result of side is high, and other test events are more suitable than performance with standard recipe (error within 5%).
The vulcanization characteristics of the sizing material of detection formula 1~5, no rotor sulphur becomes instrument Rheometer MDR2000, testing conditions
160 DEG C of 30min, as a result as shown in table 3 below.
The performance difference percentage (%) of table 3
| Glue number | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| ML | 100 | 98 | 97 | 99 | 100 |
| MH | 100 | 102 | 99 | 100 | 100 |
| T10 | 100 | 98 | 92 | 96 | 100 |
| T50 | 100 | 101 | 94 | 98 | 99 |
| T90 | 100 | 101 | 106 | 103 | 96 |
| TS1 | 100 | 102 | 101 | 102 | 98 |
| TS2 | 100 | 103 | 100 | 103 | 97 |
Table 3 illustrates that sintetics influences little to cure time, and other indexs are suitable.
The sizing material coke burning performance of detection formula 1~5,127 DEG C of Scorch@, as a result as shown in table 4 below.
The performance difference percentage (%) of table 4
| Glue number | Formula 1 | Formula 2 | Formula 3 | Formula 4 | Formula 5 |
| Initial | 100 | 96 | 96 | 94 | 107 |
| Ts2 | 100 | 103 | 103 | 100 | 102 |
| Ts3 | 100 | 102 | 102 | 96 | 107 |
| Ts5 | 100 | 103 | 103 | 98 | 109 |
| Ts35 | 100 | 103 | 103 | 101 | 110 |
Table 4 illustrates that synthetic is slightly longer compared with standard recipe time of scorch, can effectively ensure the security in rubber processing.
All-steel cord bond properties (N) conditions of vulcanization of detection formula 1~5：160℃×30min；Steel cord specification：3+9
+ 15*0.22+1, as a result as shown in table 5 below.
The performance difference percentage (%) of table 5
In the explanation of table 5 formula 2, synthesis material has preferable performance in steam ageing, also has such embodiment in other formulas.Its
His test index is suitable with standard recipe test result.
Above-described embodiment is simply to illustrate that the technical concepts and features of the present invention, in the art general its object is to allow
Logical technical staff can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is every
Equivalent change or modification according to made by the essence of present invention, should all cover within the scope of the present invention.
Claims (8)
1. a kind of rubber adhesion promotor, it is characterised in that shown in its structure such as formula (I),
In formula (I), R is Co bivalent positive ions, Ni bivalent positive ions, Zn bivalent positive ions.
2. a kind of preparation method of rubber adhesion promotor, it is characterised in that the preparation method comprises the following steps：
Step (1)：Raw material resorcinol reacts generation resorcinol list phenol in a solvent with sodium methoxide, caustic alcohol or potassium acetate
Salt；
Step (2)：The resorcinol list phenates continues to react with metal salt, prepares rubber as claimed in claim 1 and uses viscous
Close accelerator.
3. preparation method as claimed in claim 2, it is characterised in that in the step (1), the raw material resorcinol with
The mol ratio of sodium methoxide, caustic alcohol or potassium acetate is 1：1~1：1.1.
4. preparation method as claimed in claim 2, it is characterised in that in the step (1), the solvent is methanol, second
Alcohol, toluene, dimethylbenzene, DMF, THF one or more therein.
5. preparation method as claimed in claim 2, it is characterised in that in the step (2), the resorcinol list phenates
Mol ratio with metal salt is 2：1~5：1.
6. preparation method as claimed in claim 2, it is characterised in that pH=7~9 in the step (1), reaction temperature
For 70~110 degrees Celsius；Reaction temperature in the step (2) is 80~150 degrees Celsius.
7. a kind of preparation method of rubber adhesion promotor, it is characterised in that the preparation method is：Resorcinol and metal
Ammoniacal liquor reaction is continuously added after reactant salt, washing precipitation obtains rubber adhesion promotor as claimed in claim 1；Wherein,
The metal salt is Co salt, Ni salt or Zn salt；The course of reaction of the preparation method is：
Wherein, R is Co bivalent positive ions, Ni bivalent positive ions, Zn bivalent positive ions.
8. application of formula (I) the rubber adhesion promotor as described in claim 1 in rubber product is prepared.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105348459B (en) * | 2015-12-11 | 2017-08-25 | 华奇（中国）化工有限公司 | Abietyl modified resorcinol formaldehyde resin and its preparation method and application |
| CN107459614B (en) * | 2017-08-28 | 2019-07-26 | 上海超程化工科技有限公司 | A kind of environment-friendly type adhesion promotor and preparation method thereof, application |
| CN108102354A (en) * | 2017-12-29 | 2018-06-01 | 中南大学 | A kind of well lid anticorrosion material and preparation method thereof |
| CN109575837B (en) * | 2018-11-28 | 2020-10-23 | 江苏麒祥高新材料有限公司 | Cobalt-free composite metal boroacylate adhesion promoter and preparation method and application thereof |
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| US4163112A (en) * | 1977-04-04 | 1979-07-31 | Velsicol Chemical Corporation | O-alkoxy- and alkylthiophenyl carbamates |
| CN1680247A (en) * | 2005-01-12 | 2005-10-12 | 浙江工业大学 | Preparation of hydroresorcinol |
| CN103074000A (en) * | 2013-01-06 | 2013-05-01 | 北京海斯迪克新材料有限公司 | Novel environmental-friendly double-component acrylate adhesive and preparation method thereof |
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2014
- 2014-05-13 CN CN201410201617.XA patent/CN105085981B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4163112A (en) * | 1977-04-04 | 1979-07-31 | Velsicol Chemical Corporation | O-alkoxy- and alkylthiophenyl carbamates |
| CN1680247A (en) * | 2005-01-12 | 2005-10-12 | 浙江工业大学 | Preparation of hydroresorcinol |
| CN103074000A (en) * | 2013-01-06 | 2013-05-01 | 北京海斯迪克新材料有限公司 | Novel environmental-friendly double-component acrylate adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 对二苯酚铜、钴（II）配合物的合成及表征;宋力等;《信阳师范学院学报：自然科学版》;20131031;第26卷(第4期);第566-568,608页 * |
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