CN105866172B - A kind of measuring method of double imide class vulcanizing agent - Google Patents
A kind of measuring method of double imide class vulcanizing agent Download PDFInfo
- Publication number
- CN105866172B CN105866172B CN201610250687.3A CN201610250687A CN105866172B CN 105866172 B CN105866172 B CN 105866172B CN 201610250687 A CN201610250687 A CN 201610250687A CN 105866172 B CN105866172 B CN 105866172B
- Authority
- CN
- China
- Prior art keywords
- vulcanizing agent
- double imide
- imide class
- carbon atom
- class vulcanizing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4873—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a flowing, e.g. gas sample
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- 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
-
- 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
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- 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
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of test methods of double imide class vulcanizing agent, shown in the structure such as formula (I) of double imide class vulcanizing agent.This test method is the exothermic heat of reaction situation with differential scanning calorimetry test double imide class compound and sulphur under the action of vulcanizing activator zinc oxide, stearic acid and vulcanization accelerator.The reactivity and the extent of reaction that the double imide class vulcanizing agent of different structure can be distinguished by comparing the exothermic maximum temperature at exothermic heat of reaction peak and the peak area of exothermic peak, can also further speculate anti-reversion behaviour of these substances after the vulcanization of rubber is reverted.Wherein, R1Selected from carbon atom number be 1~10 straight-chain alkyl-sub, carbon atom number be 2~10 the alkylidene with branch, carbon atom number be 7~20 alkaryl or aralkyl；R2、R3、R4、R5It is identical or different, it is independently selected from the straight chain that hydrogen, carboxyl, aldehyde radical, carbon atom number are 1~5 or one of the aryl that the alkyl with branch, carbon atom number are 6~20.
Description
Technical field
The invention belongs to analyze testing field, and in particular to one kind tests double imide by differentia scanning calorimetry
Class vulcanizing agent and sulfur reaction inhale exothermic method to analyze the chemical activity of double imide class vulcanizing agent.
Background technique
The sulfidation of natural rubber is an extremely complex multiple elements chemical reaction, including vulcanizing activator, sulphur
Change promotor, the interaction between sulphur, the effect of rubber macromolecule and sulphur, effect and friendship between rubber macromolecule
Join the reaction such as shortization, rearrangement, cracking, backbone modification that key occurs.Sulfur cross-linking system effect under, in vulcanizate cross-linked network with
Based on polysulfide crosslink bond.
The main reason for caoutchouc vulcanization reverts first is that backbone modification occurs for polysulfide bond cracking, form it is a large amount of altogether
Yoke diene and triolefin, according to the Diels-Alder response feature of conjugated alkene, the compound with imide group symmetrical structure
Diels-Alder can occur with conjugated alkene to react, so that imide analog compounds can be by the cross-bond being newly broken " suture "
Get up, makes up the reduction of cross-bond.Perkalink 900 is Flexsys Products, chemical name 1,3- (lemon health imines
Methyl) benzene.Perkalink900 reacts " suture " of conjugated alkene when thermal degradation occurs in vulcanizate, forms new
The biggish carbon-carbon crosslink of rigidity, exactly because this newly generated carbon-carbon crosslink is compensated crosslink density,
And play the role of anti-recovery.
The structure of bismaleimide amine compound is similar with Perkalink 900, can also occur and Perkalink
900 similar Diels-Alder reactions.But the end group ratio Perkalink 900 of bismaleimide amine substance has lacked one
A methyl.
Liu ancestral is extensively equal, and (penylene bismaleimide is in the common sulphur of natural rubber between Liu Zuguang, Chen Chaohui, Wang Dizhen .N, N-
Application [J] synthesis material aging and application in sulphur vulcanizing system, 2003,32 (1): 12-15) HVA-2 is had studied in rubber sulphur
The mechanism of action during change.The N of DuPont Corporation, HVA-2 system production, the trade name of N '-penylene bismaleimide
Claim, also known as PDM.In the NR sizing material of the sulfur cross-linking system containing PDM, vulcanization reaction is extremely complex.In sulfide cross-linked bond
It is formed, in shortization and the thermal cracking competed therewith, decomposition and rearrangement and other change procedures, it is possible to create have promotor-sulphur
A variety of freedom such as free radical, rubber macromolecule free radical, sulphur free radical and promotor-sulphur free radical that side hanging group generates
Base.Two end group double bonds that these free radicals can trigger PDM are opened, and the cross-linking reaction of sizing material is participated in.Similarly,
Similar reaction can also occur for Perkalink 900 and 1,6- dimaleimide base hexane (BMH).
The research dynamic (dynamical) technical method of rubber sulfur cross-linking has differentia scanning calorimetry (i.e. DSC method), oscillation to turn
Sub- vulcameter method and chemical analysis method.DSC has been applied successfully to research high molecular material as a kind of heat analysis method
Physical conversion such as crystallize, melt and glass transition and chemical reaction as polymerization, solidification, crosslinking, oxidation and decompose.In
A kind of experimental method with squalene simulation Vulcanization Process of Rubber is described in state number of patent application CN201610193230.3, is used
DSC tests the reaction in its reaction process and inhales heat release situation, the activity of more different vulcanizing activators.
Summary of the invention
It is an object of the invention to propose a kind of test method of double imide class vulcanizing agent, surveyed with differential scanning calorimetry
Examination double imide class vulcanizing agent inhales heat release situation with reacting for sulphur, and the chemistry of these double imide class vulcanizing agents is judged with this
It is anti-in Vulcanization Process of Rubber to compare different end group structure, the double imide class vulcanizing agent of different carbon chain structure for reactivity
Activity is answered, and speculates anti-reversion behaviour of these double imide class vulcanizing agents after recovery occurs for sizing material.
To achieve the above object, technical solution proposed by the present invention is as follows:
Step 1: sample preparation
(1) double imide class vulcanizing agent is weighed, is added in mortar, the structure such as formula of the double imide class vulcanizing agent
(I) shown in
Wherein:
R1Selected from carbon atom number be 1~10 straight-chain alkyl-sub, carbon atom number be 2~10 the alkylidene with branch,
The alkaryl or aralkyl that carbon atom number is 7~20.
R2、R3、R4、R5It is identical or different, it is independently selected from hydrogen, carboxyl, aldehyde radical, the straight chain that carbon atom number is 1~5
Or one of the aryl that alkyl with branch, carbon atom number are 6~20.
(2) zinc oxide, stearic acid, sulphur, vulcanization accelerator is added, is fully ground, is allowed to and double imide class vulcanizing agent
It is uniformly mixed, vulcanization accelerator can be used selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, two thio
One of Carbamates, aldehyde amines, aldehyde ammonia class, imidazolines, xanthic acid salt are a variety of.
Step 2: differential scanning calorimetry (DSC) is tested
(1) crucible of two similar weights is weighed, for an empty crucible as reference crucible, one is used as sample crucible；
(2) sample prepared in step 1 is added in sample crucible；
(3) reference crucible and sample crucible are put into DSC instrument；
(4) carrier gas is passed through in DSC, the carrier gas is one of nitrogen, helium, argon gas or a variety of, carrier gas purge air-flow
Speed is 20~80mL/min；
(5) DSC test condition is set: setting Range of measuring temp and heating rate.
Step 3: DSC atlas analysis, finds out the exothermic peak in DSC map, mark temperature corresponding to exothermic maximum peak or
Time.
Wherein, zinc oxide dosage described in step 1 is the 5%~20% of double imide class vulcanizing agent quality, preferably
10%~15%；The stearic acid dosage is the 1%~10% of double imide class vulcanizing agent quality, preferably 4%~6%.Oxygen
To change zinc and stearic acid is vulcanizing activator, the two interaction generates zinc stearate, and forms complex compound with promotor effect,
Vulcanization accelerator and sulphur have been activated, reaction efficiency is improved.
Sulfur consumption described in step 1 is the 1%~10% of double imide class vulcanizing agent quality, preferably 2%~8%.
Sulphur is crosslinked with double imide class vulcanizing agent and is reacted after vulcanizing activator open loop, and it is heat release that DSC, which tests the reaction,
Reaction.Double imide class vulcanizing agent can be distinguished by the exothermic maximum temperature of exothermic peak and the size of exothermic peak peak area
Reactivity and the extent of reaction.
Vulcanization accelerator dosage described in step 1 is the 1%~30% of double imide class vulcanizing agent quality, preferably
10%~20%.The dosage of vulcanization accelerator is greater than sulfur consumption in the present invention, and the amount for increasing vulcanization accelerator can make sulphur
Sulphur chain length shortens after open loop, increases the reactivity of sulphur, enhances the exothermic heat of reaction of double imide class vulcanizing agent and sulphur.Vulcanization promotees
N cyclohexyl 2 benzothiazole sulfenamide (CBS), N oxydiethylene 2 benzothiazole sulfenamide are selected from into agent
(NOBS), N tert butyl benzothiazole 2 sulfenamide (NS), 2-mercaptobenzothiazole (MBT), dithio-bis-benzothiazole
(MBTS), tetramethyl thiuram disulfide (TMTD), N ' N- dicyclohexyl -2-[4-morpholinodithio base sulfenamide (DZ), hexichol
One of guanidine (DPG) is a variety of.
The preferred nitrogen of DSC carrier gas described in step 2, DSC carrier gas purge air velocity preferably 40~60mL/min.
DSC heating rate described in step 2 is 1~20 DEG C/min, preferably 5~10 DEG C/min.DSC heating rate is got over
Fastly, exothermic heat of reaction peak more lags.Reducing heating rate can take a long time closer to true Vulcanization Process of Rubber.When
So, steady temperature test can also be carried out.
DSC Range of measuring temp described in step 2 is 20 DEG C~250 DEG C, preferably 50~200 DEG C.Selection is suitable to survey
Examination temperature range can save the time, improve testing efficiency.
The present invention studies double imide class vulcanizing agent using sulphur as medium, using DSC, the oxidation in mixture
Zinc, stearic acid and vulcanization accelerator promote sulphur open loop, form sulphur free radical, occur with the double bond of double imide class vulcanizing agent
Reaction, carrys out response situation of the simulated dual acid imide vulcanizing agent in Vulcanization Process of Rubber with this.Double imide is tested by DSC
The suction heat release situation of class vulcanizing agent and sulfur reaction, it can be determined that the reactivity of double imide class vulcanizing agent, it can be further
Judge different end group structure, the double imide class vulcanizing agent of different carbon chain structure participates in the work of vulcanization reaction in sulfidation
Property；Heat release peak size is tested by DSC, it can be determined that crosslinking degree and vulcanization of the double imide class vulcanizing agent in sulfidation
Glue is after reverting, influence to rubber cross network, and then infers its anti-reversion behaviour.
Test method provided by the invention has the advantage that consumption sample amount is small, and sample preparation is simple, and test method is simple,
Test speed is fast, can rapidly judge the chemical activity of double imide class vulcanizing agent, provides for the design of building rubber compound composition formula
Foundation.Meanwhile the physical property measurement result that this test method can also be kneaded with natural rubber is mutually confirmed, and can be to day
The physical property measurement result of right compounding rubber is prejudged, so that physical property measurement is more targeted.
Detailed description of the invention
Fig. 1 is that the DSC test result of Examples 1 to 3 compares figure.Exo expression is exothermic effect in figure.
Specific embodiment
It is right combined with specific embodiments below in order to make those skilled in the art more fully understand technical solution of the present invention
The present invention is described in further detail.It should be pointed out that all similar substitutions and modifications carry out those skilled in the art
Say it is it will be apparent that they are considered as being included in the present invention.
Material: zinc oxide, in reach Xin Pin factory；Stearic acid, safe Ke's brownification；Sulphur, Rongcheng chemical industry；Vulcanization accelerator NS, city
It sells；1,3- (citraconimide ylmethyl) benzene (Perkalink 900), Flexsys；1,6- dimaleimide base hexane
(BMH), N, N '-penylene bismaleimide (PDM), laboratory self-control.
Instrument: differential scanning calorimeter (DSC 1STAReSystem), Mei Tele-support benefit；Assay balance AB204-S,
Plum Teller-support benefit.
Embodiment 1
20.0mg 1 is weighed, 3- (citraconimide ylmethyl) benzene (Perkalink 900) sample is added to agate mortar
In.2.0mg zinc oxide, 1.0mg stearic acid, 1.0mg sulphur, 4.0mg vulcanization accelerator NS are added, the above solid matter is filled
Divide grinding, is allowed to uniformly mixed.
The crucible of two similar weights is weighed, one is used as reference crucible, and one is used as sample crucible.It weighs on 5.0mg
The sample for stating preparation is added in sample crucible.Reference crucible and sample crucible are put into DSC instrument.50mL/ is passed through in DSC
The nitrogen of min flow velocity.DSC test condition is set as 5 DEG C/min of heating rate, and temperature range is 100 DEG C~200 DEG C.
The DSC map measured is shown in attached drawing, Fig. 1.
Embodiment 2,3
Sample preparation methods and DSC test condition are same as Example 1, and specific sample preparation formula is shown in Table 1
1 embodiment of table, 2~3 sample preparation formula (dosage of each component: mg)
| Embodiment 2 | Embodiment 3 | |
| 1,6- dimaleimide base hexane (BMH) | 20.0 | |
| N, N '-penylene bismaleimide (PDM) | 20.0 | |
| Zinc oxide | 2.0 | 2.0 |
| Stearic acid | 1.0 | 1.0 |
| Sulphur | 1.0 | 1.0 |
| Vulcanization accelerator NS | 4.0 | 4.0 |
2 exothermic maximum peak temperature of table
| Exothermic peak, DEG C | Heat release peak area, J/g | |
| Embodiment 1 | 151.0 | 22.14 |
| Embodiment 2 | 148.6 | 192.05 |
| Embodiment 3 | 170.2 | 176.13 |
It can be seen that embodiment 1,2,3 has exothermic heat of reaction peak in Fig. 1 and table 2, illustrate that they can occur with sulphur
Reaction.Embodiment 1,2 exothermic heat of reaction temperature are lower, they are higher with the activity of sulfur reaction, it is easier to react with sulphur.
But the peak area at the exothermic heat of reaction peak of embodiment 2 is significantly greater than Samples EXAMPLE 1, the exothermic heat of reaction degree of embodiment 2 is brighter
It is aobvious.Embodiment 1 is the mixture for containing bis- (citraconimide ylmethyl) benzene (Perkalink 900) of 1,3-, embodiment 2 be containing
There is the mixture of 1,6- dimaleimide base hexane (BMH).The active site of the two and sulfur reaction is the acyl at molecule both ends
Carbon-carbon double bond in imine structure, but a methyl more than on the imide structure of BMH of Perkalink 900, it is extra
This methyl is passivated imide structure, reduces the reactivity of Perkalink 900, influences the anti-of imide structure and sulphur
It answers, so the peak area at 2 exothermic heat of reaction peak of embodiment is greater than embodiment 1.Thus, it is possible to further speculate Perkalink 900
Weak in the extent of reaction in vulcanization of rubber stage and sulphur, the double bond in imide structure does not participate in vulcanization reaction completely.It is remaining
It is anti-that with the conjugated diene generated in rubber molecular chain Diels-Alder can occur for double bond after recovery occurs for vulcanized rubber
It answers, compensates for the loss of cross-bond, play the role of anti-recovery.And BMH does not have this effect of Perkalink 900, by
The heat release peak area of embodiment 2 can be seen that the imide structure of BMH will be with sulfur reaction, acid imide knot in sulfidation
Double bond in structure participates in vulcanization reaction, causes the double bond that BMH is not excessive after recovery Diels-Alder can occur anti-
It answers, the effect of anti-recovery will not be played.The temperature of the exothermic heat of reaction of embodiment 3 is higher, exothermic heat of reaction peak height and it is sharp, say
Bright N, N '-penylene bismaleimide (PDM) are low compared with Perkalink 900 and BMH with sulfur reaction activity.But once
PDM reacts with sulphur, reaction speed faster, it is more efficient, PDM also can as BMH sulfurating stage participate in react, sulphur
Diels-Alder reaction will not occur after reverting for change, will not play the role of anti-recovery.
Comparative example 1
Henning S K, Shapot S A.Multifunctional acrylates as anti-reversion
Agents in sulfur cured systems [J] .Rubber World, 2006,62 (9): 442-447.
Comparative example 1 is that Henning S K etc. compares 1,3- (citraconimide ylmethyl) benzene (CIMB in rubber compounding
Or Perkalink 900) and N, N '-penylene bismaleimide (PDM) difference.Wherein, the M of Perkalink 900HWith
Reference sizing glue material is suitable, and torque does not change over time and changes.The M of PDMHMaximum, torque sharp fall after over cure.MHIt says greatly
Bright PDM and rubber cross-linking effect under the action of sulphur are good, are crosslinked more, and the variation of torque, which then can reflect out, after over cure resists
The effect of recovery.Clearly torque does not change over time and changes after the sizing material over cure containing Perkalink 900, sulfur resistive
It is good to change effect of reverting；Torque sharp fall after sizing material over cure containing PDM, anti-recovery effect are poor.Henning S K etc.
Rubber compounding test result it is consistent with the DSC conclusion that obtains of test and its inference in the present invention.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (7)
1. a kind of test method of double imide class vulcanizing agent, which is characterized in that the described method comprises the following steps:
Step 1: sample preparation
(1) double imide class vulcanizing agent is weighed, is added in mortar, structure such as formula (I) institute of the double imide class vulcanizing agent
Show
Wherein:
R1Selected from carbon atom number be 1~10 straight-chain alkyl-sub, carbon atom number be 2~10 the alkylidene with branch, carbon atom
The alkaryl or aralkyl that number is 7~20；
R2、R3、R4、R5It is identical or different, it is independently selected from hydrogen, carboxyl, aldehyde radical, the straight chain that carbon atom number is 1~5 or has
One of the alkyl of branch, aryl that carbon atom number is 6~20；
(2) zinc oxide, stearic acid, sulphur, vulcanization accelerator is added, is fully ground, is allowed to mix with double imide class vulcanizing agent
Uniformly；The vulcanization accelerator is selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, aminodithioformic acid
One of salt, aldehyde amines, aldehyde ammonia class, imidazolines, xanthic acid salt are a variety of；
Step 2: differential scanning calorimetry is tested
(1) crucible of two similar weights is weighed, for an empty crucible as reference crucible, one is used as sample crucible；
(2) sample prepared by step 1 is added in sample crucible；
(3) reference crucible and sample crucible are put into differential scanning calorimeter；
(4) carrier gas is passed through in differential scanning calorimeter, the carrier gas is one of nitrogen, helium, argon gas or a variety of, and carrier gas is blown
Sweeping air velocity is 20~80mL/min；
(5) differential scanning calorimeter test condition is set: setting Range of measuring temp and heating rate；
Step 3: differential scanning calorimeter atlas analysis, finds out the exothermic peak in map, temperature corresponding to exothermic maximum peak is marked
Degree or time；
In the step 1 (2), zinc oxide dosage is the 5%~20% of double imide class vulcanizing agent quality, and stearic acid dosage is
The 1%~10% of double imide class vulcanizing agent quality, sulfur consumption are the 1%~10% of double imide class vulcanizing agent quality, sulphur
Change 1%~30% that accelerator dosage is double imide class vulcanizing agent quality.
2. test method according to claim 1, which is characterized in that the zinc oxide dosage is preferably double imide class
The 10%~15% of vulcanizing agent quality, stearic acid dosage are preferably the 4%~6% of double imide class vulcanizing agent quality, and sulphur is used
Amount is preferably the 2%~8% of double imide class vulcanizing agent quality, and vulcanization accelerator dosage is preferably double imide class vulcanizing agent matter
The 10%~20% of amount.
3. test method according to claim 1, which is characterized in that the vulcanization accelerator is selected from N- cyclohexyl -2-
Benzothiazole sulfenamide, N oxydiethylene 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide,
2-mercaptobenzothiazole, dithio-bis-benzothiazole, tetramethyl thiuram disulfide, N ' N- dicyclohexyl -2-[4-morpholinodithio
One of base sulfenamide, diphenylguanidine are a variety of.
4. test method according to claim 1, which is characterized in that the preferred nitrogen of carrier gas described in step 2.
5. test method according to claim 1, which is characterized in that carrier gas purge air velocity described in step 2 is excellent
Select 40~60mL/min.
6. test method according to claim 1, which is characterized in that Range of measuring temp described in step 2 is 20 DEG C
~250 DEG C, heating rate is 1~20 DEG C/min.
7. test method according to claim 6, which is characterized in that preferably 50~200 DEG C of the Range of measuring temp, rise
Warm speed preferably 5~10 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610250687.3A CN105866172B (en) | 2016-04-22 | 2016-04-22 | A kind of measuring method of double imide class vulcanizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610250687.3A CN105866172B (en) | 2016-04-22 | 2016-04-22 | A kind of measuring method of double imide class vulcanizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105866172A CN105866172A (en) | 2016-08-17 |
| CN105866172B true CN105866172B (en) | 2019-05-10 |
Family
ID=56632692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610250687.3A Active CN105866172B (en) | 2016-04-22 | 2016-04-22 | A kind of measuring method of double imide class vulcanizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105866172B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689912A (en) * | 2018-07-30 | 2018-10-23 | 山东阳谷华泰化工股份有限公司 | A kind of multifunctional rubber chemicals and its preparation process |
| CN112630262B (en) * | 2020-12-22 | 2023-12-22 | 华东理工大学 | Test method for detecting activity of vulcanization activator |
| CN113512057B (en) * | 2021-07-20 | 2022-09-20 | 山东阳谷华泰化工股份有限公司 | Bismaleimide propyl diethoxysilane, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618830A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Epoxy resin containing double bonds and curing system |
| CN101553287A (en) * | 2006-10-17 | 2009-10-07 | 费尔斯通聚合物有限责任公司 | Elastomers, process for preparation, and uses thereof |
| CN101996272A (en) * | 2010-10-28 | 2011-03-30 | 江苏科技大学 | Method for simulating vulcanization process of rubber product |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3563962A (en) * | 1967-12-13 | 1971-02-16 | Stauffer Chemical Co | Rubber vulcanization agents and methods for their preparations |
-
2016
- 2016-04-22 CN CN201610250687.3A patent/CN105866172B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618830A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Epoxy resin containing double bonds and curing system |
| CN101553287A (en) * | 2006-10-17 | 2009-10-07 | 费尔斯通聚合物有限责任公司 | Elastomers, process for preparation, and uses thereof |
| CN101996272A (en) * | 2010-10-28 | 2011-03-30 | 江苏科技大学 | Method for simulating vulcanization process of rubber product |
Non-Patent Citations (2)
| Title |
|---|
| 差示扫描量热仪在橡胶配方研究中的应用;谭亮红;《特种橡胶制品》;20020331;52-55 |
| 甲基丙烯酸镁增强EVM的硫化反应动力学;杜爱华;《2002年全国橡胶产品性能评价技术研讨会论文集》;20021231;96-99 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105866172A (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105866172B (en) | A kind of measuring method of double imide class vulcanizing agent | |
| TWI618738B (en) | Methods for crosslinking polymer compositions in the presence of atmospheric oxygen | |
| Dondi et al. | The mechanisms of the sulphur-only and catalytic vulcanization of polybutadiene: An EPR and DFT study | |
| BR112012023427B1 (en) | PNEUMATIC UNDERSTANDING AT LEAST ONE RUBBER COMPOSITION BASED ON AT LEAST ONE DIENIC ELASTOMER, AND, PROCESS TO PREPARE A RUBBER COMPOSITION FOR PNEUMATIC BASED ON AT LEAST ONE DIENE ELASTOMER | |
| EP0080451A1 (en) | Method and composition for diene rubber treatment | |
| BR112019012867B1 (en) | PNEUMATIC FOR A VEHICLE THAT HOLDS HEAVY LOADS INCLUDING A NEW TREADMILL | |
| BR112012006015B1 (en) | PROCESS FOR PRODUCTION OF NITRIL RUBBER, NITRIL RUBBER, VOLCANIZABLE MIXTURES, PROCESS FOR PRODUCTION OF VOLCANIZED, AND VULCANIZED | |
| US20210179821A1 (en) | Elastomeric composition and vulcanization accelerator used therein | |
| CN105928971B (en) | A kind of measuring method of more esters of acrylic acid vulcanizing agents | |
| JPS6151041A (en) | Rubber composition | |
| Heideman et al. | Multifunctional additives as zinc-free curatives for sulfur vulcanization | |
| JPS6323942A (en) | Rubber composition | |
| US2421352A (en) | Substituted thiocarbamo sulfenamides | |
| ES2266180T3 (en) | PIRIMIDINE DERIVATIVES AS HARDNESS STABILIZERS. | |
| JP2914733B2 (en) | Sulfenimide compound having heterocyclic thiol group and rubber composition containing the compound | |
| Barbera et al. | Serinol derivatives for the sustainable vulcanization of diene elastomers | |
| US2381392A (en) | Vulcanization accelerator | |
| JPH0468042A (en) | Rubber composition | |
| US3895060A (en) | Cycloalkylthio (nitro substituted) aniline compounds | |
| US3264254A (en) | Reacting vulcanizable elastomers with dinitrosoanilines | |
| KR100196885B1 (en) | Sulfur vulcanizable rubber compositions containing n,n'-(m-phenylene)bismaleimide | |
| EP1335900B1 (en) | Alkylthio- and aryl(heteroyl)thio-substituted p-phenylenediamines, their manufacture and their use in rubber | |
| Rostek et al. | Novel Sulfur vulcanization accelerators based on mercapto-pyridine,-pyrazine, and-pyrimidine | |
| BR102018074447A2 (en) | silane mixtures and processes for their preparation | |
| RU2693771C1 (en) | Use of n,n-(propane-1,3-dil)bis(1,7,7-trimethylbicyclo[2,2,1] heptane-2-imine) as vulcanization accelerator for rubber mixtures based on rubber of general purpose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |