CN105866172A - Method for testing bisimide vulcanizing agent - Google Patents
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Abstract
The invention discloses a method for testing a bisimide vulcanizing agent. A structure of the bisimide vulcanizing agent is as shown in a formula (I). According to the testing method, the reaction exothermal condition of a bisimide compound and sulphur under the action of a vulcanization activator zinc oxide, stearic acid and a vulcanization accelerator is tested by differential scanning calorimetry. By comparing the highest exothermal temperatures of reaction exothermal peaks and peak areas of the exothermal peaks, reactivity and reaction degrees of the bisimide vulcanizing agents with different structures can be distinguished, and anti-reversion behaviors of the substances after rubber reversion can be further speculated. With reference to the chemical formula in the description, R1 is selected from straight-chain alkylidene of which the carbon atom number is 1 to 10, alkylidene with a branched chain, of which the carbon atom number is 2 to 10, and alkaryl or aralkyl of which the carbon atom number is 7 to 20; R2, R3, R4 and R5 are the same or different, and are respectively and independently selected from one of hydrogen, carboxyl, aldehyde, alkyl with a straight chain or a branched chain, of which the carbon atom number is 1 to 5, and aryl of which the carbon atom number is 6 to 20.
Description
Technical field
The invention belongs to analyze field tests, be specifically related to a kind of method by differentia scanning calorimetry test double imide class vulcanizing agent with sulfur reaction suction heat release and analyze the chemism of double imide class vulcanizing agent.
Background technology
The sulfidation of natural rubber is an extremely complex multiple elements chemical reaction, including the interaction between vulcanizing activator, vulcanization accelerator, sulfur, shortization that the effect of rubber macromolecule and sulfur, effect between rubber macromolecule and cross-bond occur, reset, crack, the reaction such as backbone modification.Under sulfur cross-linking system effect, based on polysulfide crosslink bond in vulcanizate cross-linked network.
The one of the main reasons that caoutchouc vulcanization reverts is that polysulfide bond cracking occurs backbone modification, define substantial amounts of conjugated diene and triolefin, Diels-Alder response feature according to conjugated alkene, the compound with imide group symmetrical structure can occur Diels-Alder to react with conjugated alkene, thus the cross-bond newly ruptured can " be sewed up " by imide analog compounds, makes up the minimizing of cross-bond.Perkalink 900 is Flexsys Products, and chemical name is 1,3-(lemon health formimino group) benzene.Perkalink900 is when thermal degradation occurs in vulcanizate, " stitching " of conjugated alkene is reacted, define the carbon-carbon crosslink that new rigidity is bigger, exactly because this newly generated carbon-carbon crosslink makes crosslink density be compensated, and serve the effect of anti-recovery.
The structure of bismaleimide aminated compounds is similar with Perkalink 900, it is also possible to occur the Diels-Alder similar with Perkalink 900 to react.But the end group ratio Perkalink 900 of bismaleimide amine material has lacked a methyl.
(the Liu Zuguang such as Liu Zu Guang, Chen Chaohui, Wang Di treasure .N, penylene BMI application [J] in natural rubber common sulfur cross-linking system between N-. synthesis material aging and application, 2003,32 (1): 12-15) have studied the HVA-2 mechanism of action in Vulcanization Process of Rubber.The trade name of the N, N ' that du pont company of HVA-2 system a produces-penylene BMI, also known as PDM.In the NR sizing material of the sulfur cross-linking system containing PDM, vulcanization reaction is extremely complex.Sulfide cross-linked bond formation, shortization and the thermal cracking competed therewith, decompose and reset and in other change procedure, it is possible to create have the multiple free radicals such as free radical, rubber macromolecule free radical, sulfur free radical and accelerator-sulfur free radical that accelerator-sulfur pendant group generates.These free radicals can cause two end group double bonds of PDM to open, and participates in the cross-linking reaction of sizing material.Similarly, the reaction that Perkalink 900 and 1,6-dimaleimide base hexane (BMH) can also be similar to.
The research dynamic (dynamical) technical method of rubber sulfur cross-linking has differentia scanning calorimetry (i.e. DSC method), oscillating rotor vulcameter method and chemical analysis method.DSC has been applied successfully to the physical conversion studying macromolecular material such as crystallization, melted and glass transition and chemical reaction and has such as been polymerized, solidifies, cross-links, aoxidizes and decomposition etc. as a kind of heat analysis method.Chinese Patent Application No. CN201610193230.3 describes the experimental technique of a kind of Squalene simulation Vulcanization Process of Rubber, tests the reaction in its course of reaction with DSC and inhale heat release situation, the activity of the most different vulcanizing activators.
Summary of the invention
It is an object of the invention to propose the method for testing of a kind of double imide class vulcanizing agent, heat release situation is inhaled with the reaction of differential scanning calorimetry test double imide class vulcanizing agent with sulfur, the chemical reactivity of these double imide class vulcanizing agents is judged with this, the relatively double imide class vulcanizing agent reactivity in Vulcanization Process of Rubber of different end group structure, different carbon chain structure, and speculate these double imide class vulcanizing agent anti-reversion behaviour after sizing material generation recovery.
For achieving the above object, the technical scheme that the present invention proposes is as follows:
Prepared by step one, sample
(1) weigh double imide class vulcanizing agent, join in mortar, shown in the structure such as formula (I) of described double imide class vulcanizing agent
Wherein:
R1Selected from the straight-chain alkyl-sub-that carbon number is 1～10, carbon number be 2～10 the alkylidene with side chain, carbon number be 7～20 alkaryl or aralkyl.
R2、R3、R4、R5Identical or different, it is independently selected from hydrogen, carboxyl, aldehyde radical, carbon number are the straight chain of 1～5 or alkyl, the carbon number with side chain is the one in the aryl of 6～20.
(2) zinc oxide, stearic acid, sulfur, vulcanization accelerator are added, it is fully ground, be allowed to mix homogeneously with double imide class vulcanizing agent, vulcanization accelerator can use selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, dithiocarbamates, aldehyde amines, aldehyde ammonia class, imidazolines, xanthates apoplexy due to endogenous wind one or more.
Step 2, differential scanning calorimetry (DSC) are tested
(1) weighing the crucible of two similar weight, an empty crucible is as reference crucible, and one as sample crucible；
(2) sample of preparation in step one is joined in sample crucible；
(3) reference crucible and sample crucible are put into DSC instrument；
(4) being passed through carrier gas in DSC, described carrier gas is one or more in nitrogen, helium, argon, and carrier gas purge air velocity is 20～80mL/min；
(5) DSC test condition sets: set Range of measuring temp and programming rate.
Step 3, DSC atlas analysis, find out the exothermic peak in DSC collection of illustrative plates, marks the temperature corresponding to exothermic maximum peak or time.
Wherein, the zinc oxide dosage described in step one is the 5%～20% of double imide class vulcanizing agent quality, preferably 10%～15%；Described stearic acid dosage is the 1%～10% of double imide class vulcanizing agent quality, preferably 4%～6%.Zinc oxide and stearic acid are vulcanizing activator, and both interact generation zinc stearate, and define complex with accelerator effect, have activated vulcanization accelerator and sulfur, have improve reaction efficiency.
Sulfur consumption described in step one is the 1%～10% of double imide class vulcanizing agent quality, preferably 2%～8%.Sulfur, after vulcanizing activator open loop, crosslinks reaction with double imide class vulcanizing agent, and it is exothermic reaction that DSC tests this reaction.Reactivity and the extent of reaction of double imide class vulcanizing agent can be distinguished by the exothermic maximum temperature of exothermic peak and the size of exothermic peak peak area.
Vulcanization accelerator consumption described in step one is the 1%～30% of double imide class vulcanizing agent quality, preferably 10%～20%.In the present invention, the consumption of vulcanization accelerator is more than sulfur consumption, and after the amount of increase vulcanization accelerator can make sulfur open loop, sulfur chain length shortens, and increases the reactivity of sulfur, strengthens the exothermic heat of reaction of double imide class vulcanizing agent and sulfur.One or more in N cyclohexyl 2 benzothiazole sulfenamide (CBS), N oxydiethylene 2 benzothiazole sulfenamide (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), diphenylguanidine (DPG) of vulcanization accelerator.
The preferred nitrogen of DSC carrier gas described in step 2, DSC carrier gas purge air velocity preferably 40～60mL/min.
DSC programming rate described in step 2 is 1～20 DEG C/min, preferably 5～10 DEG C/min.DSC programming rate is the fastest, and exothermic heat of reaction peak is the most delayed.Reduce programming rate can closer to real Vulcanization Process of Rubber, but time-consumingly the longest.It is of course also possible to carry out steady temperature test.
DSC Range of measuring temp described in step 2 is 20 DEG C～250 DEG C, preferably 50～200 DEG C.Select suitable Range of measuring temp to save the time, improve testing efficiency.
The present invention is with sulfur as medium, use DSC that double imide class vulcanizing agent is studied, zinc oxide, stearic acid and vulcanization accelerator in mixture promote sulfur open loop, form sulfur free radical, react with the double bond of double imide class vulcanizing agent, carry out simulated dual acid imide vulcanizing agent response situation in Vulcanization Process of Rubber with this.Suction heat release situation by DSC test double imide class vulcanizing agent with sulfur reaction, may determine that the reactivity of double imide class vulcanizing agent, different end group structure can be determined whether, the double imide class vulcanizing agent of different carbon chain structure participates in the activity of vulcanization reaction in sulfidation；Test exothermic peak size by DSC, it can be determined that double imide class vulcanizing agent crosslinking degree in sulfidation and vulcanizate after reverting, its impact on rubber cross network, and then infer its anti-reversion behaviour.
The method of testing that the present invention provides has the advantage that consumption sample amount is little, and sample preparation is simple, and method of testing is simple, and test speed is fast, can judge the chemism of double imide class vulcanizing agent rapidly, provides foundation for the design of building rubber compound composition formula.Meanwhile, this method of testing can also the physical property measurement result mixing with natural rubber mutually be confirmed, and the physical property measurement result that natural rubber is mixing can be carried out anticipation so that physical property measurement is more targeted.
Accompanying drawing explanation
Fig. 1 is the DSC test result comparison diagram of embodiment 1～3.In figure, exo represents it is exothermic effect.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that technical scheme, below in conjunction with specific embodiment, the present invention is described in further detail.It is pointed out that all similar replacements and change apparent to those skilled in the art, they are considered as being included in the present invention.
Material: zinc oxide, Zhong Daxin product factory；Stearic acid, safe Ke's brown；Sulfur, Rongcheng chemical industry；Vulcanization accelerator NS, commercially available；1,3-(citraconimide ylmethyl) benzene (Perkalink 900), Flexsys；1,6-dimaleimide base hexane (BMH), N, a N '-penylene BMI (PDM), laboratory is made by oneself.
Instrument: differential scanning calorimeter (DSC 1STAReSystem), prunus mume (sieb.) sieb.et zucc. Teller-torr benefit；Analytical balance AB204-S, prunus mume (sieb.) sieb.et zucc. Teller-torr benefit.
Embodiment 1
Weigh 20.0mg 1,3-(citraconimide ylmethyl) benzene (Perkalink 900) sample, join in agate mortar.Add 2.0mg zinc oxide, 1.0mg stearic acid, 1.0mg sulfur, 4.0mg vulcanization accelerator NS, above solid matter is fully ground, is allowed to mix homogeneously.
Weigh the crucible of two similar weight, one as reference crucible, one as sample crucible.The sample weighing the above-mentioned preparation of 5.0mg joins in sample crucible.Reference crucible and sample crucible are put into DSC instrument.The nitrogen of 50mL/min flow velocity it is passed through in DSC.DSC test condition is set as 5 DEG C/min of programming rate, and temperature range is 100 DEG C～200 DEG C.
The DSC collection of illustrative plates measured is shown in accompanying drawing, Fig. 1.
Embodiment 2,3
Sample preparation methods is same as in Example 1 with DSC test condition, and concrete sample preparation formula is shown in Table 1
Table 1 embodiment 2～3 sample preparation formula (each amounts of components: mg)
| Embodiment 2 | Embodiment 3 | |
| 1,6-dimaleimide base hexane (BMH) | 20.0 | |
| N, a N '-penylene BMI (PDM) | 20.0 | |
| Zinc oxide | 2.0 | 2.0 |
| Stearic acid | 1.0 | 1.0 |
| Sulfur | 1.0 | 1.0 |
| Vulcanization accelerator NS | 4.0 | 4.0 |
Table 2 exothermic maximum peak temperature
| Exothermic peak, DEG C | Exothermic peak area, J/g | |
| Embodiment 1 | 151.0 | 22.14 |
| Embodiment 2 | 148.6 | 192.05 |
| Embodiment 3 | 170.2 | 176.13 |
Fig. 1 and Biao 2 can be seen that, embodiment 1,2,3 all responds exothermic peak, illustrates that they can react with sulfur.Embodiment 1,2 exothermic heat of reaction temperature is relatively low, and they are higher with the activity of sulfur reaction, it is easier to react with sulfur.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 becomes apparent from.Embodiment 1 is containing 1, and the mixture of double (citraconimide ylmethyl) benzene (Perkalink 900) of 3-, embodiment 2 is containing 1, the mixture of 6-dimaleimide base hexane (BMH).Both avtive spots with sulfur reaction are the carbon-carbon double bonds in the imide structure at molecule two ends, but Perkalink 900 is many individual methyl than on the imide structure of BMH, this methyl additional passivation imide structure, reduce the reactivity of Perkalink 900, affect the reaction of imide structure and sulfur, so the peak area at embodiment 2 exothermic heat of reaction peak is more than embodiment 1.Thus, it is possible to speculate that Perkalink 900 is weak with the extent of reaction of sulfur in the vulcanization of rubber stage further, the double bond in imide structure participates in vulcanization reaction the most completely.The double bond of residual can occur Diels-Alder to react with the conjugated diene of generation in rubber molecular chain after vulcanite generation recovery, compensate for the loss of cross-bond, plays the effect of anti-recovery.And BMH does not has this effect of Perkalink 900, be can be seen that the imide structure of BMH will be with sulfur reaction in sulfidation by the exothermic peak area of embodiment 2, double bond in imide structure participates in vulcanization reaction, cause BMH after recovery not have too much double bond that Diels-Alder can be occurred to react, 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 sharp-pointed, illustrate that N, a N '-penylene BMI (PDM) is low compared with Perkalink 900 and BMH with sulfur reaction activity.But once PDM reacts with sulfur, response speed faster, in hgher efficiency, PDM also can as BMH sulfurating stage participate in reaction, Diels-Alder will not be occurred after recovery to react, anti-recovery effect will not be played.
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 in rubber compounding, 3-(citraconimide ylmethyl) benzene (CIMB or Perkalink 900) and the difference of N, a N '-penylene BMI (PDM).Wherein, the M of Perkalink 900HSuitable with reference sizing material, and moment of torsion does not changes over time and changes.The M of PDMHMaximum, after over cure, moment of torsion significantly declines.MHBig explanation PDM is good with rubber cross-linking effect under the effect of sulfur, cross-links more, and after over cure, the change of moment of torsion then can reflect the effect of anti-recovery.After clearly containing the sizing material over cure of Perkalink 900, moment of torsion does not changes over time and changes, and anti-recovery is effective；After sizing material over cure containing PDM, moment of torsion significantly declines, anti-recovery weak effect.The rubber compounding test result of Henning S K etc. is consistent with the conclusion that DSC test in the present invention draws and inference thereof.
The above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, change or the variation of other multi-forms can also be made on the basis of the above description.Here without also cannot all of embodiment be given exhaustive.All any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, within should be included in the protection domain of the claims in the present invention.
Claims (8)
1. the method for testing of a double imide class vulcanizing agent, it is characterised in that said method comprising the steps of:
Prepared by step one, sample
(1) weigh double imide class vulcanizing agent, join in mortar, shown in the structure such as formula (I) of described double imide class vulcanizing agent
Wherein:
R1It is 7～20 selected from the alkylidene with side chain that the straight-chain alkyl-sub-that carbon number is 1～10, carbon number are 2～10, carbon number
Alkaryl or aralkyl；
R2、R3、R4、R5Identical or different, it is independently selected from hydrogen, carboxyl, aldehyde radical, carbon number are the straight chain of 1～5 or with side chain
Alkyl, carbon number are the one in the aryl of 6～20；
(2) add zinc oxide, stearic acid, sulfur, vulcanization accelerator, be fully ground, be allowed to mix homogeneously with double imide class vulcanizing agent；Described
Vulcanization accelerator selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, dithiocarbamates, aldehyde amines, aldehyde ammonia class,
Imidazolines, xanthates apoplexy due to endogenous wind one or more；
Step 2, differential scanning calorimetry are tested
(1) weighing the crucible of two similar weight, an empty crucible is as reference crucible, and one as sample crucible；
(2) sample prepared by step one is joined in sample crucible；
(3) reference crucible and sample crucible are put into differential scanning calorimeter；
(4) being passed through carrier gas in differential scanning calorimeter, described carrier gas is one or more in nitrogen, helium, argon, carrier gas purge air velocity
It is 20～80mL/min；
(5) differential scanning calorimeter test condition sets: set Range of measuring temp and programming rate；
Step 3, differential scanning calorimeter atlas analysis, find out the exothermic peak in collection of illustrative plates, marks the temperature corresponding to exothermic maximum peak or time.
Method of testing the most according to claim 1, it is characterised in that described zinc oxide dosage is the 5%～20% of double imide class vulcanizing agent quality,
Stearic acid dosage is the 1%～10% of double imide class vulcanizing agent quality, and sulfur consumption is the 1%～10% of double imide class vulcanizing agent quality, and sulfuration promotees
Enter that agent consumption is double imide class vulcanizing agent quality 1%～30%.
Method of testing the most according to claim 2, it is characterised in that described zinc oxide dosage is preferably double imide class vulcanizing agent quality
10%～15%, stearic acid dosage is preferably the 4%～6% of double imide class vulcanizing agent quality, and sulfur consumption is preferably double imide class vulcanizing agent quality
2%～8%, vulcanization accelerator consumption is preferably the 10%～20% of double imide class vulcanizing agent quality.
Method of testing the most according to claim 1, it is characterised in that described vulcanization accelerator selected from N cyclohexyl 2 benzothiazole sulfenamide,
N oxydiethylene 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, 2-mercaptobenzothiazole, dithio-bis-benzothiazole,
One or more in tetramethyl thiuram disulfide, N ' N-dicyclohexyl-2-[4-morpholinodithio base sulfenamide, diphenylguanidine.
Method of testing the most according to claim 1, it is characterised in that the preferred nitrogen of carrier gas described in step 2.
Method of testing the most according to claim 1, it is characterised in that the carrier gas purge air velocity preferably 40～60mL/min described in step 2.
Method of testing the most according to claim 1, it is characterised in that the Range of measuring temp described in step 2 is 20 DEG C～250 DEG C, heat up speed
Degree is 1～20 DEG C/min.
Method of testing the most according to claim 7, it is characterised in that described Range of measuring temp preferably 50～200 DEG C, programming rate is preferred
5～10 DEG C/min.
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Cited By (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 |
| CN112630262A (en) * | 2020-12-22 | 2021-04-09 | 华东理工大学 | Test method for detecting activity of vulcanization activator |
| CN113512057A (en) * | 2021-07-20 | 2021-10-19 | 山东阳谷华泰化工股份有限公司 | Bismaleimide propyl diethoxysilane, and preparation method and application thereof |
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