CN105928971B - A kind of measuring method of more esters of acrylic acid vulcanizing agents - Google Patents
A kind of measuring method of more esters of acrylic acid vulcanizing agents Download PDFInfo
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- CN105928971B CN105928971B CN201610250688.8A CN201610250688A CN105928971B CN 105928971 B CN105928971 B CN 105928971B CN 201610250688 A CN201610250688 A CN 201610250688A CN 105928971 B CN105928971 B CN 105928971B
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- 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
Abstract
The invention discloses a kind of test methods of more esters of acrylic acid vulcanizing agents, shown in the structure such as formula (I) of more esters of acrylic acid vulcanizing agents.Sulphur open loop under the collective effect of vulcanization accelerator and vulcanizing activator can measure the heat release situation of reaction with the carbon-carbon double bond cross-linking reaction in acrylate substance, this cross-linking reaction with differential scanning calorimetry.The reactivity and the extent of reaction of cross-linking reaction can be judged by the exothermic maximum temperature and peak area at exothermic heat of reaction peak, come compare different number acrylate structural more esters of acrylic acid vulcanizing agents reactivity.Wherein: R1Selected from carbon atom number be 1~30 straight chained alkyl, carbon atom number be 3~30 the alkyl with branch, carbon atom number be 6~30 one of aromatic radical；R2、R3It is identical or different, it is independently selected from hydrogen, the straight chained alkyl that carbon atom number is 1~5 or carbon atom number are one of 2~5 alkyl with branch；The integer that n is 1~6.
Description
Technical field
The invention belongs to analyze testing field, and in particular to one kind tests more acrylic acid by differentia scanning calorimetry
Esters vulcanizing agent and sulfur reaction inhale exothermic method to analyze the chemical activity of more esters of acrylic acid vulcanizing agents.
Background technique
Natural rubber (NR) is used as a kind of general purpose rubber, has good elasticity and mechanical property, but more in its vulcanizate
The thermal stability of sulfur-crosslinked key is poor, in sulfidation, as heated time extends, and the polysulfide crosslink bond part that originally forms
It can be broken, the crosslink density of sizing material is caused to reduce, the physical property decline of sizing material, the service performance of rubber product reduces.
With the fast development of rubber industry, researcher studies how to eliminate or reduce rubber in sulfidation and use process always
In phenomenon of reverting, while being able to maintain the mechanical performance and service performance of rubber product again, extend the service life of product.
Consider from recovery mechanism, the measure for improving NR anti-reversion behaviour, which mainly passes through, is added sulfur-donor chemical combination
Object or offset-type vulcanizing system are to make up the loss of cross-bond, such as two hydration hexa-methylenes 1,6- bisthiosulfate two is added
Sodium salt (Duralink HTS).Furthermore it is also possible to by be added chemical reagent make it when sizing material reverts and sizing material break
It splits key to chemically react, to form new cross-bond, such as bis- (the lemon acid imide methyl) benzene (PK900) of 1,3- is added.
In the mini exhibition of rubber that Ohio, USA Columbus conference centre in 2004 holds, rubber chemicals manufacturer
It is that one kind is more that Sartomer Company, which is proposed the anti-recovery agent SR534, SR534 for preventing sulfur cross-linking glue from recovery occurs,
Function acrylate, chemical name are pentaerythritol tetraacrylate, and chemical structural formula is as follows:
Acrylate substance is mainly used as the auxiliary curing agent of peroxide vulcanizing system, can participate in free radical initiation
Addition and graft reaction.Contain carbon-to-carbon double bond in acrylate substance, sulphur is total to vulcanization accelerator and vulcanizing activator
Open loop generates organic polysulfide under same-action, and organic polysulfide can be anti-with the carbon-to-carbon double bond in acrylate substance
It answers, this reaction is exothermic reaction, and the heat release situation of reaction can be measured with differential scanning calorimetry (DSC), is put according to reaction
The exothermic maximum temperature and peak area of thermal spike can judge the reactivity and reaction of acrylate substance cross-linking reaction
Degree judges the reactivity of the acrylate structural compound containing different number with this.
Differential scanning calorimeter (DSC) basic functional principle is to change (heating, cooling, constant temperature and its group in program temperature
Close) during, the differential heat flow between sample and reference substance is measured, to characterize physical and chemical changes related with fuel factor.
DSC has been applied successfully to physical conversion such as crystallization, melting and the glass of research high molecular material as a kind of heat analysis method
Change transformation and chemical reaction such as polymerization, solidification, crosslinking, oxidation and decomposes.Chinese patent CN201610193230.3 intermediary
Continued a kind of experimental method with squalene simulation Vulcanization Process of Rubber, tests the reaction in the reaction process with DSC and inhales heat release
Situation, influence of the more different vulcanizing activators to Vulcanization Process of Rubber.
Summary of the invention
The purpose of the present invention is to provide a kind of test methods of more esters of acrylic acid vulcanizing agents, using differential scanning calorimetry
The exothermic heat of reaction situation of more esters of acrylic acid vulcanizing agents and sulphur is tested in method test, is compared containing different number acrylate structural
The chemical activity and the extent of reaction of compound and sulfur reaction.
To achieve the above object, specific technical solution are as follows:
Step 1: sample preparation
(1) more esters of acrylic acid vulcanizing agent samples are weighed, are added in mortar, the knot of more esters of acrylic acid vulcanizing agents
Shown in structure such as formula (I)
Wherein:
R1Selected from carbon atom number be 1~30 straight chained alkyl, carbon atom number be 3~30 the alkyl with branch, carbon it is former
One of the aromatic radical that subnumber is 6~30；
R2、R3It is identical or different, it is independently selected from the straight chained alkyl or carbon atom number of hydrogen, carbon atom number for 1~5
For 2~5 one of the alkyl with branch；
The integer that n is 1~6.
(2) zinc oxide, stearic acid, sulphur, vulcanization accelerator is added, is fully ground, is allowed to vulcanize with more esters of acrylic acid
Agent is uniformly mixed；Vulcanization accelerator can be used selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, two sulphur
For one of Carbamates, aldehyde amines, aldehyde ammonia class, imidazolines, xanthic acid salt or 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 by above-mentioned preparation 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 test temperature, the heating rate of DSC.
Step 3: DSC atlas analysis, finds out the exothermic peak in DSC map, mark temperature corresponding to exothermic maximum peak and
Heat release peak area.
Wherein, more esters of acrylic acid vulcanizing agents described in step 1 are mostly liquid, should select high boiling more acrylic acid
Esters vulcanizing agent, boiling point are greater than 200 DEG C, and otherwise sample gasifies in DSC test process, affect to test, while can also
Pollute DSC temperature-control senser.
Zinc oxide dosage in step 1 is the 5%~20% of more esters of acrylic acid vulcanizing agent quality, and stearic acid dosage is
The 1%~10% of more esters of acrylic acid vulcanizing agent quality, sulfur consumption be more esters of acrylic acid vulcanizing agent quality 20%~
100%, vulcanization accelerator dosage is the 1%~30% of more esters of acrylic acid vulcanizing agent quality.
It is highly preferred that zinc oxide dosage is the 10%~15% of more esters of acrylic acid vulcanizing agent quality, stearic acid dosage is
The 4%~6% of more esters of acrylic acid vulcanizing agent quality.Zinc oxide and stearic acid are vulcanizing activator, and the two interaction generates
Zinc stearate, and complex compound is formd with promotor effect, vulcanization accelerator and sulphur have been activated, reaction efficiency is improved.
Sulfur consumption is preferably the 50%~70% of more esters of acrylic acid vulcanizing agent quality.Sulphur primarily serves and more propylene
The effect of esters of gallic acid vulcanizing agent crosslinking, cross-linking reaction is exothermic reaction in DSC test process.The exothermic maximum temperature of exothermic peak with
And the size of exothermic peak peak area can distinguish reactivity of more esters of acrylic acid vulcanizing agents during cross-linking reaction and
The extent of reaction.
Vulcanization accelerator dosage is preferably the 10%~20% of more esters of acrylic acid vulcanizing agent quality.Vulcanize in the present invention and promotees
Dosage into agent is greater than sulfur consumption, and the amount for increasing vulcanization accelerator can make sulphur chain length after sulphur open loop shorten, and increases sulphur
Reactivity, enhance acrylate structural and sulphur exothermic heat of reaction signal.Vulcanization accelerator is selected from N- cyclohexyl -2- benzo thiophene
Azoles sulfenamide (CBS), N oxydiethylene 2 benzothiazole sulfenamide (NOBS), N- tert-butyl -2-[4-morpholinodithio time sulphur
Amide (NS), 2-mercaptobenzothiazole (MBT), dithio-bis-benzothiazole (MBTS), tetramethyl thiuram disulfide
(TMTD), one of N ' N- dicyclohexyl -2-[4-morpholinodithio base sulfenamide (DZ), diphenylguanidine (DPG) or a variety of.
The preferred nitrogen of DSC carrier gas in step 2 is intended to guarantee sample homeostasis during the test, not occur
Redox reaction avoids generating interference signal in DSC map.
DSC carrier gas purge air velocity preferably 40~60mL/min in step 2.Carrier gas purge air-flow stablizes meeting pair
Test result has an impact.
DSC heating rate in step 2 is 1~20 DEG C/min, preferably 5~10 DEG C/min.DSC heating rate is faster, instead
Exothermic peak is answered more to lag.Heating rate is slower can be taken a long time closer to true Vulcanization Process of Rubber.Certainly,
It can carry out steady temperature test.
DSC Range of measuring temp in step 2 is 20 DEG C~250 DEG C, preferably 50~200 DEG C.The suitable test temperature of selection
Degree range can save the time, improve testing efficiency.
The beneficial effects of the present invention are:
The present invention is that more esters of acrylic acid vulcanizing agents and the exothermic method of sulfur reaction are tested with DSC, and to containing not
More esters of acrylic acid vulcanizing agents with quantity acrylate structural distinguish.With the acrylate knot of DSC test different number
More esters of acrylic acid vulcanizing agents of structure and the heat release situation of sulfur reaction, compare their exothermic heat of reaction peaks exothermic maximum temperature and
Peak area, it can be determined that the reactivity and the extent of reaction for going out their cross-linking reactions distinguish these more esters of acrylic acid vulcanizations
Agent.
DSC test has the advantage that consumption sample amount is small, and sample preparation is simple, and test method is simple, and test speed is fast.Together
When, the physical property measurement result that this test method can also be kneaded with natural rubber is mutually confirmed, and can be to natural rubber
The physical property measurement result of mixing 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 4 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；Lauryl acrylate, lark prestige；1,6- hexanediyl ester, lark prestige；Trimethylolpropane trimethacrylate, hundred
Clever prestige；Pentaerythritol tetraacrylate, lark prestige.
Instrument: differential scanning calorimeter (1 STAR of DSCeSystem), Mei Tele-support benefit；Assay balance AB204-
S, Mei Tele-support benefit.
Embodiment 1
13.6mg lauryl acrylate is weighed, is added in agate mortar.It is stearic to add 2.0mg zinc oxide, 1.0mg
Acid, 1.0mg sulphur, 4.0mg vulcanization accelerator NS, the above solid matter is fully ground, is allowed to uniformly mixed.
The crucible of two similar weights is weighed, for an empty crucible as reference crucible, one is used as sample crucible.It weighs
The sample of the above-mentioned preparation of 5.0mg is added in sample crucible.Reference crucible and sample crucible are put into DSC instrument.Lead in DSC
Enter the nitrogen of 50mL/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 2~4
Sample preparation methods and DSC test condition are same as Example 1, and specific sample preparation formula is shown in Table 1
1 sample preparation formula of table
| Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| 1,6- hexanediyl ester | 12.8 | ||
| Trimethylolpropane trimethacrylate | 16.8 | ||
| Pentaerythritol tetraacrylate | 20.0 | ||
| Zinc oxide | 2.0 | 2.0 | 2.0 |
| Stearic acid | 1.0 | 1.0 | 1.0 |
| Sulphur | 1.0 | 1.0 | 1.0 |
| Vulcanization accelerator NS | 4.0 | 4.0 | 4.0 |
2 exothermic maximum temperature of table and exothermic peak peak area
| Exothermic peak, DEG C | Heat release peak area, J/g | |
| Embodiment 1 | 189.1 | 42.2 |
| Embodiment 2 | 183.3 | 50.1 |
| Embodiment 3 | 182.3 | 81.9 |
| Embodiment 4 | 180.8 | 90.2 |
In Examples 1 to 4 in more esters of acrylic acid curative molecules structures the quantity of acrylate structural be followed successively by 1,2,
3,4, acrylate structural is identical as the molar ratio of sulphur in more esters of acrylic acid vulcanizing agents employed in embodiment, thus exists
In the identical situation of acrylate structural dosage, more esters of acrylic acid with different number acrylate structural can be compared
The chemical activity of vulcanizing agent.It can be seen that in Fig. 1 and table 2 with acrylate structural quantity in more esters of acrylic acid vulcanizing agents
Increase, the exothermic maximum temperature of reaction reduces, and the peak area of exothermic peak increases.Exothermic maximum temperature is low to illustrate acrylate structural
Big with the activity of sulfur reaction, exothermic peak peak area is big to illustrate that acrylate structural is deep with sulfur reaction, therefore, more propylene
The quantity of acrylate structural is more in esters of gallic acid curative molecules structure, and easier and sulfur reaction reacts with sulphur
Activity it is higher, the peak area of exothermic peak is bigger.It therefore, can be anti-by more esters of acrylic acid vulcanizing agents and sulphur with DSC
Answer heat release situation, carry out the quantity of acrylate structural in quickly more different more esters of acrylic acid vulcanizing agents, at the same time it can also than
Compared with the reactivity and the extent of reaction between them.
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 (6)
1. a kind of test method of more esters of acrylic acid vulcanizing agents, it is characterised in that comprise the steps of:
Step 1: sample preparation
(1) more esters of acrylic acid vulcanizing agent samples are weighed, are added in mortar, the structure of more esters of acrylic acid vulcanizing agents is such as
Shown in formula (I)
Wherein:
R1Selected from carbon atom number be 1~30 straight chained alkyl, carbon atom number be 3~30 the alkyl with branch, carbon atom number be
One of 6~30 aromatic radical；
R2、R3It is identical or different, be independently selected from hydrogen, the straight chained alkyl that carbon atom number is 1~5 or carbon atom number be 2~
5 one of the alkyl with branch；
The integer that n is 1~6；
(2) zinc oxide, stearic acid, sulphur, vulcanization accelerator is added, is fully ground, is allowed to mixed with more esters of acrylic acid vulcanizing agents
It closes uniform；Vulcanization accelerator is selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, dithiocar-bamate
One of class, 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 by above-mentioned preparation 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 test temperature, the heating rate of differential scanning calorimeter；
Step 3: differential scanning calorimeter atlas analysis, finds out the exothermic peak in map, temperature corresponding to exothermic maximum peak is marked
Degree and heat release peak area；The low activity for illustrating acrylate structural and sulfur reaction of exothermic maximum temperature is big, exothermic peak peak area
Illustrate that acrylate structural is deep with sulfur reaction greatly；
Wherein, zinc oxide dosage described in step 1 is the 5%~20% of more esters of acrylic acid vulcanizing agent quality, stearic acid dosage
Be the 1%~10% of more esters of acrylic acid vulcanizing agent quality, sulfur consumption be more esters of acrylic acid vulcanizing agent quality 50%~
70%, vulcanization accelerator dosage is the 10%~20% of more esters of acrylic acid vulcanizing agent quality；
Acrylate structural in more esters of acrylic acid vulcanizing agents is identical as the molar ratio of sulphur；
More esters of acrylic acid vulcanizing agent boiling points described in step 1 are greater than 200 DEG C.
2. test method according to claim 1, which is characterized in that the zinc oxide dosage is more esters of acrylic acid sulphur
The 10%~15% of agent quality, stearic acid dosage are the 4%~6% of more esters of acrylic acid vulcanizing agent quality.
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 the carrier gas, carrier gas purge air-flow
Speed preferably 40~60mL/min.
5. test method according to claim 1, which is characterized in that the differential scanning calorimeter Range of measuring temp
It is 20 DEG C~250 DEG C, heating rate is 1~20 DEG C/min.
6. test method according to claim 5, which is characterized in that the differential scanning calorimeter Range of measuring temp
It is 50~200 DEG C, heating rate is 5~10 DEG C/min.
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