CN105928971A - Determination method for polyacrylate vulcanizing agent - Google Patents
Determination method for polyacrylate vulcanizing agent Download PDFInfo
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Abstract
The invention discloses a determination method for a polyacrylate vulcanizing agent. The structure of the polyacrylate vulcanizing agent is as shown in a formula (I) as described in the specification. Sulfur undergoes ring opening under the action of both a vulcanizing promoter and a vulcanizing activator and may undergo cross-linking reaction with C-C double bonds in acrylate substances, and the situation of heat release of the cross-linking reaction can be measured by using differential scanning calorimetry; the reaction activity and reaction degree of the cross-linking reaction can be determined through the maximum heat release temperature and peak area of a reaction exothermic peak, so reaction activity of polyacrylate vulcanizing agents with different numbers of acrylate structures can be compared. In the formula (I), R1 is one selected from a group consisting of a straight-chain alkyl group with a carbon atom number of 1 to 30, an alkyl group with a branched chain and a carbon atom number of 3 to 30 and an aryl group with a carbon atom number of 6 to 30; R2 and R3 are same or different and independently selected from a group consisting of hydrogen, a straight-chain alkyl group with a carbon atom number of 1 to 5 and an alkyl group with a branched chain and a carbon atom number of 2 to 5; and n is an integer in a range of 1 to 6.
Description
Technical field
The invention belongs to analyze field tests, be specifically related to one and test many acrylic acid by differentia scanning calorimetry
The method of esters vulcanizing agent and sulfur reaction suction heat release analyzes the chemism of many esters of acrylic acids vulcanizing agent.
Background technology
Natural rubber (NR), as a kind of general purpose rubber, has good elasticity and mechanical property, but many in its vulcanizate
The heat stability of sulfur-crosslinked key is poor, in sulfidation, along with heated time extends, and the polysulfide crosslink bond part originally formed
Can rupture, cause the crosslink density of sizing material to reduce, the physical property of sizing material declines, and the serviceability of rubber reduces.
Along with the fast development of rubber industry, research worker studies how to eliminate or reduce rubber in sulfidation and use process always
In phenomenon of reverting, mechanical performance and the serviceability of rubber can be kept again simultaneously, extend the service life of goods.
Consider from recovery mechanism, improve the measure of NR anti-reversion behaviour mainly by adding sulfur-donor chemical combination
Thing or offset-type vulcanizing system to make up the loss of cross-bond, such as, add two hydration hexa-methylenes 1,6-bisthiosulfate two
Sodium salt (Duralink HTS).Furthermore it is also possible to by add chemical reagent make its when sizing material reverts with sizing material break
Split key generation chemical reaction, thus form new cross-bond, such as, add 1, double (the lemon acid imide methyl) benzene (PK900) of 3-.
In the mini exhibition of rubber that Ohio, USA Columbus conference centre in 2004 holds, rubber chemicals manufacturer
Sartomer Company is proposed and prevents the anti-recovery agent SR534, SR534 of sulfur cross-linking glue generation recovery is that one is many
Function acrylate, chemical name is tetramethylol methane tetraacrylate, and its chemical structural formula is as follows:
Esters of acrylic acid material is mainly used as the auxiliary curing agent of peroxide vulcanizing system, can participate in what free radical caused
Addition and graft reaction.Containing carbon-to-carbon double bond in esters of acrylic acid material, sulfur is total to vulcanization accelerator and vulcanizing activator
Under same-action, open loop generates organic polysulfide, and organic polysulfide can be anti-with the carbon-to-carbon double bond in esters of acrylic acid material
Should, this reaction is exothermic reaction, can measure the heat release situation of reaction with differential scanning calorimetry (DSC), put according to reaction
The exothermic maximum temperature of thermal spike and peak area can interpolate that out reactivity and the reaction of esters of acrylic acid material cross-linking reaction
Degree, judges the reactivity of acrylate structural compound containing varying number with this.
Differential scanning calorimeter (DSC) basic functional principle is to change (heating, cooling, constant temperature and group thereof at program temperature
Close) during, the differential heat flow between measuring samples and reference substance, to characterize the physical and chemical changes relevant with heat effect.
DSC has been applied successfully to the physical conversion studying macromolecular material such as crystallization, melted and glass as a kind of heat analysis method
Change and change and chemical reaction is such as polymerized, solidifies, cross-links, aoxidizes and decomposition etc..Chinese patent CN201610193230.3 intermediary
The experimental technique of a kind of Squalene that continued simulation Vulcanization Process of Rubber, tests the reaction in this course of reaction with DSC and inhales heat release
Situation, the impact on Vulcanization Process of Rubber of the most different vulcanizing activators.
Summary of the invention
It is an object of the invention to provide the method for testing of a kind of many esters of acrylic acids vulcanizing agent, use means of differential scanning calorimetry
Method test test many esters of acrylic acids vulcanizing agent and the exothermic heat of reaction situation of sulfur, compare containing varying number acrylate structural
The chemism of compound and sulfur reaction and the extent of reaction.
For achieving the above object, concrete technical scheme is:
Prepared by step one, sample
(1) weigh many esters of acrylic acids vulcanizing agent sample, join in mortar, the knot of described many esters of acrylic acids vulcanizing agent
Shown in structure such as formula (I)
Wherein:
R1Former selected from the alkyl with side chain that the straight chained alkyl that carbon number is 1～30, carbon number are 3～30, carbon
Subnumber is the one in the aromatic radical of 6～30；
R2、R3Identical or different, be independently selected from hydrogen, carbon number be 1～5 straight chained alkyl or carbon number
It it is the one in the alkyl with side chain of 2～5；
N is the integer of 1～6.
(2) add zinc oxide, stearic acid, sulfur, vulcanization accelerator, be fully ground, be allowed to vulcanize with many esters of acrylic acids
Agent mix homogeneously；Vulcanization accelerator can use selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, two sulfur
For Carbamates, 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 above-mentioned preparation 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, carrier gas purge air-flow
Speed is 20～80mL/min；
(5) DSC test condition sets: set the test temperature of DSC, programming rate.
Step 3, DSC atlas analysis, find out the exothermic peak in DSC collection of illustrative plates, mark the temperature corresponding to exothermic maximum peak and
Exothermic peak area.
Wherein, the many esters of acrylic acids vulcanizing agent described in step one mostly is liquid, should select high boiling many acrylic acid
Esters vulcanizing agent, boiling point is more than 200 DEG C, otherwise sample gasification in DSC test process, brings impact to test, the most also can
Pollute DSC temperature-control senser.
Zinc oxide dosage in step one is the 5%～20% of many esters of acrylic acids vulcanizing agent quality, and stearic acid dosage is
The 1%～10% of many esters of acrylic acids vulcanizing agent quality, sulfur consumption be many esters of acrylic acids vulcanizing agent quality 20%～
100%, vulcanization accelerator consumption is the 1%～30% of many esters of acrylic acids vulcanizing agent quality.
It is highly preferred that zinc oxide dosage is many esters of acrylic acids vulcanizing agent quality 10%～15%, stearic acid dosage is
The 4%～6% of many esters of acrylic acids vulcanizing agent quality.Zinc oxide and stearic acid are vulcanizing activator, and both interact generation
Zinc stearate, and define complex with accelerator effect, activate vulcanization accelerator and sulfur, improve reaction efficiency.
Sulfur consumption is preferably the 50%～70% of many esters of acrylic acids vulcanizing agent quality.Sulfur primarily serves and many propylene
The effect of esters of gallic acid vulcanizing agent crosslinking, in DSC test process, cross-linking reaction is exothermic reaction.The exothermic maximum temperature of exothermic peak with
And the size of exothermic peak peak area can distinguish many esters of acrylic acids vulcanizing agent reactivity during cross-linking reaction and
The extent of reaction.
Vulcanization accelerator consumption is preferably the 10%～20% of many esters of acrylic acids vulcanizing agent quality.In the present invention, sulfuration promotees
The consumption entering agent is more than sulfur consumption, and after the amount of increase vulcanization accelerator can make sulfur open loop, sulfur chain length shortens, and increases sulfur
Reactivity, strengthen the exothermic heat of reaction signal of acrylate structural and sulfur.Vulcanization accelerator is selected from N-cyclohexyl-2-benzo thiophene
Azoles sulfenamide (CBS), N oxydiethylene 2 benzothiazole sulfenamide (NOBS), the N-tert-butyl group-2-[4-morpholinodithio time sulphur
Amide (NS), 2-mercaptobenzothiazole (MBT), dithio-bis-benzothiazole (MBTS), tetramethyl thiuram disulfide
(TMTD), one or more in N ' N-dicyclohexyl-2-[4-morpholinodithio base sulfenamide (DZ), diphenylguanidine (DPG).
The preferred nitrogen of DSC carrier gas in step 2, is intended to ensure sample homeostasis in test process, does not occurs
Redox reaction, it is to avoid produce interference signal in DSC collection of illustrative plates.
DSC carrier gas purge air velocity preferably 40～60mL/min in step 2.Carrier gas purge air-flow stably can be right
Test result produces impact.
DSC programming rate in step 2 is 1～20 DEG C/min, preferably 5～10 DEG C/min.DSC programming rate is the fastest, instead
Answer exothermic peak the most delayed.Programming rate the slowest can closer to real Vulcanization Process of Rubber, but time-consumingly the longest.Certainly, also
Steady temperature test can be carried out.
DSC Range of measuring temp in step 2 is 20 DEG C～250 DEG C, preferably 50～200 DEG C.Select suitably to test temperature
Degree scope can be saved the time, improves testing efficiency.
The beneficial effects of the present invention is:
The present invention is the method with DSC test many esters of acrylic acids vulcanizing agent with sulfur reaction heat release, and to containing not
Make a distinction with many esters of acrylic acids vulcanizing agent of quantity acrylate structural.Acrylate knot with DSC test varying number
Many esters of acrylic acids vulcanizing agent of structure and the heat release situation of sulfur reaction, compare they exothermic heat of reaction peaks exothermic maximum temperature and
Peak area, it can be determined that go out reactivity and the extent of reaction of they cross-linking reactions, distinguishes the sulfuration of these many esters of acrylic acids
Agent.
DSC test 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.With
Time, this method of testing can also the physical property measurement result mixing with natural rubber mutually confirm, and can be to natural rubber
Mixing physical property measurement result carries out anticipation so that physical property measurement is more targeted.
Accompanying drawing explanation
Fig. 1 is the DSC test result comparison diagram of embodiment 1～4.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 pair
The present invention is described in further detail.It is pointed out that all similar replacements and change those skilled in the art are come
Saying and be apparent from, 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, city
Sell；Lauryl acrylate, lark prestige；1,6-hexanediyl ester, lark prestige；Trimethylolpropane trimethacrylate, hundred
Spirit prestige；Tetramethylol methane tetraacrylate, lark prestige.
Instrument: differential scanning calorimeter (DSC 1 STAReSystem), 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 13.6mg lauryl acrylate, join in agate mortar.Add 2.0mg zinc oxide, 1.0mg tristearin
Acid, 1.0mg sulfur, 4.0mg vulcanization accelerator NS, be fully ground above solid matter, be allowed to mix homogeneously.
Weighing the crucible of two similar weight, an empty crucible is as reference crucible, and one as sample crucible.Weigh
The sample of the above-mentioned preparation of 5.0mg joins 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 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 2～4
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 sample preparation formula
| Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| 1,6-hexanediyl ester | 12.8 | ||
| Trimethylolpropane trimethacrylate | 16.8 | ||
| Tetramethylol methane tetraacrylate | 20.0 | ||
| Zinc oxide | 2.0 | 2.0 | 2.0 |
| Stearic acid | 1.0 | 1.0 | 1.0 |
| Sulfur | 1.0 | 1.0 | 1.0 |
| Vulcanization accelerator NS | 4.0 | 4.0 | 4.0 |
Table 2 exothermic maximum temperature and exothermic peak peak area
| Exothermic peak, DEG C | Exothermic 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 embodiment 1～4 in many esters of acrylic acids curative molecules structure the quantity of acrylate structural be followed successively by 1,2,
3,4, in the many esters of acrylic acids vulcanizing agent employed in embodiment, acrylate structural is identical with the mol ratio of sulfur, thus exists
In the case of acrylate structural consumption is identical, the many esters of acrylic acids with varying number acrylate structural can be compared
The chemism of vulcanizing agent.Fig. 1 and Biao 2 can be seen that along with acrylate structural quantity in many esters of acrylic acids vulcanizing agent
Increasing, the exothermic maximum temperature of reaction reduces, and the peak area of exothermic peak increases.Exothermic maximum temperature low explanation acrylate structural
Big with the activity of sulfur reaction, exothermic peak peak area big explanation acrylate structural is deep with sulfur reaction, therefore, and many propylene
In esters of gallic acid curative molecules structure, the quantity of acrylate structural is the most, and the easiest and sulfur reaction reacts with sulfur
Activity the highest, the peak area of exothermic peak is the biggest.Therefore, it can with DSC anti-with sulfur by many esters of acrylic acids vulcanizing agent
Answer heat release situation, quickly compare the quantity of acrylate structural in different many esters of acrylic acids vulcanizing agent, at the same time it can also be ratio
The relatively reactivity between them and the extent of reaction.
The above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, can also make on the basis of the above description
The change of other multi-forms or variation.Here without also cannot all of embodiment be given exhaustive.All the present invention's
Any amendment, equivalent and the improvement etc. made within spirit and principle, should be included in the protection of the claims in the present invention
Within the scope of.
Claims (8)
1. the method for testing of esters of acrylic acid vulcanizing agent more than a kind, it is characterised in that comprise the steps of
Prepared by step one, sample
(1) weighing many esters of acrylic acids vulcanizing agent sample, join in mortar, the structure of described many esters of acrylic acids vulcanizing agent is such as
Shown in formula (I)
Wherein:
R1Selected from the alkyl with side chain that the straight chained alkyl that carbon number is 1～30, carbon number are 3～30, carbon number it is
One in the aromatic radical of 6～30；
R2、R3Identical or different, be independently selected from hydrogen, carbon number be 1～5 straight chained alkyl or carbon number be 2～
One in the alkyl with side chain of 5；
N is the integer of 1～6；
(2) add zinc oxide, stearic acid, sulfur, vulcanization accelerator, be fully ground, be allowed to mix with many esters of acrylic acids vulcanizing agent
Close uniformly；Vulcanization accelerator is selected from sulfenamide, thiazoles, thiurams, Thiourea, guanidine, dithiocar-bamate
Class, 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 of above-mentioned preparation 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, and carrier gas is blown
Scavenging Flow Velocity is 20～80mL/min；
(5) differential scanning calorimeter test condition sets: set the test temperature of differential scanning calorimeter, 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
Degree and exothermic peak area.
Method of testing the most according to claim 1, it is characterised in that the many esters of acrylic acids vulcanizing agent described in step one
Boiling point is more than 200 DEG C.
Method of testing the most according to claim 1, it is characterised in that the zinc oxide dosage described in step one is many acrylic acid
The 5%～20% of esters vulcanizing agent quality, stearic acid dosage is the 1%～10% of many esters of acrylic acids vulcanizing agent quality, sulfur
Consumption is the 20%～100% of many esters of acrylic acids vulcanizing agent quality, and vulcanization accelerator consumption is many esters of acrylic acids vulcanizing agent
The 1%～30% of quality.
Method of testing the most according to claim 3, it is characterised in that described zinc oxide dosage is many esters of acrylic acids sulfur
The 10%～15% of agent quality, stearic acid dosage is the 4%～6% of many esters of acrylic acids vulcanizing agent quality, and sulfur consumption is
The 50%～70% of many esters of acrylic acids vulcanizing agent quality, vulcanization accelerator consumption is many esters of acrylic acids vulcanizing agent quality
10%～20%.
Method of testing the most according to claim 1, it is characterised in that described 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 or more in base sulfenamide, diphenylguanidine.
Method of testing the most according to claim 1, it is characterised in that the preferred nitrogen of described carrier gas, carrier gas purge air-flow
Speed preferably 40～60mL/min.
Method of testing the most according to claim 1, it is characterised in that described differential scanning calorimeter Range of measuring temp
Being 20 DEG C～250 DEG C, programming rate is 1～20 DEG C/min.
Method of testing the most according to claim 7, it is characterised in that described differential scanning calorimeter Range of measuring temp
Being 50～200 DEG C, programming rate is 5～10 DEG C/min.
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| CN112630262A (en) * | 2020-12-22 | 2021-04-09 | 华东理工大学 | Test method for detecting activity of vulcanization activator |
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