CN109867833A - Two step vulcanization reinforcement nitrile rubber of salt unsaturated carboxylic acid - Google Patents
Two step vulcanization reinforcement nitrile rubber of salt unsaturated carboxylic acid Download PDFInfo
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Abstract
The present invention provides a kind of salt unsaturated carboxylic acid reinforced rubbers, it is prepared by following raw materials: rubber, sulphur, vulcanizing agent, salt unsaturated carboxylic acid, rubber additive.The crosslink density of gained rubbery system significantly improves, and in the case where keeping rubber tensile intensity, elongation at break and Compression Set performance are significantly improved.In addition, the vulcanizate tensile strength of gained rubber, compression modulus, tear resistance, Compression Set are also stepped up with the increase of salt unsaturated carboxylic acid in system.The present invention is had excellent performance and regulatable reinforced rubber, has a extensive future.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of to utilize salt unsaturated carboxylic acid, pass through two step sulphur
The reinforcement nitrile rubber of change method preparation.
Background technique
Rubber is a kind of important high molecular material, contour in space technology, biotechnology, electronic information, auto industry
There is irreplaceable role in frontier and daily life.Rubber material especially synthetic rubber, itself strong
It spends poor, needs reinforcement to meet various uses.Reinforced filling can be improved the tensile strength, tearing strength and hardness of rubber,
Assign the performances such as good weather-proof, the warping strength, oil resistant of rubber, cold-resistant, heat-resisting and abrasion performance.
The activity why reinforced filling can have excellent reinforcing effect to be reinforced filling particle surface rubber
Point interacts with rubber molecule, such as physical absorption, chemical bonding etc., has very high infiltration or knot with rubber matrix
It is right.The partial size of reinforced filling particle is smaller, and specific surface area is bigger, also stronger with the interaction of rubber molecule, and particle
Surface-active is higher, also higher with the conjugation of rubber, also bigger to the constraint effect of rubber.As carbon black has, partial size is small, table
The big feature of face activity, can form with rubber molecule " in conjunction with glue ".A small amount of carbon nanotube, graphene can greatly improve rubber
Modulus and rigidity, but on condition that need that they are dispersed in rubber matrix by various any special measures.
By in rubber matrix " in-situ polymerization " formed nanoparticle to reinforcing rubber and a kind of effective method.
For example the substance with reactive functional groups is previously added in rubber, so that its polymerization is formed nanoparticle under certain condition and exists
Network structure is formed in rubber, and reinforcement is carried out to rubber.Metallic salts of unsaturated carboxylate reinforced rubber just belongs to " in-situ polymerization "
Mode.
But the performance of reinforced rubber that the prior art has been prepared need to be advanced optimized, it is also necessary to which research is more
Add simple, effective method, using the reinforcement phase that can be dispersed in rubber, prepares the more excellent rubber of mechanical property
Glue.
Summary of the invention
The object of the present invention is to provide a kind of salt unsaturated carboxylic acid reinforcement nitrile rubbers that mechanical property is more excellent.
The present invention provides a kind of salt unsaturated carboxylic acid reinforced rubbers, it is prepared by following raw materials:
Rubber, sulphur, vulcanizing agent, salt unsaturated carboxylic acid, rubber additive.
Further, the vulcanizing agent is peroxide vulcanizing agent；And/or the rubber additive includes plasticizer, sulphur
Change one of activating agent, vulcanization accelerator, anti-aging agent, reinforcing agent or a variety of.
Further, the plasticizer is stearic acid, and vulcanizing activator ZnO, vulcanization accelerator is DM and TMTD, is prevented old
Agent is 4010, and reinforcing agent is carbon black, and rubber is nitrile rubber, and vulcanizing agent is cumyl peroxide, and salt unsaturated carboxylic acid is first
Base zinc acrylate resin.
Further, the weight proportion of each raw material are as follows: 100 parts of rubber, 1.3~1.7 parts of sulphur, vulcanizing agent 1.8~
2.2 parts, 10~40 parts of salt unsaturated carboxylic acid, 9~30 parts of rubber additive；
Preferably, include in the rubber additive: 0.9~1.1 part of plasticizer, 4.9~5.1 parts of vulcanizing activator, sulphur
Change altax 2.4~2.6,0.24~0.26 part of TMTD, 0.9~1.1 part of anti-aging agent, or also include carbon black 14~16
Part.
Further, the weight proportion of each raw material are as follows: 100 parts of rubber, 1.5 parts of sulphur, 2 parts of vulcanizing agent, unsaturated
10~40 parts of carboxylate, 1 part of plasticizer, 5 parts of vulcanizing activator, 2.5 parts of accelerator DM, 0.25 part of TMTD, anti-aging agent 1
Part, or also include 15 parts of carbon black.
Further, the zinc methacrylate is 20~40 parts, preferably 30~40 parts, more preferable 40 parts.
Further, the reinforced rubber is prepared by the method vulcanized by two steps, is specifically included:
(1), each raw material is weighed in proportion, is kneaded using open mill, and rubber compound is obtained；
(2), rubber compound obtained by step (1) is vulcanized, control reaction temperature is 120~140 DEG C, carries out first step sulphur
Change reaction；Then control reaction temperature is 160~180 DEG C, carries out second step vulcanization reaction, obtains reinforced rubber.
The present invention also provides a kind of method for preparing above-mentioned reinforced rubber, preparation step includes:
(1), each raw material is weighed in proportion, is kneaded using open mill, and rubber compound is obtained；
(2), rubber compound obtained by step (1) is vulcanized, control reaction temperature is 120~140 DEG C, carries out first step sulphur
Change reaction；Then control reaction temperature is 160~180 DEG C, carries out second step vulcanization reaction, obtains reinforced rubber.
Further, in step (1), the mixing process includes: a. opening open mill, and it is thin logical to carry out rubber；B. make rubber
Glue packet roller is added Sulfur, Bao Tong, and taps rubber and turn refining；C. vulcanizing activator, anti-aging agent, plasticizer is added, is slow added into 1/3
~1/2 salt unsaturated carboxylic acid, left and right cutter, Bao Tong；D. remaining salt unsaturated carboxylic acid is added, alternately rubber tapping turns refining for left and right；e.
Vulcanization accelerator and vulcanizing agent is added, or continuously adds reinforcing agent, continues rubber tapping and turns refining, be sufficiently mixed each raw material, Bao Tong
Bottom sheet；
And/or in step (2), the first step vulcanization reaction temperature is 130 DEG C, and the reaction time is 40~60 minutes, excellent
It selects 50 minutes；Second step vulcanization reaction temperature is 170 DEG C, and the reaction time is 5~10 minutes, preferably 8 minutes.
Further, in the step a, the mixing roll temperature for controlling open mill is 50 DEG C, and roller speed ratio is 1: 1.1~1:
1.2, open mill roll spacing is 0.5mm, and thin logical number is 4 times；And/or in step b, thin logical number is 2~3 times；And/or step
In c, cutter number is 3 times；And/or in step d, controlling the number alternately tapped rubber and turned refining is 2~4 times；And/or in step e,
When thin logical bottom sheet, roll spacing 2mm.
The experimental results showed that the present invention is with rubber, sulphur, vulcanizing agent, salt unsaturated carboxylic acid and rubber additive are raw material,
By two step vulcanizations, reinforced type nitrile rubber has been prepared.The crosslink density of gained rubbery system significantly improves, and
In the case where keeping rubber tensile intensity, elongation at break and Compression Set performance are significantly improved.In addition, with system
The increase of middle salt unsaturated carboxylic acid, the vulcanizate tensile strength of gained rubber, compression modulus, tear resistance, Compression Set
Also it is stepped up.The present invention is had excellent performance and regulatable reinforced rubber, has a extensive future.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the crosslink density (a) of different system nitrile rubbers, and wherein Vr indicates that total crosslink density, Vr1 indicate covalently to hand over
Join density；Vr2 indicates ionomer density；S/D-30Z system crosslink density/torque and vulcanization time curve (b).
Fig. 2 are as follows: a) trend that different system storage modulus vary with temperature；(b) different maximum system energy losses become with temperature
The trend of change.
Fig. 3 is that different systems break face appearance structure figure.
Fig. 4 difference system cure kinetics matched curve: (a) Kissinger equation；(b) side Flynn-Wall-Ozawa
Journey.
Fig. 5 is degree of conversion alpha of the S/D-30Z system under different heating rates and temperature T curve.
Fig. 6 is ln β under S/D-30Z system difference state of cure (vulcanization) to the straight line fitting of 1/T.
Fig. 7 is the mechanical property phenogram of different systems: (a) tensile strength；(b) elongation at break；(c) compression modulus；
(d) Compression Set.
Fig. 8 is the curing curve figure of different systems.
Fig. 9 is that different systems join density curve, and wherein Vr indicates that total crosslink density, Vr1 indicate covalent cross-linking density；Vr2
Indicate ionomer density.
Figure 10 is that the mechanical property of different systems characterizes: (a) tensile strength；(b) elongation at break；(c) compression modulus；
(d) Compression Set.
Specific embodiment
Material: nitrile rubber (NBR): Japanese JSR, trade mark N230S；Taiwan Nan Di company, the trade mark 1052；Methacrylic acid
Zinc (ZDMA): Xi'an Organic Chemical Plant；Sulphur (S), stearic acid (SA), zinc oxide (ZnO), dibenzothiazyl disulfide (DM),
Vulcanization accelerator TMTD, antioxidant 4010, cumyl peroxide (DCP), rubber black N330 are commercial product.
The preparation of embodiment 1, two step vulcanization reinforcement nitrile rubber S/D-10Z of salt unsaturated carboxylic acid of the present invention
Step (1) is kneaded: according to the weight proportion of each raw material of S/D-10Z shown in table 1, weighing each raw material.Control open mill
Mixing roll temperature be 50 DEG C, roller speed ratio be 1: open mill roll spacing is adjusted to 0.5mm, carries out the thin of raw rubber by (1.1~1.2)
It is logical, Bao Tong 4 times；Roll spacing is suitably tuned up later, makes sizing material packet roller, sulphurization, Bao Tong 2~3 times, and tap rubber and turn refining.Then plus
ZnO, 4010, stearic acid, are slowly added to 1/3~1/2 zinc methacrylate, and left and right cutter 3 times, Bao Tong.Then it is added remaining
Zinc methacrylate, alternately rubber tapping turns refining 2~4 for left and right.Add remaining DM, TMTD, cumyl peroxide and other originals
Material continues rubber tapping and turns refining.So that compounding agent is sufficiently mixed with sizing material, roll spacing is then adjusted to 2mm, thin logical bottom sheet obtains
Rubber compound.
Step (2) vulcanization: after rubber compound obtained by step (1) is placed 24 hours at room temperature, using vulcanizing press into
Row compression molding, first step vulcanization: 130 DEG C, 50min, second step vulcanization: 170 DEG C, 8min.Obtain reinforcement butyronitrile of the invention
Rubber S/D-10Z.
Embodiment 2-5, salt unsaturated carboxylic acid of the present invention two step vulcanization reinforcement nitrile rubber S/D-20Z, S/D-30Z, S/
The preparation of D-40Z, N/Z-S/D
According to the weight proportion of each raw material of S/D-20Z, S/D-30Z, S/D-40Z shown in table 1, according to S/D- in embodiment 1
Reinforcement nitrile rubber S/D-20Z, S/D-30Z, S/D-40Z, N/Z-S/ of the invention is prepared in the preparation method of 10Z respectively
D。
The raw material weight proportioning of soup processed of 1 each two step vulcanization reinforcement nitrile rubber of salt unsaturated carboxylic acid of the present invention of table
The preparation of comparative example 1-4.N-S/D, S/D-0Z, N-S, Z-S, Z-D control nitrile rubber
According to the weight proportion of each raw material of N-S/D, S/D-0Z, N-S, Z-S, Z-D shown in table 2, according to S/D- in embodiment 1
Control nitrile rubber N-S/D, S/D-0Z, N-S, Z-S, Z-D is prepared in the preparation method of 10Z respectively.
The raw material weight proportioning of soup processed of the control nitrile rubber of table 2
Beneficial effects of the present invention are further illustrated below by way of experimental example.
1, test material:
Salt unsaturated carboxylic acid two step vulcanization reinforcement nitrile rubber S/D-10Z, S/D- of 1-5 of embodiment of the present invention preparation
20Z,S/D-30Z,S/D-40Z；Control nitrile rubber N-S/D, S/D-0Z, N-S, Z-S of reference examples 1-4 preparation.
2, test and characterization
The test of 2.1 curing curves
Using Beijing friend depth electronic instrument C2000E without progress curability test on rotor rheometer.
The test of 2.2 crosslink densities
The sample that about 0.5g is cut in the test piece of 2mm thickness claims original quality M on assay balance0, 3 are swollen in toluene
Weigh M after its balance1, the dry 36 hours weighing M of vacuum drying oven are put at 90 DEG C2, total crosslink density is calculated according to formula.It will be upper
It states sample and is put into toluene-solution of trichloroacetic acid immersion 5 days, cut off ionic bond, be again dipped into toluene to be swollen 2 days and weigh after balance
M1', the dry 36 hours weighing M of vacuum drying oven are put at 90 DEG C2', covalent cross-linking density is calculated according to formula.Ionomer density
=total crosslink density-covalent cross-linking density.
The preparation of toluene-solution of trichloroacetic acid: it weighs 40.5g trichloroacetic acid and is added in conical flask, add 475ml first
Benzole soln is sufficiently stirred and makes it dissolve, and obtains toluene-solution of trichloroacetic acid that 500ml volume ratio is 95:5.
Crosslink density: the volume fraction Vr of rubber in swelling network is calculated by following formula:
In formula:
m0The original weight m of-sample1The weight of sample is swollen after one sample swelling equilibrium
m2The weight percent of pure rubber in mono- sample of weight φ after-swelling sample removing solvent
The density of mono- solvent of density p s of the pure glue vulcanizate of ρ r mono-
The analysis of 2.3 dynamic thermomechanicals
The Q880 type dynamic thermomechanical analysis apparatus of TA company, U.S. production, selects single cantilever beam beam mode, test frequency
1HZ, 3 DEG C/min of heating rate, -60 DEG C -60 DEG C of temperature range.
2.4 appearance structures characterization
Scanning electron microscope analysis (SEM): using the JSM-5900 electron microscope of Tokyo JOEL company, to examination
Sample section carries out metal spraying processing.
2.5 vulcanizing kinetics parameter fittings
Differential scanning calorimeter (DSC): using the DSC204 type differential scanning calorimetric analysis instrument of Netzcsh company, Germany,
5-8mg rubber compound is placed in crucible, and different heating rates rise to 250 DEG C from 30 DEG C, using Kissinger method and Flynn-
Wall-Ozawa method fitting vulcanization activation energy.
The characterization of 2.6 mechanical properties
Compression Set performance test is carried out according to GB/T7759-2014, other mechanics use Instron universal material
Testing machine, according to GB/T528-2009 (tensile property), GB/T7757-2009 (compression stress strain property), GB/T529-
2008 (tear resistances) are tested.
3, results and discussion
3.1 curing curve
The addition that can be seen that ZDMA from the curing curve of the different systems of Fig. 8 present invention increases vulcanization time, but with
The increase variation of ZDMA less, is primarily due in initial vulcanization step, and the polysulfide that sulphur and promotor generate may be with
ZDMA reacts, and causes significantly to vulcanize delay.When sulfur cross-linking early period, with the addition of ZDMA, invention crosslink density increases
Greatly；ZDMA reacts with sulphur, there is certain perfect effect to rubber cross network.
3.2 crosslink density
According to Fig. 1 as can be seen that the total crosslink density of S/D-30Z system for the two step vulcanizations preparation that the present invention uses is greater than
Sulphur system is only used in reference examples with peroxide systems or only.When only using sulfur cross-linking, ZDMA hinders the crosslinking of sulphur, makes
The decline of system crosslink density is obtained, and measures minute quantity ionic bond in system.
The Vr value of S/D-30Z sizing material is consistent with curing curve with the variation tendency of vulcanization time, as vulcanization time extends
It gradually increases, more than kept stable after 50min, 56min is started to warm up, and vulcanizate crosslink density at this time increases sharply,
The cross-linked network of system basically forms perfect after a few minutes.It is worth noting that, Vr2 value with DCP vulcanization occur it is one " small
Peak " value, i.e. value increase sharply at the beginning of vulcanization, and then some value is fallen back in decline, then again as vulcanization time prolongs
It grows and increases.
Further, from fig. 9, it can be seen that ZDMA is added, the total crosslink density of system increases, but covalent cross-linking density drops
Low, because a part of sulphur or DCP are reacted with ZDMA, the crosslinking agent that initiation matrix generates cross-linking reaction in this way is reduced, and is covalently handed over
Joining density reduces.With the increase of ZDMA content, ZDMA takes part in cross-linking reaction, while auto polymerization reaction occurs, and generates P-
ZDMA, to improve crosslinking degree, but under the certain feelings of amount of peroxide, ZDMA be increased to certain dosage with
Afterwards, for ZDMA, excessive portion is not initiated, and is not involved in cross-linking process, thus continues growing ZDMA dosage, to friendship
Connection degree influences little.
The analysis of 3.3 dynamic thermomechanicals
According to fig. 2 as can be seen that compared with sulphur system, two step vulcanizing systems of the invention are because crosslink density increases, Tg
It increases, storage modulus E ' increases.S/D-30Z system is compared with Z-D system, although two step vulcanizing system crosslink densities increase,
It is that joined the small-molecule substances such as stearic acid, anti-aging agent, plays plasticization, Tg is reduced instead.
3.4 appearance structures characterization
According to Fig. 3 as can be seen that addition reinforcing agent ZDMA, when only using sulphur as vulcanizing agent, ZDMA particle does not have substantially
It reacts, remains as micron-scale, it is not close in conjunction with matrix, it is easy to fall off from matrix under stretching action, does not play and answer
Some reinforcing effects, are intended only as inert filler and exist.When being vulcanized using peroxide DCP, ZDMA primary partical disappears,
It reacts under DCP effect, generates the P-ZDMA particle with reinforcing effect, vulcanizate has accordion section.
In two step vulcanizing systems, the first step introduces the strong polysulfide crosslink bond of deformability, has matrix good
Flexible structure.Second step ZDMA polymerization under the initiation of DCP generates the nanometer P-ZDMA particle of reinforcing effect, reaction it is in situ into
Row, is uniformly dispersed among matrix, and introduce a large amount of ionic bonds, has excellent reinforcing effect to matrix.Due to two steps
The characteristics of vulcanization cross-linking system, in external load effect, base fracture fold face is greatly increased, good dissipation energy,
Play the role of activeness and quietness.
3.5 vulcanizing kinetics parameter fittings
Vulcanizing kinetics parameter is intended by Kissinger equation and Flynn-Wall-Ozawa equation respectively
It closes, as a result such as table 3 and Fig. 4.As can be seen that the addition of ZDMA is a significant increase vulcanization reaction for sulphur system
Activation energy results in rate of cure and slows down, and vulcanizes induction period and vulcanization time increases.
ZDMA system DCP addition makes to vulcanize activation energy reduction.When vulcanization, ZDMA is reacted with DCP, reduces entire body
The activation energy of system, so that the covalent cross-linking reaction of NBR matrix can carry out simultaneously with the polymerization reaction of ZDMA, and cross-linked network
It can quickly form.
The cure kinetics fitting data of the different systems of table 3
Further study degree of conversion alpha of the S/D-30Z system of two step vulcanizations preparation of the invention under different heating rates
With temperature T curve, and to ln β under different states of cure (vulcanization) to the straight line fitting of 1/T.As a result see Fig. 5, Fig. 6.
As can be seen that at the same temperature, state of cure (vulcanization) is reduced with the raising of heating rate β.With the raising of β,
Reach temperature required for same state of cure (vulcanization) to gradually rise.When β is increased, the time that system is sufficiently reacted subtracts
Less, corresponding temperature needs to improve when therefore reaching same state of cure (vulcanization).
Moreover, can be seen that by activation energy data (table 4 and table 5) of the different systems at differentiated yields α
The addition of ZDMA increases the activation energy (table 5) of whole system initial reaction.This is because vulcanization reaction first
Stage (α=0%-30%), DCP initial decomposition, predominantly sulphur decompose cross-linking reaction.One side system is to generate for crosslinking
Free radical, need more energy to carry out anakmetomeres, the activation energy needed is relatively high.Another aspect ZDMA and sulfur reaction are living
The main reason for changing can be larger, this is the activation energy increase for making system.With the progress (after α=40%) of reaction, DCP starts
A large amount of to decompose, less, whole system vulcanization reaction process follows single kinetics mechanism for reaction activity variation.Reaction activation
Can be lower than initial stage, illustrate DCP vulcanization matrix or react with initiation ZDMA to be easier than sulphur, react rapider.
In addition, the S/D-30Z system of two step vulcanizations preparation of the invention vulcanizes on the whole with the raising of state of cure (vulcanization) α
The apparent activation energy of reaction, which first increases then to reduce, tends to definite value (table 4).This is because vulcanization reaction first stage (α=0%-
30%), system is the free radical generated for crosslinking, needs more energy to carry out anakmetomeres, the activation energy needed is relatively high.
As reaction proceeds to second stage (α=30%-80%), sulphur decomposes under the action of promotor reaches a certain concentration, this
The numerical value change section very little of single order stage activation energy, is close to constant, shows that the vulcanization reaction process follows single dynamics
Mechanism.When state of cure (vulcanization) α is by 80%-100%, DCP, which is decomposed, reaches maximum rate, in system increasingly for the free radical of reaction
More, macromolecular chain segment movement is active, and exothermic reaction rate of heat flow is higher and higher, and activation energy needed for vulcanization reaction reduces.
Activation energy data under the S/D-30Z system differentiated yields α of the present invention of table 4
Activation energy data under the different system differentiated yields α of table 5
The characterization of 3.6 mechanical properties
Compared with according to Fig. 7 as can be seen that with only with DCP when, two step vulcanizing systems introduce flexible sulfide linkage, when removing external force
System recovery capacity greatly increases, and Compression Set is reduced, for the ZDMA system with ionic cross-linked bond,
Compression Set drops to 5% or so from 18%.Compared with only with sulphur when, it is stronger that two step vulcanizing systems introduce rigidity
C-C key, system crosslink density increase, and Compression Set reduces, and compression modulus increases.
Further, from fig. 10 it can be seen that with ZDMA content increase, vulcanizate tensile strength compression modulus, tears
Fragility energy, Compression Set increase.This is because nanoparticle and ionic bond that ZDMA is formed are more difficult under external force
It being destroyed, forming new ionic bond in new position again once be destroyed, compressive strength and Compression Set increase.
To sum up, the present invention is with rubber, and sulphur, vulcanizing agent, salt unsaturated carboxylic acid and rubber additive are raw material, passes through two steps
Reinforced type nitrile rubber has been prepared in vulcanization.The crosslink density of gained rubbery system significantly improves, and is keeping rubber
In the case where tensile strength, elongation at break and Compression Set performance are significantly improved.In addition, with unsaturated in system
The increase of carboxylate, the vulcanizate tensile strength of gained rubber, compression modulus, tear resistance, Compression Set also gradually increase
Add.The present invention is had excellent performance and regulatable reinforced rubber, has a extensive future.
Claims (10)
1. a kind of salt unsaturated carboxylic acid reinforced rubber, it is prepared by following raw materials:
Rubber, sulphur, vulcanizing agent, salt unsaturated carboxylic acid, rubber additive.
2. reinforcement nitrile rubber according to claim 1, it is characterised in that: the vulcanizing agent is peroxide vulcanizing agent；
And/or the rubber additive include one of plasticizer, vulcanizing activator, vulcanization accelerator, anti-aging agent, reinforcing agent or
It is a variety of.
3. reinforced rubber according to claim 1 or 2, it is characterised in that: the plasticizer is stearic acid, vulcanizing activator
For ZnO, vulcanization accelerator is DM and TMTD, and anti-aging agent 4010, reinforcing agent is carbon black, and rubber is nitrile rubber, and vulcanizing agent is
Cumyl peroxide, salt unsaturated carboxylic acid are zinc methacrylate.
4. reinforced rubber according to claim 1 to 3, it is characterised in that: the weight proportion of each raw material are as follows: rubber
100 parts of glue, 1.3~1.7 parts of sulphur, 1.8~2.2 parts of vulcanizing agent, 10~40 parts of salt unsaturated carboxylic acid, rubber additive 9~30
Part；
Preferably, include in the rubber additive: 0.9~1.1 part of plasticizer, 4.9~5.1 parts of vulcanizing activator, vulcanization promotees
Into agent DM2.4~2.6, TMTD0.24~0.26 part, 0.9~1.1 part of anti-aging agent, or also include 14~16 parts of carbon black.
5. reinforced rubber according to claim 4, it is characterised in that: the weight proportion of each raw material are as follows: rubber 100
Part, 1.5 parts of sulphur, 2 parts of vulcanizing agent, 10~40 parts of salt unsaturated carboxylic acid, 1 part of plasticizer, 5 parts of vulcanizing activator, vulcanization promotes
DM2.5 parts of agent, TMTD0.25 parts, 1 part of anti-aging agent, or also include 15 parts of carbon black.
6. reinforced rubber according to claim 5, it is characterised in that: the zinc methacrylate is 20~40 parts, preferably
30~40 parts, more preferable 40 parts.
7. -6 any reinforced rubber according to claim 1, it is characterised in that: the reinforced rubber is vulcanized by two steps
Method preparation, specifically include:
(1), each raw material is weighed in proportion, is kneaded using open mill, and rubber compound is obtained；
(2), rubber compound obtained by step (1) is vulcanized, control reaction temperature is 120~140 DEG C, and it is anti-to carry out first step vulcanization
It answers；Then control reaction temperature is 160~180 DEG C, carries out second step vulcanization reaction, obtains reinforced rubber.
8. a kind of method for preparing any reinforced rubber of claim 1~7, preparation step include:
(1), each raw material is weighed in proportion, is kneaded using open mill, and rubber compound is obtained；
(2), rubber compound obtained by step (1) is vulcanized, control reaction temperature is 120~140 DEG C, and it is anti-to carry out first step vulcanization
It answers；Then control reaction temperature is 160~180 DEG C, carries out second step vulcanization reaction, obtains reinforced rubber.
9. preparation method according to claim 8, it is characterised in that: in step (1), the mixing process includes: a. to beat
Open mill is opened, it is thin logical to carry out rubber；B. make rubber bag roller, Sulfur, Bao Tong is added, and tap rubber and turn refining；C. be added vulcanizing activator,
Anti-aging agent, plasticizer are slow added into 1/3~1/2 salt unsaturated carboxylic acid, left and right cutter, Bao Tong；D. remaining unsaturation is added
Carboxylate, alternately rubber tapping turns refining for left and right；E. vulcanization accelerator and vulcanizing agent is added, or continuously adds reinforcing agent, continues to tap rubber
It turns refining, is sufficiently mixed each raw material, thin logical bottom sheet；
And/or in step (2), the first step vulcanization reaction temperature be 130 DEG C, the reaction time be 40~60 minutes, preferably 50
Minute；Second step vulcanization reaction temperature is 170 DEG C, and the reaction time is 5~10 minutes, preferably 8 minutes.
10. preparation method according to claim 9, it is characterised in that: in the step a, control the mixing roller of open mill
Temperature is 50 DEG C, and roller speed ratio is 1: 1.1~1:1.2, and open mill roll spacing is 0.5mm, and thin logical number is 4 times；
And/or in step b, thin logical number is 2~3 times；And/or in step c, cutter number is 3 times；And/or in step d,
Controlling the number alternately tapped rubber and turned refining is 2~4 times；And/or in step e, when thin logical bottom sheet, roll spacing 2mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111363210A (en) * | 2020-03-18 | 2020-07-03 | 陕西科技大学 | Ionic crosslinked rubber and preparation, recovery and secondary vulcanization method thereof |
| CN113667201A (en) * | 2021-07-23 | 2021-11-19 | 华南理工大学 | Hydrogenated carboxyl nitrile rubber material and preparation method and application thereof |
| CN113667201B (en) * | 2021-07-23 | 2022-07-26 | 华南理工大学 | Hydrogenated carboxyl nitrile rubber material and preparation method and application thereof |
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