CN110204806A - A kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and preparation method thereof - Google Patents
A kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and preparation method thereof Download PDFInfo
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- CN110204806A CN110204806A CN201910604985.1A CN201910604985A CN110204806A CN 110204806 A CN110204806 A CN 110204806A CN 201910604985 A CN201910604985 A CN 201910604985A CN 110204806 A CN110204806 A CN 110204806A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention provides a kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and preparation method thereof, modified butadiene acrylonitrile rubber is kneaded by following raw material and is made, and the raw material includes nitrile rubber, modification of aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；The modification of aramid fiber-nitrile rubber masterbatch is kneaded by modification of aramid fiber and nitrile rubber and is made；The modification of aramid fiber is made using coupling agent is modified to aramid fiber；The coupling agent is selected from one of silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine or a variety of.The raw material for preparing of the modified butadiene acrylonitrile rubber includes being kneaded modification of aramid fiber-nitrile rubber masterbatch obtained by modification of aramid fiber and nitrile rubber, it with nitrile rubber in the presence of sulphur, activator, promotor after being kneaded, modification of aramid fiber is well dispersed in nitrile rubber, and then improves the tensile strength and stress at definite elongation of nitrile rubber.
Description
Technical field
The invention belongs to field of rubber technology more particularly to a kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and its preparation sides
Method.
Background technique
Aromatic polyamide fibre, abbreviation aramid fiber (PPTA), refers to and is connected with each other structure by the aromatic rings of amide bond
At linear macromolecule, pass through organic polymer fiber made of fiber spinning from crystalline state.Federal Trade Commission is by aramid fiber
It is defined as polyamide made of amido bond (- CONH-) and two phenyl ring at least in the presence of 85% are connected directly.Aramid fiber structure
It is regular, not only have high intensity, high-modulus, resistance to acid and alkali, chemical resistance, fatigue durability, high temperature resistant, light weight etc. excellent
Performance, and wearability and rubber adhesion performance with height.Early in the 1960s, E.I.Du Pont Company starts just fragrance
The expansion research of polyamide fiber, and in the scale volume production of realization aramid fiber in 1972, it is gradually replaced in many fields
Steel wire and glass fibre are widely used in the fields such as aerospace, geotextile, national defense facility, rubber product.
Aramid fiber has both the physical property of inorfil and the processing performance of organic fiber, is a kind of excellent reinforcing material
Material, can be used as the framework material of the composite materials such as reinforced plastics, rubber.However, aramid fiber is in apparent skin-core structure, surface
Lattice is fine and close, molecular chain structure and biggish steric effect with highly crystalline, so that amide group and other atoms or base
Group is difficult that chemical reaction or other effects occur.Meanwhile aramid fiber surface lacks chemical activity functional group, forms the ability of hydrogen bond
Low, surface wettability is poor, and the high-crystallinity in fibre structure leads to fiber surface high degrees of smoothness, cause aramid fiber with
Rubber matrix caking property is poor, significantly limits application of the aramid fiber in rubber materials.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber and its preparation sides
Method, modified butadiene acrylonitrile rubber tensile strength with higher.
The present invention provides a kind of modified butadiene acrylonitrile rubber, be kneaded and be made by following raw material, the raw material include nitrile rubber,
Modification of aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；
The modification of aramid fiber-nitrile rubber masterbatch is kneaded by modified Nano aramid fiber and nitrile rubber and is made；
The modification of aramid fiber is modified aramid fiber using coupling agent obtained；
The coupling agent is in silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine
It is one or more.
Preferably, the mass ratio of nitrile rubber, modification of aramid fiber, sulphur, activating agent and promotor be 100:3.5~
4.5:1.7~2.3:5~8:1.7~2.3.
Preferably, the mass content of modification of aramid fiber is in the modified Nano aramid fiber-nitrile rubber masterbatch
17~20%.
Preferably, the aramid fiber be selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or
It is a variety of；The mass ratio of the coupling agent and aramid fiber is 0.8~2.5:10.
Preferably, the diameter of the aramid nano-fiber is 50~80nm；The draw ratio of aramid nano-fiber be 2000~
5000:1。
Preferably, the activator is selected from stearic acid and zinc oxide；
The promotor is selected from sulfenamide type accelerators.
Preferably, the modification of aramid fiber is specifically included using be made modified to aramid fiber of coupling agent:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it is modified
Aramid fiber；
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving；Again by the pre- modifying aramid fiber point
It dissipates in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain modification of aramid fiber；
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, it is modified
Aramid fiber；
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
Preferably, the time reacted in the step a) is 1~5h；Rotate 10~40min；Dry temperature is 40~80
℃；
The time impregnated in the step b) is 1~5h；Revolving and the time rotated again are 10~40min.
The present invention provides a kind of preparation methods of modified butadiene acrylonitrile rubber described in above-mentioned technical proposal, comprising the following steps:
Nitrile rubber is plasticated 55~65s, sulphur is added and plasticates 18~23s, adds modification of aramid fiber-nitrile rubber
Masterbatch is plasticated 105~135s, and activator is added after mixing and is kneaded 22~28s, is added promotor and is kneaded 27~34s,
Obtain modified butadiene acrylonitrile rubber.
The present invention provides a kind of modified butadiene acrylonitrile rubber, be kneaded and be made by following raw material, the raw material include nitrile rubber,
Modification of aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；The modification of aramid fiber-nitrile rubber masterbatching
Glue is kneaded by modification of aramid fiber and nitrile rubber and is made；The modification of aramid fiber is made using coupling agent is modified to aramid fiber；
The coupling agent is selected from one of silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine or more
Kind.The raw material for preparing of modified butadiene acrylonitrile rubber provided by the invention includes changing as made from modification of aramid fiber and nitrile rubber mixing
Property aramid fiber-nitrile rubber masterbatch, after being kneaded in the presence of sulphur, activator, promotor with nitrile rubber,
Modification of aramid fiber is well dispersed in nitrile rubber, and then improves the tensile strength of nitrile rubber.Also improve butyronitrile rubber
The stress at definite elongation of glue.The results showed that the tensile strength in the direction L for the modified butadiene acrylonitrile rubber that the present invention improves be 5.7~
8MPa, 100% stress at definite elongation are 1.7~2.6MPa, and 300% stress at definite elongation is 4.5~7.5MPa；The tensile strength in the direction T is
5.5~7.6MPa, 100% stress at definite elongation are 1.7~2.2MPa, and 300% stress at definite elongation is 4.4~6.8MPa.
Detailed description of the invention
Fig. 1 is that the stress-strain of the modified butadiene acrylonitrile rubber of the unmodified nitrile rubber of the present invention and Examples 1 to 3 preparation is bent
Line chart.
Specific embodiment
The present invention provides a kind of modified butadiene acrylonitrile rubber, be kneaded and be made by following raw material, the raw material include nitrile rubber,
Modification of aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；
The modification of aramid fiber-nitrile rubber masterbatch is kneaded by modified Nano aramid fiber and nitrile rubber and is made；
The modified Nano aramid fiber is made using coupling agent is modified to aramid fiber；
The coupling agent is in silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine
It is one or more.
The raw material for preparing of modified butadiene acrylonitrile rubber provided by the invention includes being kneaded system by modification of aramid fiber and nitrile rubber
Modification of aramid fiber-nitrile rubber the masterbatch obtained, passes through and nitrile rubber is in the presence of sulphur, activator, promotor
After mixing, modification of aramid fiber is well dispersed in nitrile rubber, and then improves the tensile strength of nitrile rubber.It also improves
The stress at definite elongation of nitrile rubber.
Modified butadiene acrylonitrile rubber provided by the invention is kneaded by following raw material and is made, and the raw material includes nitrile rubber.
The raw material includes modification of aramid fiber-nitrile rubber masterbatch, the modified Nano aramid fiber-nitrile rubber
Masterbatch is kneaded by modification of aramid fiber and nitrile rubber and is made；The modified Nano aramid fiber changes aramid fiber using coupling agent
Property be made；The coupling agent is selected from silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine (DA)
It is one or more.The present invention is by selecting the coupling agent of mentioned kind to be modified aramid fiber, the modified Nano virtue made
Synthetic fibre fiber can be preferably dispersed in nitrile matrix, improve the effect of aramid fiber reinforcement nitrile rubber, nitrile rubber
100% stress at definite elongation and 300% stress at definite elongation and tensile strength increase.
In the present invention, the aramid fiber is preferably selected from the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber
It is one or more；The diameter of the aramid filament is preferably 9~11 μm, and more preferably 10 μm；The draw ratio of aramid filament is excellent
Choosing >=10000.The diameter of the short fibre of aramid fiber is preferably 9~11 μm, and more preferably 10 μm, the draw ratio of the short fibre of aramid fiber is preferably
500~5000.The length of the Fanglun slurry cake is preferably 2.0~3.0mm, and surface area is 5~8m2/g.The aramid filament, virtue
The short fine and Fanglun slurry cake of synthetic fibre is all made of commercial goods.In the present invention, the diameter of the aramid nano-fiber be preferably 50~
80nm；The draw ratio of aramid nano-fiber is aramid nano-fiber described in 2000~5000:1 preferably by patent of invention
Method described in CN105153413A is made.
The coupling agent is selected from silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine (DA)
One of or it is a variety of；In a particular embodiment, the coupling agent is selected from dopamine and/or Si-69；The coupling agent and aramid fiber
Mass ratio be 0.8~2.5:10.
In the present invention, the modification of aramid fiber is specifically included using be made modified to aramid fiber of coupling agent:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it is modified
Aramid fiber；
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving；Again by the pre- modifying aramid fiber point
It dissipates in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain modification of aramid fiber；
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, it is modified
Aramid fiber；
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
In the present invention, when modifying agent is used alone, modification of aramid fiber can be made in accordance with the following methods:
It disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, obtain modified virtue
Synthetic fibre fiber.
In the present invention, the organic solvent is preferably selected from one of acetonitrile, methanol, ethyl alcohol, acetone and tetrahydrofuran
Or it is a variety of, it is more preferably selected from tetrahydrofuran.In the present invention, the quality of aramid fiber and the volume ratio of organic solvent be preferably (0.5~
2.0)g:100mL.The mass ratio of aramid fiber and modifying agent is 0.8~2.5:10.The rate of the stirring is preferably 200~
500rpm；The reaction time is preferably 1~5h；The time of the revolving is preferably 10~40min, removes big portion by revolving
Divide solvent.The temperature of the drying is preferably 40~80 DEG C；It is preferred that dry to constant weight.
In the present invention, the aramid fiber is contracted in N-Methyl pyrrolidone solvent by p-phenylenediamine and paraphthaloyl chloride
It is poly- to be made.The temperature of the polycondensation is preferably 0~10 DEG C；The time of polycondensation is preferably 10~30min.More specifically, the virtue
By p-phenylenediamine and paraphthaloyl chloride, aramid fiber micelle is made in the polycondensation in N-Methyl pyrrolidone solvent to synthetic fibre, then passes through high speed
Stirring or spinning obtain aramid fiber；The rate of the high-speed stirred is preferably 500~2000rpm.
In the present invention, modifying agent and used time, modification of aramid fiber can also be made in accordance with the following methods:
The present invention impregnates aramid fiber and modifying agent, washing, obtains pre- modifying aramid fiber after revolving；Again by the pre- modifying aramid fiber
It is scattered in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain modifying aramid fiber fibre
Dimension.
In the present invention, the time of the dipping is 1~5h；Revolving and the time rotated again are 10~40min.
When if the coupling agent used when modified for the first time is dopamine, preparation method specifically:
Tris-HCl (trishydroxymethylaminomethane) is configured to the buffer solution of the water of pH=8.5, Ba An hydrochlorate is added
Dopamine solution is obtained, dopamine solution and aramid fiber are impregnated into 1-5h, washing filters, and obtains the modified PPTA of dopamine, then revolve
Steam 10~40min；
Again modifying agent is added in the modified PPTA dispersion of dopamine again in organic solvent, is reacted under stirring condition, then
Secondary revolving, it is dry, obtain modification of aramid fiber.
In the present invention, if coupling agent is added in polycondensation process, the preparation method of the modification of aramid fiber, packet
Include following steps:
In the aramid fiber polycondensation later period, modifying agent to micelle is added and generates, at fine, washing, rotates, it is dry, obtain modifying aramid fiber
Fiber.
In the present invention, the aramid fiber polycondensation later period, system viscosity increase, and coupling agent is added, and reaction to micelle generates, warp
At fine, washing, rotate, it is dry, obtain modification of aramid fiber.
Above-mentioned preparation method is simple, at low cost, and treatment effeciency is high, is suitable for Large scale processes and produces.
The raw material includes sulphur, activator and promotor；The activator is preferably selected from stearic acid (SA) and zinc oxide；
The promotor is selected from sulfenamide type accelerators；The sulfenamide type accelerators is selected from model C Z-80.
The present invention provides a kind of preparation methods of modified butadiene acrylonitrile rubber described in above-mentioned technical proposal, comprising the following steps:
Nitrile rubber is plasticated 55~65s, sulphur is added and plasticates 18~23s, adds modified Nano aramid fiber-butyronitrile
Rubber masterbatch is plasticated 105~135s, and activator is added after mixing and is kneaded 22~28s, add promotor be kneaded 27~
34s obtains modified butadiene acrylonitrile rubber.
In the present invention, the modification of aramid fiber-nitrile rubber masterbatch is preferably made in accordance with the following methods:
Modification of aramid fiber dispersion liquid and nitrile rubber solution are mixed, rotated, it is dry, obtain modification of aramid fiber-fourth
Nitrile rubber masterbatch.
In the present invention, the fourth in the modification of aramid fiber and nitrile rubber solution in the modification of aramid fiber dispersion liquid
The mass ratio of nitrile rubber is preferably 0.9~1.1:1, more preferably 1:1.
The modification of aramid fiber dispersion liquid is to disperse tetrahydrofuran solvent for aramid fiber to be made；The matter of aramid fiber
Amount and the volume ratio of tetrahydrofuran are preferably (0.9~1.1) g:100mL, more preferably 1g:100mL.Nitrile rubber solution be by
Nitrile rubber is dissolved in tetrahydrofuran solvent and is made；The quality of nitrile rubber and the volume ratio of tetrahydrofuran be preferably (14~
15) g:100mL, more preferably 14.3g:100mL.
In the present invention, the temperature when nitrile rubber is plasticated is preferably 48~53 DEG C, and more preferably 50 DEG C；Butyronitrile rubber
Roll spacing when glue is plasticated is preferably 0.75~0.85mm, more preferably 0.8mm.Promotor back roller is added away from being set as 0.3mm.Add
Enter and set 1.4mm for roll spacing again after rubber compound is beaten triangle bag 5 times after promotor is kneaded, rubber compound bubble removing, bottom sheet obtain
To modified butadiene acrylonitrile rubber.
For the present invention by the way that above-mentioned modification of aramid fiber to be modified nitrile rubber, method is simple, and treatment effeciency is high, fits
For being mass produced.
In order to further illustrate the present invention, below with reference to embodiment to a kind of modified butadiene acrylonitrile rubber provided by the invention and its
Preparation method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under nitrogen protection, 100mL is passed through into the solvent N-methyl pyrilidone except water process, be added in reactor,
It is added with stirring hydrotropy salt CaCl26g and surfactant octadecyl salt cation alkyl imidazoline 4g, and is heated to 90 DEG C
Hydrotropy salt and surfactant are dissolved, the solution of hydrotropy salt and surfactant, heating time 60min, Zhi Houleng are obtained
Water-bath cooling 10min or so to 5 DEG C, reaction vessel is added in 4.326g p-phenylenediamine, holds reaction after p-phenylenediamine dissolution
Device is cooled to -5 DEG C, adds paraphthaloyl chloride, quickening mixing speed is to 2000rpm, the reaction was continued 8min, reaction temperature -5
DEG C, stop stirring after gelatin phenomenon occurs in above-mentioned reaction system, obtains frozen glue body；
1L dispersing agent N-Methyl pyrrolidone is added into above-mentioned frozen glue body, is swollen frozen glue body, by the frozen glue after swelling
Body is by high-speed stirred at uniform system, mixing speed 4000rpm, mixing time 5min, by above-mentioned uniform system strong
Strong to be added with stirring butanol, mixing speed 6000rpm, mixing time 10min are obtained containing p-aramid fiber nanofiber
Even stable suspension liquid containing p-aramid fiber nanofiber is heated concentration, heating temperature 117 by even stable suspension liquid
DEG C, heating time 6h obtains the p-aramid fiber nanofiber suspension of high concentration (fiber content 25%)；
Dry freeze-drying is carried out to above-mentioned p-aramid fiber nanofiber suspension, obtains aramid nano-fiber；The aramid fiber
The diameter of nanofiber is 50~80nm；The draw ratio of aramid nano-fiber is 2000~5000:1.
It disperses above-mentioned nanometer aramid fiber in organic solvent THF, changes according to the addition of Si-69:PPTA=1:1 mass ratio
Property agent Si-69, it is agitated, be uniformly mixed reaction 2h, dry 2h by revolving, 60 DEG C of vacuum ovens, obtain Si-69 modification and receive
Rice aramid fiber (Si-69-PPTA).
It disperses the above-mentioned modified Nano aramid fiber of 5g in 500mL tetrahydrofuran solvent, it is fine to obtain modified Nano aramid fiber
Tie up dispersion liquid；Then 100g nitrile rubber is dissolved in 700mL tetrahydrofuran solvent, obtains nitrile rubber solution.
According to modified Nano aramid fiber dispersion liquid: nitrile rubber solution=1:1~2.5:1 (mass ratio) is by nanometer aramid fiber
Fiber dispersion is uniformly mixed with nitrile rubber solution, then removes most of solvent through revolving, and in 60 DEG C of vacuum oven
Dry 6h, obtains PPTA-NBR masterbatch；In PPTA-NBR masterbatch the mass content of modified Nano aramid fiber be 8%~
25%；
Mass ratio according to nitrile rubber, modified Nano aramid fiber, sulphur, zinc oxide, stearic acid and promotor is
100:4:2:5:2:2 is weighed, and two-roll mill temperature and roll spacing are respectively set to 50 DEG C and 0.8mm, and NBR is added and plasticates
1min is added sulphur (S) and plasticates 20s, and above-mentioned PPTA-NBR masterbatch is then added and plasticates 2min.It is to be mixed uniformly after, simultaneously
Stearic acid (SA) is added and zinc oxide (ZnO) is kneaded 25s, accelerant CZ -80 is added afterwards and is kneaded 30s, roll spacing, which is then arranged, is
0.3mm beats rubber compound triangle bag 5 times, and it is 1.4mm that roll spacing, which is finally arranged, by rubber compound bubble removing, bottom sheet, obtains modified fourth
Nitrile rubber.
Embodiment 2
The buffer solution of the water of pH=8.5 is configured to using Tris-HCl, it is dense that addition dopamine hydrochloride obtains dopamine
Degree is the dopamine solution of 2g/L, impregnates 2h according to aramid nano-fiber prepared by 100mL solution, 1g embodiment 1, washing filters
The modified nanometer aramid fiber of dopamine is obtained, rotated, remove solvent, 60 DEG C of vacuum oven 2h drying, it is modified to obtain DA
Nanometer aramid fiber (DA-PPTA)；
Modified butadiene acrylonitrile rubber is prepared in above-mentioned DA modified Nano aramid fiber by the step of according to embodiment 1.
Embodiment 3
It disperses DA-PPTA prepared by example 2 in organic solvent THF, according to coupling agent Si-69:DA-PPTA=1:1
Si-69 is added thereto by mass ratio, is then stirred, is uniformly mixed reaction 2h, most of solvent is removed in the way of revolving, most
It is dry to constant weight through 2h in 60 DEG C of vacuum ovens afterwards, obtain the modified nanometer aramid fiber of coupling agent Si69 and dopamine D A
(DA-Si69-PPTA)；
Modified butyronitrile is prepared in above-mentioned DA-Si69-PPTA and nitrile rubber by the step of being further continued for according to embodiment 1
Rubber.
Embodiment 4
It disperses aramid fiber short fine (diameter is 9~11 μm, and length is 1~3mm) in organic solvent THF, according to Si-69:
Modifying agent Si-69, agitated, uniformly mixed reaction 2h, by revolving, 60 DEG C of vacuum ovens is added in PPTA=1:1 mass ratio
2h is dried, Si-69 modification of aramid fiber (Si-69-PPTA) is obtained.
It disperses the above-mentioned modification of aramid fiber of 5g in 500mL tetrahydrofuran solvent, obtains modification of aramid fiber dispersion liquid；
Then 100g nitrile rubber is dissolved in 700mL tetrahydrofuran solvent, obtains nitrile rubber solution.
According to modification of aramid fiber dispersion liquid: nitrile rubber solution=1:1~3.75:1 (mass ratio) divides aramid fiber
Dispersion liquid is uniformly mixed with nitrile rubber solution, then removes most of solvent through revolving, and in 60 DEG C of vacuum oven dry 6h,
Obtain PPTA-NBR masterbatch；The mass content of modification of aramid fiber is 8~30% in PPTA-NBR masterbatch；
It is 100:4 according to the mass ratio of nitrile rubber, modification of aramid fiber, sulphur, zinc oxide, stearic acid and promotor:
2:5:2:2 is weighed, and two-roll mill temperature and roll spacing are respectively set to 50 DEG C and 0.8mm, and NBR is added and plasticates 1min,
Sulphur (S) is added to plasticate 20s, above-mentioned PPTA-NBR masterbatch is then added and plasticates 2min, it is to be mixed uniformly after, while being added hard
Resin acid (SA) and zinc oxide (ZnO) are kneaded 25s, and accelerant CZ -80 is added afterwards and is kneaded 30s, and it is 0.3mm that roll spacing, which is then arranged, will
Rubber compound is beaten triangle bag 5 times, roll spacing is arranged finally as 1.4mm and rubber compound bubble removing, bottom sheet are obtained modified butadiene acrylonitrile rubber.
Embodiment 5
By Fanglun slurry cake, (length of Fanglun slurry cake is 2.0~3.0mm, and surface area is 5~8m2/ g) it is scattered in organic solvent
In THF, modifying agent Si-69, agitated, uniformly mixed reaction 2h, by rotation is added according to Si-69:PPTA=1:1 mass ratio
It steams, 60 DEG C of vacuum ovens drying 2h, obtains Si-69 modification of aramid fiber (Si-69-PPTA).
It disperses the above-mentioned modifying aramid fiber pulp of 5g in 500mL tetrahydrofuran solvent, obtains modifying aramid fiber pulp dispersions；
Then 100g nitrile rubber is dissolved in 700mL tetrahydrofuran solvent, obtains nitrile rubber solution.
According to modifying aramid fiber pulp dispersions: nitrile rubber solution=1:1~3.75:1 (mass ratio) divides Fanglun slurry cake
Dispersion liquid is uniformly mixed with nitrile rubber solution, then removes most of solvent through revolving, and in 60 DEG C of vacuum oven dry 6h,
Obtain PPTA-NBR masterbatch；The mass content of modification of aramid fiber is 8%~30% in PPTA-NBR masterbatch；
It is 100:4 according to the mass ratio of nitrile rubber, modification of aramid fiber, sulphur, zinc oxide, stearic acid and promotor:
2:5:2:2 is weighed, and two-roll mill temperature and roll spacing are respectively set to 50 DEG C and 0.8mm, and NBR is added and plasticates 1min,
Sulphur (S) is added to plasticate 20s, above-mentioned PPTA-NBR masterbatch is then added and plasticates 2min, it is to be mixed uniformly after, while being added hard
Resin acid (SA) and zinc oxide (ZnO) are kneaded 25s, and accelerant CZ -80 is added afterwards and is kneaded 30s, and it is 0.3mm that roll spacing, which is then arranged, will
Rubber compound is beaten triangle bag 5 times, roll spacing is arranged finally as 1.4mm and rubber compound bubble removing, bottom sheet are obtained modified butadiene acrylonitrile rubber.
Comparative example 1
Unmodified PPTA.
Referring to Fig. 1, Fig. 1 is answering for the modified butadiene acrylonitrile rubber of the unmodified nitrile rubber of the present invention and Examples 1 to 5 preparation
Force-strain curve figure.
The modified butadiene acrylonitrile rubber that the present invention prepares Examples 1 to 5 carries out tensile strength, 100% stress at definite elongation, 300%
The test of stress at definite elongation and elongation at break, the results are shown in Table 1:
The modified butadiene acrylonitrile rubber of 1 Examples 1 to 5 of table preparation and the mechanical experimental results of unmodified nitrile rubber
Note: L be it is common cut out sample prescription to, T be perpendicular to common sanction sample prescription to；" --- " indicates that batten elongation at break is less than
300%.
As can be seen from Table 1: for the unmodified nitrile rubber of comparative example 1, embodiment 1, embodiment 2 and implementation
The tensile strength and stress at definite elongation of nitrile rubber prepared by example 3 are significantly raised, but elongation at break reduces, and illustrate that PPTA passes through
After coupling agent modified, dispersion degree of the PPTA in NBR matrix can be improved, to improve PPTA to the reinforcing effect of NBR.Its
In, compared to for one pack system coupling agent, bi-component coupling agent becomes apparent the reinforcing effect of NBR.
As seen from the above embodiment, the present invention provides a kind of modified butadiene acrylonitrile rubbers, are kneaded and are made by following raw material, described
Raw material includes nitrile rubber, modification of aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；The modifying aramid fiber
Fiber-nitrile rubber masterbatch is kneaded by modification of aramid fiber and nitrile rubber and is made；The modification of aramid fiber is using coupling
Agent is modified to aramid fiber to be made；The coupling agent is selected from silane coupling agent Si-69, Si-75, KH-550, KH570, KH-151, KH-
One of 792 and dopamine are a variety of.The raw material for preparing of modified butadiene acrylonitrile rubber provided by the invention includes by modifying aramid fiber fibre
Peacekeeping nitrile rubber is kneaded modification of aramid fiber-nitrile rubber masterbatch obtained, passes through and nitrile rubber is in sulphur, activation
After being kneaded in the presence of agent, promotor, modification of aramid fiber is well dispersed in nitrile rubber, and then improves nitrile rubber
Tensile strength.Also improve the stress at definite elongation of nitrile rubber.The results showed that the L for the modified butadiene acrylonitrile rubber that the present invention improves
The tensile strength in direction be 5.7~8MPa, 100% stress at definite elongation be 1.7~2.6MPa, 300% stress at definite elongation be 4.5~
7.5MPa；The tensile strength in the direction T is 5.5~7.6MPa, and 100% stress at definite elongation is 1.7~2.2MPa, 300% stress at definite elongation
For 4.4~6.8MPa.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of nanometer of aramid fiber modified butadiene acrylonitrile rubber is kneaded by following raw material and is made, the raw material includes nitrile rubber, changes
Property aramid fiber-nitrile rubber masterbatch, sulphur, activator and promotor；
The modification of aramid fiber-nitrile rubber masterbatch is kneaded by modification of aramid fiber and nitrile rubber and is made；The modification
Aramid fiber is made using coupling agent is modified to aramid fiber；
The coupling agent is selected from one of silane coupling agent Si-69, KH-550, KH570, KH-151, KH-792 and dopamine
Or it is a variety of.
2. modified butadiene acrylonitrile rubber according to claim 1, which is characterized in that nitrile rubber, modification of aramid fiber, sulphur,
The mass ratio of activating agent and promotor is 100:3.5~4.5:1.7~2.3:5~8:1.7~2.3.
3. modified butadiene acrylonitrile rubber according to claim 1, which is characterized in that the modified Nano aramid fiber-butyronitrile rubber
The mass content of modification of aramid fiber is 17~20% in glue masterbatch.
4. modified butadiene acrylonitrile rubber according to claim 1, which is characterized in that it is short that the aramid fiber is selected from aramid filament, aramid fiber
One of fine, Fanglun slurry cake and aramid nano-fiber are a variety of；The mass ratio of the coupling agent and aramid fiber is 0.8~2.5:
10。
5. modified butadiene acrylonitrile rubber according to claim 4, which is characterized in that the diameter of the aramid nano-fiber be 50~
80nm；The draw ratio of aramid nano-fiber is 2000~5000:1.
6. modified butadiene acrylonitrile rubber according to claim 1, which is characterized in that the activator is selected from stearic acid and oxidation
Zinc；
The promotor is selected from sulfenamide type accelerators.
7. modified butadiene acrylonitrile rubber according to claim 1, which is characterized in that the modification of aramid fiber uses coupling agent pair
Modified be made of aramid fiber specifically includes:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, obtain modifying aramid fiber
Fiber；
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving；Again disperse the pre- modifying aramid fiber in
In organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain modification of aramid fiber；
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, obtain modifying aramid fiber
Fiber；
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
8. modified butadiene acrylonitrile rubber according to claim 7, which is characterized in that the time reacted in the step a) is 1~
5h；Rotate 10~40min；Dry temperature is 40~80 DEG C；
The time impregnated in the step b) is 1~5h；Revolving and the time rotated again are 10~40min.
9. a kind of preparation method of any one of claim 1~8 modified butadiene acrylonitrile rubber, comprising the following steps:
Nitrile rubber is plasticated 55~65s, sulphur is added and plasticates 18~23s, adds modification of aramid fiber-nitrile rubber masterbatching
Glue is plasticated 105~135s, and activator is added after mixing and is kneaded 22~28s, is added promotor and is kneaded 27~34s, obtains
Modified butadiene acrylonitrile rubber.
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| CN113321857A (en) * | 2021-04-30 | 2021-08-31 | 宁波市大器密封科技有限公司 | Aramid fiber pressing ring and preparation method thereof |
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Application publication date: 20190906 |