CN105482179A

CN105482179A - Cis-polybutadiene rubber material and preparation method thereof

Info

Publication number: CN105482179A
Application number: CN201510941952.8A
Authority: CN
Inventors: 高芳
Original assignee: Hefei Jieming New Material Technology Co Ltd
Current assignee: Hefei Jieming New Material Technology Co Ltd
Priority date: 2015-12-16
Filing date: 2015-12-16
Publication date: 2016-04-13

Abstract

The invention discloses a cis-polybutadiene rubber material. The cis-polybutadiene rubber material is prepared from, by weight, 30-40 parts of carbon nanotubes, 50-60 parts of hydroxyl-terminated polybutadiene, 200-300 parts of n-methylpyrrolidone, 5-7 parts of boric oxide, 160-200 parts of cis-polybutadiene rubber, 2-3 parts of zinc oxide, 2-3 parts of anti-aging agent 4010, 1.3-2 parts of sulfur and 10-17 parts of epoxy butyl oleate. The preparation method comprises the steps that carboxylation treatment is conducted on the carbon nanotubes firstly, and then the treated carbon nanotubes are reacted with the hydroxyl-terminated polybutadiene; the strength of the rubber material can be enhanced due to the fact that carboxyls on the surfaces of the carbon nanotubes are reacted with hydroxyls in the hydroxyl-terminated polybutadiene, and the surfaces of the carbon nanotubes are connected with molecular chains of the hydroxyl-terminated polybutadiene through covalent bonds. Therefore, dispersity of the carbon nanotubes in a substrate is improved, the bonding force of the carbon nanotubes and the rubber substrate is enhanced, and a good reinforcing effect in the rubber substrate is achieved.

Description

A kind of cis-1,4-polybutadiene rubber material and preparation method thereof

Technical field

The present invention relates to field of rubber technology, particularly relate to a kind of cis-1,4-polybutadiene rubber material and preparation method thereof.

Background technology

Carbon nanotube is widely used in polymkeric substance to the heat conduction of raising polymkeric substance, conduction and physicals etc. because of the structure of its uniqueness and the physical and chemical performance of excellence.But carbon nanotube itself has very high surface free energy, easily reunites, and not easily disperses in polymeric matrix, limit its application.The surface modification treatment of carbon nanotube is one of important channel of improving its dispersive ability in the polymer and then the excellent carbon nano-tube/polymer composite material of processability;

Hydroxy-terminated polybutadienes is liquid because of it at normal temperatures, and transparency is good, the low good processability of viscosity; And it and chainextender, linking agent react the cured article that can generate tridimensional network at ambient temperature or elevated temperature, this cured article has excellent mechanical property, good oil resistant and water resistance, particularly acid and alkali-resistance, wear-resisting, low temperature resistant and electrical insulation capability is better, become output in distant pawl series of fluids rubber maximum, purposes is a kind the most widely, is mainly used in the aspects such as solid propellant tackiness agent, polyurethane elastomer, material of construction, speciality coating, tackiness agent, Embedding Material, rubber and plastic and epoxy resin modification.Hydroxy-terminated polybutadienes gives its more characteristic by modification later, improves its performance, has widened the Application Areas of hydroxy-terminated polybutadienes.

Summary of the invention

The object of the invention is exactly the defect in order to make up prior art, provides a kind of cis-1,4-polybutadiene rubber material and preparation method thereof.

The present invention is achieved by the following technical solutions:

A kind of cis-1,4-polybutadiene rubber material, it is made up of the raw material of following weight parts:

Carbon nanotube 30-40, hydroxy-terminated polybutadienes 50-60, n-methyl-2-pyrrolidone 200-300, boron oxide 5-7, cis-1,4-polybutadiene rubber 160-200, zinc oxide 2-3, antioxidant 4010 2-3, sulphur 1.3-2, epoxyoleic acid butyl ester 10-17.

A preparation method for described cis-1,4-polybutadiene rubber material, comprises the following steps:

(1) above-mentioned carbon nanotube is placed in its weight 40-50 doubly, massfraction is the aqueous hydrogen peroxide solution ultrasonic disperse 30-40 minute of 0.3-0.5%, is incubated 100-120 minute, filters, vacuum-drying at 75-80 DEG C, obtains pre-treatment carbon nanotube;

(2) get sulfuric acid that volume ratio is 3-4:1, salpeter solution mixing, stir, described sulfuric acid concentration is 70-75%, concentration of nitric acid is 80-85%;

(3) pre-treatment carbon nanotube obtained above is joined in above-mentioned mixed acid solution, ultrasonic 100-110 minute at 50-60 DEG C, filtration under diminished pressure, be neutral by carbon nanotube deionized water repetitive scrubbing to the filtrate obtained, the vacuum drying oven putting into 76-80 DEG C is dried, and obtains acidifying carbon nanotube;

(4) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2-3 minute, join in said n-methyl-2-pyrrolidone, ultrasonic 10-16 minute, suction filtration, by filter cake dry 20-30 minute at 100-105 DEG C, obtains hydroxyl modification acidifying carbon nanotube;

(5) mixed with boron oxide by above-mentioned hydroxyl modification acidifying carbon nanotube, ball milling is even; Being sent to concentration is in the phosphoric acid solution of 10-15%, constant temperature dipping 120-130 minute at 150-160 DEG C, discharging, and dry, send in reactor, under nitrogen protection, thermal treatment 100-120 minute at 400-450 DEG C, obtains phosphate impregnation compounded mix;

(6) by phosphate impregnation compounded mix, epoxyoleic acid butyl ester, cis-1,4-polybutadiene rubber mixing, plasticate 2-3 minute at 46-50 DEG C, add zinc oxide, antioxidant 4010, sulphur successively, mixing 4-6 minute, the rubber unvulcanizate obtained is placed in two roller mills, mixing 6-10 minute is supplemented at 30-40 DEG C, discharging, at room temperature parks 20-25 hour by sizing material, sends in vulcanizing press, at 150-155 DEG C, carry out sulfuration, to obtain final product;

The preparation method of described a kind of cis-1,4-polybutadiene rubber material, the weight of described mixed acid solution is 18-20 times of pre-treatment carbon nanotubes.

Advantage of the present invention is:

First the present invention carries out Carboxylation process to carbon nanotube, then react with hydroxy-terminated polybutadienes, the intensity of sizing material can be strengthened, this is due to the hydroxyl reaction in the carboxyl of carbon nano tube surface and hydroxy-terminated polybutadienes, carbon nano tube surface is connected by covalent linkage with hydroxy-terminated polybutadienes molecular chain, thus improve its dispersiveness in the base, and enhance the bounding force of itself and rubber matrix, make it in rubber matrix, show better reinforcing effect;

Then the carboxylic acid carbon nanotube after hydroxy-terminated polybutadienes process is mixed with boron oxide, use phosphate impregnation compounded mix, the pyrogenous origin product P 4O10 of phosphoric acid is phosphorus oxygen glass structure, introduce B2O3 in the melt, [BPO4] structural unit can be formed, glass structure is made to change rack-like into by chain, these rack-like structures are cross-linked with each other, strengthen network structure, strengthen the bonding strength with matrix, one deck coating can be covered at matrix surface, covering surfaces hole more effectively, confining surface active site, effective prevention oxidizing gas enters intrinsic silicon by micropore or crackle, effectively raise physical strength and the antioxidant property of finished product.

Embodiment

Carbon nanotube 30, hydroxy-terminated polybutadienes 50, n methyl-2-pyrrolidone 200, boron oxide 5, cis-1,4-polybutadiene rubber 160, zinc oxide 2, antioxidant 4010 2, sulphur 1.3, epoxyoleic acid butyl ester 10.

(1) above-mentioned carbon nanotube is placed in its weight 40 times, massfraction be 0.3% aqueous hydrogen peroxide solution ultrasonic disperse 30 minutes, at 75 DEG C, be incubated 100 minutes, filter, vacuum-drying, obtain pre-treatment carbon nanotube;

(2) get sulfuric acid that volume ratio is 3:1, salpeter solution mixing, stir, described sulfuric acid concentration is 70%, concentration of nitric acid is 80%;

(3) pre-treatment carbon nanotube obtained above is joined in above-mentioned mixed acid solution, at 50 DEG C ultrasonic 100 minutes, carbon nanotube deionized water repetitive scrubbing to the filtrate obtained was neutral by filtration under diminished pressure, the vacuum drying oven putting into 76 DEG C is dried, and obtains acidifying carbon nanotube;

(4) above-mentioned acidifying carbon nanotube is mixed with hydroxy-terminated polybutadienes, magnetic agitation 2 minutes, join in said n methyl-2-pyrrolidone, ultrasonic 10 minutes, suction filtration, by filter cake at 100 DEG C dry 20 minutes, obtain hydroxyl modification acidifying carbon nanotube;

(5) mixed with boron oxide by above-mentioned hydroxyl modification acidifying carbon nanotube, ball milling is even; Being sent to concentration is in the phosphoric acid solution of 10%, and at 150 DEG C, constant temperature floods 120 minutes, discharging, dry, and send in reactor, under nitrogen protection, at 400 DEG C, thermal treatment 100 minutes, obtains phosphate impregnation compounded mix;

(6) by phosphate impregnation compounded mix, epoxyoleic acid butyl ester, cis-1,4-polybutadiene rubber mixing, plasticate at 46 DEG C 2 minutes, add zinc oxide, antioxidant 4010, sulphur successively, mixing 4 minutes, the rubber unvulcanizate obtained is placed in two roller mills, supplement mixing 6 minutes at 30 DEG C, discharging, at room temperature parks 20 hours by sizing material, sends in vulcanizing press, at 150 DEG C, carry out sulfuration, to obtain final product;

The preparation method of described a kind of cis-1,4-polybutadiene rubber material, the weight of described mixed acid solution is 18 times of pre-treatment carbon nanotubes.

Stretch breaking strength (MPa): 18.5;

Surely modulus 100%(MPa is stretched): 2.5;

Mooney viscosity: 64;

70 DEG C × 70h air oven aging test:

Tensile strength at yield reduced rate: 4.3%, elongation at break reduced rate: 8.5%.

Claims

1. a cis-1,4-polybutadiene rubber material, is characterized in that, it is made up of the raw material of following weight parts:

2. a preparation method for cis-1,4-polybutadiene rubber material as claimed in claim 1, is characterized in that, comprise the following steps:

(6) by phosphate impregnation compounded mix, epoxyoleic acid butyl ester, cis-1,4-polybutadiene rubber mixing, plasticate 2-3 minute at 46-50 DEG C, add zinc oxide, antioxidant 4010, sulphur successively, mixing 4-6 minute, the rubber unvulcanizate obtained is placed in two roller mills, mixing 6-10 minute is supplemented at 30-40 DEG C, discharging, at room temperature parks 20-25 hour by sizing material, sends in vulcanizing press, at 150-155 DEG C, carry out sulfuration, to obtain final product.

3. the preparation method of a kind of cis-1,4-polybutadiene rubber material according to claim 2, is characterized in that, the weight of described mixed acid solution is 18-20 times of pre-treatment carbon nanotubes.