CN108276619A - High intensity vulcanized rubber preparation method - Google Patents
High intensity vulcanized rubber preparation method Download PDFInfo
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- CN108276619A CN108276619A CN201711366627.9A CN201711366627A CN108276619A CN 108276619 A CN108276619 A CN 108276619A CN 201711366627 A CN201711366627 A CN 201711366627A CN 108276619 A CN108276619 A CN 108276619A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
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- Oral & Maxillofacial Surgery (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high intensity vulcanized rubber preparation methods, and the material injecting mould after cure stirred evenly is formed, 120 130 DEG C of curing temperature, 0.3 0.5Mpa of sulfide stress, vulcanization time 40 60 minutes.High intensity vulcanized rubber preparation method of the present invention; production method is simple; materials demand is not high; convenient for gathering materials on the spot; and meet large-scale processing making; add nontoxic auxiliary additive; it is effectively anti-aging and have antibacterial action; enhance service life; rubber product made from the preparation method has many advantages, such as water-fast, resistance to ozone, resistance to electric arc, corona, high-low temperature resistant, weather-resistant; it can be widely applied to the daily necessities such as rubber overshoes, industrial-mining boots, raincoat and stamp, dipping, demoulding, protective coating, medical material, radio component, sealing element etc..
Description
Technical field
The present invention relates to a kind of rubber more particularly to a kind of high intensity vulcanized rubber preparation methods.
Background technology
Rubber is divided into natural rubber and synthetic rubber by raw material.It is divided into blocky raw rubber, latex, liquid rubber and powder by form
Last rubber.Latex is the colloidal aqueous dispersion of rubber；Liquid rubber is the oligomer of rubber, generally sticky before unvulcanized
Liquid；Powdered rubber be latex is processed into it is powdered, with sharp dispensing and processing and fabricating.The thermoplasticity of exploitation the 1960s
Rubber is not necessarily to chemical cure, and the processing method for using thermoplastic shapes.By using, to be divided into be universal and extraordinary to rubber
Two class of type.Insulator, it is not easy to it is conductive, but if get wet or different temperature if, it is possible to become conductor.Conduction is to close
It is easy situation in the conduction of substance interior molecules or the electronics of ion.
Natural rubber is mainly derived from para ruber, when the epidermis of this rubber tree is cut open, will flow out milky white
The juice of color, referred to as latex, latex through cohesion, washing, be molded, be drying to obtain natural rubber.Rubber product synthetic rubber be by
Prepared by artificial synthesis, can synthesize different types of rubber using different raw materials (monomer).1900-1910
The structure that year chemist C.D. Harris (Harris) determines natural rubber is the high polymer of isoprene, this is just artificial closes
Approach is opened at rubber.1910 Russia's chemist SV NIKOLAY LEBEDEVs (Lebedev, 1874-1934) with metallic sodium be cause
Agent makes 1,3-butadiene aggregate into buna, later again occur many new synthetic rubber kinds successively, as butadiene rubber,
Neoprene, butadiene-styrene rubber etc..The yield of synthetic rubber has substantially exceeded natural rubber, and it is butylbenzene rubber that wherein yield is maximum
Glue.
Raw rubber or rubber product during processing, storage or use, can be influenced by factors such as heat, oxygen, light and by
Physics and chemical change gradually occurs, so that its performance is declined, and lose purposes, this phenomenon is known as the aging of rubber.Ageing of rubber
In the process usually can with some notable phenomenons, such as in appearance it can be found that the natural rubber softening stored for a long time, stickness,
There is spot；Rubber product has deformation, becomes fragile, is hardened, being cracked, is mouldy, loss of gloss and color change etc..The rubber in physical property
There is the change of swelling, rheological property etc..Tensile strength, elongation at break, impact strength, bending can occur in mechanical property by force
The indexs such as degree, compression ratio, elasticity decline.
Invention content
Aiming at the above shortcomings existing in the prior art, the first technical problem to be solved by the present invention is to provide a kind of high
Intensity vulcanized rubber preparation method.
Purpose of the present invention is to what is be achieved through the following technical solutions：
A kind of high intensity vulcanized rubber preparation method forms the material injecting mould after cure stirred evenly, vulcanization temperature
120-130 DEG C, sulfide stress 0.3-0.5Mpa of degree, vulcanization time 40-60 minutes.
The raw material is composed of the following components in parts by weight：1400-1600 parts of natural rubber, butadiene-styrene rubber 280-320
Part, 190-210 parts of butadiene rubber, 15-25 parts of tetramethylthiuram disulfide, 15-25 parts of dibenzothiazyl disulfide, stearic acid
10-15 parts, 20-25 parts of sulphur, 3500-3700 parts of precipitated calcium carbonate, 15-25 parts of dibutyl phthalate, mercapto propyl front three
15-25 parts of oxysilane, 5-15 parts of tetraisopropyl titanate, 20-40 parts of age resister, 10-30 parts of inorganic antiseptic.
Preferably, the inorganic antiseptic is mixture one or more in magnesium aluminate, magnesium titanate, magnesium tungstate.
It is highly preferred that the inorganic antiseptic is mixed by magnesium aluminate, magnesium titanate, magnesium tungstate, the magnesium aluminate, titanium
Sour magnesium, magnesium tungstate mass ratio be (1-3)：(1-3)：(1-3).
Preferably, the age resister is phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-t-butyls
Phenol) -4,4- xenyls diphosphites, mixing one or more in bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites
Object.
It is highly preferred that the age resister is by phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- bis- tertiary fourths
Base phenol) -4,4- xenyls diphosphites, bis- (2,4- di-tert-butyl-phenyl) phenyl phosphites mix, the phosphorous
Acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites, bis- (bis- uncles of 2,4-
Butyl phenyl) phenyl phosphites mass ratio be (1-3)：(1-3)：(1-3).
High intensity vulcanized rubber preparation method of the present invention, production method is simple, and materials demand is not high, convenient for taking on the spot
Material, and meet large-scale processing making, nontoxic auxiliary additive is added, effectively anti-aging and have antibacterial action, enhancing uses the longevity
It orders, rubber product made from the preparation method has water-fast, resistance to ozone, resistance to electric arc, corona, high-low temperature resistant, weather-resistant etc.
Advantage can be widely applied to the daily necessities such as rubber overshoes, industrial-mining boots, raincoat and stamp, dipping, demoulding, protective coating, medical material
Material, radio component, sealing element etc..
Specific implementation mode
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention
Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents be changed to the equivalent embodiment changed on an equal basis.Without departing from the concept of the present invention, according to the present invention
Technical spirit any simple modification that following embodiment is made or equivalent variations, all fall in protection scope of the present invention.
Each raw material introduction in embodiment：
Natural rubber, using the natural rubber for the model SCR10 that white sand Yuan Long rubber development corporation, Ltd. provides.
Butadiene-styrene rubber, using the butylbenzene for the model 1502 that Sinopec Qilu Branch Company provides
Rubber.
Butadiene rubber uses the trade mark that SINOPEC Beijing Yanshan Company provides for BR9000
Butadiene rubber.
Tetramethylthiuram disulfide, No. CAS：137-26-8.
Dibenzothiazyl disulfide, No. CAS：120-78-5.
Stearic acid, No. CAS：57-11-4.
Sulphur, No. CAS：7704-34-9.
Precipitated calcium carbonate, No. CAS：471-34-1, it is specific to jump what river titanium white heavy chemicals Co., Ltd provided using Shanghai
1250 mesh superfine light calcium carbonates.
Dibutyl phthalate, No. CAS：84-74-2.
Mercaptopropyl trimethoxysilane, No. CAS：4420-74-0.
Tetraisopropyl titanate, No. CAS：546-68-9.
Magnesium titanate, No. CAS：12032-35-8,5 μm of grain size.
Magnesium tungstate, No. CAS：13573-11-0,5 μm of grain size.
Magnesium aluminate, No. CAS：12068-51-8,5 μm of grain size.
Four (2,4- di-tert-butylphenol) -4,4- xenyl diphosphites, No. CAS：119345-01-6.
Bis- (2,4- di-tert-butyl-phenyl) phenyl phosphites, No. CAS：70146-21-3.
Phosphorous acid -4- nonyl phenyl double tridecyl esters, No. CAS：84787-77-9.
Embodiment 1
Raw material (parts by weight)：1500 parts of natural rubber, 300 parts of butadiene-styrene rubber, 200 parts of butadiene rubber, tetramethyl
20 parts of thiuram, 20 parts of dibenzothiazyl disulfide, 13 parts of stearic acid, 22 parts of sulphur, 3600 parts of precipitated calcium carbonate, O-phthalic
20 parts of dibutyl phthalate, 20 parts of mercaptopropyl trimethoxysilane, 9 parts of tetraisopropyl titanate, 24 parts of age resister, inorganic antiseptic 15
Part.
The inorganic antiseptic is 1 in mass ratio by magnesium aluminate, magnesium titanate, magnesium tungstate：1：1 is uniformly mixed
It arrives.
The age resister is by phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4-
Xenyl diphosphites, bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites are 1 in mass ratio：1：1 is uniformly mixed
It obtains.
High intensity vulcanized rubber preparation method：Natural rubber, butadiene-styrene rubber, butadiene rubber, tetramethyl autumn is blue
Nurse, dibenzothiazyl disulfide, stearic acid, sulphur, precipitated calcium carbonate, dibutyl phthalate, mercapto propyl trimethoxy silicon
Alkane, tetraisopropyl titanate, age resister, inorganic antiseptic are uniformly mixed for 10 minutes with 400 revs/min of stirrings, obtain raw material, will be former
Vulcanized after material injection vulcanizer, 130 DEG C, sulfide stress 0.3Mpa of curing temperature, vulcanization time 40 minutes.Obtain embodiment
1 high intensity vulcanized rubber.
Embodiment 2
It is substantially the same manner as Example 1, it differs only in：The inorganic antiseptic presses quality by magnesium titanate, magnesium tungstate
Than being 1：1 is uniformly mixed to obtain.Obtain the high intensity vulcanized rubber of embodiment 2.
Embodiment 3
It is substantially the same manner as Example 1, it differs only in：The inorganic antiseptic presses quality by magnesium aluminate, magnesium tungstate
Than being 1：1 is uniformly mixed to obtain.Obtain the high intensity vulcanized rubber of embodiment 3.
Embodiment 4
It is substantially the same manner as Example 1, it differs only in：The inorganic antiseptic presses quality by magnesium aluminate, magnesium titanate
Than being 1：1 is uniformly mixed to obtain.Obtain the high intensity vulcanized rubber of embodiment 4.
Embodiment 5
It is substantially the same manner as Example 1, it differs only in：The age resister by four (2,4- di-tert-butylphenols) -4,
4- xenyls diphosphites, bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites are 1 in mass ratio：1 is uniformly mixed
It obtains.Obtain the high intensity vulcanized rubber of embodiment 5.
Embodiment 6
It is substantially the same manner as Example 1, it differs only in：The age resister is by phosphorous acid -4- nonyls phenyl double ten
Trialkyl ester, bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites are 1 in mass ratio：1 is uniformly mixed to obtain.Obtain reality
Apply the high intensity vulcanized rubber of example 6.
Embodiment 7
It is substantially the same manner as Example 1, it differs only in：The age resister is by phosphorous acid -4- nonyls phenyl double ten
Trialkyl ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites are 1 in mass ratio：1 is uniformly mixed
It arrives.Obtain the high intensity vulcanized rubber of embodiment 7.
Test case 1
Tensile strength is carried out by GB/T528-1998 to the high intensity vulcanized rubber that embodiment 1-7 is prepared, by HG/
T4301-2012 carries out fungicidal properties test.Specific test result is shown in Table 1.
Table 1：Tensile strength and fungicidal properties test result table
| Tensile strength, MPa | Mould proof grade | |
| Embodiment 1 | 21 | Level-one |
| Embodiment 2 | 16 | Three-level |
| Embodiment 3 | 13 | Level Four |
| Embodiment 4 | 17 | Three-level |
| Embodiment 5 | 19 | Two level |
| Embodiment 6 | 20 | Two level |
| Embodiment 7 | 19 | Three-level |
Comparing embodiment 1 and embodiment 2-4, (magnesium aluminate, the magnesium titanate, magnesium tungstate compounding) tensile strength of embodiment 1 and anti-
Mouldiness can be substantially better than embodiment 2-4 (both arbitrary compounding in magnesium aluminate, magnesium titanate, magnesium tungstate)；Comparing embodiment 1 and implementation
Example 5-7, (phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenol) -4,4- xenyls two are sub- for embodiment 1
Phosphate, bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites compounding) tensile strength and fungicidal properties be substantially better than embodiment
5-7 is (phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites, double
Both arbitrary compounding in (2,4- di-tert-butyl-phenyls) phenyl phosphites).
Test case 2
According to artificial weathering aging experimental standard GB/T 16585-1996, to the high intensity vulcanized rubber of embodiment 1-7 into
Row artificially roughening (70 DEG C, 500h).Specific test result is shown in Table 2.
Table 2：Anti-aging property tests table (70 DEG C, 500h)
| Stretching strength retentivity, % | |
| Embodiment 1 | 99.8 |
| Embodiment 2 | 96.7 |
| Embodiment 3 | 94.4 |
| Embodiment 4 | 95.3 |
| Embodiment 5 | 93.1 |
| Embodiment 6 | 95.9 |
| Embodiment 7 | 93.6 |
Comparing embodiment 1 and embodiment 2-4, embodiment 1 (magnesium aluminate, magnesium titanate, magnesium tungstate compounding) anti-aging property are bright
It is aobvious to be better than embodiment 2-4 (both arbitrary compounding in magnesium aluminate, magnesium titanate, magnesium tungstate)；Comparing embodiment 1 and embodiment 5-7, it is real
Apply example 1 (phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites,
Bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites compounding) anti-aging property is substantially better than embodiment 5-7 (phosphorous acid -4- nonyls
Base phenyl double tridecyl ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites, bis- (2,4- di-tert-butyls
Base) both arbitrary compounding in phenyl phosphites).
Claims (5)
1. a kind of high intensity vulcanized rubber preparation method, which is characterized in that by the material injecting mould after cure stirred evenly
At, 120-130 DEG C of curing temperature, sulfide stress 0.3-0.5Mpa, vulcanization time 40-60 minutes；
The raw material is composed of the following components in parts by weight：It is 1400-1600 parts of natural rubber, 280-320 parts of butadiene-styrene rubber, suitable
190-210 parts of buna, 15-25 parts of tetramethylthiuram disulfide, 15-25 parts of dibenzothiazyl disulfide, stearic acid 10-15
Part, 20-25 parts of sulphur, 3500-3700 parts of precipitated calcium carbonate, 15-25 parts of dibutyl phthalate, mercapto propyl trimethoxy silicon
15-25 parts of alkane, 5-15 parts of tetraisopropyl titanate, 20-40 parts of age resister, 10-30 parts of inorganic antiseptic.
2. high intensity vulcanized rubber preparation method as described in claim 1, it is characterised in that：The inorganic antiseptic is aluminium
One or more mixture in sour magnesium, magnesium titanate, magnesium tungstate.
3. high intensity vulcanized rubber preparation method as claimed in claim 2, it is characterised in that：The inorganic antiseptic is by aluminium
Sour magnesium, magnesium titanate, magnesium tungstate mix, the magnesium aluminate, magnesium titanate, magnesium tungstate mass ratio be（1-3）：（1-3）：（1-
3）.
4. high intensity vulcanized rubber preparation method as claimed in any one of claims 1-3, it is characterised in that：Described is anti-ageing
Agent be phosphorous acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites,
One or more mixture in bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites.
5. high intensity vulcanized rubber preparation method as claimed in claim 4, it is characterised in that：The age resister is by phosphorous
Acid -4- nonyl phenyl double tridecyls ester, four (2,4- di-tert-butylphenols) -4,4- xenyls diphosphites, bis- (bis- uncles of 2,4-
Butyl phenyl) phenyl phosphites mix, the phosphorous acid -4- nonyls phenyl double tridecyl ester, four (2,4- bis- tertiary fourths
Base phenol) -4,4- xenyls diphosphites, bis- (2,4- di-tert-butyl-phenyls) phenyl phosphites mass ratio be（1-3）：
（1-3）：（1-3）.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400972A (en) * | 2018-09-25 | 2019-03-01 | 天长市富宝橡塑制品有限公司 | A kind of high resiliency pet tennis and preparation method thereof based on rubber material |
| CN110684256A (en) * | 2019-11-05 | 2020-01-14 | 宁波故乡行雨具有限公司 | Preparation method of anti-aging antibacterial raincoat |
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