CN109294004A - A kind of ozone resistant rubber and preparation method thereof - Google Patents
A kind of ozone resistant rubber and preparation method thereof Download PDFInfo
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- CN109294004A CN109294004A CN201811148098.XA CN201811148098A CN109294004A CN 109294004 A CN109294004 A CN 109294004A CN 201811148098 A CN201811148098 A CN 201811148098A CN 109294004 A CN109294004 A CN 109294004A
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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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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a kind of ozone resistant rubbers and preparation method thereof, in parts by mass, including following components: 2 mass parts of zinc oxide, 1 mass parts of stearic acid, 1.5 mass parts of accelerant CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, 1~10 mass parts of polyisobutene, 100 mass parts of unsaturated rubber.The ozone resistant rubber the preparation method comprises the following steps: weighing zinc oxide, stearic acid, promotor, sulphur, polyisobutene and unsaturated rubber by formula；By weighed unsaturated rubber and the pre- hot mixing of polyisobutene, weighed zinc oxide, stearic acid, accelerant CZ, altax is then added and is kneaded, sulphur is added in dumping, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.Ozone resistant rubber produced by the present invention has the advantages that excellent anti-oxidant and ozone resistance, while having the basic performances such as good heat-resisting, chemicals-resistant, weather-proof, UV resistant, acidproof, alkaline-resisting.
Description
Technical field
The invention belongs to rubber applications fields, and in particular to a kind of ozone resistant rubber and preparation method thereof.
Background technique
Rubber industry is one of important foundation industry of national economy.It is indispensable that it not only provides daily life for people
The light industrys rubber product such as daily, medical, and mentioned to the heavy industry such as digging, traffic, building, machinery, electronics and new industry
For various rubber system production equipments or rubber components.As it can be seen that the product category of rubber industry is various, backward industry is very wide.
Rubber is a variety of, and the most commonly used is natural rubber (NR), butadiene-styrene rubber (SBR), butyl rubbers (IIR), hydrogenated butyronitrile
Rubber (HNBR), EP rubbers (EPDM), nitrile rubber (NBR), neoprene (CR).Rubber material environment locating at present is just
By growing pollution, wherein it is the most outstanding be exactly ozone influence, especially natural rubber (NR), butadiene-styrene rubber
(SBR), the not ozone proof rubber clone such as butadiene rubber (BR), isoprene rubber (IR), inside have unsaturated double-bond, in ozone
Lower double bond fracture, the serious performance for destroying rubber product are acted on, the service life for how extending rubber product becomes more and more important.
It is many about the research of antiozonant both at home and abroad, but as auxiliary agent make an addition in rubber inevitably can to rubber other
Performance changes.Polyisobutene (PIB) is a kind of sticky or semi-solid material colourless, tasteless, the five poisonous creatures: scorpion, viper, centipede, house lizard, toad are nontoxic, is had good
Heat-resisting, chemicals-resistant and weather-proof, UV resistant, acidproof, alkaline resistance properties, it is often more important that it is with oxytolerant and ozone resistance.
Polyisobutene (PIB) is divided into low molecular polyisobutylene of the relative molecular weight between 350 to 5000,1 ten thousand to 10 ten thousand
Middle molecule polyisobutene and polyphosphazene polymer isobutene greater than 100,000, with the increase of molecular weight, molecule chain end α-double bond
Content increase, excellent properties can be also consequently increased with increase, price.It can be filled more when mixing the compounding rubber of polyisobutene
More filler, moreover it is possible to improve waterproofness, gas permeability, heat resistance, uv resistance and physical strength etc..
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of ozone resistant rubber
Preparation method.
Another object of the present invention is to provide above-mentioned ozone resistant rubbers.
The object of the invention is achieved through the following technical solutions:
A kind of ozone resistant rubber, in parts by mass, preparing raw material includes following components: 2 mass parts of zinc oxide, stearic acid 1
Mass parts, 1.5 mass parts of accelerant CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, 1~10 mass parts of polyisobutene
With 100 mass parts of unsaturated rubber.
The liquid polyisobutene that polyisobutene (PIB) preferred molecular weight is 1 ten thousand to 5 ten thousand, the molecular weight of more preferable PIB
It is 15800, liquid has good mobility, and can play " solvent " effect is sufficiently mixed each component uniformly.
Polyisobutene (PIB) preferably 5~10 mass parts.
Polyisobutene (PIB) preferably 5 mass parts.
The unsaturated rubber is natural rubber (NR), butadiene-styrene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR)
One of or it is a variety of.
The preparation method of above-mentioned ozone resistant rubber, comprising the following steps:
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, 1~10 mass parts of polyisobutene (PIB), insatiable hunger
With 100 mass parts of rubber；
(2) it mixing and molding: first by weighed unsaturated rubber and polyisobutene (PIB) pre- hot mixing, is then added and weighs
Zinc oxide, stearic acid, accelerant CZ, altax be kneaded, sulphur is added in dumping, and tabletting, bottom sheet is cooling, park,
Ozone resistant rubber is made.
Step (2) described compounding conditions are as follows: controlled with dump temperature and be kneaded terminal, dump temperature is 110~140 DEG C, excellent
120 DEG C are selected, mixing cycle is 10~20min, preferably 20min.
The temperature of step (2) described preheating is 60 ± 5 DEG C.
Step (2) mixing refers to mixer mixing.
Described be kneaded of step (2) is preferably conventional mixing method, i.e. one-part form is kneaded, but is not limited to conventional mixing side
Method, other are kneaded method.
The chemical name of accelerant CZ of the present invention is N- cyclohexyl -2-[4-morpholinodithio base sulfenamide；Altax
Chemical name 2,2'- dithio-bis-benzothiazole.
Compared with prior art, the present invention has the following advantages and beneficial effects:
Ozone resistant rubber produced by the present invention can not only improve the basic performance of rubber product: heat-resisting, chemicals-resistant, resistance to
Time, UV resistant, acidproof, alkaline resistance properties, moreover it is possible to effectively improve the anti-oxidant and ozone resistants of rubber product.
Detailed description of the invention
Fig. 1 is influence of the different PIB volumes to rubber dynamic ozone resistance.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The test method of made rubber product in the embodiment of the present invention:
1, according to the ozone resistants of GB/T 7762-2014 measurement rubber, ozone concentration is (50 ± 5) × 10-8G/L, temperature
For (40 ± 2) DEG C, relative humidity is 60 ± 5%, using the method B in standard, the lower measurement of 10% strain is selected not to be cracked
Maximum duration；
2, the mechanical property of rubber material is measured by GB/T 528-1999；
3, the heat-resistant aging of rubber material is executed by standard GB/T 3512-2001, wherein temperature (100 ±) DEG C, time
24h。
It is Vietnam 3L glue that natural rubber (NR) is used in embodiment；Polyisobutene (PIB) is limited by Dongguan City gold most plastic cement
Company's production.
Embodiment 1
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 15800
(PIB) 1 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.
Embodiment 2
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 15800
(PIB) 5 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.
Embodiment 3
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 15800
(PIB) 10 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.
Embodiment 4
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 10080
(PIB) 5 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.
Embodiment 5
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 49870
(PIB) 5 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber is made.
Comparative example 1
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 3580
(PIB) 5 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber 2-1 is made.
Comparative example 2
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the solid-state polyisobutene that molecular weight is 76500
(PIB) 5 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber 2-2 is made.
Comparative example 3
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide (ZnO), 1 mass parts of stearic acid (SA), promotees
Into 1.5 mass parts of agent CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, the liquid polyisobutene that molecular weight is 15800
(PIB) 20 mass parts, 100 mass parts of natural rubber；
(2) mixing and molding: first by 60 DEG C of pre- hot mixings of weighed natural rubber (NR) and polyisobutene (PIB), then plus
Enter weighed zinc oxide, stearic acid, accelerant CZ, altax and carry out mixer mixing, then mixing cycle 20min exists
Sulphur is added in dumping at 120 DEG C, and tabletting, bottom sheet is cooling, parks, and ozone resistant rubber 2-3 is made.
Fig. 1 is influence of the different PIB volumes to rubber dynamic ozone resistance, wherein 0 indicates not mixing liquid polyisobutene
(PIB) control sample, PIB volume is 1 mass parts, 5 mass parts, corresponding 10 mass parts are that embodiment 1,2,3 is made
Rubber sample.The result shows that the addition of liquid polyisobutene (PIB) is so that the ozone resistance of rubber is significantly improved, so
And the improvement with the increase of volume, to after 5 mass parts (natural rubber is 100 mass parts), to rubber ozone resistance
It is not linear to increase, but slowed down.
The influence of 1 different molecular weight of table, difference PIB volume to rubber anti-aging property
Table 1 is the influence of different molecular weight, difference PIB volume to ageing of rubber performance, and 0 indicates not mixing liquid polyisobutene
The control sample of PIB.After mixing the liquid PIB that molecular weight is 15800, the tensile strength before ageing of rubber does not have too big change substantially
Change, slightly improves；And then having greatly to the performance after ageing of rubber improves, and mixes 1 mass parts (compared to the day of 100 mass parts
Right rubber) liquid polyisobutene aging after tensile strength improve 10.14%, increase the stretching after 5 mass parts after aging
Intensity improves 36.58%, is further continued for increasing PIB mass (10 mass parts, 20 mass parts), the improvement of tensile strength is not
It is linear to increase, but slowed down, furthermore cost can also increase therewith.
Same volume is 5 mass parts, and the incorporation of macromolecule (76500) PIB is so that mechanical performance is equal before and after ageing of rubber
Declined, the reason is that the how inert solid-state of macromolecule PIB, is not easy to mix, glue refining；After small-molecular-weight PIB (3580) incorporation,
Mechanical performance before ageing of rubber, after aging is respectively before the ageing of rubber than mixing middle-molecular-weihydroxyethyl (15800) PIB, after aging
Mechanical performance is more excellent, but on the one hand incorporation small-molecular-weight PIB dramatically increase rubber cost can, on the other hand because of small molecule
The PIB of amount is when being kneaded since double bond can excessively have addition reaction, and in addition to this there are residues in prepared rubber material
Double bond, cause its ozone resistance seriously reduce (sample do not occur be cracked maximum duration be 52h, it is big compared to middle-molecular-weihydroxyethyl
It is decreased obviously in 100h).
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of ozone resistant rubber, which is characterized in that in parts by mass, preparing raw material includes following components: 2 mass of zinc oxide
Part, 1 mass parts of stearic acid, 1.5 mass parts of accelerant CZ, 0.5 mass parts of altax, 2 mass parts of sulphur, polyisobutene 1
100 mass parts of~10 mass parts and unsaturated rubber；
The polyisobutene is the liquid polyisobutene that molecular weight is 1 ten thousand to 5 ten thousand.
2. ozone resistant rubber according to claim 1, which is characterized in that the molecular weight of the polyisobutene is 15800.
3. ozone resistant rubber according to claim 1 or claim 2, which is characterized in that 5~10 mass parts of polyisobutene.
4. ozone resistant rubber according to claim 3, which is characterized in that 5 mass parts of polyisobutene.
5. ozone resistant rubber according to claim 1 or claim 2, which is characterized in that the unsaturated rubber is natural rubber, butylbenzene
One of rubber, butadiene rubber, isoprene rubber are a variety of.
6. the preparation method of any one of Claims 1 to 5 ozone resistant rubber, which comprises the following steps:
(1) it weighs each component: in parts by mass, weighing 2 mass parts of zinc oxide, 1 mass parts of stearic acid, 1.5 mass of accelerant CZ
Part, 0.5 mass parts of altax, 2 mass parts of sulphur, 1~10 mass parts of polyisobutene, 100 mass parts of unsaturated rubber；
(2) mixing and molding: first by weighed unsaturated rubber and the pre- hot mixing of polyisobutene, be then added weighed zinc oxide,
Stearic acid, accelerant CZ, altax are kneaded, dumping, and sulphur is added, and tabletting, bottom sheet is cooling, parks, and ozone-resistant is made
Rubber.
7. the preparation method of ozone resistant rubber according to claim 6, which is characterized in that the condition of step (2) described mixing
Are as follows: dump temperature is 110~140 DEG C, and mixing cycle is 10~20min.
8. the preparation method of ozone resistant rubber according to claim 7, which is characterized in that the condition of step (2) described mixing
Are as follows: dump temperature is 120 DEG C, mixing cycle 20min.
9. the preparation method of ozone resistant rubber described according to claim 6 or 7, which is characterized in that the temperature of step (2) described preheating
Degree is 60 ± 5 DEG C.
10. the preparation method of ozone resistant rubber described according to claim 6 or 7, which is characterized in that step (2) it is described mixing be
Refer to mixer mixing.
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| CN201811148098.XA CN109294004B (en) | 2018-09-29 | 2018-09-29 | Anti-ozone rubber and preparation method thereof |
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| CN201811148098.XA CN109294004B (en) | 2018-09-29 | 2018-09-29 | Anti-ozone rubber and preparation method thereof |
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Cited By (1)
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| CN112778585A (en) * | 2020-12-31 | 2021-05-11 | 青岛铁路橡胶厂 | Positioning node rubber composition and preparation method thereof |
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