CN104292528A - High strength rubber and preparation method thereof - Google Patents
High strength rubber and preparation method thereof Download PDFInfo
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- CN104292528A CN104292528A CN201310306904.2A CN201310306904A CN104292528A CN 104292528 A CN104292528 A CN 104292528A CN 201310306904 A CN201310306904 A CN 201310306904A CN 104292528 A CN104292528 A CN 104292528A
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K3/02—Elements
- C08K3/06—Sulfur
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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
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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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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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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- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The invention relates to a high strength rubber and a preparation method thereof. The high strength rubber comprises 100 parts of rubber, 10-50 parts of a semi-reinforcing agent, 1-10 parts of an activator, 1-5 parts of sulfur, 1-5 parts of a vulcanization accelerator and 20-50 parts of a modifier. The preparation method comprises the following steps: weighing the above components, and mixing the components in an open rubber mixer to obtain a semi-finished product; and vulcanizing the semi-finished product in a dynamic vulcanization machine while applying shearing at a vulcanization machine temperature of 80-180DEG C under a vulcanizing pressure of 10-20MPa for 10-30min, and cooling the obtained product in a temperature control system. The preparation method adopting a dynamic vulcanization technology has the advantages of simplicity and low cost. Compared with rubber products prepared through a static vulcanization technology, the rubber product prepared in the invention has the advantages of greatly increased mechanical performances, above 2 times improved tensile strength, and greatly improved heat and aging resistance, and is of important significance to the enlargement of industrial production.
Description
Technical field
The present invention relates to a kind of rubber and preparation method thereof, specifically a kind of high-strength rubber and preparation method thereof.
Background technology
The develop rapidly of science and technology in recent years, especially field of rubber technology, the performance that cannot replace due to other macromolecular materials such as snappiness of elastomeric material and make the dependency of every profession and trade to elastomeric material increasing, therefore to elastomeric material, the performance requriements of rubber product is more and more harsher, as: the method that tradition improves rubbery intensity is simple interpolation auxiliary agent or carries out rubber and blend rubber, rubber and the blended mode of filler improve the performance of goods, but the compatibility problem often ignored between rubber matrix and other rubber or filler, cause elastomeric material can cause other degradation while lifting tensile strength.
The rubber such as polybutadiene rubber, polyisoprene rubber is all the good unsaturated rubbers of taxis, himself has excellent elasticity, dielectricity, but the stress at definite elongation of himself, draws refreshing strength ratio lower, limits its application in industrial circle.
Summary of the invention
First technical problem to be solved by this invention is to provide that a kind of tensile property is good, resistance toheat and the good high-strength rubber of ageing-resistant performance.
Second technical problem to be solved by this invention is to provide a kind of preparation method of high-strength rubber, the interface shearing technological guide molecule of dynamic vulcanization is utilized to carry out orientations, rubber molecule segment is easy to produce strain-crystallization under effects of strain, the tensile property tool of the rubber item obtained is had a more substantial increase, and improves resistance toheat and the ageing-resistant performance of rubber simultaneously.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of high-strength rubber, is characterized in that component and by mass fraction be:
As preferably, described rubber is any one in polybutadiene rubber or polyisoprene rubber.Because the taxis of these two kinds of rubber is better, be beneficial to and apply in shear history at dynamic vulcanization, the crystallization of molecule segment generation induced orientation.
As preferably, the carbon black of described semi-reinforcing agent to be the trade mark be N330.For high abrasion furnace black(HAF), reinforcing favorable dispersity very well in rubber matrix, can give rubber good tensile property.
As preferably, described activator is zinc oxide and stearic acid.
Preferred again, described vulcanization accelerator is one or more in benzothiazyl disulfide, N cyclohexyl 2 benzothiazole sulfenamide, tetramethyl-thiuram disulfide, tetra-sulfurized pair pentamethylene thiuram, ziram.
As improvement, also comprise 20 ~ 50 parts of enhancement fillers, described enhancement filler is chopped strand, any one in organic modification montmonrillonite that plasma treatment is crossed.Chopped strand has the advantages such as Gao Dingshen, cut resistant, tear-resistant, low compression deformation; Organic modification montmonrillonite has good dispersing property, improves shock resistance, antifatigue, dimensional stability and gas barrier property etc., thus plays the effect strengthening polymkeric substance comprehensive physical performance.
Finally, the chopped strand that described plasma treatment is crossed be length-to-diameter ratio between 100-200, length is at the superhigh molecular weight polyethylene fibers of 3-5mm; Described organic modification montmonrillonite is through silane coupler modified sodium-based montmorillonite.Superhigh molecular weight polyethylene fibers is the synthon that ultrahigh molecular weight polyethylene(UHMWPE) is spun into.Its molecular weight is generally 1,000,000 ~ 3,000,000.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of preparation method of high-strength rubber, is characterized in that comprising the following steps:
1) take raw material according to component proportion, rubber, activator, semi-reinforcing agent, vulcanizing agent, vulcanization accelerator are carried out mixing on opening rubber mixing machine, obtains work in-process;
2) work in-process are carried out sulfuration on dynamic vulcanization machine, apply to shear simultaneously in sulfidation; Vulcanizer temperature 80-180 DEG C, sulfide stress 10-20MPa, composite sulfuration time 10-30min, then cools in temperature control system;
3) place more than 8h after cooling to eliminate stress, namely obtain finished product.
Compared with prior art, the invention has the advantages that: utilize dynamic vulcanization technology to make rubber mechanical means in sulfidation apply to shear to rubber item, make rubber induced orientation arrangement under stress, be beneficial to molecular orientation crystallization.The rubber item that the present invention prepares and rubber item prepared by static vulcanization technology contrast, its mechanical property increases substantially, tensile strength improves more than 2 times, thermotolerance and ageing-resistant performance also improve a lot, preparation technology of the present invention is simple, with low cost, significant for expansion industrial production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The performance test that the present invention carries out---Mechanics Performance Testing, the test of fracture tensile strength, elongation at break and stress at definite elongation is carried out according to GB/T528-1998 standard.
Embodiment 1.
Formulating of recipe is carried out according to following component and content:
According to said ratio weighing, opening rubber mixing machine carries out mixing 20min.Mixing rear sizing material is placed 8h and carry out sulfuration after being eliminated stress.Curing temperature is 160 ± 5 DEG C, and sulfide stress is 15MPa, and curing time is 15min.After sulfuration completes, goods are taken out from mould, be placed in temperature control system and cool.Place 10h to eliminate stress, with 2 type dumbbell shaped cut-off knife sample preparations on sheet-punching machine, then test on mechanical stretch trier.
The elastomeric material tensile strength 10.70MPa obtained, elongation at break is 327%.
Embodiment 2.
Formulating of recipe is carried out according to following component and content:
According to said ratio weighing, opening rubber mixing machine carries out mixing 20min.Mixing rear sizing material is placed 8h and carry out sulfuration after being eliminated stress.Curing temperature is 160 ± 5 DEG C, and sulfide stress is 15MPa, and curing time is 15min.Apply to shear in sulfidation, shearing frequency is 10rad/s, and shearing amplitude is 50%.After sulfuration completes, goods are taken out from mould, be placed in temperature control system and cool.After placing 10h, carry out sample preparation, test.The elastomeric material tensile strength 25.60MPa obtained, elongation at break is 434%.
Embodiment 3.
Formulating of recipe is carried out according to following component and content:
According to said ratio weighing, opening rubber mixing machine carries out mixing 20min.Mixing rear sizing material is placed 8h and carry out sulfuration after being eliminated stress.Curing temperature is 160 ± 5 DEG C, and sulfide stress is 15MPa, and curing time is 15min.Apply to shear in sulfidation, shearing frequency is 10rad/s, and shearing amplitude is 50%.After sulfuration completes, goods are taken out from mould, be placed in temperature control system and cool.After placing 10h, carry out sample preparation, test.The elastomeric material tensile strength 29.12MPa obtained, elongation at break is 406%.
Embodiment 4.
Formulating of recipe is carried out according to following component and content:
According to said ratio weighing, opening rubber mixing machine carries out mixing 20min.Mixing rear sizing material is placed 8h and carry out sulfuration after being eliminated stress.Curing temperature is 160 ± 5 DEG C, and sulfide stress is 15MPa, and curing time is 15min.Apply to shear in sulfidation, shearing frequency is 10rad/s, and shearing amplitude is 50%.After sulfuration completes, goods are taken out from mould, be placed in temperature control system and cool.After placing 10h, carry out sample preparation, test.The elastomeric material tensile strength 21.60MPa obtained, elongation at break is 395%.
Comparative example 1-5
| ? | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Vulcanization accelerator | CZ | TT | TT/M | M/DM | DM/PZ |
| Tensile strength (MPa) | 22.14 | 23.64 | 24.48 | 24.46 | 20.26 |
| Elongation at break (%) | 388 | 375 | 429 | 399 | 412 |
Note: comparative example 1-5 preparation technology is with embodiment 2.
Comparative example 6-8
Note: comparative example 6-8 preparation technology is with embodiment 3.
Comparative example 9-11
Note: comparative example 9-11 preparation technology is with embodiment 4.
Claims (8)
1. a high-strength rubber, is characterized in that the component comprising following mass fraction:
2. high-strength rubber according to claim 1, is characterized in that: described rubber is any one in polybutadiene rubber or polyisoprene rubber.
3. high-strength rubber according to claim 1, is characterized in that: the carbon black of described semi-reinforcing agent to be the trade mark be N330.
4. high-strength rubber according to claim 1, is characterized in that: described activator is zinc oxide and stearic acid.
5. high-strength rubber according to claim 1, is characterized in that: described vulcanization accelerator is one or more in benzothiazyl disulfide, N cyclohexyl 2 benzothiazole sulfenamide, tetramethyl-thiuram disulfide, tetra-sulfurized pair pentamethylene thiuram, ziram.
6. high-strength rubber according to claim 1, is characterized in that: also comprise 20 ~ 50 parts of enhancement fillers, and described enhancement filler is chopped strand, any one in organic modification montmonrillonite that plasma treatment is crossed.
7. high-strength rubber according to claim 6, is characterized in that: the chopped strand that described plasma treatment is crossed be length-to-diameter ratio between 100-200, length is at the superhigh molecular weight polyethylene fibers of 3-5mm; Described organic modification montmonrillonite is through silane coupler modified sodium-based montmorillonite.
8. a preparation method for the high-strength rubber according to the arbitrary claim of claim 1 to 7, is characterized in that comprising the following steps:
1) take raw material according to component proportion, rubber, activator, semi-reinforcing agent, vulcanizing agent, vulcanization accelerator are carried out mixing on opening rubber mixing machine, obtains work in-process;
2) work in-process are carried out sulfuration on dynamic vulcanization machine, apply to shear simultaneously in sulfidation; Vulcanizer temperature 80-180 DEG C, sulfide stress 10-20MPa, composite sulfuration time 10-30min, then cools in temperature control system;
3) place more than 8h after cooling to eliminate stress, namely obtain finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310306904.2A CN104292528A (en) | 2013-07-18 | 2013-07-18 | High strength rubber and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310306904.2A CN104292528A (en) | 2013-07-18 | 2013-07-18 | High strength rubber and preparation method thereof |
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| CN104292528A true CN104292528A (en) | 2015-01-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204799A (en) * | 2019-06-06 | 2019-09-06 | 江苏通用科技股份有限公司 | A kind of absorbing sound and lowering noise tyre stock and preparation method thereof |
| CN114541043A (en) * | 2022-02-25 | 2022-05-27 | 青岛科技大学 | Preparation method of real-time vulcanized elastomer fiber membrane |
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| CN101392074A (en) * | 2007-09-20 | 2009-03-25 | 固特异轮胎和橡胶公司 | Tire with component containing cellulose |
| CN101475715A (en) * | 2009-01-14 | 2009-07-08 | 青岛大学 | Preparation of oil-extended montmorillonite-extended solution co-coagulating rubber |
| CN102040754A (en) * | 2010-12-13 | 2011-05-04 | 四川轮胎橡胶（集团）股份有限公司 | Bias tire shoulder stock |
| CN102575052A (en) * | 2009-09-10 | 2012-07-11 | 埃克森美孚化学专利公司 | Elastomeric copolymers, copolymer compositions, and their use in articles |
| CN102964641A (en) * | 2012-11-14 | 2013-03-13 | 沈阳化工大学 | Method for preparing rubber by using illegal cooking oil as plasticizer |
| WO2013090464A1 (en) * | 2011-12-12 | 2013-06-20 | Vorbeck Materials Corp | Rubber compositions comprising graphene and reinforcing agents and articles made therefrom |
| CN103183853A (en) * | 2011-12-28 | 2013-07-03 | 韩国轮胎株式会社 | Rubber composite used for bonding belt ply of tire and tire manufactured with the composite |
-
2013
- 2013-07-18 CN CN201310306904.2A patent/CN104292528A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392074A (en) * | 2007-09-20 | 2009-03-25 | 固特异轮胎和橡胶公司 | Tire with component containing cellulose |
| CN101475715A (en) * | 2009-01-14 | 2009-07-08 | 青岛大学 | Preparation of oil-extended montmorillonite-extended solution co-coagulating rubber |
| CN102575052A (en) * | 2009-09-10 | 2012-07-11 | 埃克森美孚化学专利公司 | Elastomeric copolymers, copolymer compositions, and their use in articles |
| CN102040754A (en) * | 2010-12-13 | 2011-05-04 | 四川轮胎橡胶（集团）股份有限公司 | Bias tire shoulder stock |
| WO2013090464A1 (en) * | 2011-12-12 | 2013-06-20 | Vorbeck Materials Corp | Rubber compositions comprising graphene and reinforcing agents and articles made therefrom |
| CN103183853A (en) * | 2011-12-28 | 2013-07-03 | 韩国轮胎株式会社 | Rubber composite used for bonding belt ply of tire and tire manufactured with the composite |
| CN102964641A (en) * | 2012-11-14 | 2013-03-13 | 沈阳化工大学 | Method for preparing rubber by using illegal cooking oil as plasticizer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110204799A (en) * | 2019-06-06 | 2019-09-06 | 江苏通用科技股份有限公司 | A kind of absorbing sound and lowering noise tyre stock and preparation method thereof |
| CN110204799B (en) * | 2019-06-06 | 2021-12-14 | 江苏通用科技股份有限公司 | Sound-absorbing noise-reducing tire rubber material and preparation method thereof |
| CN114541043A (en) * | 2022-02-25 | 2022-05-27 | 青岛科技大学 | Preparation method of real-time vulcanized elastomer fiber membrane |
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