CN110157134A - A kind of modified styrene-butadiene-styrene block copolymer material and preparation method thereof - Google Patents
A kind of modified styrene-butadiene-styrene block copolymer material and preparation method thereof Download PDFInfo
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- CN110157134A CN110157134A CN201810147902.6A CN201810147902A CN110157134A CN 110157134 A CN110157134 A CN 110157134A CN 201810147902 A CN201810147902 A CN 201810147902A CN 110157134 A CN110157134 A CN 110157134A
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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
- C08K13/06—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
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- 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
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/20—Carboxylic acid amides
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- 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
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a kind of modified styrene-butadiene-styrene block copolymer materials and preparation method thereof, by 70-90 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS), 10-30 parts of calcium carbonate, 0.5-1.0 parts of primary antioxidant, 0.5-1.0 parts of auxiliary antioxidant, 1 0.2-0.5 parts of dispersing agent；2 0.2-0.5 parts of dispersing agent, 3-10 parts of carbon black are formed through mixing, extruding pelletization.The present invention is to carry out blending and modifying by SBS and calcium carbonate to form, and low-durometer material can replace TPE material of less demanding.
Description
Technical field
The invention belongs to technical field of polymer processing, are related to a kind of modified styrene-butadiene-styrene
Object material and preparation method thereof.
Background technique
SBS be in SBCs yield maximum (accounting for 70% or more), cost it is minimum, using a wider kind, be with benzene second
Alkene, the triblock copolymer that butadiene is monomer, have the characteristic of plastics and rubber concurrently, referred to as " third generation synthetic rubber ".With
Butadiene-styrene rubber is similar, and SBS can be contacted with water, weak acid, alkali etc., has excellent tensile strength, big surface friction coefficient, low temperature
The characteristics such as performance is good, excellent electrical properties, and processing performance is good become the maximum thermoplastic elastomer (TPE) of current consumption figure.
SBS possesses the incomparable advantage of thermoset rubber in processed and applied: (1) can with thermoplastics processing equipment into
Row machine-shaping, such as squeeze, injection, blow molding, shaping speed is faster than conventional vulcanized rubbers technique；(2) it is not required to vulcanize, can save
Vulcanization process in general thermoset rubber process, thus equipment investment is few, production energy consumption is low, simple process, processing week
Phase is short, high production efficiency, and processing charges is low；(3) plus angle clout can be recycled repeatedly, saved resource, be conducive to environmental protection.
Chinese patent (CN 102391424B) discloses a kind of modification of Styrene-Butadiene-Styrene Block Copolymer
Method is to use sulfydryl-vinyl addition reaction to carry out a variety of functionalization and modifications to SBS, reaches and carry out a variety of functions to SBS
Change modified purpose.The patent is to be achieved the purpose that by polymerization reaction modified, and the present invention is blended by Macroscopic physical
It is modified to achieve the purpose that.Chinese patent (CN 103030746B) discloses a kind of preparation side of styrene-butadiene copolymer
Method, the patent are the polybutadiene segments obtained by the adjustment of the arrangement mode to polystyrene chain segment, polybutadiene segments
The styrene-butadiene copolymer that can be move freely is to be reached by the adjustment of polymerization methods and proportion, and the present invention is
The improved composition obtained by physical blending.Chinese patent (CN 104193928A) discloses a kind of modified phenylethylene-fourth two
Alkene-styrene block copolymer preparation method and the adhesive for using the copolymer.The patent is by by styrene, fourth
Diene and glucose response obtain, which obtains s-B-S block copolymerization also with polymerization
Object.
Summary of the invention
For the limitation of the above prior art, the object of the present invention is to provide a kind of modified styrene-butadiene-benzene second
Alkene block copolymer material and preparation method thereof.
Technical scheme is as follows:
A kind of modified styrene-butadiene-styrene block copolymer material, is prepared by weight by following components
It forms:
The SBS melt flow rate (MFR) be 1-3g/10min, tearing strength >=40KN/m, shore hardness=85-95A, break
Split elongation >=700%.
The calcium carbonate mesh number is 1000-2000 mesh.
The primary antioxidant is Hinered phenols antioxidant；The auxiliary antioxidant is phosphite ester antioxidant or Containing Sulfur
Close object.
The Hinered phenols antioxidant is single phenol antioxidant, bis-phenolic antioxidants or polyphenol antioxidant.
The dispersing agent 1 is titanate coupling agent.
The dispersing agent 2 is erucyl amide.
The particle size carbon black is 26-30nm.
Another goal of the invention of the invention is to provide above-mentioned modified styrene-butadiene-styrene block copolymer material
The preparation method of material comprising following steps:
(1) first 1 0.2-0.5 parts of dispersing agent, 10-30 parts of calcium carbonate are put into high mixer, are carried out in 80-90 DEG C of temperature
Mix 3-8min；
(2) high mixer is cooled to room temperature again, Styrene-Butadiene-Styrene Block Copolymer (SBS) 70-90 is added
Part, 0.5-1.0 parts of primary antioxidant, 0.5-1.0 parts of auxiliary antioxidant, 2 0.2-0.5 parts of dispersing agent, 3-10 parts of carbon black continues to mix
3-8min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified styrene-butadiene-styrene block copolymer material.
The present invention compared with the existing technology, has the advantages that
1, composition produced by the invention is soft material, can partially replace automobile soft material.
2, SBS material price used in the present invention is higher, but the additive amount of inorganic filler calcium carbonate is 10-30 parts, this is big
The totle drilling cost of composition is reduced greatly, and does not influence the hardness of composition.
3, in the preparation method of composition of the invention, first dispersing agent 1 is mixed with calcium carbonate, it is therefore an objective to carbonic acid
Calcium surface is handled, and on the one hand can be made calcium carbonate is more uniform to be scattered in SBS matrix, on the other hand can be made to combine
The performance of object is more excellent.
Specific embodiment
The present invention is further illustrated with reference to embodiments.
The draw ratio 30:1 of double screw extruder used in the embodiment of the present invention, manufacturer are German BRABEBDER
Company.
SBS melt flow rate (MFR) used below be 2.2g/10min, tearing strength >=40KN/m, shore hardness=85A, break
Split elongation >=700%；
Antioxidant 1010 used, irgasfos 168, titanate coupling agent, erucyl amide are commercially available.
Comparative example is commercially available using TPE raw material.
Product of the invention is tested using the standard of ISO, is squeezed out pellet and is formed to obtain test specimens by injection molding machine
Item, stabilization is tested for the property afterwards for 24 hours under the conditions of 23 DEG C, relative humidity 50%, and the physical mechanical property test carried out has:
Melt index: it is tested according to 1133 standard sample preparation of ISO；
Tensile strength, elongation at break: it is tested according to 527 standard sample preparation of ISO；
Shore hardness: it is tested according to 868 standard sample preparation of ISO.
Embodiment 1
(1) first 0.25 part of titanate coupling agent, 10 parts of calcium carbonate are put into high mixer, are mixed in 80 DEG C of temperature
8min；
(2) high mixer is cooled to room temperature again, be added 90 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
0.5 part of antioxidant 1010,0.5 part of irgasfos 168,0.2 part of erucyl amide, 3 parts of carbon black continues to mix 6min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Embodiment 2
(1) first 0.2 part of titanate coupling agent, 10 parts of calcium carbonate are put into high mixer, are mixed in 90 DEG C of temperature
5min；
(2) high mixer is cooled to room temperature again, be added 90 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
1.0 parts of antioxidant 1010,1.0 parts of irgasfos 168,0.25 part of erucyl amide, 3 parts of carbon black continues to mix 3min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Embodiment 3
(1) first 0.5 part of titanate coupling agent, 30 parts of calcium carbonate are put into high mixer, are mixed in 85 DEG C of temperature
5min；
(2) high mixer is cooled to room temperature again, be added 70 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
0.6 part of antioxidant 1010,0.6 part of irgasfos 168,0.5 part of erucyl amide, 10 parts of carbon black continues to mix 8min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Embodiment 4
(1) first 0.3 part of titanate coupling agent, 15 parts of calcium carbonate are put into high mixer, are mixed in 80 DEG C of temperature
3min；
(2) high mixer is cooled to room temperature again, be added 85 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
0.7 part of antioxidant 1010,0.7 part of irgasfos 168,0.3 part of erucyl amide, 5 parts of carbon black continues to mix 5min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Embodiment 5
(1) first 0.35 part of titanate coupling agent, 20 parts of calcium carbonate are put into high mixer, are mixed in 90 DEG C of temperature
6min；
(2) high mixer is cooled to room temperature again, be added 80 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
0.8 part of antioxidant 1010,0.8 part of irgasfos 168,0.4 part of erucyl amide, 7 parts of carbon black continues to mix 5min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Embodiment 6
(1) first 0.4 part of titanate coupling agent, 25 parts of calcium carbonate are put into high mixer, are mixed in 90 DEG C of temperature
6min；
(2) high mixer is cooled to room temperature again, be added 75 parts of Styrene-Butadiene-Styrene Block Copolymer (SBS),
0.9 part of antioxidant 1010,0.9 part of irgasfos 168,0.35 part of erucyl amide, 9 parts of carbon black continues to mix 5min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to obtain
Modified polypropylene material.
The performance test results are shown in Table 1.
Table 1
| Embodiment | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | TPE |
| Melt index/g/10min | 2.1 | 2.2 | 1.7 | 2.0 | 2.0 | 1.8 | 1.8 |
| Tensile strength/MPa | 7.3 | 7.2 | 8.9 | 8.0 | 8.2 | 8.5 | 7.2 |
| Elongation at break/% | > 500 | > 500 | 450 | > 500 | > 500 | > 500 | 450 |
| Shore hardness A | 85 | 85 | 93 | 86 | 88 | 90 | 85 |
From table 1 it follows that calcium carbonate additive amount is high, shore hardness A can become larger slightly, but change rate is relatively low,
And in embodiment 3, when calcium carbonate additive amount increases to 30%, shore hardness A is 93, also can satisfy the hardness of soft material
It is required that；The results of property of embodiment 1-6 and TPE very close to can part generation in the case where of less demanding to TPE product
It replaces.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (9)
1. a kind of modified styrene-butadiene-styrene block copolymer material, it is characterised in that: its be by following components by
Parts by weight are prepared:
70-90 parts of SBS；
10-30 parts of calcium carbonate；
0.5-1.0 parts of primary antioxidant；
0.5-1.0 parts of auxiliary antioxidant；
1 0.2-0.5 parts of dispersing agent；
2 0.2-0.5 parts of dispersing agent；
3-10 parts of carbon black.
2. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
State SBS melt flow rate (MFR) be 1-3g/10min, tearing strength >=40KN/m, shore hardness=85-95A, elongation at break >=
700%。
3. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
The calcium carbonate mesh number stated is 1000-2000 mesh.
4. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
Stating primary antioxidant is Hinered phenols antioxidant；The auxiliary antioxidant is phosphite ester antioxidant or sulfur-containing compound.
5. modified styrene-butadiene according to claim 4-styrene block copolymer material, it is characterised in that: institute
Stating Hinered phenols antioxidant is single phenol antioxidant, bis-phenolic antioxidants or polyphenol antioxidant.
6. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
Stating dispersing agent 1 is titanate coupling agent.
7. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
Stating dispersing agent 2 is erucyl amide.
8. modified styrene-butadiene according to claim 1-styrene block copolymer material, it is characterised in that: institute
The particle size carbon black stated is 26-30nm.
9. a kind of modified styrene-butadiene-styrene block copolymer material preparation as described in claim any one of 1-8
Method, it is characterised in that: the following steps are included:
(1) first 1 0.2-0.5 parts of dispersing agent, 10-30 parts of calcium carbonate are put into high mixer, are mixed in 80-90 DEG C of temperature
3-8min；
(2) high mixer is cooled to room temperature again, SBS 70-90 parts, 0.5-1.0 parts of primary antioxidant, auxiliary antioxidant 0.5- is added
1.0 parts, 2 0.2-0.5 parts of dispersing agent, 3-10 parts of carbon black continues to mix 3-8min；
(3) progress extruding pelletization in the double screw extruder that each area's temperature is 160-190 DEG C is added in mixed material to be modified
Styrene-Butadiene-Styrene Block Copolymer material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810147902.6A CN110157134A (en) | 2018-02-12 | 2018-02-12 | A kind of modified styrene-butadiene-styrene block copolymer material and preparation method thereof |
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| CN201810147902.6A CN110157134A (en) | 2018-02-12 | 2018-02-12 | A kind of modified styrene-butadiene-styrene block copolymer material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248858A (en) * | 2021-04-26 | 2021-08-13 | 深圳市真味生物科技有限公司 | Disposable electronic cigarette holder kit and preparation method thereof |
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2018
- 2018-02-12 CN CN201810147902.6A patent/CN110157134A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248858A (en) * | 2021-04-26 | 2021-08-13 | 深圳市真味生物科技有限公司 | Disposable electronic cigarette holder kit and preparation method thereof |
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