CN101250306A - High-toughness thermoplastic elastomer/polystyrene composite material and preparation method thereof - Google Patents
High-toughness thermoplastic elastomer/polystyrene composite material and preparation method thereof Download PDFInfo
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- CN101250306A CN101250306A CNA2008100352467A CN200810035246A CN101250306A CN 101250306 A CN101250306 A CN 101250306A CN A2008100352467 A CNA2008100352467 A CN A2008100352467A CN 200810035246 A CN200810035246 A CN 200810035246A CN 101250306 A CN101250306 A CN 101250306A
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- thermoplastic elastomer
- polystyrene
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a high ductility thermoplastic elastomer/ polystyrene composite material and a preparation process. The composite material is formed by thermoplastic elastomer and polystyrene. And the preparation process comprises: blending thermoplastic elastomer/ polystyrene and extruding through a twin-screw extruder and preliminarily shaping through an injection machine, generating forcing flow for material in solid state form under the single shaft pressure which is provided by a vulcanizing press and in the die which limits lateral boundaries, thereby making the inner structure change. The impact ductility of the composite material is increased at large amplitude, and the other mechanical properties such as the tension strength, flexural modulus and breaking elongation percentage and the like are significantly improved. The preparation process has simple demanded device, easy operation, small energy and time consumption, which can reach the continuous batch production in industry.
Description
Technical field
The invention belongs to poly styrene composite material and preparation field thereof, particularly relate to matrix material of a kind of polystyrene (PS) and thermoplastic elastomer (SBS) composition and preparation method thereof.
Background technology
Polystyrene (PS) plastics are meant and include cinnamic class plastics in the macromolecular chain, are one of general-purpose plastics of present consumption maximum.The constructional feature of PS is that macromolecular main chain is a saturated hydrocarbon polymer, and side group is bulky phenyl ring, thereby PS has good electrical properties, chemical property, tensile property, rigidity, dimensional stability and higher hardness.Yet the also existence of side phenyl just activates the locational hydrogen atom on the main chain backbone, and easily oxidation generates superoxide in air, and then causes that degraded reduces molecular weight, causes PS to have the weakness of poor, the easy embrittlement of low-temperature impact resistance.Chinese scholars has been carried out a large amount of study on the modification work to PS for this reason, to improve the toughness of polystyrene.
Traditional method for toughening is to introduce a spot of rubber-like elastic component mostly, and tangible toughening effect is generally all arranged.But this method for toughening usually makes material when resistance to impact shock improves owing to introduced low modulus, low intensive rubber phase, and its rigidity, tensile strength and processing characteristics all have reduction to some extent.
Tang Weihua, Tang Jian, Jin Riguang (Tang Weihua, Tang Jian, Jin Riguang, plastics industry, 2002,30 (1): 15-16) studied polyphenyl elastomerics (PSE) and the influence of polystyrene (PS) blend to the PS mechanical property.The result shows that PSE resin and PS can be compatible, and this consistency increases with the raising of vinylbenzene massfraction in the resin.PSE and PS blend can obtain the toughness material of mechanical property excellence.
The Xiaxin river (Xiaxin river etc., Chinese plastics, 1998, (4): 45) coat legal system and be equipped with the SBR-g-St powder of particle diameter less than 1mm with cohesion, and with itself and PS blend.The result shows: the SBR-g-St melt flow rate (MFR) is 24.3, and percentage of grafting is 28.1%, and the mass ratio of SBS and grafting St is that the unnotched impact strength of 65/35 o'clock blend can reach 48.5KJ/m among the SBR-g-St
2, be 21.6 times of increase-volume PS not; But its flexural strength and tensile strength descend to some extent.
Also useful cis-1,4-polybutadiene rubber (BR) and styrene-butadiene rubber(SBR) (SBR) are as the properties-correcting agent of PS in the method for toughening, and toughness increases to some extent, but effect is not too obvious, and its reason is that rubber phase is relatively poor with resin consistency mutually.And the thermoplastic elastomer SBS is the segmented copolymer of vinylbenzene (S) and divinyl (B), and the S block is identical with PS homopolymer structure among the SBS.Can judge according to the similar compatibility principle: the two consistency is better.SBS has snappiness, great friction coefficient, and low-temperature performance is good, and the good and SBS of acid-fast alkali-proof does not need special sulfidation man-hour adding.It is feasible having human SBS that PS is carried out modification, but because PS thermotolerance bad (70 ℃-98 ℃), the thermotolerance and the impact-resistance that therefore improve PS are the important topics of its modification always.
Yuan Shaoyan, (Yuan Shaoyan such as Huang Rui, Huang Rui etc. China Synthetic Rubber Industry, 2002,25 (4): 251) studied nano-calcium carbonate and SBS and PS blend, the result shows that nano-calcium carbonate and SBS can coordination plasticizing PS, and the blend tensile strength is improved, and its physical and mechanical properties meets or exceeds HIPS.The shock strength of PS/SBS blend improves with the adding of SBS, but tensile strength and thermal characteristics all descend with the raising of SBS content; The thermal characteristics of ternary blends is improved behind the adding lime carbonate; Shock strength and tensile strength descend with the increase of calcium carbonate content.
At present, for only adding SBS in PS, not only can improve its shock strength but also can improve its tensile strength does not also have relevant report.
Summary of the invention
The object of the present invention is to provide thermoplastic elastomer (SBS)/polystyrene (PS) matrix material of a kind of high tenacity and preparation method thereof, change material internal microscopic pattern structure by changing the moulding processing mode, thereby obtain the significantly lifting of this material impact intensity, improve simultaneously other mechanical properties such as modulus in flexure, tensile strength and elongation at break to a certain extent, this method required equipment is simple, easy to operate, little during consumption energy consumption, can improve the continuous batch production that reaches industrial, prospect is considerable.
The thermoplastic elastomer of a kind of high tenacity of the present invention (SBS)/polystyrene (PS) matrix material, be to be prepared from through pressure inducement flowing shaping (PIFP) by thermoplastic elastomer (SBS) and polystyrene (PS), wherein, the mass ratio of SBS and PS is 0～40/100～60.
Used polystyrene PS is a kind of water white thermoplastics among the present invention, and hard and crisp, impact resistance is poor.
Used thermoplastic elastomer SBS (YH-792) is the macromolecular compound between rubber and plastics among the present invention, is to have caoutchouc elasticity under a kind of normal temperature, again can be as thermoplastics under the high temperature thermoplastic elastomer of melt flow.
The preparation method of the thermoplastic elastomer of high tenacity of the present invention (SBS)/polystyrene (PS) matrix material comprises concrete steps:
(1) exsiccant polystyrene (PS) is pressed different mass ratio (0～40/100～60) pre-mixings with thermoplastic elastomer (SBS), through twin screw extruder blend granulation, obtain required matrix material, four sections temperature ranges extruding are 120～196 ℃;
(2) with after the above-mentioned pellet vacuum-drying, through the first one-step forming of injection moulding machine processing, the injection moulding machine temperature out is 175～225 ℃, and melten gel pressure is 80.0～120.0bar;
(3) the injection moulding batten being put into it, width equates, length is the mould of 80mm, use vulcanizing press to pressurize in material depth (vertical) direction, batten produces mobile with solid-state form under pressure towards two, the temperature of mould and material is 0～150 ℃, pressure is 0.1～100GPa, and the dwell time is 1～150 minute;
(4) after pressurize finished, sample was taken out in the demoulding, promptly gets product.
Temperature in the described step (3) is preferably 40～120 ℃, the preferred 0.1～2GPa of pressure, and 200～700MPa most preferably, the dwell time is preferably 1～20 minute.
The present invention prepares thermoplastic elastomer (SBS)/polystyrene (PS) matrix material of certain component concentration earlier and passes through injection moulding machine one-step forming just; Under the uniaxial tension that vulcanizing press provides, material forces mobile in the mould on constrained side border with solid-state form, thereby its internal structure is changed.Under the comprehensive action, every mechanical property especially impelling strength obtains greatly to improve.
Beneficial effect of the present invention:
Method of the present invention can improve the toughness of thermoplastic elastomer (SBS)/polystyrene (PS) matrix material.Different processing conditionss has different modification degree to the material of different SBS content, and under appropriate condition, the shock strength of material can be brought up to nearly 8 times before the modification.Method of the present invention also improves 1～2 times with its tensile strength and modulus when improving thermoplastic elastomer (SBS)/polystyrene (PS) matrix material shock strength, and keeps or increase elongation at break slightly.
Method of the present invention can be improved other mechanical properties such as tensile strength, modulus in flexure and elongation at break simultaneously to a certain extent to increase substantially very much the impelling strength of thermoplastic elastomer (SBS)/polystyrene (PS) matrix material.
Present method does not influence the molecular structure of material, do not reduce other performance, and is very little when simple, the easy operation of equipment, consumption energy consumption, can accomplish the industrial application that continuous batch is produced by simple further improvement, and its application prospect is considerable.
Description of drawings
Fig. 1 is the dynamic mechanical analysis collection of illustrative plates of SBS/PS (10/90) matrix material.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Exsiccant polystyrene (PS) is pressed different mass ratio (0～40/100～60) pre-mixings with thermoplastic elastomer (SBS), through twin screw extruder blend granulation, obtain required matrix material, four sections temperature ranges extruding are 120～196 ℃.After above-mentioned pellet vacuum-drying, through the first one-step forming of injection moulding machine processing, the injection moulding machine temperature out is 175～225 ℃, and melten gel pressure is 80.0～120.0bar, obtains testing required batten.Putting into the injection moulding batten with it, width equates, length is the mould of 80mm, use vulcanizing press to pressurize in material depth (vertical) direction, batten produces mobile with solid-state form under pressure towards two, the temperature of mould and material is 0～150 ℃, pressure is 0.1～100GPa, and the dwell time is 1～150 minute.After pressurize finished, sample was taken out in the demoulding, promptly gets product.
Embodiment 2
Under 300MPa pressure, change processing temperature as the SBS/PS (0/100) of example 1 gained, the microtexture of pressure inducement flowing shaping after 5 minutes changes little and shock strength does not significantly improve.As table 1.
The shock strength of table 1.SBS/PS (0/100) behind pressure inducement flowing shaping (300MP, 5min)
Embodiment 3
Under 300MPa pressure, change processing temperature as the SBS/PS (10/90) of example 1 gained, the microtexture of pressure inducement flowing shaping after 5 minutes changes and the raising of shock strength.As table 2.
The shock strength of table 2.SBS/PS (10/90) behind pressure inducement flowing shaping (300MP, 5min)
Embodiment 4
Under 300MPa pressure, change processing temperature as the SBS/PS (10/90) of example 1 gained, the microtexture of pressure inducement flowing shaping after 5 minutes changes and the variation of tensile strength.As table 3.
The tensile strength of table 3.SBS/PS (10/90) behind pressure inducement flowing shaping (300MP, 5min)
Embodiment 5
Under 300MPa pressure, change processing temperature as the SBS/PS (40/60) of example 1 gained, the microtexture of pressure inducement flowing shaping after 5 minutes changes and the variation of tensile strength.As table 4.
The tensile strength of table 4.SBS/PS (10/90) (40/60) behind pressure inducement flowing shaping (300MP, 5min)
Embodiment 6
Under 70 ℃ temperature condition, change pressure as the SBS/PS (10/90) of example 1 gained and SBS/PS (40/60), the microtexture of pressure inducement flowing shaping after 5 minutes changes and the variation of tensile strength.As table 5.
The tensile strength of table 5.SBS/PS (10/90) (40/60) behind pressure inducement flowing shaping (70 ℃, 5min)
Claims (5)
1. the thermoplastic elastomer SBS of a high tenacity/polystyrene PS matrix material, it is characterized in that: this material is to be prepared from through pressure inducement flowing shaping by thermoplastic elastomer and polystyrene, wherein, the mass ratio of SBS and PS is 0～40/100～60.
2. the preparation method of the thermoplastic elastomer SBS of a high tenacity/polystyrene PS matrix material comprises concrete steps:
(1) exsiccant polystyrene PS is pressed different mass ratio (0～40/100～60) pre-mixings with the thermoplastic elastomer SBS, through twin screw extruder blend granulation, obtain required matrix material, four sections temperature ranges extruding are 120～196 ℃;
(2) with after the above-mentioned pellet vacuum-drying, through the first one-step forming of injection moulding machine processing, the injection moulding machine temperature out is 175～225 ℃, and melten gel pressure is 80.0～120.0bar;
(3) the injection moulding batten is put into mould, use vulcanizing press in the pressurization of material depth direction, batten produces mobile under pressure towards two with solid-state form, and the temperature of mould and material is 0～150 ℃, pressure is 0.1～100GPa, and the dwell time is 1～150 minute;
(4) after pressurize finished, sample was taken out in the demoulding, promptly gets product.
3. the preparation method of the thermoplastic elastomer SBS of high tenacity according to claim 2/polystyrene PS matrix material is characterized in that: described mould be equate with injection moulding batten width, length is the mould of 80mm.
4. the preparation method of the thermoplastic elastomer SBS of high tenacity according to claim 2/polystyrene PS matrix material, it is characterized in that: the temperature in the described step (3) is 40～120 ℃, and pressure is 0.1～2GPa, and the dwell time is 1～20 minute.
5. the preparation method of the thermoplastic elastomer SBS of high tenacity according to claim 4/polystyrene PS matrix material, it is characterized in that: the pressure in the described step (3) is 200～700MPa.
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Cited By (10)
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| CN102146197A (en) * | 2011-04-20 | 2011-08-10 | 东华大学 | Method for preparing nanomontmorillonite intercalated epoxy resin exfoliated composite material |
| CN103554699A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Modified polystyrene insulating material for toughened flame-retardant wiring harness for household appliances |
| CN103554700A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Low-temperature resistant anti-impact insulating material for wire harness of home appliance |
| CN104672739A (en) * | 2015-03-17 | 2015-06-03 | 昆山恒光塑料制品有限公司 | Modified PS composite material strap and manufacturing process thereof |
| CN106674788A (en) * | 2016-12-05 | 2017-05-17 | 天津金发新材料有限公司 | Flame-retardant thermoplastic elastomer alloy material and preparation method thereof |
| CN106674782A (en) * | 2016-12-05 | 2017-05-17 | 天津金发新材料有限公司 | Thermoplastic elastomer alloy material and preparation method thereof |
| CN106700302A (en) * | 2016-12-05 | 2017-05-24 | 天津金发新材料有限公司 | Antibacterial electro-thermoplastic elastomer alloy material |
| CN106751080A (en) * | 2016-12-05 | 2017-05-31 | 天津金发新材料有限公司 | A kind of Antistatic thermoplastic elastomer alloy material |
| CN107820447A (en) * | 2015-06-08 | 2018-03-20 | 康宁股份有限公司 | The pipette that readable and toughness is improved |
| CN114833988A (en) * | 2022-05-18 | 2022-08-02 | 南京威杰新材料有限公司 | Preparation process of impact-resistant modified plastic particles |
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Cited By (12)
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| CN102146197A (en) * | 2011-04-20 | 2011-08-10 | 东华大学 | Method for preparing nanomontmorillonite intercalated epoxy resin exfoliated composite material |
| CN103554699A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Modified polystyrene insulating material for toughened flame-retardant wiring harness for household appliances |
| CN103554700A (en) * | 2013-10-31 | 2014-02-05 | 合肥得润电子器件有限公司 | Low-temperature resistant anti-impact insulating material for wire harness of home appliance |
| CN104672739A (en) * | 2015-03-17 | 2015-06-03 | 昆山恒光塑料制品有限公司 | Modified PS composite material strap and manufacturing process thereof |
| CN107820447A (en) * | 2015-06-08 | 2018-03-20 | 康宁股份有限公司 | The pipette that readable and toughness is improved |
| US10894253B2 (en) | 2015-06-08 | 2021-01-19 | Corning Incorporated | Pipette with improved readability and toughness |
| CN106674788A (en) * | 2016-12-05 | 2017-05-17 | 天津金发新材料有限公司 | Flame-retardant thermoplastic elastomer alloy material and preparation method thereof |
| CN106674782A (en) * | 2016-12-05 | 2017-05-17 | 天津金发新材料有限公司 | Thermoplastic elastomer alloy material and preparation method thereof |
| CN106700302A (en) * | 2016-12-05 | 2017-05-24 | 天津金发新材料有限公司 | Antibacterial electro-thermoplastic elastomer alloy material |
| CN106751080A (en) * | 2016-12-05 | 2017-05-31 | 天津金发新材料有限公司 | A kind of Antistatic thermoplastic elastomer alloy material |
| CN106751080B (en) * | 2016-12-05 | 2019-07-26 | 天津金发新材料有限公司 | A kind of Antistatic thermoplastic elastomer alloy material |
| CN114833988A (en) * | 2022-05-18 | 2022-08-02 | 南京威杰新材料有限公司 | Preparation process of impact-resistant modified plastic particles |
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