CN101921438A - Co-catalysis compatibilization modified polystyrene alloy material and preparation method thereof - Google Patents

Co-catalysis compatibilization modified polystyrene alloy material and preparation method thereof Download PDF

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Publication number
CN101921438A
CN101921438A CN2010101523107A CN201010152310A CN101921438A CN 101921438 A CN101921438 A CN 101921438A CN 2010101523107 A CN2010101523107 A CN 2010101523107A CN 201010152310 A CN201010152310 A CN 201010152310A CN 101921438 A CN101921438 A CN 101921438A
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catalysis
alloy material
modified polystyrene
preparation
compatibilization
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郭正虹
方征平
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Ningbo Institute of Technology of ZJU
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Ningbo Institute of Technology of ZJU
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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
    • B29C2948/92514—Pressure
    • 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
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/92885—Screw or gear
    • 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
    • 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
    • B29C2948/92904—Die; Nozzle zone

Abstract

The invention discloses a co-catalysis compatibilization modified polystyrene alloy material and a preparation method thereof. The preparation method comprises the following steps of: mixing raw materials of polystyrene, an ethylene-octylene copolymer, a co-catalysis system, an antioxidant and a lubricating agent in proportion and stirring evenly for about 5-10 min by using a stirring machine; placing into a double-screw extruder for melt extrusion, wherein the temperature of a feed cylinder is 150-170 DEG C in a feeding region, 165-185 DEG C in a melting region and 170-190 DEG C in a reaction region, the die orifice temperature is 160-180 DEG C, the handpiece pressure is 3-6 Mpa, and the screw speed is 60-90 rpm; and extruding the material, cooling and granulating to prepare a product of cylindrical particles with colors from light green, dark green to dark brown according to different proportions. The alloy material has simple preparation method, low cost, excellent comprehensive performance and wide market prospect, and can be applied to some industrial occasions through wholly or partly replacing the modified polystyrene.

Description

Co-catalysis compatibilization modified polystyrene alloy material and preparation method thereof
Technical field
The present invention relates to the processing of macromolecular material or the technological process of batching, be specifically related to a kind of co-catalysis compatibilization modified polystyrene alloy material and preparation method thereof.
Background technology
That polystyrene has is transparent, good moldability, rigidity height, chemical property and electrical insulating property is good, agent of low hygroscopicity and advantage such as cheap, be widely used in industries such as packing, building, automobile, household electrical appliances instrument, daily necessities and toy, become current four big general-purpose plastics it.But polystyrene is because of himself inevitable shortcoming, as poor toughness, not resisting environmental stress and cracking and solvent, heat-drawn wire relatively low (70-98 ℃) etc., has been subjected to certain restriction in the engineering application facet.Crisp in order to change its matter, the not high shortcoming of shock strength, many p-poly-phenyls ethene carries out modification, to widen its Application Areas.Make a general survey of various method of modifying, prepare advantages such as polystyrene alloy is little with its investment, process of manufacture is flexible, the cycle is short, always be the focus of modified polystyrene by blending method.At present, by polystyrene and polyolefin prepared blend alloy, obtaining certain effect aspect raising polystyrene shock strength and the toughness.But because the consistency between each blend component all has very big influence to many performances of blend in the modified polystyrene alloy, therefore, when design and exploitation, consistency is one of the problem that must consider.
At present common modified polystyrene alloy material block or the graft copolymers that adopt direct interpolation to prepare in advance more, these blocks or graft copolymer are as expanding material, in the melt-processed process by and body material between physical action, make the polymer segment at matrix and dispersed phase interface place take place to tangle or bridging, reduce interfacial tension, improve interface adhesion, thereby improved the consistency of incompatible co-mixing system effectively.But, block and graft copolymer that direct interpolation prepares in advance come with some shortcomings as expanding material: (1) most of segmented copolymers all are the microphase-separated state under blending temperature, have very high viscosity, are difficult in the two-phase interface place and fully disperse, therefore, be unfavorable for blend processing; (2) segmented copolymer of Jia Ruing is dispersed in the homogeneous phase with the form of microcapsule possibly, rather than the phase interface place, thereby can not play the minimizing interfacial tension, improves interface adhesion, improves the purpose of the consistency of incompatible co-mixing system; (3) compatilizer of block and graft copolymer class costs an arm and a leg, and consumption is more, is unfavorable for reducing production costs.
Summary of the invention
The present invention is directed to the above-mentioned deficiency of prior art, and provide a kind of and reduce interfacial tension, improve interface adhesion, consistency is good, and the low co-catalysis compatibilization modified polystyrene alloy material of production cost.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of co-catalysis compatibilization modified polystyrene alloy material, and this material is prepared from by following components by mass percentage:
Polystyrene 70.0%～90.0%
Ethylene-octene copolymer 9.5%～27.0%
Be total to catalyst system 0.3%～2.0%
Oxidation inhibitor 0.1%～0.5%
Lubricant 0.1%～0.5%.
The above-mentioned common catalyst system of the present invention is that mass ratio is 4: 3 the aluminum trichloride (anhydrous) and the mixture of styrene monomer, and promptly aluminum trichloride (anhydrous) and styrene monomer are to mix at 4: 3 with mass ratio.
The above-mentioned oxidation inhibitor of the present invention is that mass ratio is 3: 1 the polyphenol antioxidant 1010 and the mixture of phosphite antioxidant 168, and promptly antioxidant 1010 and oxidation inhibitor 168 are to mix at 3: 1 with mass ratio.
The above-mentioned lubricant of the present invention is a calcium stearate.
Another technical problem that the present invention will solve, provide a kind of preparation method of above-mentioned co-catalysis compatibilization modified polystyrene alloy material, concrete preparation process is as follows: press formula rate with polystyrene (70.0%～90.0%), ethylene-octene copolymer (9.5%～27.0%), be total to catalyst system (0.3%～2.0%), oxidation inhibitor (0.1%～0.5%), be stirred in lubricant (0.1%～0.5%) the adding stirrer and mix (about 5～10min) between each material, then the material that mixes is changed in the twin screw extruder and melt extrude, barrel temperature is: 150～170 ℃ of charging zones, 165～185 ℃ of melting zones, 170～190 ℃ of reaction zones, 160～185 ℃ of die temperature, head pressure: 3～6MPa, screw speed 60-90rpm, material is extruded postcooling, granulation can make color from light green according to the proportioning difference, deep green is to the product of dark-brown cylindrical pellet.
Compared with prior art, the advantage that has of the present invention and useful effect are:
It is toughner that the present invention adopts ethylene-octene copolymer, with aluminum trichloride (anhydrous) and styrene monomer mixture as catalyst system altogether, wherein aluminum trichloride (anhydrous) plays the effect of Lewis acid catalyst, styrene monomer then provides positive ion as co-catalyst for aluminum trichloride (anhydrous), thereby cause the Friedel-Crafts alkylated reaction between polystyrene and the ethylene-octene copolymer, ethylene-octene copolymer is grafted on the benzene ring of polystyrene, then this graft copolymer that obtains this moment can serve as expanding material, inconsistent polystyrene/ethylene-octene copolymer is carried out capacity increasing modifying, thereby reach co-catalysis compatibilization modified effect, compared with prior art have outstanding substantive distinguishing features and marked improvement.Wherein the oxidation inhibitor of Jia Ruing can prevent that material from degrading owing to being heated in the course of processing, and lubricant then can improve the processing fluidity of material.And the co-catalysis compatibilization modified polystyrene alloy material of the present invention, two kinds of catalyzer ratios in the selected common catalyst system are easier to obtain, and it is cheap, have inexpensive, be easy to reclaim, the catalytic efficiency advantages of higher, waste polystyrene (PS) is material modified to have a very big economic potential for recycling.
The preparation method of co-catalysis compatibilization modified polystyrene alloy material of the present invention has also that reaction conditions gentleness, technology are simple, the advantage of easy handling, the easy blend processing of preparation process.
Embodiment
Below by specific embodiment the present invention is done to describe in further detail, but the present invention not only is confined to following examples.
Embodiment
Preparation process is as follows: press formula rate with polystyrene, ethylene-octene copolymer, be total to catalyst system, oxidation inhibitor, be stirred in the lubricant adding stirrer and mix (about 5～10min) between each material, then the material that mixes is changed in the twin screw extruder and melt extrude, barrel temperature is: 150～170 ℃ of charging zones, 165～185 ℃ of melting zones, 170～190 ℃ of reaction zones, 160～185 ℃ of die temperature, head pressure: 3～6MPa, screw speed 60-90rpm, material is extruded postcooling, granulation obtains the product of cylindrical pellet, and the experiment parameter that each embodiment correspondence is concrete is as shown in the table:
The prescription of the co-catalysis compatibilization modified polystyrene alloy material of the embodiment of the invention, processing temperature and products thereof performance is as shown in table 1 below:
Table 1 material embodiment 1～7 set of dispense ratio of the present invention, processing condition and properties of sample
Figure GSA00000072128200031
Figure GSA00000072128200041
From last table 1 as can be known, the simple beam impact strength of co-catalysis compatibilization modified polystyrene alloy material of the present invention is 3.2～9.8kJ/m 2, therefore elongation at break, has good toughness and intensity, thereby is with a wide range of applications between 8.6～28.5%.

Claims (5)

1. co-catalysis compatibilization modified polystyrene alloy material, it is characterized in that: this material is prepared from by following components by mass percentage:
Polystyrene 70.0%～90.0%
Ethylene-octene copolymer 9.5%～27.0%
Be total to catalyst system 0.3%～2.0%
Oxidation inhibitor 0.1%～0.5%
Lubricant 0.1%～0.5%.
2. co-catalysis compatibilization modified polystyrene alloy material according to claim 1 is characterized in that: described catalyst system altogether is that mass ratio is 4: 3 the aluminum trichloride (anhydrous) and the mixture of styrene monomer.
3. co-catalysis compatibilization modified polystyrene alloy material according to claim 1 is characterized in that: described oxidation inhibitor is that mass ratio is 3: 1 the polyphenol antioxidant 1010 and the mixture of phosphite antioxidant 168.
4. co-catalysis compatibilization modified polystyrene alloy material according to claim 1 is characterized in that: described lubricant is a calcium stearate.
5. the preparation method of the described co-catalysis compatibilization modified polystyrene alloy material of a claim 1, it is characterized in that: preparation process is as follows: with each raw material polystyrene 70.0%～90.0% of following mass percent, ethylene-octene copolymer 9.5%～27.0%, be total to catalyst system 0.3%～2.0%, oxidation inhibitor 0.1%～0.5%, be stirred between each material in lubricant 0.1%～0.5% adding stirrer and mix, then the material that mixes is changed in the twin screw extruder and melt extrude, barrel temperature is: 150～170 ℃ of charging zones, 165～185 ℃ of melting zones, 170～190 ℃ of reaction zones, 160～185 ℃ of die temperature, head pressure: 3～6MPa, screw speed 60-90rpm, material is extruded postcooling, granulation obtains the product of cylindrical pellet.
CN2010101523107A 2010-04-15 2010-04-15 Co-catalysis compatibilization modified polystyrene alloy material and preparation method thereof Pending CN101921438A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623134A (en) * 2014-11-21 2016-06-01 合肥杰事杰新材料股份有限公司 Catalysis compatibilization PS/POE composite material
CN114276641A (en) * 2021-11-26 2022-04-05 中国电器科学研究院股份有限公司 In-situ compatibilization and chain extension based regenerated HIPS/PP alloy material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1737049A (en) * 2005-09-09 2006-02-22 浙江大学 In situ bulk filling polystyrene/polyolefin elastomer blending alloy and preparation process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1737049A (en) * 2005-09-09 2006-02-22 浙江大学 In situ bulk filling polystyrene/polyolefin elastomer blending alloy and preparation process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《高分子学报》 20090831 郭正虹等 F-C烷基化反应原位增容PS/POE共混物中降解的抑制和增容效果的优化 第763-768页 1-4 , 第8期 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105623134A (en) * 2014-11-21 2016-06-01 合肥杰事杰新材料股份有限公司 Catalysis compatibilization PS/POE composite material
CN105623134B (en) * 2014-11-21 2019-07-05 合肥杰事杰新材料股份有限公司 A kind of catalysis compatibilization PS/POE composite material
CN114276641A (en) * 2021-11-26 2022-04-05 中国电器科学研究院股份有限公司 In-situ compatibilization and chain extension based regenerated HIPS/PP alloy material and preparation method thereof
CN114276641B (en) * 2021-11-26 2023-06-06 中国电器科学研究院股份有限公司 Regenerated HIPS/PP alloy material based on in-situ compatibilization and chain extension and preparation method thereof

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