CN103694564B - A kind of PP/PMMA alloy material and preparation method thereof - Google Patents

A kind of PP/PMMA alloy material and preparation method thereof Download PDF

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Publication number
CN103694564B
CN103694564B CN201310743694.3A CN201310743694A CN103694564B CN 103694564 B CN103694564 B CN 103694564B CN 201310743694 A CN201310743694 A CN 201310743694A CN 103694564 B CN103694564 B CN 103694564B
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pmma
alloy
pmma alloy
compatilizer
temperature
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CN103694564A (en
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徐东
张乐福
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Polymer Science Anhui New Material Co Ltd
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Polymer Science Anhui New Material Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92514Pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention discloses a kind of PP/PMMA alloy material and preparation method thereof.This PP/PMMA alloy material includes following component: PP70~90%, PMMA2~15%, compatilizer 2~15%, antioxidant 0.1~0.3%, lubricant 0.1~5% by weight percentage.The present invention, with PP as matrix, works in coordination with the enhancing hardness of alloy material, scraping and wiping resistance performance and room temperature shock resistance by doping component PMMA in PP, and makes material have good gloss.Meanwhile, also by adding compatilizer and antioxidant in PP/PMMA alloy material, not only prevent PMMA from high temperature degrading, and make two kinds of incompatible polymers of crystal type PP and non-crystalline type PMMA realize compatible, thus form rock-steady structure.

Description

A kind of PP/PMMA alloy material and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, particularly relate to a kind of PP/PMMA alloy material and Preparation method.
Background technology
Polypropylene (PP) is translucent Crystalline plastics, has plasticity, and odorless is nontoxic.Owing to PP ties Structure is regular and highly crystallized, therefore fusing point may be up to 167 DEG C, has good room temperature shock resistance, and Heat-resisting, corrosion-resistant, density is little, is the lightest general-purpose plastics.But, due to the molecular structure of PP Regular so that PP toughness is poor, and PP case hardness is the highest, easy snag.It addition, current pure PP Material in use easily light, heat and the effect of oxygen and aging, and bad need that can not meet market of coloring Ask.
Polymethyl methacrylate (PMMA) is the transparent material of a kind of excellent combination property, its average molecular Quality is about 2,000,000, and the strand formed is the most soft, and therefore, PMMA mechanical strength is higher, hardness Preferably.And, PMMA has fabulous light transmission, have certain thermostability, winter resistance, weatherability and Corrosion resistance, and insulating properties are good, but its thermal stability is poor, and room temperature impact resistance is the best, the most always Change and therefore limit his application in many fields.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, it is provided that a kind of have excellence glossiness, Hardness and room temperature shock resistance, and the PP/PMMA alloy material that the compatibility is good.
It is a further object of the present invention to provide the preparation method of this PP/PMMA alloy material.
In order to realize foregoing invention purpose, technical scheme is as follows:
A kind of PP/PMMA alloy material, includes following component by weight percentage:
And, the preparation method of a kind of PP/PMMA alloy material, comprise the following steps:
Each component is weighed according to the formula of above-mentioned PP/PMMA alloy material;
Above-mentioned PP, PMMA, compatilizer, antioxidant and lubricant are carried out mixing treatment, obtains mixed material;
Said mixture material is melt extruded, pelletize, be dried, obtain PP/PMMA alloy material.
Above-mentioned PP/PMMA alloy material is with PP as matrix, by doping component PMMA in PP not Only improve the room temperature impact strength of the case hardness of PP, scratch-resistant, and reinforced PMMA, collaborative enhancing The hardness of PP/PMMA alloy material, scratch resistance performance and room temperature shock resistance, and it is good that material is had Good gloss.Meanwhile, also by adding compatilizer and antioxidant in PP/PMMA alloy material, not only Effectively prevent PMMA from degrading under the high temperature conditions, and make crystal type PP and non-crystalline type PMMA Two kinds of incompatible polymers realize compatible, thus form rock-steady structure.
The preparation method of above-mentioned PP/PMMA alloy material is easy and simple to handle, with low cost, is suitable to PP/PMMA The industrialized production of alloy material.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of embodiment of the present invention PP/PMMA alloy material preparation method.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, with Under in conjunction with the embodiments with accompanying drawing, the present invention is further elaborated.Should be appreciated that described herein Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of glossiness, hardness and room temperature shock resistance with excellence, and phase The PP/PMMA alloy material that capacitive is good, includes following component by weight percentage:
Specifically, above-mentioned PP/PMMA alloy material is higher by mechanical strength of adulterating in PP matrix component And the component PMMA enhancing case hardness of PP, glossiness and the mechanical property that light transmission is fabulous, and due to PP molecular structure is regular, highly crystallized, can the room temperature impact resistance of effective reinforcing material.Therefore, PP, PMMA has a preferred embodiment below:
As the presently preferred embodiments, above-mentioned matrix component PP be HOPP, COPP, homopolymerization gather Any one in the mixture of propylene and COPP, its melt index is 20~50g/10min(230 DEG C / 2.16Kg), notch impact strength is 50~150J/M.Due to HOPP only with propylene as monomer, its Symmetry is good, beneficially the room temperature impact resistance of raising material, thus, it is further preferred that this matrix group Dividing PP is HOPP.
As another preferred embodiment, the melt index of above-mentioned PMMA is preferably 10~20g/10min (200 DEG C/5Kg), the good fluidity in the course of processing of the PMMA in this numerical range, beneficially material Machine-shaping.
Owing to PP is Crystalline plastics, PMMA is non-crystalline type polymer, PMMA and PP presents Different is biphase, and therefore PP with PMMA is incompatible.Compatible for realizing PMMA and PP, improve material Stability, the present embodiment preferably polyethylene grafted maleic anhydride is compatilizer, and its percent grafting is 0.3-1%. Wherein, it is further preferred that the preparation method of this Research of Grafting Malaic Anhydride Onto Polyethylene comprises the following steps:
(1) weigh by weight percentage polyethylene 94.2~97.3%, styrene 1~2%, maleic anhydride 1.5~3%, Crosslinking agent B IBP0.2~0.8%;
(2) crosslinking agent B IBP is dissolved in styrene, mixes with PP afterwards, obtain mixed material;
(3) maleic anhydride is added in mixed material melt extrude, obtain Research of Grafting Malaic Anhydride Onto Polyethylene.
Above-mentioned preparation method is with styrene as compatilizer, under the initiation of crosslinking agent B IBP so that poly- The side base anhydride bond of ethylene (PE) grafted maleic anhydride (MAH), the ester group of rear and PMMA further combined with, And PE with PP is fully compatible, so so that the interfacial free energy of PP, PMMA blend and PE-MAH Free entropy reduce, the final free energy reducing blend, thus reach PP, PMMA, PE-MAH Fully compatible purpose.
In a particular embodiment, in above-mentioned steps (1), with Research of Grafting Malaic Anhydride Onto Polyethylene percentage by weight it is 100% calculates, and this polyethylene is 96%, styrene is 1.6%, maleic anhydride is 2%, cross-linking agent is BIBP 0.4%;The step that melt extrudes of step (3) is: being 170-190 DEG C at extrusion temperature, screw speed is Under conditions of 300-400r/min, by the screw rod shearing of screw extruder, mixing, fused materials, depend on afterwards Secondary carry out extruding, pelletize, dried, it is thus achieved that Research of Grafting Malaic Anhydride Onto Polyethylene.
Due to PP, PMMA component in use easily light, heat and the effect of oxygen and aging, and PP with PMMA both high polymers are the most degradable, cause the mechanical property of material and transparency obvious Declining, color and luster is deteriorated, and therefore, adds antioxidant in above-mentioned PP/PMMA alloy material.
As the presently preferred embodiments, above-mentioned antioxidant was four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] seasons Doutrate, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester, three [2.4-di-tert-butyls Base] any one or two or more mixture of phosphite ester, select this kind antioxidant to be conducive to itself and alloy Each component of material is compatible, thus can improve the stability of PP/PMMA alloy material performance.Further Preferably, this antioxidant is that three of the above antioxidant carries out compounding acquisition according to mass ratio 1:1:1-2.
For improving mobility and the release property of material in processing, prevent material from adhering in machine or in mould and producing The defects such as raw flake, and for improving the dispersion during above-mentioned each component such as melt extrudes in preparation process Uniformity, adds lubricant in above-described embodiment.Preferably, this lubricant be zinc stearate, calcium stearate, Any one or two or more mixture of ethylene bis stearamide.It is further preferred that this lubricant is Three of the above lubricant carries out compounding acquisition according to mass ratio 1:1:1.5-3.
Above-mentioned PP/PMMA alloy material is with PP as matrix, by doping component PMMA in PP not Only improve the room temperature impact strength of the case hardness of PP, scratch-resistant, and reinforced PMMA, collaborative enhancing The hardness of PP/PMMA alloy material, scratch resistance performance and room temperature shock resistance, and it is good that material is had Good gloss.Meanwhile, also by adding antioxidant, compatilizer and lubrication in PP/PMMA alloy material Agent effectively prevents PP and PMMA from degrading under the high temperature conditions, improves crystal type PP and non-crystalline type The incompatible performance of PMMA, and promote each component dispersed and mobility in the course of processing, thus shape Become stable PP/PMMA alloy material.
Correspondingly, the embodiment of the present invention also provides for the preparation method of above-mentioned PP/PMMA alloy material, its work Process flow is as shown in Figure 1.The method comprises the following steps:
S01. each component of PP/PMMA alloy material is weighed: by joining of above-mentioned PP/PMMA alloy material Side weighs each component;
S02. each component is carried out mixing treatment: each component weighed in step S01 is carried out mixing treatment, Obtain mixed material;
S03. mixed material is melt extruded process: melt extruded by mixed material, pelletize, be dried, Obtain PP/PMMA alloy material.
In above-mentioned steps S03, the technological parameter melt extruded is preferably: district's temperature is 100-120 DEG C, Two district's temperature are 200-220 DEG C, and three district's temperature are 200-220 DEG C, and four district's temperature are 200-220 DEG C, mould Temperature is 100-120 DEG C.Wherein, as long as can realize above-mentioned melt extruding process, total class of concrete extruder It is not limited at this.
Glossiness height, hardness can be obtained greatly, often by the preparation method of above-mentioned PP/PMMA alloy material Temperature excellent shock resistance, and the PP/PMMA alloy material that the compatibility is good, improve its yields.It addition, This preparation method is easy and simple to handle, with low cost, is suitable to the industrialized production of PP/PMMA alloy material.
Now as a example by the formula and preparation method of PP/PMMA alloy material, the present invention is carried out the most in detail Describe in detail bright.
In following all embodiments, PP is HOPP PPH, selected from Sinopec V30G;PMMA The very beautiful CM205 selected from Zhenjiang, Taiwan;Compatilizer is Research of Grafting Malaic Anhydride Onto Polyethylene, its preparation method as above institute State, do not repeat them here;Antioxidant is by four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] tetramethylolmethane Ester, β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid positive octadecanol ester and three (2.4-di-tert-butyl-phenyl) phosphorous Three kinds of antioxidant of acid esters are that 1:1:2 carries out compounding acquisition according to mass ratio;Lubricant profit is by zinc stearate, hard Fat acid calcium, three kinds of lubricants of ethylene bis stearamide carry out compounding acquisition according to mass ratio 1:1:1.5.
Embodiment 1~5
In embodiment 1~5, each PP/PMMA alloy material concrete component by weight percentage see table 1.
In above-described embodiment 1~5, the preparation method of each PP/PMMA alloy material is identical, all includes following step Rapid:
S1. whole components of PP/PMMA alloy material each in above-described embodiment 1~5 are pressed in table 1 respectively Concrete ratio weigh each component;
S2. above-mentioned each component is carried out mixing treatment in a mixer, obtain mixed material;
S3. mixed material is placed in screw extruder and carries out melt extruding, pelletize, be dried and cooling, To PP/PMMA alloy material.Wherein, each zone temperatures of extruder is: 120 DEG C of a district, two 200 DEG C of districts, Three 210 DEG C of districts, four 220 DEG C of districts;Melt pressure is 20MPa, and mold temperature is 100 DEG C, screw speed 130-150 rev/min, side feeding rotating speed 50-80 rev/min.
Comparative example 1~2
In comparative example 1~2, alloy material concrete component by weight percentage see table 1.
In comparative example 1~2, the preparation method of each alloy material is closed with each PP/PMMA in above-described embodiment 1~5 The preparation method of gold copper-base alloy is identical.
Performance test:
By above-described embodiment 1~5 and the PP/PMMA alloy material for preparing of comparative example 1~2 exist The convection oven of 70-90 DEG C is dried 4-6 hour, drier material is existed according to same injecting condition Preparing test bars on 80T injection machine, concrete injecting condition is, injection temperature: 220-250 DEG C, injection Pressure: 70-120Mpa, mold temperature: 40-70 DEG C.Concrete physical property detection project is as follows:
Hot strength is tested according to ASTM D638 standard;
Cantilever beam impact strength is tested according to ASTM D256 standard;
Bending strength and bending modulus are tested by ASTM D790 standard;
Resistance to pencil scraping grade measures according to ISO15194 standard.
Above-described embodiment 1~5 and the performance of PP/PMMA alloy material for preparing of comparative example 1~2 survey Test result see table 1.
Table 1
From upper table 1, in the PP/PMMA alloy material of embodiment 1~5 preparation, the addition of PP, Be conducive to the raising of the room temperature shock resistance of above-mentioned alloy material, but its hardness reduces;PMMA is with compatible The increase of agent content, the scraping and wiping resistance performance of alloy material and hardness strengthen, but its room temperature shock resistance reduces, It is thus desirable to the compound proportion adjusted between PP, PMMA and compatilizer, the above-mentioned alloy of raising could be worked in coordination with The mechanical property of material;And when without (comparative example 1) in the presence of PMMA and compatilizer, the bending of alloy material Intensity and bending modulus are poor, and material the most not scratch-resistant;(comparative example in the presence of without PP and compatilizer 2), the room temperature shock resistance of alloy material is poor, also limit the application of this alloy material.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention Protection domain within.

Claims (8)

1. a PP/PMMA alloy material, includes following component by weight percentage:
PP72.5%;
PMMA12.5%;
Compatilizer 13.75%;
Antioxidant 0.25%;
Lubricant 1%,
Described lubricant by zinc stearate, calcium stearate, ethylene bis stearamide according to mass ratio 1:1:1.5 Compounding acquisition.
2. PP/PMMA alloy material as claimed in claim 1, it is characterised in that described PP is equal Any one in the mixture of poly-polypropylene, COPP, HOPP and COPP, it melts Melting index is 20~50g/10min, and test condition is 230 DEG C/2.16Kg, notch impact strength be 50~ 150J/M。
PP/PMMA alloy material the most according to claim 1, it is characterised in that described PMMA Melt index be 10~20g/10min, test condition is 230 DEG C/5Kg.
PP/PMMA alloy material the most according to claim 1, it is characterised in that described compatilizer For Research of Grafting Malaic Anhydride Onto Polyethylene, its percent grafting is 0.3~1%.
PP/PMMA alloy material the most according to claim 4, it is characterised in that described polyethylene Grafted maleic anhydride is got by following steps preparation:
It is 100% calculating with described Research of Grafting Malaic Anhydride Onto Polyethylene percentage by weight, weighs polyethylene 94.2~97.3%, styrene 1~2%, maleic anhydride 1.5~3%, crosslinking agent B IBP 0.2~0.8%;
Described crosslinking agent B IBP is dissolved in described styrene, mixes with described polyethylene afterwards, Mixed material;
Described maleic anhydride added melted in described mixed material and extrude, obtaining described polycthylene grafted horse Carry out anhydride.
6. the PP/PMMA alloy material as described in Claims 1 to 5 is arbitrary, it is characterised in that described anti- Oxygen agent is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester, β-(3,5-di-t-butyl-4- Hydroxy phenyl) propanoic acid positive octadecanol ester, three (2.4-di-tert-butyl-phenyl) phosphite ester any one or two Plant above mixture.
7. a preparation method for PP/PMMA alloy material, comprises the following steps:
Each component is weighed according to the formula of the arbitrary described PP/PMMA alloy material of claim 1~6;
Described PP, PMMA, compatilizer, antioxidant and lubricant are carried out mixing treatment, obtains mixed material;
Described mixed material is melt extruded, pelletize, be dried, obtain described PP/PMMA alloy material.
The preparation method of PP/PMMA alloy material the most according to claim 7, it is characterised in that The described technological parameter that melt extrudes is: district's temperature is 100-120 DEG C, and two district's temperature are 200-220 DEG C, Three district's temperature are 200-220 DEG C, and four district's temperature are 200-220 DEG C, and mold temperature is 100-120 DEG C.
CN201310743694.3A 2013-12-27 2013-12-27 A kind of PP/PMMA alloy material and preparation method thereof Expired - Fee Related CN103694564B (en)

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CN105713331A (en) * 2016-04-28 2016-06-29 苏州新区华士达工程塑胶有限公司 High-temperature corrosion-resistant plastic
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CN108250586B (en) * 2017-12-29 2021-02-02 青岛海尔新材料研发有限公司 PP/PMMA alloy material and preparation method and application thereof
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CN111057304A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 High-gloss and high-rigidity polypropylene composite material and preparation method thereof
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CN102532771A (en) * 2010-12-23 2012-07-04 上海日之升新技术发展有限公司 Environment-friendly polyethylene compatilizer and preparation method thereof
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