CN103059507B - A kind of High-performance polyether-ether-ketoplastic plastic alloy and preparation method thereof - Google Patents
A kind of High-performance polyether-ether-ketoplastic plastic alloy and preparation method thereof Download PDFInfo
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- CN103059507B CN103059507B CN201310015385.4A CN201310015385A CN103059507B CN 103059507 B CN103059507 B CN 103059507B CN 201310015385 A CN201310015385 A CN 201310015385A CN 103059507 B CN103059507 B CN 103059507B
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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
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Abstract
The invention discloses a kind of High-performance polyether-ether-ketoplastic plastic alloy and preparation method thereof, poly ether ether ketone plastic alloy is to be prepared from by 100 parts of polyether-ether-ketones, 50 ~ 150 parts of polyphenylene sulfides and 5 ~ 20 parts of polyphenylene sulfide graft glycidyl methacrylates.The present invention passes through the polyphenylene sulfide graft glycidyl methacrylate of preparation as compatilizer, the compatibility being obviously improved between polyphenylene sulfide and polyether-ether-ketone, uses the alloy combination property of compatilizer of the present invention to improve more than 25% than the alloy combination property using tradition compatilizer；The final poly ether ether ketone plastic alloy preparing excellent combination property, it is adaptable to the domain requirements such as Aero-Space, weaponry, precise electronic electrical equipment.
Description
Technical field
The present invention relates to field of high polymer material modification, particularly relate to a kind of High-performance polyether-ether-ketoplastic plastic alloy and
Its preparation method.
Background technology
Along with the development of modern science and technology, the application of high performance engineering plastics composite is particularly important with development, but
In the past use single engineering plastics as study on the modification object, but some special dimension such as Aero-Space, weaponry,
The fields such as automobile, single engineering plastics can not meet its development need.In recent years, by two or more plastics profit
The high-performance that obtains with physical blending or the method for chemical graft, functionalization, the engineering plastic alloy of customizations, can improve or
Improve the performance of existing plastics and reduce cost, be widely used in automobile, electronics, precision instrument, office equipment, packaging material,
The fields such as construction material.The problem that engineering plastic alloy is maximum at present is exactly the consistency problem between two kinds of plastics, and it is compatible
Agent directly determines the combination property of engineering plastic alloy.
Polyether-ether-ketone (PEEK) is that the repetitive containing a ketonic bond and two ehter bonds in backbone structure is constituted
High polymer, has high temperature resistant, chemical resistance corrosion, self-lubricating, the wear-resistant and characteristic such as resisting fatigue, anti-flammability, many special
The field such as different field such as Aero-Space, auto industry, electric and medical apparatus and instruments can be with the traditional material such as alternative metals, pottery
It is used as the parts of various high accuracy, high request.But expensive due to polyether-ether-ketone, limit its in some fields should
With.It addition, its impact strength is poor, in order to improve its performance further, to meet the combination property of every field and various
Change and need, can use filling, be blended, cross-link, it is modified by the method such as grafting, mould with the PEEK obtaining performance more excellent
Material alloy or PEEK composite.
Polyphenylene sulfide (PPS) is a kind of novel high-performance thermoplastic resin, has that mechanical strength is high, high temperature resistant, chemically-resistant
The advantages such as medicine, difficult combustion, Heat stability is good, electrical property are excellent, all have extensive answering at electronics, automobile, machinery and chemical field
With.
According to available data, have and polyether-ether-ketone and polyphenylene sulfide are prepared more preferable mechanical property and anti-flammability jointly
Plastic alloy, but owing to polyphenylene sulfide is poor with the compatibility of polyether-ether-ketone, the combination property of its plastic alloy is not ideal.
Such as " engineering plastics application ", 02 phase Chen Xiaoyuan in 2007 etc. have studied the compatibility of Peek/pps
And mechanical property, it can be seen that both compatibilitys are poor, composite materials property is general.
Summary of the invention
The present invention is contemplated to solve problems of the prior art, and the compatibility is good, mechanical property is excellent to be prepared for one
Different poly ether ether ketone plastic alloy and preparation method thereof.
A kind of High-performance polyether-ether-ketoplastic plastic alloy, is prepared from by weight by following component:
Polyether-ether-ketone: 100 parts
Polyphenylene sulfide: 50 ~ 150 parts
Polyphenylene sulfide graft glycidyl methacrylate: 5 ~ 20 parts.
The preferred version of such scheme be described polyphenylene sulfide graft glycidyl methacrylate be by following component
Composition by weight:
Polyphenylene sulfide: 100 parts
Glycidyl methacrylate: 2 ~ 15 parts
Initiator: 0.1 ~ 1 part
Solvent: 5 ~ 20 parts.
It is further preferred that all polyphenylene sulfides of the present invention are cladodification type.
Described initiator is that cumyl peroxide forms for 1:1 ~ 4:1 in mass ratio with aluminum chloride.
Described solvent is acetone.
A kind of method preparing above-mentioned High-performance polyether-ether-ketoplastic plastic alloy, comprises the following steps:
(1) polyphenylene sulfide graft glycidyl methacrylate is prepared:
By weight, glycidyl methacrylate and initiator are dissolved in acetone solvent, add polyphenylene sulfide
Carry out mixed at high speed 2 ~ 5 minutes, by the material that mixes by after extruder grafting with melt extrusion, cooled, be dried and to obtain polyphenyl
Thioether graft glycidyl methacrylate；
(2) poly ether ether ketone plastic alloy is prepared；
The polyphenylene sulfide grafted methacrylic acid (+)-2,3-Epoxy-1-propanol by weight prepared by polyether-ether-ketone, polyphenylene sulfide and (1)
Ester, after high-speed mixer dispersion mixing, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy.
In described step (1) rotating speed of mixer be 100 ~ 200 revs/min, temperature be 40 ~ 80 DEG C；Described extruder
Temperature is 240 DEG C ~ 285 DEG C, and extruder screw draw ratio is 40 ~ 50, rotating speed is 100 ~ 200 revs/min, rate of feeding is 10 ~
20 revs/min.
In described step (2), the speed of mixer is 100 ~ 200 revs/min, incorporation time is 2 ~ 8 minutes, temperature be 40 ~
80℃；The temperature of described extruder is 200 ~ 350 DEG C, and extruder screw draw ratio is 30 ~ 50, rotating speed is 100 ~ 300 revs/min
Clock, rate of feeding is 10 ~ 40 revs/min.
In the present invention, the preparation technology of polyphenylene sulfide graft glycidyl methacrylate mainly has some needs following
Stress:
A: melt extruding temperature is 240 DEG C ~ 285 DEG C.When temperature is higher than 285 DEG C, glycidyl methacrylate can be sent out
Solution estranged；When temperature is less than 240 DEG C, polyphenylene sulfide cannot plastify or plastify bad.
B: extrusion screw rod draw ratio is between 40 ~ 50.When screw slenderness ratio is more than 50, material time of staying in screw rod is long
Easily degraded；When screw slenderness ratio is less than 40, material is plasticizing inequality in screw rod.
C: extrusion screw rod rotating speed is 100 ~ 200 revs/min.When screw speed is higher than 200 revs/min, on the one hand shearing force
Crossing conference and cause the degraded of polyphenylene sulfide and glycidyl methacrylate, the opposing party's fabric time of staying in screw rod is too short
Cause graft reaction incomplete；It is anti-that when screw speed is less than 100 revs/min, shearing force is too small, mixing inequality also results in grafting
Should be incomplete.
D: rate of feeding is 10 ~ 20 revs/min.When rate of feeding is higher than 20 revs/min, too fast under material in the unit interval
Too much can cause mixing inequality；When rate of feeding is less than 10 revs/min, material deficiency in screw rod, cause shearing inequality.
The method have the advantages that
(1) the polyphenylene sulfide graft glycidyl methacrylate that the present invention passes through to prepare is as compatilizer, this phase
Holding agent more preferable than traditional compatilizer effect, testing inspection is learnt by contrast, uses the alloy combination property of compatilizer of the present invention
More than 25% is improved than the alloy combination property using tradition compatilizer；
(2) compatibility between polyphenylene sulfide and polyether-ether-ketone can be obviously improved, gathering of final prepared excellent combination property
Polyether-ether-ketoplastic plastic alloy, it is adaptable to the domain requirements such as Aero-Space, weaponry, precise electronic electrical equipment；
(3) processing technique of the present invention is simple, and easy extruding pelletization has widened the application of polyphenylene sulfide and polyether-ether-ketone alloy
Scope.
Detailed description of the invention
In all examples below and comparative example, test event is performed both by corresponding testing standard, i.e. hot strength and holds
Row GB/T 1040, draw speed 50mm/min；Bending strength performs GB/T 9341, crooked test speed 2mm/min；Cantilever beam
Notch impact strength performs GB/T 1843；Heat distortion temperature performs GB/T 1634, load 1.8MPa.
Embodiment 1
(1) by multiple to 2 parts of glycidyl methacrylate and 0.05 part of cumyl peroxide and 0.05 part of aluminum chloride
Joining initiator to be dissolved in 5 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity is
120 revs/min, mixing temperature is 60 DEG C.The material mixed is passed through extruder grafting with melt extrusion, finally cools down, be dried
Polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
(2) by 100 parts of polyether-ether-ketones, 50 parts of polyphenylene sulfides and above-mentioned 5 parts of prepared polyphenylene sulfide grafted methacrylic acid
Ethylene oxidic ester is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is 3min, mixed
Closing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried and to obtain poly ether ether ketone plastic alloy, wherein extruder temperature from
Feeding is followed successively by 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335 DEG C, 335 DEG C to head,
Extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
In order to preferably embody the superior effect of the poly ether ether ketone plastic alloy of the present invention, special by the formula group of prior art
Become, prepare three comparative examples by preparation method disclosed by the invention and further contrast.Wherein comparative example 1
It is to select polyether-ether-ketone and polyphenylene sulfide to be prepared from；And comparative example 2,3 all adds compatilizer, concrete preparation
Journey is as follows:
Comparative example 1
By 100 parts of polyether-ether-ketones and 55 parts of polyphenylene sulfides after high-speed mixer dispersion mixing, mixed at high speed motor speed is
150 turns/min, incorporation time is 3min, and mixing temperature is 40 DEG C, melted by extruder, extrude, cool down, be dried, pelletizing and
Packaging；Extruder temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C,
335 DEG C, 335 DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, rate of feeding is 20 turns/
Minute.
Comparative example 2
By 100 parts of polyether-ether-ketones, 50 parts of polyphenylene sulfides and 5 parts of compatilizer maleic anhydride graft phenylethene-hydrogenation polybutadienes
Alkene-styrene block copolymer is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, incorporation time
For 3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried, pelletizing and packaging；Extruder temperature is from feeding
Expect that head is followed successively by 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335 DEG C, 335 DEG C, squeeze
Going out screw slenderness ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Comparative example 3
By 100 parts of polyether-ether-ketones, 50 parts of polyphenylene sulfides and 5 parts of compatilizer glycidyl methacrylate graft benzene second
Alkene-hydrogenated butadiene polymer-styrene block copolymer after high-speed mixer dispersion mixing, mixed at high speed motor speed is 150 turns/
Min, incorporation time is 3min, and mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried, pelletizing and packaging；Squeeze
Out-of-machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Carry out being molded into standard by poly ether ether ketone plastic alloy material prepared with comparative example 1-3 for above-described embodiment 1
Batten is tested, and its injection temperature is followed successively by 320 DEG C, 330 DEG C, 335 DEG C, 340 DEG C from feeding to head, injection pressure
80MPa, 10 seconds injection times.The data of each hot strength, bending strength, Izod notched impact strength and heat distortion temperature are such as
Shown in table 1 below:
The alloy material key property contrast table of table 1 embodiment 1 and comparative example 1-3
| Test event | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Hot strength/MPa | 96 | 68 | 71 | 74 |
| Bending strength/MPa | 141 | 112 | 114 | 122 |
| Bending modulus/GPa | 4.1 | 2.9 | 3.2 | 3.3 |
| Izod notched impact strength/(KJ/m2) | 8.2 | 4.3 | 5.1 | 5.6 |
| Heat distortion temperature/DEG C | 136 | 108 | 111 | 120 |
Can be seen that from upper table 1, the poly ether ether ketone plastic alloy material of the present invention is than the alloy material using tradition compatilizer
Combination property such as hot strength, bending strength, Izod notched impact strength all improve more than 25%.
Embodiment 2
The first step: by 15 parts of glycidyl methacrylate and 0.8 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 20 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 3
The first step: by 5 parts of glycidyl methacrylate and 0.4 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 10 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 80 parts of polyphenylene sulfides and 8 parts prepared polyphenylene sulfide grafting methyl-prop
Olefin(e) acid ethylene oxidic ester is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 4
The first step: by 10 parts of glycidyl methacrylate and 0.5 part of cumyl peroxide and 0.15 part of tri-chlorination
Aluminum compounds initiator and is dissolved in 15 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing speed
Degree is 120 revs/min, and mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cool down,
It is dried to obtain polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrudes temperature from feeding to head, be followed successively by 240
DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45,
Extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 100 parts of polyphenylene sulfides and 10 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 5
The first step: by 12 parts of glycidyl methacrylate and 0.6 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 16 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 120 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 6
The first step: by 10 parts of glycidyl methacrylate and 0.7 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 15 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 135 parts of polyphenylene sulfides and 18 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 7
The first step: by 15 parts of glycidyl methacrylate and 0.8 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 120 parts of polyphenylene sulfides and 12 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 8
The first step: by 13 parts of glycidyl methacrylate and 0.15 part of cumyl peroxide and 0.05 part of tri-chlorination
Aluminum compounds initiator and is dissolved in 10 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing speed
Degree is 120 revs/min, and mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cool down,
It is dried to obtain polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrudes temperature from feeding to head, be followed successively by 240
DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45,
Extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 100 parts of polyphenylene sulfides and 13 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 9
The first step: by 14 parts of glycidyl methacrylate and 0.75 part of cumyl peroxide and 0.25 part of tri-chlorination
Aluminum compounds initiator and is dissolved in 18 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing speed
Degree is 120 revs/min, and mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cool down,
It is dried to obtain polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrudes temperature from feeding to head, be followed successively by 240
DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45,
Extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 130 parts of polyphenylene sulfides and 16 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
The poly ether ether ketone plastic alloy material that above-described embodiment 2-9 prepares is carried out be molded into standard batten test,
Its injection temperature is followed successively by 320 DEG C, 330 DEG C, 335 DEG C, 340 DEG C from feeding to head, injection pressure 80MPa, injection time 10
Second.Each hot strength, bending strength, Izod notched impact strength are as shown in table 2 below with the data of heat distortion temperature:
The poly ether ether ketone plastic alloy material key property of table 2 embodiment 2 ~ 9
| Test event | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 |
| Hot strength/MPa | 99 | 101 | 98 | 97 | 104 | 98 | 87 | 89 |
| Bending strength/MPa | 148 | 152 | 145 | 144 | 149 | 146 | 135 | 143 |
| Bending modulus/GPa | 4.7 | 4.8 | 4.7 | 4.6 | 4.9 | 4.7 | 4.4 | 5.0 |
| Izod notched impact strength/(KJ/m2) | 8.6 | 8.9 | 8.6 | 8.4 | 8.9 | 8.7 | 8.3 | 8.5 |
| Heat distortion temperature/DEG C | 138 | 146 | 140 | 135 | 143 | 139 | 132 | 135 |
In order to preferably embody the initiator mistake preparing polyphenylene sulfide graft glycidyl methacrylate in the present invention
The optimum proportioning of oxidation diisopropylbenzene (DIPB) and aluminum chloride is 1:1 ~ 4:1, therefore has carried out example 10 below ~ 12 and contrast enforcement
Example 4 ~ 5, concrete proportioning and preparation method are as follows:
Embodiment 10
The first step: by 15 parts of glycidyl methacrylate and 0.5 part of cumyl peroxide and 0.5 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 11
The first step: by 15 parts of glycidyl methacrylate and 0.65 part of cumyl peroxide and 0.35 part of tri-chlorination
Aluminum compounds initiator and is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing speed
Degree is 120 revs/min, and mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cool down,
It is dried to obtain polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrudes temperature from feeding to head, be followed successively by 240
DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45,
Extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Embodiment 12
The first step: by 15 parts of glycidyl methacrylate and 0.8 part of cumyl peroxide and 0.2 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Comparative example 4
The first step: by 15 parts of glycidyl methacrylate and 0.2 part of cumyl peroxide and 0.8 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
Comparative example 5
The first step: by 15 parts of glycidyl methacrylate and 0.9 part of cumyl peroxide and 0.1 part of aluminum chloride
Compounding initiator is dissolved in 20 parts of acetone, then by mixed solution and 100 parts of polyphenylene sulfide mixed at high speed 2 minutes, mixing velocity
Being 120 revs/min, mixing temperature is 60 DEG C.The particle mixed is passed through extruder grafting with melt extrusion, finally cools down, do
Dry polyphenylene sulfide graft glycidyl methacrylate, wherein melt extrude temperature be followed successively by from feeding to head 240 DEG C,
250 DEG C, 260 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 270 DEG C, 280 DEG C, 280 DEG C, 285 DEG C, extrusion screw rod draw ratio is 45, extrusion
Screw speed is 150 revs/min, and rate of feeding is 15 revs/min.
Second step: by above-mentioned to 100 parts of polyether-ether-ketones, 150 parts of polyphenylene sulfides and 15 parts prepared polyphenylene sulfide grafting methyl
Glycidyl acrylate is after high-speed mixer dispersion mixing, and mixed at high speed motor speed is 150 turns/min, and incorporation time is
3min, mixing temperature is 40 DEG C, is melted by extruder, extrudes, cools down, is dried to obtain poly ether ether ketone plastic alloy, wherein extrudes
Machine temperature be followed successively by from feeding to head 200 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 330 DEG C, 330 DEG C, 335 DEG C, 335 DEG C, 335
DEG C, 335 DEG C, extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 150 revs/min, and rate of feeding is 20 revs/min.
The poly ether ether ketone plastic alloy material that above-described embodiment 10-12 and comparative example 4-5 prepares is molded into
Standard batten is tested, and its injection temperature is followed successively by 320 DEG C, 330 DEG C, 335 DEG C, 340 DEG C from feeding to head, injection pressure
80MPa, 10 seconds injection times.The data of each hot strength, bending strength, Izod notched impact strength and heat distortion temperature are such as
Shown in table 3 below:
Table 3: the alloy material key property contrast table of embodiment 10-12 and comparative example 4-5
| Test event | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative example 4 | Comparative example 5 |
| Hot strength/MPa | 101 | 105 | 100 | 92 | 90 |
| Bending strength/MPa | 149 | 152 | 147 | 126 | 125 |
| Bending modulus/GPa | 4.9 | 5.1 | 4.8 | 4.4 | 4.5 |
| Izod notched impact strength/(KJ/m2) | 8.8 | 9.3 | 8.4 | 6.9 | 7.0 |
| Heat distortion temperature/DEG C | 142 | 148 | 139 | 131 | 129 |
From all above embodiment and comparative example it can be seen that polyphenylene sulfide grafted methacrylic acid is contracted by the present invention
Water glyceride as compatilizer, makes the mechanical property of the plastic alloy that polyphenylene sulfide prepares with polyether-ether-ketone significantly improve, hence it is evident that
Improve the compatibility of polyphenylene sulfide and polyether-ether-ketone, and better than the compatibilization effect of common compatilizer.
The hot strength of composite from the contrast of embodiment 1 and comparative example 1-3 it can be seen that in embodiment 1
For 96MPa, bending strength be 141MPa, bending modulus be 4.1GPa, Izod notched impact strength be 8.2 KJ/m2, heat become
Shape temperature is 136 DEG C, and the hot strength not adding the composite of the comparative example 1 of any compatilizer is 68MPa, bends by force
Degree is 112MPa, bending modulus is 2.9GPa, Izod notched impact strength is 4.3 KJ/m2, heat distortion temperature be 108 DEG C,
Add common compatilizer glycidyl methacrylate graft styrene-hydrogenated butadiene polymer-styrene block copolymer
The hot strength of the composite of comparative example 3 is 74MPa, bending strength is 122MPa, bending modulus is 3.3GPa, cantilever
Beam notch impact strength is 5.6KJ/m2, heat distortion temperature be 120 DEG C.
From embodiment 10 ~ 12 contrast with comparative example 4 ~ 5, it is evident that only initiator cumyl peroxide with
When the quality proportioning of aluminum chloride is 1:1 ~ 4:1, the hot strength of alloy, bending strength, Izod notched impact strength performance
Preferably, go beyond the scope as super, then its performance can be decreased obviously.As: the hot strength of embodiment 11 alloy is 105MPa, bending
Intensity is 152MPa, bending modulus is 5.1GPa, Izod notched impact strength is 9.3 KJ/m2, heat distortion temperature be 148
℃；And the hot strength of comparative example 5 alloy be 90MPa, bending strength be 125MPa, bending modulus be 4.5GPa, cantilever beam lack
Mouth impact strength is 7.0KJ/m2, heat distortion temperature be 129 DEG C, significantly decrease trend.So initiator is in the present invention
Cumyl peroxide and aluminum chloride be 1:1 ~ 4:1 composition in mass ratio, have plastic alloy prepared by the increase present invention
Mechanical property.
Claims (8)
1. a High-performance polyether-ether-ketoplastic plastic alloy, it is characterised in that: it is prepared from by weight by following component:
Polyether-ether-ketone: 100 parts
Polyphenylene sulfide: 50 ~ 150 parts
Polyphenylene sulfide graft glycidyl methacrylate: 5 ~ 20 parts.
A kind of High-performance polyether-ether-ketoplastic plastic alloy, it is characterised in that: described polyphenylene sulfide is grafted
Glycidyl methacrylate is made up of by weight following component:
Polyphenylene sulfide: 100 parts
Glycidyl methacrylate: 2 ~ 15 parts
Initiator: 0.1 ~ 1 part
Solvent: 5 ~ 20 parts.
A kind of High-performance polyether-ether-ketoplastic plastic alloy the most according to claim 1 or claim 2, it is characterised in that: described polyphenylene sulfide
For cladodification type.
A kind of High-performance polyether-ether-ketoplastic plastic alloy, it is characterised in that: described initiator is peroxide
Changing diisopropylbenzene (DIPB) with aluminum chloride is 1:1 ~ 4:1 composition in mass ratio.
A kind of High-performance polyether-ether-ketoplastic plastic alloy, it is characterised in that: described solvent is acetone.
6. the method preparing High-performance polyether-ether-ketoplastic plastic alloy as claimed in claim 5, it is characterised in that: include with
Lower step:
(1) polyphenylene sulfide graft glycidyl methacrylate is prepared:
By weight, glycidyl methacrylate and initiator are dissolved in acetone solvent, add polyphenylene sulfide and carry out
Mixed at high speed 2 ~ 5 minutes, by the material that mixes by after extruder grafting with melt extrusion, cooled, be dried and to obtain polyphenylene sulfide
Graft glycidyl methacrylate；
(2) poly ether ether ketone plastic alloy is prepared；
The polyphenylene sulfide graft glycidyl methacrylate warp by weight prepared by polyether-ether-ketone, polyphenylene sulfide and (1)
After high-speed mixer dispersion mixing, melted by extruder, extrude, cool down, be dried to obtain poly ether ether ketone plastic alloy.
Preparation method the most according to claim 6, it is characterised in that: in described step (1), the rotating speed of mixer is 100 ~ 200
Rev/min, temperature be 40 ~ 80 DEG C；The temperature of described extruder is 240 DEG C ~ 285 DEG C, extruder screw draw ratio is 40 ~ 50,
Rotating speed is 100 ~ 200 revs/min, and rate of feeding is 10 ~ 20 revs/min.
Preparation method the most according to claim 6, it is characterised in that: in described step (2), the speed of mixer is 100 ~ 200
Rev/min, incorporation time is 2 ~ 8 minutes, temperature is 40 ~ 80 DEG C；The temperature of described extruder is 200 ~ 350 DEG C, extruder spiral shell
Bar draw ratio is 30 ~ 50, rotating speed is 100 ~ 300 revs/min, and rate of feeding is 10 ~ 40 revs/min.
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| CN107778769A (en) * | 2017-11-15 | 2018-03-09 | 惠州市永耐宝新材料有限公司 | A kind of fiberglass reinforced PPS/PEEK alloys and its preparation technology |
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| CN101781460A (en) * | 2009-01-20 | 2010-07-21 | 深圳市科聚新材料有限公司 | Polyphenylene sulfide/ polyethylene terephthalate (PPS/PET) composite material and preparation method thereof |
| CN102329477A (en) * | 2011-06-24 | 2012-01-25 | 深圳市科聚新材料有限公司 | Modification-enhanced polyether ether ketone material and preparation method thereof |
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| CN101541876A (en) * | 2007-03-01 | 2009-09-23 | Prs地中海有限公司 | Process for producing compatibilized polymer blends |
| CN101781460A (en) * | 2009-01-20 | 2010-07-21 | 深圳市科聚新材料有限公司 | Polyphenylene sulfide/ polyethylene terephthalate (PPS/PET) composite material and preparation method thereof |
| CN102329477A (en) * | 2011-06-24 | 2012-01-25 | 深圳市科聚新材料有限公司 | Modification-enhanced polyether ether ketone material and preparation method thereof |
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