CN106349677B - A kind of PC alloy materials and its preparation method and application - Google Patents
A kind of PC alloy materials and its preparation method and application Download PDFInfo
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- CN106349677B CN106349677B CN201610843787.7A CN201610843787A CN106349677B CN 106349677 B CN106349677 B CN 106349677B CN 201610843787 A CN201610843787 A CN 201610843787A CN 106349677 B CN106349677 B CN 106349677B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- B29C48/92—Measuring, controlling or regulating
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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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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Abstract
The invention discloses a kind of PC alloy materials.The PC alloy materials include the following component calculated by weight：54 ~ 91 parts of makrolon；4 ~ 60 parts of 1,4 cyclohexanedimethanoester ester of polyethylene terephthalate；30 parts of bat wool is not more than more than 0；0 ~ 6 part of other auxiliary agents.The present invention is modified PC alloy materials using polyester, the PC alloy materials of acquisition are made to overcome the deficiency of existing PC alloy materials, it has good mobility, warpage performance, internal stress performance, demolding performace, color and luster simultaneously, especially suitable for thin-gage goods is made.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of PC alloy materials and preparation method thereof and answer
With.
Background technology
Makrolon (PC) is the engineering plastics haveing excellent performance, and has good comprehensive performance, high mechanical strength, impact resistance
Good toughness, dimensionally stable, electrical insulating property are good；But PC also has simultaneously, and melt viscosity is big, poor fluidity, poor solvent resistance, in solvent
With stress cracking and swelling easily occur under alkaline environment, larger to the sensibility of notch, when processing, is easy to happen stress cracking, and
Processing temperature is higher.It selects particular polyesters to improve PC performances, obtains the composite material of excellent combination property, being one kind more has
Effect, easy modification approach.
Polyethylene terephthalate -1,4 cyclohexane dimethanol ester has impact strength height, transparency outstanding, height
Gloss, heat-resist, bending does not whiten, is mar-proof, is ageing-resistant, antistatic, chemical resistance is excellent, hydrolysis, good fluidity,
Color power is strong, is easy to the advantages that processing and forming, wholesomeness good (meeting FDA).
PC is changed using polyethylene terephthalate -1,4 cyclohexane dimethanol ester although the prior art has
Property, but its product fails to reach good effect in mobility, warpage performance, internal stress performance, demolding performace, color and luster etc.
Fruit, especially as in terms of thin-gage goods, the deficiency of above-mentioned performance is especially apparent.
Invention content
It is an object of the present invention to solve the deficiency of the existing technology and provide a kind of PC alloy materials, which has simultaneously
There are good mobility, warpage performance, internal stress performance, demolding performace, color and luster, especially suitable for thin-gage goods is made.
Another object of the present invention is to provide the preparation methods of the PC alloy materials.
Another object of the present invention is to provide the applications of the PC alloy materials.
The above-mentioned purpose of the present invention is achieved by following technical solution.
A kind of PC alloy materials, including the component that calculates by weight as follows：
54~91 parts of makrolon；
Polyethylene terephthalate -4~60 parts of 1,4 cyclohexane dimethanol ester；
Bat wool is more than 0 and is not more than 30 parts；
0~6 part of other auxiliary agents.
Preferably, the PC alloy materials include the following component calculated by weight：
54~91 parts of makrolon；
Polyethylene terephthalate -4~60 parts of 1,4 cyclohexane dimethanol ester；
1~30 part of bat wool；
0~6 part of other auxiliary agents；
In the PC alloy materials, containing aluminium element and zr element, the content of aluminium element is 0.1~500ppm；Zr element
Content be 0.1~500ppm；
Wherein, the bat wool includes bat wool I and bat wool II：
Bat wool I：It is made of the bat wool that length is 100um~300um, accounts for the weight of bat wool
Percentage is 40%~60%；
Bat wool II：It is made of the bat wool that length is more than 300um but is no more than 500um, accounts for threadiness
The weight percent of filler is 20%~30%.
Bat wool length and the test method of distribution：By 2g PC alloy materials in 600 DEG C of concentrated sulfuric acids and hydrofluoric acid
It is adjusted by hydrogen peroxide titration after burning solution and arrives neutrality, the burning solution liquid of obtained clear, liquid passes through shifting after being cooled to room temperature
Liquid pipe pipettes 2ml in clean sheet glass from bottom, and drop is paved into the water layer that thickness is 2mm, secondary element image instrument amplification times
Number calculates fibrous to take pictures under conditions of under 200 times according to the statistical method of the bat wool form of photo
Pack length and distribution.
When the PC alloy materials contain aluminium element and zr element, contained by aluminium element and zr element content according to
Following method is tested：
The particle 2g of accurate weighing PC alloy materials in assay balance pours into 100ml resolution bottles, is then added 97%
Concentrated sulfuric acid 5ml, heated 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, then add 68% nitric acid 5ml,
Heating 20 minutes is kept again, particulate matter is made to decompose postcooling completely to room temperature, is added in the hydrogen peroxide of 20ml and acid to pH value
After 7, aforesaid liquid is diluted with deionized water, liquid is imported by sample feeding pipe and measures aluminium element and zirconium in ICP detecting instruments
The content of element.
Inventors be surprised to learn that in above-mentioned formula, aluminium element and zr element are extraly added, and control its content at certain
In range, while the length of control fiber shape filler and when being distributed in above range, it can further promote poly terephthalic acid second
The warpage performance of the ester modified PC of glycol -1,4 cyclohexane dimethanol, internal stress performance, demolding performace, color and luster.
When the aluminium element of addition and/or any constituent content of zr element is excessively high and/or the distribution of bat wool not
When in the range, said effect can not be played.
Preferably, in the PC alloy materials, the content of aluminium element is preferably 1~300ppm, more preferably 1~
100ppm.Further, the preferred content of aluminium element is 10~90ppm, more preferably 20~70ppm.
Preferably, in the PC alloy materials, the content of zr element is preferably 1~300ppm, more preferably 1~
100ppm.Further, the preferred content of zr element is 6~80ppm, more preferably 12~60ppm.
Preferably, aluminium element in the form of the oxide of aluminium salt or aluminium to be present in PC alloy materials.The aluminium salt includes
But be not limited to aluminium chloride, aluminum sulfate, aluminum nitrate or aluminum phosphate etc..The oxide of the aluminium includes but not limited to alundum (Al2O3).
Preferably, zr element in the form of the oxide of zirconates or zirconium to be present in PC alloy materials.The zirconates includes
But it is not limited to zirconium chloride, zirconium nitrate, zirconium sulfate, basic zirconium phosphate.The oxide of the zirconium includes but not limited to zirconium oxide.
Preferably, the fusing point of the polyethylene terephthalate -1,4-CHDM ester is 290~310 DEG C.
It is highly preferred that 1,4-CHDM in the polyethylene terephthalate -1,4-CHDM ester
The molar ratio of structural unit (CHDM) and ethylene glycol structure unit (EG) is 80:20~20:80.
It is highly preferred that 1,4-CHDM in the polyethylene terephthalate -1,4-CHDM ester
The molar ratio of structural unit (CHDM) and ethylene glycol structure unit (EG) is 60:40~70:30 or 30:70~40:60.
The bat wool can be one or more of metallic fiber, carbon fiber, plastic optical fibre, glass fibre；
It is preferred that glass fibre；Wherein, the one kind or several of the glass fibre in slubbing fiber, long glass fibres, short glass fiber
Kind, preferably one or more of M- glass, E- glass, A- glass, S- glass, R- glass, C- glass, more preferably E- glass
Glass, A- glass, C- glass.The above glass fibre can be surface-treated by slurry and adhesion promotor, can also
It is that can also be surface without any processing surface portion covering treatment；A diameter of 1um of the glass fibre~
25um, preferably 3um~20um, most preferably 4um~15um.
According to different purposes needs, PC alloy materials of the invention can further include other auxiliary agents, such as antioxygen
It is agent, light stabilizer, impact modifier, fire retardant, fluorescent whitening agent, lubricant, plasticizer, toughener, thickener, antistatic
Agent, releasing agent, pigment etc..
The antioxidant can be antioxidant commonly used in the art, can be selected from suffocated amine antioxidant, hindered phenol
One kind in one or more of kind antioxidant or phosphite ester kind antioxidant, such as 1010,168,1076,445,1098 or
The mixture of two kinds of person or more.
The toughener can be toughener commonly used in the art, such as EVA types toughener, EMA types toughener, ASA types
It is one or more mixed in toughener, AES types toughener, SAS types toughener, esters of acrylic acid toughener, organosilicon toughener
Close object.
The light stabilizer can be light stabilizer commonly used in the art, such as in hindered amines or ultra-violet absorber
One or more of mixing, specific examples thereof include one kind or two in UV-944, UV-234,770DF, 328,531,5411
Kind or more mixture.
The impact modifier can be impact modifier commonly used in the art, such as PTW, styrene-ethylene/butylene-
One or two kinds of mixture in styrene block copolymer SEBS.
The fire retardant can be fire retardant commonly used in the art, such as phosphorus flame retardant, and it is double to be specifically as follows bisphenol-A
(diphenyl phosphoester) BDP, RDP, dimethyl methyl phosphonate (DMMP) and one kind in diethyl ethylphosphate (DEEP) or
Two kinds or more of mixture.
The fluorescent whitening agent can be fluorescent whitening agent commonly used in the art, such as double triazine amino-stilbenes.
The lubricant can be lubricant commonly used in the art, such as one kind in pentaerythritol ester, montanin wax, silicone oil
Or two kinds or more of mixture.
The plasticizer can be plasticizer commonly used in the art, such as glycerine, citric acid, butyl citrate, epoxy are big
One or two kinds of or more mixture in soya-bean oil etc..
The thickener can be thickener commonly used in the art, such as inorganic thickening agent, polyacrylic ester thickener.
The antistatic agent is permanent antistatic agent, can be permanent antistatic agent commonly used in the art, such as
One or two kinds of or more mixture in PELESTAT-230, PELESTAT-6500, SUNNICO ASA-2500.
The releasing agent can be releasing agent commonly used in the art, such as one in silicone oil, paraffin, White Mineral Oil, vaseline
Kind or two kinds or more of mixture.
The pigment can be in pigment, such as carbon black, titanium dioxide, black race, phthalocyanine blue, fluorescent orange commonly used in the art etc.
One or two kinds of or more mixture.
The warpage properties of the PC alloy materials observe deviation distance using Quadratic Finite Element, and maximum angularity γ is less than 50, surface
Tension is more than 44 dynes, and color and luster deviation is less than 1%.
Surface tension test is referred to following method and carries out：Using the prepared different dyne solution of second alcohol and water, use
Cotton swab dips in a certain dyne of solution and is coated with (spreading area ＞ 3cm on the square plate surface kept flat2), it is not shunk in 2 seconds such as, it can be again
Using scale value relatively up to because solvent retries；If being shunk in 2 seconds, many droplets are broken into, then show that the last time makes
Dyne solvent institute target number is exactly the plate surface tension.
Color and luster test is referred to following method and carries out：Using color difference meter, surveys tri- groups of data of color L, a, b and calculate colorimetric
Tetra- groups of chromatism datas of △ E, △ L, △ a, △ b afterwards.
Calculate aberration △ E=(△ L2+△a2+△b2)1/2。
The preparation method of PC alloy materials of the present invention, includes the following steps：
1) each component, and makrolon, the poly terephthalic acid second that preliminary drying dry-cure will be needed are weighed according to formulation content
Glycol -1,4 cyclohexane dimethanol ester, bat wool, other auxiliary agents carry out 120 DEG C~130 DEG C preliminary drying dry-cure；
2) by the makrolon of preliminary drying dry-cure, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, threadiness
Filler, other auxiliary agents, respectively by high mixer be uniformly mixed；
3) by uniformly mixed makrolon, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, other help
Respectively by main spout, bat wool passes through main spout for the oxide and zirconates of agent, aluminium salt or aluminium or the oxide of zirconium
Or side spout, it is added in double screw extruder, the temperature control setting temperature of double screw extruder is 200 DEG C~280 DEG C；
4) cooling, pelletizing.
Preferably, the preparation method of the PC alloy materials, includes the following steps：
1) each component, and makrolon, the poly terephthalic acid second that preliminary drying dry-cure will be needed are weighed according to formulation content
Glycol -1,4-CHDM ester, bat wool, other auxiliary agents carry out 120 DEG C~130 DEG C preliminary drying dry-cure, prebake
Time is set as 4h~6h, obtains makrolon, the polyethylene terephthalate -1,4-CHDM of preliminary drying dry-cure
Ester, bat wool, other auxiliary agents；
2) by the makrolon of preliminary drying dry-cure, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, threadiness
Filler, other auxiliary agents, respectively by high mixer be uniformly mixed, mixing temperature be 30 DEG C~50 DEG C, incorporation time is set in 5min
~15min；
3) by uniformly mixed makrolon, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, other help
Respectively by main spout, bat wool passes through main spout for the oxide and zirconates of agent, aluminium salt or aluminium or the oxide of zirconium
Or side spout, it being added in double screw extruder, the temperature control setting temperature of double screw extruder is 200 DEG C~280 DEG C, wherein
And at least one is set and is vacuumized, vacuumize the end that can be located at conveying section, the front end of melt zone and metering segment portion；
4) melt will be obtained and pass through die head, die holes quantitative range is 4~30, therefore can obtain a diameter of 0.5mm
The melting strip of the bar compositions of~10mm；Strip is melted by 20 DEG C~25 DEG C of sink cooling vent, is introduced into pelleter
In be homogenized pelletizing, obtained particle after sieving empty conveying dehumidifying by obtaining final PC alloy materials.
Preferably, by the following method, bat wool I and fiber with specific length range and content distribution are obtained
The PC alloy materials of shape filler II, include the following steps：
1) each component, and makrolon, the poly terephthalic acid second that preliminary drying dry-cure will be needed are weighed according to formulation content
Glycol -1,4-CHDM ester, bat wool, other auxiliary agents carry out 120 DEG C~130 DEG C preliminary drying dry-cure, prebake
Time is set as 4h~6h, obtains makrolon, the polyethylene terephthalate -1,4-CHDM of preliminary drying dry-cure
Ester, bat wool, other auxiliary agents；
2) by the makrolon of preliminary drying dry-cure, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, threadiness
Filler, other auxiliary agents respectively by high mixer be uniformly mixed, mixing temperature be 30 DEG C~50 DEG C, incorporation time be set in 5min~
15min；
3) by uniformly mixed makrolon, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, other help
Respectively by spout 1 as shown in Figure 1, bat wool is logical for the oxide and zirconates of agent, aluminium salt or aluminium or the oxide of zirconium
Spout 1,2 or 3 as shown in Figure 1 is crossed, is added in double screw extruder, the temperature control setting temperature of double screw extruder is
200 DEG C~280 DEG C, wherein and at least one be set vacuumize, vacuumize the end that can be located at conveying section, the front end of melt zone
And metering segment portion；
4) it by combining the number of bat wool added by spout and each spout of control, obtains containing specific length
The melt of range and the bat wool I and bat wool II of content range distribution；
5) the molten of the bat wool I being distributed containing specific length range and content range and bat wool II will be obtained
Body passes through die head, and die holes quantitative range is 4~30, therefore can obtain the bar compositions of a diameter of 0.5mm~10mm
Melting strip；Strip is melted by 20 DEG C~25 DEG C of sink cooling vent, is introduced into pelleter and is homogenized pelletizing, obtain
Particle by obtaining final PC alloy materials after sieving empty conveying dehumidifying.
Compared with prior art, the present invention has the advantages that：
The present invention is modified PC alloys using polyester, and the PC alloy materials of acquisition is made to overcome existing PC alloy materials
Deficiency, simultaneously there is good mobility, warpage performance, internal stress performance, demolding performace, color and luster, especially suitable for system
At thin-gage goods.Particularly, in the aluminium element and zr element and control fiber shape filler of PC alloy materials addition certain content
Distribution of lengths in PC alloy materials and content, the warpage performances of gained PC alloy materials, internal stress performance, demolding performace,
Color and luster is further promoted.
Description of the drawings
Fig. 1 is the structural schematic diagram of double screw extruder.
Specific implementation mode
The present invention is illustrated below in conjunction with specific embodiment, however protection scope of the present invention is not intended to be limited to
Following embodiment, the explanation of embodiment are merely used to help understand the method and its core concept of the present invention.It is all in this patent
All any modification, equivalent and improvement etc. made by within spirit and principle, should be included in the present invention claims protection domain
Within.
In embodiment, each performance is tested according to following scheme：
(1) fluidity testing MFR：According to ASTM D1238 are measured, test condition is 260 DEG C, 5kg.
(2) warpage performance
Deviation distance is observed using Quadratic Finite Element, is characterized with maximum angularity：
γ=h/l*a.
H is the maximum distance of product and references object product, and l is projected length of the product in references object, and a hangs down for product
Directly in the length in references object direction.
(3) internal stress is tested
Acetone soak is tested：It is impregnated 1 hour in the acetone solvent of PC alloy materials at normal temperatures, takes out and seen after air-drying
Examine cracking situation.
No visible crack evaluation preferably, has crack to be judged to difference.
(4) adhesion strength, surface tension test
Appraisal procedure is, when surface tension≤44 dyne are determined as difference, when 44 dynes of judgements of surface tension ＞ preferably.
Test method is as follows：
Using the prepared different dyne solution of second alcohol and water, a certain dyne of solution is dipped in the alloy square plate kept flat with cotton swab
Surface is coated with (spreading area ＞ 3cm2), it is not shunk in 2 seconds such as, scale value can be reused relatively up to because solvent retries；If 2
It is shunk in second, is broken into many droplets, then show that the last dyne solvent institute target number used is exactly the plate
Surface tension.
Whether depainting is easy：
The variation of surface tension, when being embodied in PC alloy material product japannings, if be easy to cause depainting.Surface tension
Bigger, paint is more secured with the conjugation of PC alloy materials, it is not easy to fall paint.
Paint film situation is tested using cross frame method, GB/T 9286, edge of a knife width is about 10mm~12mm, per 1mm~
1.2mm is interval, shares 10 lattice, straight line draw under when will appear the identical straight line tool marks in 10 intervals, in the vertical of straight line tool marks
Under position is drawn, the square of 100 lattice for 10*10 is become, cross-cut tester stroke should cut when going down and see ground, can not be only
It cuts on coating, otherwise tests just invalid.After cross-cut tester has been drawn, it can or can not be fallen off with adhesive tape test, first, adhesive tape patch
It sets, is closely attached adhesive tape with finger pressure, then torn up adhesive tape with the power of moment, the coating on visual material in hundred cases
Whether there is obscission in addition, for JIS standards, specifies the Transparent Tape 600 of label and model 3M.
(5) release property, injection temperature is at 280 DEG C, in injection speed 50%, cooling time 10s, can material and mold
Directly it is detached from.Easily removing (being not necessarily to manual pickup) judgement preferably, needs manual pickup to be determined as difference.
(6) color and luster uses following methods：Magnesia standard white plate is as benchmark under standard illuminant-C, from sample to it is red,
Green, blue three color light reflectivity calculates the numerical value of gained, evaluates its partially yellow degree, and numerical value is the smaller the better.
Bat wool length and the test method of distribution：By 2g PC alloy materials in 600 DEG C of concentrated sulfuric acids and hydrofluoric acid
It is adjusted by hydrogen peroxide titration after burning solution and arrives neutrality, the burning solution liquid of obtained clear, liquid passes through shifting after being cooled to room temperature
Liquid pipe pipettes 2ml in clean sheet glass from bottom, and drop is paved into the water layer that thickness is 2mm, secondary element image instrument amplification times
Number calculates fibrous to take pictures under conditions of under 200 times according to the statistical method of the bat wool form of photo
Pack length and distribution.
The content of aluminium element and zr element contained by PC alloy materials is tested as follows：
The particle 2g of accurate weighing PC alloy materials in assay balance pours into 100ml resolution bottles, is then added 97%
Concentrated sulfuric acid 5ml, heated 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, then add 68% nitric acid 5ml,
Heating 20 minutes is kept again, particulate matter is made to decompose postcooling completely to room temperature, is added in the hydrogen peroxide of 20ml and acid to pH value
After 7, aforesaid liquid is diluted with deionized water, liquid is imported by sample feeding pipe and measures aluminium element and zirconium in ICP detecting instruments
The content of element.
In embodiment and comparative example, the source of aluminium element used is the oxide of commercially available aluminium salt or aluminium, used
The source of zr element is the oxide of commercially available zirconates or zirconium, other raw materials not specialized are ordinary commercial products.
Makrolon is the aromatic copolycarbonate (trade mark：PC L-1250Y).
Bat wool is that glass fibre is purchased from PPG companies, a diameter of 4.5um.
Polyethylene terephthalate -1,4 cyclohexane dimethanol ester is Eastman products：
Polyester A is polyethylene terephthalate -1,4-CHDM ester, and fusing point is 290 DEG C, n (CHDM):n
(EG)=80:20.
Polyester B is polyethylene terephthalate -1,4-CHDM ester, and fusing point is 295 DEG C, n (CHDM):n
(EG)=65:35.
Polyester C is polyethylene terephthalate -1,4-CHDM ester, and fusing point is 300 DEG C, n (CHDM):n
(EG)=50:50.
Polyester D is polyethylene terephthalate -1,4-CHDM ester, and fusing point is 305 DEG C, n (CHDM):n
(EG)=35:65.
Polyester E is polyethylene terephthalate -1,4-CHDM ester, and fusing point is 310 DEG C, n (CHDM):n
(EG)=20:80.
In embodiment and comparative example, the preparation method of the PC alloy materials includes the following steps：
1) each component, and makrolon, the poly terephthalic acid second that preliminary drying dry-cure will be needed are weighed according to formulation content
Glycol -1,4-CHDM ester, bat wool, other auxiliary agents carry out 120 DEG C~130 DEG C preliminary drying dry-cure, prebake
Time is set as 4h~6h, obtains makrolon, the polyethylene terephthalate -1,4-CHDM of preliminary drying dry-cure
Ester, bat wool, other auxiliary agents；
2) by the makrolon of preliminary drying dry-cure, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, threadiness
Filler, other auxiliary agents respectively by high mixer be uniformly mixed, mixing temperature be 30 DEG C~50 DEG C, incorporation time be set in 5min~
15min；
3) by uniformly mixed makrolon, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, other help
Respectively by spout 1 as shown in Figure 1, bat wool passes through the oxide of the oxide of agent, aluminium salt or aluminium, zirconates or zirconium
Spout 1,2 or 3 as shown in Figure 1, is added in double screw extruder, and the temperature control setting temperature of double screw extruder is 200
DEG C~280 DEG C, wherein and at least one be set vacuumize, vacuumize the end that can be located at conveying section, the front end of melt zone and
Metering segment portion；
4) it by combining the number of bat wool added by spout and each spout of control, obtains containing specific length
The melt of range and the bat wool I and bat wool II of content range distribution；
5) the molten of the bat wool I being distributed containing specific length range and content range and bat wool II will be obtained
Body passes through die head, and die holes quantitative range is 4~30, therefore can obtain the bar compositions of a diameter of 0.5mm~10mm
Melting strip；Strip is melted by 20 DEG C~25 DEG C of sink cooling vent, is introduced into pelleter and is homogenized pelletizing, obtain
Particle by obtaining final PC alloy materials after sieving empty conveying dehumidifying.
Such as：
1) 70Kg polycarbonate resins, 30Kg polyethylene terephthalates -1,4-CHDM ester, 1kg glass are taken
Glass fiber carries out 120 DEG C~130 DEG C preliminary drying dry-cure；
2) prebake treated makrolon, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, glass fibers
Dimension is uniformly mixed by high mixer respectively；
3) makrolon that will be uniformly mixed, polyethylene terephthalate -1,4-CHDM ester, take relative to
Polycarbonate resin and the alundum (Al2O3) of polyethylene terephthalate -1,4 cyclohexane dimethanol ester total weight 0.06%,
Respectively by spout 1 as shown in Figure 1, the feed postition of glass fibre is 0.05% zirconium oxide：With glass fibre gross weight
Based on amount, glass fibre addition of spout 1 from figure of glass fibre total weight 30% is accounted for, using glass fibre total weight as base
Plinth, the glass fibre for accounting for glass fibre total weight 35% are added from spout 2, based on glass fibre total weight, account for glass
The glass fibre of total weight of fiber 35% is added from spout 3, and the temperature control setting temperature of double screw extruder is 200 DEG C~280
DEG C, melt is obtained,
4) above-mentioned melt is passed through into die head, die holes quantitative range is 4~30, therefore can obtain a diameter of 0.5mm
The melting strip of the bar compositions of~10mm；Strip is melted by 20 DEG C~25 DEG C of sink cooling vent, is introduced into pelleter
In be homogenized pelletizing, obtained particle after sieving empty conveying dehumidifying by obtaining final PC alloy materials.To aluminium member in pellet
The content of element and zr element is detected, and it is 311ppm to measure wherein aluminium element content, and zr element content is 307ppm.To pellet
Middle glass fibre distribution is detected, and length is the glass fibre of 100um~300um, and the weight percent for accounting for glass fibre is
50%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is 25%.
In other embodiments, using feed way 3), the pellet being distributed with above-mentioned glass fibre can be also obtained.
Embodiment 32:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 40% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
35% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 25%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 40%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
25%.
Embodiment 33:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 20% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
35% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 45%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 60%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
25%.
Embodiment 34:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 30% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
30% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 40%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 50%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
20%.
Embodiment 35:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 30% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
20% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 50%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 50%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
30%.
Embodiment 36：3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 50% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
25% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 25%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 50%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
25%.
Embodiment 37：3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 70% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
20% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 10%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 50%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
25%.
Comparative example 4:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 40% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
60% glass fibre is added from spout 2.Length is the glass fibre of 100um~300um in the pellet made, accounts for glass
The weight percent of fiber is 30%；300um is more than by length but no more than the glass fibre of 500um, accounts for the weight of glass fibre
It is 30% to measure percentage.
Comparative example 5:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 80% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
20% glass fibre is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for glass
The weight percent of fiber is 70%；300um is more than by length but no more than the glass fibre of 500um, accounts for the weight of glass fibre
It is 20% to measure percentage.
Comparative example 6:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 40% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
20% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 40%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 40%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
10%.
Comparative example 7:3) feed postition of glass fibre is in：Based on glass fibre total weight, it is total to account for glass fibre
The glass fibre of weight 30% spout 1 from figure is added, and based on glass fibre total weight, accounts for glass fibre total weight
60% glass fibre is added from spout 2, based on glass fibre total weight, accounts for the glass of glass fibre total weight 10%
Fiber is added from spout 3.Length is the glass fibre of 100um~300um in the pellet made, accounts for the weight of glass fibre
Percentage is 40%；300um is more than by length but no more than the glass fibre of 500um, the weight percent for accounting for glass fibre is
40%.
Embodiment 0~37 and comparative example 1~7
By table 1 to the formula of table 7, the PC alloy materials of preparation embodiment 0~37 and comparative example 1~7, performance test,
It is shown in Table 8.From embodiment 0~37 as can be seen that when addition aluminium element and zr element and control fiber shape filler in PC alloy materials
Length and be distributed in specific sections, the warpage of PC alloy materials, internal stress, release property, colour properties are obviously improved.From right
Ratio 1~7 is as can be seen that one of the arbitrary too high levels of the aluminium element and zr element that add in the PC alloy materials, either
When the length of bat wool and distribution be not in the range, the warpages of PC alloy materials, internal stress, colour properties can be by
It is apparent to influence.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Claims (12)
1. a kind of PC alloy materials, which is characterized in that including the component calculated by weight as follows：
54 ~ 91 parts of makrolon；
Polyethylene terephthalate -4 ~ 60 parts of 1,4 cyclohexane dimethanol ester；
1 ~ 30 part of bat wool；
0 ~ 6 part of other auxiliary agents；
In the PC alloy materials, containing aluminium element and zr element, the content of aluminium element is 0.1 ~ 500ppm；The content of zr element
For 0.1 ~ 500ppm；
Wherein, the bat wool includes bat wool I and bat wool II：
Bat wool I：It is made of the bat wool that length is 100um~300um, accounts for the weight percent of bat wool
Than being 40%~60%；
Bat wool II：It is made of the bat wool that length is more than 300um but is no more than 500um, accounts for bat wool
Weight percent be 20%~30%.
2. PC alloy materials according to claim 1, which is characterized in that the content of the aluminium element is 1 ~ 300 ppm；It is described
The content of zr element is 1 ~ 300 ppm.
3. PC alloy materials according to claim 1, which is characterized in that the content of the aluminium element is 1 ~ 100ppm；It is described
The content of zr element is 1 ~ 100ppm.
4. PC alloy materials according to claim 1, which is characterized in that aluminium element in the form of the oxide of aluminium salt or aluminium to deposit
It is in PC alloy materials；Zr element in the form of the oxide of zirconates or zirconium to be present in PC alloy materials.
5. according to the PC alloy materials of claim 1 or 4, which is characterized in that aluminium element with aluminium chloride, aluminum nitrate, aluminum sulfate,
The form of aluminum phosphate or alundum (Al2O3) is present in PC alloy materials；Zr element is with zirconium chloride, zirconium nitrate, zirconium sulfate, phosphoric acid
The form of zirconium or zirconium oxide is present in PC alloy materials.
6. PC alloy materials according to claim 1, which is characterized in that the polyethylene terephthalate-Isosorbide-5-Nitrae-hexamethylene
The fusing point of alkane diformazan alcohol ester is 290 ~ 310 DEG C.
7. PC alloy materials according to claim 6, which is characterized in that the polyethylene terephthalate-Isosorbide-5-Nitrae-hexamethylene
The molar ratio of 1,4 cyclohexane dimethanol ester structure unit and ethylene glycol terephthalate structural unit is in alkane diformazan alcohol ester
80:20~20:80。
8. PC alloy materials according to claim 1, which is characterized in that in the PC alloy materials, aluminium element and zr element
Content tested as follows：The particle 2g of accurate weighing PC alloy materials, pours into 100ml and disappears in assay balance
It solves in bottle, 97% concentrated sulfuric acid 5ml is then added, heats 10 minutes in 300 DEG C of iron plate heating instruments of preset temperature, then again
68% nitric acid 5ml is added, then keeps heating 20 minutes, so that particulate matter is decomposed postcooling completely to room temperature, the dioxygen of 20ml is added
After being 7 with acidity to pH value in water, aforesaid liquid is diluted with deionized water, liquid, which is passed through sample feeding pipe, imports ICP detecting instruments
The middle concentration for measuring aluminium element and zr element.
9. PC alloy materials according to claim 1, which is characterized in that in the PC alloy materials, bat wool length
And the test method of distribution is：2g PC alloy materials are titrated after 600 DEG C of concentrated sulfuric acids and hydrofluoric acid burn solution by hydrogen peroxide
Neutrality is adjusted, the burning solution liquid of obtained clear, liquid is cooled to after room temperature and pipettes 2ml dry from bottom by pipette
Net sheet glass, drop be paved into thickness be 2mm water layer, secondary element image instrument amplification multiple be 200 times under under conditions of into
Row is taken pictures, and bat wool length and distribution are calculated according to the statistical method of the bat wool form of photo.
10. PC alloy materials according to claim 1, which is characterized in that the warpage properties of the PC alloy materials are using secondary
Member observation deviation distance, maximum angularity γ are less than 50, and surface tension is more than 44 dynes, and color and luster deviation is less than 1%.
11. the preparation method of PC alloy materials, includes the following steps described in claim 1 ~ 10 any one：
1）Each component, and makrolon, the polyethylene terephthalate-that preliminary drying dry-cure will be needed are weighed according to formulation content
1,4 cyclohexane dimethanol ester, bat wool, other auxiliary agents carry out 120 DEG C ~ 130 DEG C preliminary drying dry-cure；
2）The makrolon of preliminary drying dry-cure, polyethylene terephthalate -1,4 cyclohexane dimethanol ester, threadiness are filled out
Material, other auxiliary agents are uniformly mixed by high mixer respectively；
3）By uniformly mixed makrolon, polyethylene terephthalate -1,4-CHDM ester, other auxiliary agents, aluminium
Respectively by main spout, bat wool is fed by main spout or side for the oxide and zirconates of salt or aluminium or the oxide of zirconium
Material mouth is added in double screw extruder, and the temperature control setting temperature of double screw extruder is 200 DEG C ~ 280 DEG C；
4）Cooling, pelletizing.
12. application of the PC alloy materials in preparing thin-gage goods described in claim 1 ~ 10 any one.
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