CN105733231B - Calcium sulfate whisker modified polycarbonate alloy material and preparation method thereof - Google Patents
Calcium sulfate whisker modified polycarbonate alloy material and preparation method thereof Download PDFInfo
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 270
- 239000000956 alloy Substances 0.000 title claims abstract description 178
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 167
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 174
- 238000002156 mixing Methods 0.000 claims abstract description 126
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 97
- 239000002270 dispersing agent Substances 0.000 claims abstract description 57
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 51
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 51
- 239000000314 lubricant Substances 0.000 claims abstract description 49
- 239000007822 coupling agent Substances 0.000 claims abstract description 43
- 238000001125 extrusion Methods 0.000 claims abstract description 43
- 238000005469 granulation Methods 0.000 claims abstract description 14
- 230000003179 granulation Effects 0.000 claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 7
- 238000005275 alloying Methods 0.000 claims description 65
- 239000008188 pellet Substances 0.000 claims description 65
- 238000001994 activation Methods 0.000 claims description 35
- 239000012994 photoredox catalyst Substances 0.000 claims description 30
- -1 compatilizer Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 18
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052602 gypsum Inorganic materials 0.000 claims description 5
- 239000010440 gypsum Substances 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 150000008301 phosphite esters Chemical class 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000029936 alkylation Effects 0.000 claims description 4
- 238000005804 alkylation reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 2
- 230000008859 change Effects 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 238000005461 lubrication Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 235000011132 calcium sulphate Nutrition 0.000 description 59
- 238000005453 pelletization Methods 0.000 description 30
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 16
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 229920007019 PC/ABS Polymers 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000006353 environmental stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009818 secondary granulation Methods 0.000 description 3
- 239000004425 Makrolon Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000001175 calcium sulphate Substances 0.000 description 1
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a calcium sulfate whisker modified polycarbonate alloy material and a preparation method thereof, and the preparation method comprises the following steps: mixing CSW and a coupling agent according to a weight ratio of 5-20: 1, mixing and activating to obtain semi-modified CSW; and then mixing with a dispersing agent and white oil according to a weight ratio of 2-10: 1: 10-20 blending treatment to obtain the super-dispersed semi-modified CSW; and mixing the mixture with a PC alloy blend according to the weight ratio of 1: 100-600 to form a CSW-PC mixture; performing melt extrusion granulation, and cooling to obtain surface modified CSW-PC alloy particles; according to the weight ratio of 10-30: 40-90: 1-5: 0.1-0.6: 0.1-0.6 mixing the surface modified CSW-PC alloy particles, the PC alloy blend, the compatilizer, the antioxidant and the lubricant, and then carrying out melt extrusion granulation to obtain the polycarbonate alloy material modified by the calcium sulfate whiskers. The invention can improve the dispersibility of CSW in the polyester alloy.
Description
Technical field
It is calcium sulfate whisker modified poly- more particularly to a kind of surface modification the present invention relates to the preparation of polycarbonate alloy technology
Carbonic ester alloy and its preparation technology.
Background technology
Makrolon (PC) alloy is a kind of engineering plastics of excellent combination property, has impact strength height, creep resistance
Can with good stability of the dimension, heat-resisting, transparent, water absorption rate is low, nontoxic, dielectric properties are excellent the advantages that, in each industrial department especially
It is widely used in fields such as electric, auto industry, medicine equipment, building and lighting apparatus.But PC materials also have molten
Body viscosity is big, machine-shaping is difficult, easy stress cracking, to notch sensitive, aging and the shortcomings of wear no resistance, limit it and enter one
The application of step.Based on above mentioned problem, using the blending and modifying PC alloy materials such as all kinds of toughener, bulking agent, surface modifier, carry
The performances such as high material resisting environmental stress and cracking have become the focus studied now.
Calcium sulfate crystal whiskers (CSW), also known as crystal whisker of gypsum, it is the fibrous monocrystal of calcium sulfate, there is specific cross section
Long-pending, complete profile and structure.CSW as a kind of new whisker structure material, it have as gypsum anhydrous, half water and
Point of two water, wherein anhydrous and half-H 2 O calcium sulphate has intensity height, high temperature resistant, resist chemical, good toughness, and the polymerization such as rubber
The advantages that affinity of thing is strong.The industries such as plastics, rubber and environmental project are can be widely applied to, and its price is very cheap, tool
There are wide application and market prospects.
CSW can be good at improving the performances such as the resisting environmental stress and cracking of alloy material, mainly due to CSW draw ratio
Greatly, intensity is high, and during alloy material cracks, CSW is not easy, generation de- glutinous with matrix resin by shearing force
The mainly CSW of fracture, because it absorbs more energy in fracture process, it is thus possible to hinder the generation of crackle.
In Chinese patent CN102304268, " a kind of modified acrylonitrile-butadiene-styrene copolymer and its preparation technology " is disclosed,
This method can improve the impact strength of material with calcium sulfate whisker modified copolymer, suitable for making housing of TV set, essence
Close Instrument shell, apparatus structure part etc..However, when CSW improves polyester alloy material, CSW is scattered there is also in the alloy
Property is poor, the shortcomings of agglomeration easily occurs.
Therefore, a kind of modified CSW how is developed, to improve dispersivenesses of the CSW in polyester alloy, reduces agglomeration
Occur, become those skilled in the art's urgent problem to be solved.
The content of the invention
It is an object of the invention to provide a kind of with calcium sulfate whisker modified Polycarbonate alloy material and its preparation method, make
During it can overcome existing calcium sulfate whisker modified polycarbonate alloy, the problem of calcium sulfate crystal whiskers are easily reunited.
To achieve the above object, the present invention provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material preparation side
Method, comprise the following steps：
1) by CSW (calcium sulfate crystal whiskers) and organosilicon alkanes coupling agent by weight 5~20：1 mixing and activation process, are obtained
To semi-modified CSW；The mixing and treatment conditions of activation process are：90~160 DEG C of temperature, mixing speed 300~
1000rpm, 10~50min of mixing time；
2) by semi-modified CSW, dispersant and the white oil by weight 2~10：1：10~20 blendings handle to obtain oversubscription
Dissipate semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and PC (makrolon) alloys blend composition by weight 1：100~600 mixing
Form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation, cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 10~30：40~90：1~5：0.1~0.6：0.1~0.6 mixing surface is modified CSW-
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, then carry out melting extrusion and be granulated to obtain with calcium sulfate crystalline substance
The Polycarbonate alloy material that must be modified.
The CSW that the present invention is applied, it is very easy in mixture while the Mechanical Processability of PC materials is improved
Reunite in system, i.e. bad dispersibility.Therefore, the present invention has carried out the ultra-dispersed modifications of CSW to PC, is prepared into surface and is modified CSW-
PC alloying pellets, dispersivenesses of the CSW in polycarbonate alloy is improved, reduce the defects of composite boundary produces, fill
Its toughness reinforcing, reinforcing effect are waved in distribution.
Specifically, in the inventive method step 1), CSW is modified using organosilicon alkanes coupling agent first.
Organosilicon alkanes coupling agent is pollution-free, is applicable that wide, cost is low.It is coupled although having in the prior art using titanate ester
Agent, but have very big influence to the health of ecological environment and human body, using with great limitation, too late organosilan
Class coupling agent.For reaction principle, the hydrolyzable groups of organo silane coupling agent are through hydrolyzing retraction synthesis oligomer, with sulfuric acid
Group on calcium pyroborate inorganic material surface forms hydrogen bond, whisker surface is covered by silane coupler, is formed semi-modified
CSW.After it is with PC melt blendings, the organo-functional group of the organic group of silane coupler then with PC chemically reacts.Cause
This organosilicon alkanes coupling agent improves the interface interaction between CSW and PC, improves CSW in base as a kind of " molecular bridge "
Dispersiveness in body phase (PC).
, it is necessary to by activation process after CSW whiskers are mixed with coupling agent, can just whisker be set to be uniformly covered on coupling agent
On.Soak time and activation temperature directly affects the draw ratio of CSW whiskers, and suitable draw ratio can be such that CSW divides well
It is dispersed in PC alloy-based body phases.Unfavorable activation temperature and time, the draw ratio of whisker is not only influenceed, be also unfavorable for CSW crystalline substances
Hydrogen bond must be formed with organo silane coupling agent, destroy " molecular bridge " effect of coupling agent.Therefore, limited in technical solution of the present invention
Determining the treatment conditions for mixing simultaneously activation process is：90~160 DEG C, 300~1000rpm of mixing speed of temperature, mixing time
10~50min.Under this condition, it is ensured that reach expected technique effect.
In addition, in order to be further ensured that technique effect, in the step 2) of the present invention, dispersant and CSW are also passed through into thing
Reason method is combined together, and forms ultra-dispersed CSW, improves the dispersivenesses of CSW in the alloy, reduces whisker agglomeration.
Further, the present invention step 3) to step 5), disclose the technical characteristic of secondary granulation of the present invention.Oversubscription
Dissipate semi-modified CSW and PC once granulation, CSW organic group and PC functional group is chemically reacted, it is microcosmic on, PC
Matrix phase forms " parcel " (PC wraps up CSW) with CSW, can be called masterbatch.During secondary granulation, because CSW is with masterbatch
Form and PC alloy molten blending extrusions, substantially increase dispersiveness of the CSW whiskers in alloy material.The technical side of the present invention
Case, CSW is modified with coupling agent first, then carried out ultra-dispersed processing, finally further ensured again by secondary granulation
Dispersivenesses of the CSW in PC alloys, each technological means comprehensive function, ensure that the realization of the technology of the present invention effect.
Wherein, in step 1), CSW is half water or anhydrous gypsum whisker being prepared by the natural gypsum or crown filler
Material.
Wherein, in step 1), coupling agent is organosilicon alkanes coupling agent；The organosilicon alkanes coupling agent be TESPT,
One or more in TESPD, KH550 or A-189.
Wherein, in step 1), by calcium sulfate crystal whiskers and coupling agent by weight 10~15：1 mixing and activation process.
Wherein, in step 1), the treatment conditions of the mixing and activation process (calcium sulfate crystal whiskers and coupling agent) enter one
Step is preferably 110~120 DEG C, 500~800rpm of mixing speed, 20~30min of mixing time of temperature.
Wherein, in step 2), dispersant is alkylation polyesters dispersant, sodium ethylene diamine tetracetate class dispersant, wood
One or more in quality class dispersant or polycarboxylic acid salt's dispersant.
Wherein, in step 2), by semi-modified CSW, dispersant and the white oil by weight 2~6：1：10~18 blendings
Processing obtains ultra-dispersed semi-modified CSW.
Wherein, in step 2), the treatment conditions of the blending processing (semi-modified CSW, dispersant and white oil) are：Temperature
90~160 DEG C, 300~900rpm of mixing speed, 10~50min of mixing time.
Wherein, in step 2), the treatment conditions of the blending processing are more preferably：100~110 DEG C of temperature, is stirred
Mix 500~700rpm of speed, 20~30min of mixing time.
Wherein, in step 3), the polycarbonate alloy blend composition of addition refers to that (ABS is acrylic nitrile-butadiene two to PC with ABS
Alkene-styrol copolymer) blend composition, PC and ABS weight proportion are 50~99：50~1, the weight proportion is preferably 80：
20。
Wherein, in step 3), by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition by weight 1：
400~450 are mixed to form CSW-PC mixtures.
Wherein, in step 4), for the CSW-PC mixtures are moved into double screw extruder melting extrusion, rotating speed is extruded
(screw speed) 20~60r/min, preferably 25~55r/min, extrusion temperature are 180~250 DEG C, preferably 210~230 DEG C.
Wherein, in step 5), the compatilizer is modified maleic acid anhydride grafted ABS, and grafting rate is 1~10%, preferably
4%~6%.
Wherein, in step 5), the antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant.
Wherein, in step 5), the lubricant is EBS (vinyl bis-stearamides) lubricant.
Wherein, in step 5), according to weight than 12~17：60~80：2~4：0.2~0.4：0.2~0.4 mixing institute
State surface and be modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant.
Wherein, in step 5), mix the surface and be modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, anti-
Oxygen agent, the temperature of lubricant are 100~170 DEG C, preferably 110~160 DEG C；Mixing speed is 300~900rpm, preferably 400~
700rpm；Mixing time is 10~60min, preferably 25~35min.
Wherein, in step 5), extrusion temperature that the melting extrusion is granulated is 200~250 DEG C, preferably 220~235
℃；Extrude rotating speed (screw speed) 20~60r/min, preferably 30~50r/min.
The present invention also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via above method system
.
The present invention prepare with calcium sulfate whisker modified Polycarbonate alloy material, carried due to having carried out ultra-dispersed modification
The high dispersivenesses of CSW in the alloy, it is thus possible to overcome in existing CSW modified polycarbonates alloy process, with CSW dosages
Increase, the dispersion effects of CSW in the alloy decline and the phenomenon reunited occur.The method of the present invention improves CSW in alloy
Dispersiveness in material, the defects of composite boundary produces is reduced, its toughness reinforcing, reinforcing effect are given full play to, with the present invention
Method production product improve environmental stress cracking resistance, improve processing characteristics, automobile, electricity can be preferably applied for
Son, office machine-tool industry etc..
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, but not as a limitation of the invention.
Brief description of the drawings
Fig. 1 is the calcium sulfate whisker modified Polycarbonate alloy material preparation method flow chart of the present invention.
Embodiment
Technical scheme is described in detail below in conjunction with specific embodiment, to be easier to understand the present invention
Purpose, technology contents, feature and performance, and listed illustrative embodiments are only used as illustration, are not intended as the limit of the present invention
System.
Fig. 1 is refer to, it is calcium sulfate whisker modified Polycarbonate alloy material preparation method flow chart of the invention.It is existing
During having calcium sulfate whisker modified polycarbonate alloy, calcium sulfate crystal whiskers are easily reunited.To solve this problem, it is of the invention
There is provided a kind of with calcium sulfate whisker modified Polycarbonate alloy material and its preparation method, comprise the following steps：
1) by calcium sulfate crystal whiskers (CSW) and coupling agent by weight 5~20：1 mixing and activation process, are obtained semi-modified
CSW；
2) by semi-modified CSW, dispersant and the white oil by weight 2~10：1：10~20 blendings handle to obtain oversubscription
Dissipate semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy (PC alloys) blend composition by weight 1：100~600
It is mixed to form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation, cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 10~30：40~90：1~5：0.1~0.6：0.1~0.6 mixing surface is modified CSW-
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, then carry out melting extrusion and be granulated to obtain with calcium sulfate crystalline substance
The Polycarbonate alloy material that must be modified.
Wherein, in step 1), CSW is half water or anhydrous gypsum whisker being prepared by the natural gypsum or crown filler
Material.
Wherein, in step 1), coupling agent is organosilicon alkanes coupling agent；The organosilicon alkanes coupling agent be TESPT,
One or more in TESPD, KH550 or A-189.
Wherein, in step 1), by calcium sulfate crystal whiskers and coupling agent by weight 10~15：1 mixing and activation process.
Wherein, in step 1), the treatment conditions of the mixing and activation process (calcium sulfate crystal whiskers and coupling agent) are：Temperature
90~160 DEG C, 300~1000rpm of mixing speed, 10~50min of mixing time of degree.
Wherein, in step 1), the treatment conditions of the mixing and activation process are more preferably temperature 110~120
DEG C, 500~800rpm of mixing speed, 20~30min of mixing time.
Wherein, in step 2), dispersant is alkylation polyesters dispersant, sodium ethylene diamine tetracetate class dispersant, wood
One or more in quality class dispersant or polycarboxylic acid salt's dispersant.
Wherein, in step 2), by semi-modified CSW, dispersant and the white oil by weight 2~6：1：10~18 blendings
Processing obtains ultra-dispersed semi-modified CSW.
Wherein, in step 2), the treatment conditions of the blending processing (semi-modified CSW, dispersant and white oil) are：Temperature
90~160 DEG C, 300~900rpm of mixing speed, 10~50min of mixing time.
Wherein, in step 2), the treatment conditions of the blending processing are more preferably：100~110 DEG C of temperature, is stirred
Mix 500~700rpm of speed, 20~30min of mixing time.
Wherein, in step 3), the polycarbonate alloy blend composition of addition refers to that (ABS is acrylic nitrile-butadiene two to PC with ABS
Alkene-styrol copolymer) blend composition, PC and ABS weight proportion are 50~99：50~1, the weight proportion is preferably 80：
20。
Wherein, in step 3), by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition by weight 1：
400~450 are mixed to form CSW-PC mixtures.
Wherein, in step 4), for the CSW-PC mixtures are moved into double screw extruder melting extrusion, rotating speed is extruded
(screw speed) 20~60r/min, preferably 25~55r/min, extrusion temperature are 180~250 DEG C, preferably 210~230 DEG C.
Wherein, in step 5), the compatilizer is modified maleic acid anhydride grafted ABS, and grafting rate is 1~10%, preferably
4%~6%.
Wherein, in step 5), the antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant.
Wherein, in step 5), the lubricant is EBS (vinyl bis-stearamides) lubricant.
Wherein, in step 5), according to weight than 12~17：60~80：2~4：0.2~0.4：0.2~0.4 mixing institute
State surface and be modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant.
Wherein, in step 5), mix the surface and be modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, anti-
Oxygen agent, the temperature of lubricant are 100~170 DEG C, preferably 110~160 DEG C；Mixing speed is 300~900rpm, preferably 400~
700rpm；Mixing time is 10~60min, preferably 25~35min.
Wherein, in step 5), extrusion temperature that the melting extrusion is granulated is 200~250 DEG C, preferably 220~235
℃；Extrude rotating speed (screw speed) 20~60r/min, preferably 30~50r/min.
The present invention also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via above method system
.
Embodiment a
The present embodiment provides a kind of preparation method with calcium sulfate whisker modified Polycarbonate alloy material, including following step
Suddenly：
1) by calcium sulfate crystal whiskers and organosilicon alkanes coupling agent TESPD by weight 20：1 mixing and activation process (temperature
160 DEG C, mixing speed 1000rpm, mixing time 50min), obtain semi-modified CSW；
2) by the semi-modified CSW, sodium ethylene diamine tetracetate class dispersant and white oil by weight 10：1：20 blendings are handled
(160 DEG C of temperature, mixing speed 900rpm, mixing time 50min) obtains ultra-dispersed semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition (PC and ABS, 99：1) by weight 1：
600 are mixed to form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation (extrusion rotating speed 60r/min, extrusion temperature 250
DEG C), cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 30：90：5：0.6：The 0.6 mixing surface is modified CSW-PC alloying pellets, the blending of PC alloys
Material, compatilizer (modified maleic acid anhydride grafted ABS, grafting rate 10%), phosphite ester kind antioxidant, EBS lubricants (mixing temperature
Degree is 170 DEG C, and mixing speed is 900rpm, and mixing time is 60min), then melting extrusion granulation is carried out, extrusion temperature 250
DEG C, extrude rotating speed 60r/min), obtain with calcium sulfate whisker modified Polycarbonate alloy material.
The present embodiment also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via the above method
It is made.
Embodiment b
The present embodiment provides a kind of preparation method with calcium sulfate whisker modified Polycarbonate alloy material, including following step
Suddenly：
1) by calcium sulfate crystal whiskers and organosilicon alkanes coupling agent TESPT by weight 5：1 mixing and activation process (temperature 90
DEG C, mixing speed 300rpm, mixing time 10min), obtain semi-modified CSW；
2) by the semi-modified CSW, alkylation polyesters dispersant and white oil by weight 2：1：10 blendings handle (temperature
90 DEG C, mixing speed 300rpm, mixing time 10min) obtain ultra-dispersed semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition (PC and ABS, 50：50) by weight 1：
100 are mixed to form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation (extrusion rotating speed 20r/min, extrusion temperature 180
DEG C), cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 10：40：1：0.1：The 0.1 mixing surface is modified CSW-PC alloying pellets, the blending of PC alloys
Material, compatilizer (modified maleic acid anhydride grafted ABS, grafting rate 1%), Hinered phenols antioxidant, EBS lubricant (mixing temperatures
100 DEG C, mixing speed is 300rpm, and mixing time is 10min), then carry out melting extrusion granulation (extrusion temperature be 200 DEG C,
Extrude rotating speed 20r/min), obtain with calcium sulfate whisker modified Polycarbonate alloy material.
The present embodiment also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via the above method
It is made.
Embodiment c
The present embodiment provides a kind of preparation method with calcium sulfate whisker modified Polycarbonate alloy material, including following step
Suddenly：
1) by calcium sulfate crystal whiskers and organosilicon alkanes coupling agent KH550 by weight 10：1) mixing and activation process (temperature
110 DEG C, mixing speed 500rpm, mixing time 20min), obtain semi-modified CSW；
2) by semi-modified CSW, lignin type and the white oil by weight 2：1：10 blendings handle (temperature 100
DEG C, mixing speed 500rpm, mixing time 20min) obtain ultra-dispersed semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition (PC and ABS, 70：25) by weight 1：
400 are mixed to form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation (extrusion rotating speed 25r/min, extrusion temperature 210
DEG C), cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 12：60：2：0.2：The 0.2 mixing surface is modified CSW-PC alloying pellets, the blending of PC alloys
Material, modified maleic acid anhydride grafted ABS (grafting rate 4%), Hinered phenols antioxidant, EBS lubricants (mixing temperature is 110 DEG C,
Mixing speed is 400pm, and mixing time is 25min), then carry out melting extrusion granulation (extrusion temperature be 220 DEG C, extrude rotating speed
30r/min), obtain with calcium sulfate whisker modified Polycarbonate alloy material.
The present invention also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via above method system
.
Embodiment d
The present embodiment provides a kind of preparation method with calcium sulfate whisker modified Polycarbonate alloy material, including following step
Suddenly：
1) by calcium sulfate crystal whiskers and organosilicon alkanes coupling agent A-189 by weight 15：1 mixing and activation process (temperature
120 DEG C, mixing speed 800rpm, mixing time 30min), obtain semi-modified CSW；
2) by the semi-modified CSW, polycarboxylic acid salt's dispersant and white oil by weight 6：1：18 blendings handle (temperature
110 DEG C, mixing speed 700rpm, mixing time 30min) obtain ultra-dispersed semi-modified CSW；
3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition (PC and ABS, 80：40) by weight 1：
450 are mixed to form CSW-PC mixtures；
4) the CSW-PC mixtures are subjected to melting extrusion granulation (extrusion rotating speed 55r/min, extrusion temperature 230
DEG C), cool down to obtain surface modification CSW-PC alloying pellets；
5) according to weight than 17：80：4：0.4：0.4) mix the surface and be modified CSW-PC alloying pellets, the blending of PC alloys
Material, compatilizer (modified maleic acid anhydride grafted ABS, grafting rate 6%), phosphite ester kind antioxidant, EBS lubricants (mixing temperature
Degree is 160 DEG C, and mixing speed is 700rpm, and mixing time is 35min), then carry out melting extrusion granulation (extrusion temperature 235
DEG C, extrude rotating speed 50r/min), obtain with calcium sulfate whisker modified Polycarbonate alloy material.
The present embodiment also provides a kind of with calcium sulfate whisker modified Polycarbonate alloy material, and it is via the above method
It is made.
The present invention prepare with calcium sulfate whisker modified Polycarbonate alloy material, carried due to having carried out ultra-dispersed modification
The high dispersivenesses of CSW in the alloy, it is thus possible to overcome in existing CSW modified polycarbonates alloy process, with CSW dosages
Increase, the dispersion effects of CSW in the alloy decline and the phenomenon reunited occur.The method of the present invention improves CSW in alloy
Dispersiveness in material, the defects of composite boundary produces is reduced, its toughness reinforcing, reinforcing effect are given full play to, with the present invention
Method production product improve environmental stress cracking resistance, improve processing characteristics, automobile, electricity can be preferably applied for
Son, office machine-tool industry etc..
Below by the embodiment under different technology conditions and its experimental data to the calcium sulfate whisker modified poly- of the present invention
Carbonic acid ester alloy material and preparation method are described further, to clearly show that its technique effect.
Embodiment 1
(1) CSW surface is modified
6/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, in 600rpm mixing speeds, 115
Activation process 40min is carried out at DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 4:1:
10, dispersant and white oil are weighed, and be blended in high-speed mixer；500/1 PC alloy blend compositions are weighed in proportion, add and mix
After closing uniformly, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 1 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 1：
| Surface is modified CSW-PC alloying pellets | 12 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 84.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 2
(1) CSW surface is modified
10/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 6:
1:10, dispersant and white oil are weighed, and be blended in high-speed mixer；500/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 2 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 2：
| Surface is modified CSW-PC alloying pellets | 12 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 84.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 3
(1) CSW surface is modified
10/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 5:
1:15, dispersant and white oil are weighed, and be blended in high-speed mixer；500/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 3 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 3：
| Surface is modified CSW-PC alloying pellets | 12 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 84.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 4
(1) CSW surface is modified
10/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 6:
1:12, dispersant and white oil are weighed, and be blended in high-speed mixer；500/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 4 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 4：
| Surface is modified CSW-PC alloying pellets | 15 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 81.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 5
(1) CSW surface is modified
12/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 7:
1:10, dispersant and white oil are weighed, and be blended in high-speed mixer；500/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 5 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 5：
| Surface is modified CSW-PC alloying pellets | 19 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 77.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 6
(1) CSW surface is modified
8/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, in 600rpm mixing speeds, 115
Activation process 40min is carried out at DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 7:1:
15, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, add and mix
After closing uniformly, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 6 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 6：
| Surface is modified CSW-PC alloying pellets | 19 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 77.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 7
(1) CSW surface is modified
18/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 8:
1:13, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 7 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 7：
| Surface is modified CSW-PC alloying pellets | 16 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 80.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 8
(1) CSW surface is modified
18/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 5:
1:14, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 8 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 8：
| Surface is modified CSW-PC alloying pellets | 26 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 70.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 9
(1) CSW surface is modified
13/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 4:
1:16, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified CSW- in ratio shown in the formula table of embodiment 9 (being weight ratio described in table)
PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, by double
Melt pelletization at 225 DEG C of screw extruder, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in Table 1.
The formula table of embodiment 9：
| Surface is modified CSW-PC alloying pellets | 15 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 81.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 10
(1) CSW surface is modified
5/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, in 600rpm mixing speeds, 115
Activation process 40min is carried out at DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 10:1:
20, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, add and mix
After closing uniformly, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 10 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 10：
| Surface is modified CSW-PC alloying pellets | 15 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 81.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 11
(1) CSW surface is modified
5/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, in 600rpm mixing speeds, 115
Activation process 40min is carried out at DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 10:1:
10, dispersant and white oil are weighed, and be blended in high-speed mixer；300/1 PC alloy blend compositions are weighed in proportion, add and mix
After closing uniformly, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 11 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 11：
| Surface is modified CSW-PC alloying pellets | 15 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 81.4 |
| Compatilizer (grafting rate 1.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 12
(1) CSW surface is modified
11/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 40min is carried out at 115 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 2:
1:10, dispersant and white oil are weighed, and be blended in high-speed mixer；400/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 12 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 12：
| Surface is modified CSW-PC alloying pellets | 15 |
| (PC/ABS, proportioning is 85/15) for PC alloys blend composition | 81.4 |
| Compatilizer (grafting rate 5.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 13
(1) CSW surface is modified
12/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 25min is carried out at 120 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 2:
1:17, dispersant and white oil are weighed, and be blended in high-speed mixer；400/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 13 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 13：
| Surface is modified CSW-PC alloying pellets | 20 |
| (PC/ABS, proportioning is 85/15) for PC alloys blend composition | 76.4 |
| Compatilizer (grafting rate 5.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 14
(1) CSW surface is modified
20/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 25min is carried out at 120 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 3:
1:20, dispersant and white oil are weighed, and be blended in high-speed mixer；400/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 14 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 14：
| Surface is modified CSW-PC alloying pellets | 16 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 80.4 |
| Compatilizer (grafting rate 5.2%) | 3 |
| Antioxidant | 0.3 |
| Lubricant | 0.3 |
Embodiment 15
(1) CSW surface is modified
14/1 (weight ratio) weighs CSW, coupling agent in proportion, adds in high-speed mixer, 600rpm mixing speeds,
Activation process 25min is carried out at 120 DEG C；A certain amount of semi-modified CSW is weighed, the ratio according to CSW, dispersant, white oil is 8:
1:11, dispersant and white oil are weighed, and be blended in high-speed mixer；450/1 PC alloy blend compositions are weighed in proportion, added simultaneously
After well mixed, the extruding pelletization at 210~230 DEG C, obtain surface and be modified CSW-PC alloying pellets.
(2) preparation of modified PC alloy materials
Surface well prepared in advance is modified in ratio shown in the formula table of embodiment 15 (being weight ratio described in table)
CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant, after being sufficiently mixed in high-speed mixer, lead to
Melt pelletization at 225 DEG C of double screw extruder is crossed, is able to calcium sulfate whisker modified Polycarbonate alloy material.Test performance is shown in
Table 1.
The formula table of embodiment 15：
| Surface is modified CSW-PC alloying pellets | 13 |
| (PC/ABS, proportioning is 80/20) for PC alloys blend composition | 83.2 |
| Compatilizer (grafting rate 5.2%) | 3 |
| Antioxidant | 0.4 |
| Lubricant | 0.4 |
Experimental result
Table 1 is embodiment 1-15 every Mechanics Performance Testing experimental result：
The embodiment product mechanical property of table 1 compares
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (17)
- It is 1. a kind of with calcium sulfate whisker modified Polycarbonate alloy material preparation method, it is characterised in that to comprise the following steps：1) by calcium sulfate crystal whiskers and organosilicon alkanes coupling agent by weight 5~20：1 mixing and activation process, are obtained semi-modified CSW；The mixing and treatment conditions of activation process are：90~160 DEG C, 300~1000rpm of mixing speed of temperature, during stirring Between 10~50min；2) by semi-modified CSW, dispersant and the white oil by weight 2~10：1：10~20 blendings handle to obtain ultra-dispersed half Modify CSW；The dispersant is alkylation polyesters dispersant, sodium ethylene diamine tetracetate class dispersant, lignin type or One or more in polycarboxylic acid salt's dispersant；3) by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition by weight 1：100~600 are mixed to form CSW- PC mixtures；4) the CSW-PC mixtures are subjected to melting extrusion granulation, cool down to obtain surface modification CSW-PC alloying pellets；And5) according to weight than 10~30：40~90：1~5：0.1~0.6：0.1~0.6 mixing surface is modified CSW-PC and closed Gold grain, PC alloys blend composition, compatilizer, antioxidant, lubricant, then carry out melting extrusion and be granulated to obtain to change with calcium sulfate crystal whiskers The Polycarbonate alloy material of property.
- 2. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 1), CSW is half water or anhydrous gypsum crystal whisker materials being prepared by the natural gypsum or crown filler.
- 3. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 1), the organosilicon alkanes coupling agent is the one or more in TESPT, TESPD, KH550 or A-189.
- 4. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 1), by calcium sulfate crystal whiskers and coupling agent by weight 10~15：1 mixing and activation process.
- 5. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 1), the treatment conditions of the mixing and activation process are：110~120 DEG C of temperature, mixing speed 500~ 800rpm, 20~30min of mixing time.
- 6. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 2), by semi-modified CSW, dispersant and the white oil by weight 2~6：1：10~18 blendings, which are handled, to be surpassed Disperse semi-modified CSW.
- 7. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 2), the treatment conditions of the blending processing are：90~160 DEG C, 300~900rpm of mixing speed of temperature, stirring 10~50min of time.
- 8. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 3), the polycarbonate alloy blend composition of addition refers to PC and ABS blend composition, and PC and ABS weight proportion are 50~99：50~1.
- 9. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 3), by the ultra-dispersed semi-modified CSW and polycarbonate alloy blend composition by weight 1：400~450 mixing Form CSW-PC mixtures.
- 10. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 4), for the CSW-PC mixtures are moved into double screw extruder melting extrusion, 20~60r/ of extrusion rotating speed Min, extrusion temperature are 180~250 DEG C.
- 11. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), the compatilizer is modified maleic acid anhydride grafted ABS, and grafting rate is 1~10%.
- 12. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), the antioxidant is Hinered phenols antioxidant or phosphite ester kind antioxidant.
- 13. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), the lubricant is EBS lubricants.
- 14. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), according to weight than 12~17：60~80：2~4：0.2~0.4：0.2~0.4 mixing surface is modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubricant.
- 15. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), mixing the surface and be modified CSW-PC alloying pellets, PC alloys blend composition, compatilizer, antioxidant, lubrication The temperature of agent is 100~170 DEG C, and mixing speed is 300~900rpm, and mixing time is 10~60min.
- 16. according to claim 1 existed with calcium sulfate whisker modified Polycarbonate alloy material preparation method, its feature In in step 5), the extrusion temperature that the melting extrusion is granulated is 200~250 DEG C, 20~60r/min of extrusion rotating speed.
- It is 17. a kind of with calcium sulfate whisker modified Polycarbonate alloy material, it is characterised in that its be via claim 1~ Any one method is made in 16.
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| CN109135236A (en) * | 2018-07-18 | 2019-01-04 | 望江县天长光学仪器有限公司 | A kind of polycarbonate optical lenses material |
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| CN101671848A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Preparation method of high length-diameter ratio anhydrous calcium sulfate whisker |
| CN102115586A (en) * | 2011-04-15 | 2011-07-06 | 刘立文 | Polycarbonate composite material with modified calcium sulfate whisker and preparation method thereof |
| CN103073907A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial thermoplastic plastic composition and preparation method thereof |
| CN103074800A (en) * | 2012-11-20 | 2013-05-01 | 东莞上海大学纳米技术研究院 | Method for coating and modifying surface of inorganic paper making fiber calcium sulfate whisker and application |
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| CN101671848A (en) * | 2009-09-28 | 2010-03-17 | 清华大学 | Preparation method of high length-diameter ratio anhydrous calcium sulfate whisker |
| CN102115586A (en) * | 2011-04-15 | 2011-07-06 | 刘立文 | Polycarbonate composite material with modified calcium sulfate whisker and preparation method thereof |
| CN103073907A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial thermoplastic plastic composition and preparation method thereof |
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