CN105418836A - Preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening - Google Patents
Preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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Abstract
The invention provides a preparation method of acrylate polymer/nanometer silicon dioxide composite particles for polycarbonate toughening. According to the method, acrylate polymer emulsion is prepared by selecting emulsifier dosage and nanometer silicon dioxide dosage, utilizing a seeded emulsion polymerization technology, performing preparation of a seed stage elastomer, increase of elastomer particle size and in-situ coating of a plastic outer layer and adjusting an initiator adding mode, then nanometer silicon dioxide pre-emulsion and the acrylate polymer emulsion are mixed evenly, and the acrylate polymer/nanometer silicon dioxide composite particles are obtained through emulsion breaking. A little amount of the composite particles is added into polycarbonate, the toughness of a polycarbonate substrate material can be remarkably improved by adding the acrylate polymer/nanometer silicon dioxide composite particles 1.96%, low-temperature notch impact strength of the composite material is improved by 287% compared with purer polycarbonate, the breaking elongation rate is improved by 298%, and meanwhile the tensile strength is improved by 157%.
Description
Technical field
The present invention relates to and belong to polymer modification field, be specially the preparation method of a kind of polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles.
Background technology
Giving material special purpose to particle shape and structure design is study hotspot in recent years.The method of multilayered structure emulsion polymerisation particles is more, and polymerization process is as mechanism such as semi-continuous seed emulsion polymerization, swelling seeding polymerization, micro-emulsion polymerizations.The major advantage that acrylic ester impact-resisting hits properties-correcting agent (ACR) has: good impact modification effect, wider processing temperature scope, low-shrinkage, product size are stable; Have processing aid feature concurrently, the fusion plastification time of compound can be shortened, improve co-mixing system moulding processability; And also there is good weathering resistance.Polycarbonate belongs to one of five large-engineering plastics, has the features such as heat-resisting, creep resistance, resistance to chemical attack, electrical isolation, is widely used in the field such as actinic material, medicine equipment and foodstuffs industry, material of construction, electronic apparatus.But polycarbonate has the shortcoming of easy stress cracking, this will limit it in very many-sided application.In recent years, research worker carrys out Toughening Modification of Polycarbonate engineering plastics with particle having multilayer structure, and achieves certain effect.XiaodongLiu and HansBertilsson utilizes the PC/ABS blend of nucleocapsid structure anti-impact modifier (MBS) the toughness reinforcing recovery of MBS.PC/ABS (80/20, mass ratio) add 5 parts of MBS and can show good tensile toughness and notch impact toughness, elongation at break improves 5%, tensile strength have dropped 7.42%, notched Izod impact strength is 1.81 times of (XiaodongLiu of initial blend, HansBertilsson.RecyclingofABSandABS/PCBlends.JournalofAp pliedPolymerScience, 1999,74:510-515).Chen Jianfei etc. adopt hud typed silicon rubber toughening modifying is carried out to PC reclaimed materials, research find: silicon rubber be stratum nucleare, Surface coating polymethyl acrylic acid shell time, if do not add other expanding materials, to PC without toughening effect; When adding 15% epoxy resin (DGEBA) expanding material, obvious toughness is had to improve, notched Izod impact strength is original 3 times, tensile strength decline 11.11% (Chen Jianfei, what Yadong, Sun Shuanyue etc. " core-shell structure copolymer " type silicon rubber is to the toughness reinforcing and flame-retardant modified research of polycarbonate reclaimed materials. plastics industry, 2010,2:19-24).Guo Baohua etc. have studied MBS (MBS) to the toughening effect of polycarbonate and toughening mechanism, they have studied the impact of different MBS add-on on polycarbonate, find: when MBS content reaches 15%, shock strength reaches maximum, for pure PC 3 times [toughening effect of .MBS to polycarbonate and the discussion of toughening mechanism thereof such as Guo Baohua, Xu Xiaolin, Xu Jun. China Rubber/plastics Technology and equipment, 2006,32 (7): 23-27].
Though MBS, ABS type core-shell particles has certain toughening effect, containing double bond structure in its main chain, resistance to weathering is poor.And utilize polyacrylic ester multi-layer core-shell structure ACR modified polycarbonate, usually need larger addition (more than 12wt%), just can play good toughening effect, this will greatly reduce the tensile strength of polycarbonate matrix material.
The Peculiar function of nano material, the performance that macromolecular material is much special can be given, yardstick due to nano-silicon dioxide particle is in the transitional region that cluster molecule and macro object replace, thus show many special propertys, correspondingly to nano silicon and and the physicochemical property of poyblend and matrix material become the focus of research.Zhang Zhiyi has prepared nano-silicon dioxide modified dose of a small amount of polymethylmethacrylate of Surface coating by emulsion polymerization, and it is blended that this properties-correcting agent and polycarbonate are pressed 10:90, investigates the performance variation of modified polycarbonate.Experiment finds, the shock strength of modified polycarbonate improves 50%, tensile strength is 1.45 times of [Zhang Zhiyis of pure matrix resin, Zhao Ning, Wei Wei, Deng. the preparation of nucleocapsid structure and laminate structure properties-correcting agent and the impact [J] on PC performance thereof. engineering plastics are applied, and 2007,33 (3): 5-8.].The modified polycarbonate tensile strength of material that the method obtains is improved really, but required nano-silicon dioxide modified dose of consumption is more reaches 10%, and toughness improves less only 50%.
In order to expand the use of engineering plastics at extremely frigid zones, the low-temperature performance of engineering plastics must be improved, usually add rubber elastomer, as the CN101870751A of this group application, the butyl polyacrylate elastomerics of use.The index characterizing cold tolerance is the glass transition temperature (T of rubber elastomer
g); T
gbe worth lower, show that its winter hardiness is better.The T of butyl polyacrylate
gvalue is-23 DEG C (1Hz), but still can not meet service requirements at extremely frigid zones.If improved, such as by changing the methods such as monomeric substance, relate to the selection of the materials such as emulsifying agent again, as the dodecyl Biphenyl Ether sodium sulfonate emulsifying agent in patent CN102352002A and CN102351977A, but it is greatly water-soluble, the condensation product that polymerization process is produced is too much, can not meet service requirements; And address this problem in process, easily cause again instantaneous number of free radical excessive, make polymerization system unstable because of local superheating, cause and be polymerized unsuccessfully.Carry out modification if directly directly added in polycarbonate by nano silicon, as CN101759943A and CN102464845A, often meeting be difficult to the dispersed silicon-dioxide reinforced effects that causes in the base because silicon-dioxide is reunited not good.
Summary of the invention
The object of the invention is to for current need to add to polycarbonate matrix resin toughening more than 10% rubber elastomer properties-correcting agent, its notched Izod impact strength just can be made to reach service requirements, this declines make the tensile strength of polycarbonate to more than 15%, the deficiency of the poor processability of blend, provides the preparation method of a kind of polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles.The method is by selecting emulsifier and nano silicon consumption, utilize seeded emulsion polymerization technology, through the elastomeric preparation of seed stage, the growth of elastomerics particle diameter and the in-stiu coating of plastic outer layer, and adjust the feed postition of initiator, prepare acrylate polymer emulsion, subsequently nano silicon pre-emulsion is mixed with aforesaid propylene acid ester polymer emulsion, obtain acrylic ester polymer/nano silicon composite particles through breakdown of emulsion.A small amount of composite particles is joined in polycarbonate, low-temperature impact toughness and the tensile strength of polycarbonate composite material can be significantly improved.Acrylic ester polymer/nano silicon the composite particles of interpolation 1.96% just can significantly improve the toughness of polycarbonate matrix material, the purer polycarbonate of low temperature notched shock strength of matrix material improve 377%, tension set improves 298%, and tensile strength adds 157% simultaneously.
Technical scheme of the present invention is:
A preparation method for polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles, comprises the steps:
A. the pre-emulsification of seed monomer
According to above proportioning, in reactor, add emulsifying agent and deionized water, and mix and blend; Add acrylic ester monomer and linking agent again, and mix and blend, namely obtain internal layer seed monomer pre-emulsion, for subsequent use;
B. the pre-emulsification of stratum nucleare build phase monomer
Above-mentioned each component is put into a container, mix and blend, namely obtain stratum nucleare build phase monomer pre-emulsion, for subsequent use;
C. the pre-emulsification of outer monomer
Composition mass fraction
Emulsifying agent 0.80 ~ 1.20
Esters of acrylic acid mix monomer 40 ~ 60
Above-mentioned each component is put into another container, mix and blend, namely obtains outer monomer pre-emulsion, for subsequent use;
Described esters of acrylic acid mix monomer is methyl methacrylate and acrylic acid mixture, and wherein vinylformic acid quality accounts for the 1.6%-2.5% of esters of acrylic acid mix monomer;
D. the pre-emulsification of nano silicon
Above-mentioned nano silicon, emulsifying agent and deionized water are put into the 3rd container, mix and blend, namely obtains the pre-emulsion of nano silicon, for subsequent use;
Acrylic ester monomer in described step a, b is acrylic acid-2-ethyl monooctyl ester;
Emulsifying agent used in described step a, b, c, d is anionic emulsifier;
In step a, b, linking agent is 1,4 butanediol diacrylate;
The preparation of e. acrylic ester polymer/nano silicon composite particles
Fill to a step in the reactor of internal layer seed monomer pre-emulsion, vacuumize rear nitrogen replacement three times; Then continue to pass into nitrogen, in condenser, logical water of condensation, is warming up to 78.5 DEG C by reactant under whipped state, and after homo(io)thermism, at the uniform velocity dripped initiator solution 1 at 10 minutes, then continue reaction 50 minutes, the Seeded polymerization stage terminates; Then in reaction system, the obtained stratum nucleare build phase monomer pre-emulsion of b step is dripped with the first continuously and smoothly of identical speed, and then continuously and smoothly drips the obtained outer monomer pre-emulsion of step c, two kinds of pre-emulsions dropwise 180 minutes continuously and smoothlies, and continuously and smoothly drips initiator solution 2 these 180 minutes while; Afterwards, insulation reaction 120 minutes, then be down to room temperature; Nano silicon pre-emulsion Step d obtained joins in the emulsion of above-mentioned preparation and stirs 30 minutes, obtains acrylic ester polymer/nano silicon composite particles; Finally the composite particles of preparation is obtained polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles through freezing, washing, suction filtration, drying and other steps.
Wherein, add material mass ratio be seed monomer pre-emulsion: stratum nucleare build phase monomer pre-emulsion: outer monomer pre-emulsion: nano silicon pre-emulsion=(165.75 ~ 165.95): (126.98 ~ 147.54): (40.80 ~ 61.20): (50.504 ~ 52.520).
Initiator used is persulphate, adds in the mode of the aqueous solution, and concrete proportioning is as follows:
Wherein, quality is than initiator solution 1: seed monomer pre-emulsion: initiator solution 2=20.33:(160.75 ~ 160.95): 30.25
The concrete quality of above material, not to the restriction of invention, in actual production, expands according to desired product amount according to above-mentioned mass ratio entirety or reduces.
In the preparation method of above-mentioned modified polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles, in described step a, b, c, d, anionic emulsifier used is dihexyl adipate sodium sulfonate.
In the preparation method of above-mentioned modified polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles, initiator used in described step e is Potassium Persulphate.
The invention has the beneficial effects as follows:
For fragility and half fragility polar plas, usually adopt butyl polyacrylate as the elastomeric properties-correcting agent of rubber phase to improve its toughness.In order to expand the use of these plastics at extremely frigid zones, their resistance to low temperature must be improved.The index characterizing resistance to low temperature is the elastomeric glass transition temperature (T of rubber phase
g), T
gbe worth lower, show that its lower temperature resistance is better.The T of butyl polyacrylate
gvalue is-23 DEG C (1Hz), but still can not meet service requirements at extremely frigid zones.The present invention adopts acrylic acid-2-ethyl monooctyl ester as monomer, its T
gbe worth lower, be-51 DEG C (1Hz), resistance to low temperature is better.Now, according to dodecyl Biphenyl Ether sodium sulfonate as emulsifying agent, because it is greatly water-soluble, the condensation product (waste) that polymerization process is produced is too much, can not meet service requirements.On great many of experiments basis, the present invention adopts anionic emulsifier dihexyl adipate sodium sulfonate, realizes the stable of emulsion polymerization systems.In previous literature, the water soluble starter that emulsion polymerization adopts is disposable adding, and this easily causes instantaneous number of free radical excessive, makes polymerization system unstable because of local superheating, causes and be polymerized unsuccessfully.Therefore the present invention also have adjusted the initiator concentration of seed latex grain build phase, and at the uniform velocity drip after being made into initiator solution, final stage is incubated 2 hours again, achieve high monomer conversion (>98.5%), and as the condensation product content low (<0.5%) of waste material, namely the transformation efficiency of monomer improves, and simplifies the last handling process of residual monomer in emulsion polymeric product.Nano silicon is dispersed in acrylate polymer emulsion, the nano-meter characteristic that obtained properties-correcting agent had both possessed nano silicon plays significant reinforced effects to polycarbonate matrix, and the characteristic possessing again acrylic ester polymer plays significant low temperature toughening effect to polycarbonate matrix.Modified polycarbonate is carried out with the acrylic ester polymer prepared by the present invention/nano silicon composite particles, acrylic ester polymer/nano silicon the composite particles of interpolation 1.96% just can significantly improve the toughness of polycarbonate matrix material, the purer polycarbonate of low temperature notched shock strength of matrix material improve 377%, tension set improves 298%, tensile strength adds 157% simultaneously, obtains the beyond thought toughness reinforcing and reinforced effects of polycarbonate matrix resin.
Accompanying drawing illustrates:
Fig. 1 is the variation diagram of embodiment 1 acrylic ester polymer preparation process monomer conversion with the reaction times.
Fig. 2 is the variation diagram of embodiment 1 acrylic ester polymer preparation process latex particle size with the reaction times.
Fig. 3 is tensile strength and the low temperature notched shock strength graph of a relation of pure polycarbonate, comparative example and embodiment 1-9 acrylic ester polymer/nano silicon composite particles modified polycarbonate matrix material.
Below in conjunction with drawings and Examples, the present invention is further described.
Embodiment
Embodiment 1
A. the pre-emulsification of seed monomer
First, in 500ml four-hole boiling flask, add 0.71g anionic emulsifier dihexyl adipate sodium sulfonate and 150g deionized water, and mix and blend 30 minutes; In reactor, add 15g acrylic acid-2-ethyl monooctyl ester monomer and 0.04g linking agent 1,4 butanediol diacrylate again, and to be placed in induction stirring mix and blend 20 minutes, namely obtain seed monomer pre-emulsion, for subsequent use;
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.81g anionic emulsifier dihexyl adipate sodium sulfonate, 145g acrylic acid-2-ethyl monooctyl ester monomer and 0.73g linking agent 1,4-butylene glycol diacrylate joins in 400ml beaker, then to be placed in induction stirring mix and blend 20 minutes, namely to obtain second layer monomer pre-emulsion, for subsequent use;
C. the pre-emulsification of outer monomer
0.8g anionic emulsifier dihexyl adipate sodium sulfonate, 40g methyl methacrylate monomer and 1.0g vinylformic acid are joined in 400ml beaker, to be then placed in induction stirring mix and blend 20 minutes, namely to obtain outer monomer pre-emulsion, for subsequent use;
D. the pre-emulsification of nano silicon
1.20g nano silicon (10 ~ 20nm), 0.012g dihexyl adipate sodium sulfonate and 50g deionized water are joined in 400ml beaker, to be placed in induction stirring mix and blend 60 minutes, namely to obtain the pre-emulsion of nano silicon, for subsequent use;
E. the preparation of acrylic ester emulsion
Fill to a step in the reactor of internal layer seed monomer pre-emulsion, vacuumize rear nitrogen replacement three times, to remove oxygen, realize the inert atmosphere of system; Then continue to pass into nitrogen, logical water of condensation in condenser, under whipped state, reactant is warming up to 78.5 DEG C, after homo(io)thermism, constant pressure funnel continuously and smoothly instills 20.33g initiator solution and dropwises for 1,10 minutes; Continue reaction after 50 minutes, the Seeded polymerization stage terminates.Then in reaction system, the obtained stratum nucleare build phase monomer pre-emulsion of b step is dripped with the first continuously and smoothly of identical speed, after dropwising, continuously and smoothly drips the obtained outer monomer pre-emulsion of step c immediately, two kinds of monomer pre-emulsion dropwise 180 minutes continuously and smoothlies, and continuously and smoothly drips 30.25g initiator solution 2 these 180 minutes while; Afterwards, insulation reaction 120 minutes, then be down to room temperature; Nano silicon pre-emulsion Step d obtained under agitation joins in the emulsion of above-mentioned preparation, stirs 30 minutes, obtains acrylic ester polymer/nano silicon composite particles; Finally the composite particles of preparation is obtained the acrylic ester polymer/nano silicon composite particles with hybrid structure through freezing, washing, suction filtration, drying and other steps.
Initiator used is Potassium Persulphate.Need add deionized water with certain proportion in use, and stirring and dissolving makes initiator solution in 20 minutes on magnetic stirrer.Concrete proportioning is as follows:
To preparation acrylic ester polymer and and polycarbonate composite material characterize as follows:
(1) acrylic ester polymer
The present invention is in polymer emulsion preparation process, at interval of 30 minutes sampling 2ml, 0.05ml is after deionized water dilution, detecting latex particle size at MalvernZetasizerNano-ZS90 dynamic laser particle-size analyzer is 256nm, and the emulsion particle measured value of differential responses time is consistent with calculated value, as shown in Figure 2; In addition, latex particle size dispersion index is 0.036.Therefore, the latex particle size of this emulsion is controlled.
Remaining 1.95ml part, for measuring instantaneous conversion rate and the total conversion rate of polymerization single polymerization monomer, is shown in Fig. 1.After weighing, (note wet combustion cup weight) puts into dry 24 hours of the baking oven of 80 DEG C, weigh to mass conservation (note dry combustion method cup weight) again.
The mensuration of solid content
Solid content S is calculated as follows:
In formula: m
0for the quality of dry empty bottle, m
1for adding the quality after emulsion (wet combustion cup quality), m
2for the quality (dry combustion method cup quality) after oven dry in loft drier.
The calculating of monomer conversion
Total conversion rate OC:
Instantaneous conversion rate IC:
In formula: M
iemulsion total mass when being the i-th sub-sampling, S
ibe solid content during the i-th sub-sampling, m' is the total mass to adding initiator during the i-th sub-sampling, and Δ m is the total mass to adding emulsifying agent, linking agent during the i-th sub-sampling, M
0for adding the total mass of monomer, M is the quality to adding monomer during the i-th sub-sampling.
Theoretical Grain Size can be calculated by following formula:
Wherein: d
sfor the particle diameter that the particle size values of latex particle at the end of seed stage is surveyed when namely second time samples, M
sfor the amount of monomer that seed stage adds, M
tfor the amount of monomer that t adds, I is the instantaneous conversion rate of t.
Agglomerated thing cubage formula is as follows:
In formula: w' is the total mass of dry front agglomerated thing and beaker, w is the total mass of dry rear agglomerated thing and beaker, w
0for the total mass of acrylic ester monomer used in formula.
(2) polycarbonate composite material
By the vacuum-drying after 12 hours at 80 DEG C respectively of the acrylic ester polymer/nano silicon composite particles, polycarbonate and acrylic ester polymer of preparation, 2:100 mixing in mass ratio, granulation after TE-34 (L/D=28) twin screw extruder of Nanjing Ke Ya extrusion machinery institute production is extruded, screw speed is per minute 65 turns, and twin screw temperature controls to be followed successively by: 250,258,258,258,258,255 DEG C.By the composite material granular of gained through the JPH30 type injection moulding machine injection moulding with Guangdong Hongli Machine Co., Ltd.'s production after 12 hours of vacuum-drying at 80 DEG C, injection temperature controls to be followed successively by: 253,253,258,258 DEG C, 40MPa injection pressure, obtains test bars.The batten obtained carries out tensile property and impact property test, and probe temperature is-25 DEG C.
Embodiment 2 ~ 9
Other step is with embodiment 1, but the change of a step seed stage emulsifying agent 1 used, Step d nano silicon quality and emulsifying agent 2 quality in embodiment 2 ~ 9, specifically as shown in table 1.
Comparative example
A. the pre-emulsification of seed monomer
First, in 500ml four-hole boiling flask, add 0.71g anionic emulsifier dihexyl adipate sodium sulfonate and 150g deionized water, and mix and blend 30 minutes; In reactor, add 15g acrylic acid-2-ethyl monooctyl ester monomer and 0.04g linking agent 1,4 butanediol diacrylate again, and to be placed in induction stirring mix and blend 20 minutes, namely obtain seed monomer pre-emulsion, for subsequent use;
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.81g anionic emulsifier dihexyl adipate sodium sulfonate, 145g acrylic acid-2-ethyl monooctyl ester monomer and 0.73g linking agent 1,4-butylene glycol diacrylate joins in 400ml beaker, then mix and blend is placed in induction stirring 20 minutes, namely stratum nucleare build phase monomer pre-emulsion is obtained, for subsequent use;
C. the pre-emulsification of outer monomer
0.8g anionic emulsifier dihexyl adipate sodium sulfonate, 40g methyl methacrylate monomer and 1.0g vinylformic acid are joined in 400ml beaker, to be then placed in induction stirring mix and blend 20 minutes, namely to obtain outer monomer pre-emulsion, for subsequent use;
D. the preparation of acrylic ester emulsion
Fill to a step in the reactor of internal layer seed monomer pre-emulsion, vacuumize rear nitrogen replacement three times, to remove oxygen, realize the inert atmosphere of system; Then continue to pass into nitrogen, in condenser, logical water of condensation, is warming up to 78.5 DEG C by reactant, after homo(io)thermism, drips initiator solution 1 10 minutes continuously and smoothlies under whipped state, and continue reaction after 50 minutes, the Seeded polymerization stage terminates.Then stratum nucleare build phase monomer pre-emulsion that b step obtains and the obtained outer monomer pre-emulsion of step c is dripped to continuously and smoothly in reaction system, two kinds of monomer pre-emulsion dropwise 180 minutes continuously and smoothlies, and continuously and smoothly drips initiator solution 2 these 180 minutes while; Afterwards, insulation reaction 120 minutes, then be down to room temperature; Finally the emulsion of preparation is obtained acrylic ester polymer through freezing, washing, suction filtration, drying and other steps.
Initiator used is Potassium Persulphate.Need add deionized water with certain proportion in use, and stirring and dissolving makes initiator solution in 20 minutes on magnetic stirrer.Concrete proportioning is as follows:
The quality of some components in table 1 embodiment 1 ~ 9
In embodiment 1 ~ 5, the polymerization parameter of acrylic ester polymer is listed in table 2, and the mechanical property of these acrylic ester polymers/nano silicon composite particles and polycarbonate composite material is listed in table 3.
The polymerization parameter of table 2 acrylic ester polymer
The mechanical property of table 3 acrylic ester polymer/nano silicon composite particles and polycarbonate composite material
Fig. 1 is the variation diagram of embodiment 1 acrylic ester polymer preparation process monomer conversion with the reaction times.As shown in Figure 1, in embodiment 1, the instantaneous conversion rate of each stage monomer is all greater than 90%, illustrate that the monomer major part added there occurs polyreaction, the monomeric species namely added, the add-on of initiator and polymeric reaction temperature three are couplings, and this is also important to the control of latex particle size.If when the monomer newly added, unreacted monomer content is high, easily in emulsion system, form new micella, cause the monomer newly added to be failed completely in former emulsion particle surface growth.Fig. 2 is the variation diagram of embodiment 1 acrylic ester polymer preparation process latex particle size with the reaction times.From Fig. 2 result, (to react 60 minutes) for benchmark at the end of seed stage, during at interval of reaction 30 minutes, the emulsion particle Theoretical Grain Size calculated is basically identical with actual measurement particle diameter, illustrate do not have new micelle formation, the monomer newly added grows at former emulsion particle surface aggregate; And add in monomer into emulsification dosage be also suitable.If newly add in monomer add into emulsification dosage too low, then the easy breakdown of emulsion of emulsion particle, causes condensation product content to raise; And add into emulsifier content too high, then can generate new micella, make the particle diameter of the emulsion particle of growth uncontrollable.Table 2 is the polymerization parameter of each embodiment acrylic ester polymer.As shown in Table 2, along with the increase of seed stage emulsifier, when adding identical seed monomer, the micella increased number of generation, causes the particle diameter of emulsion particle to diminish, as embodiment 1 ~ 5.When the mineral filler in polymeric matrix reaches nanometer scale dispersion, the performances such as the nano composite material mechanics of formation present the huge difference with traditional material.Nano silicon random dispersion is in acrylate polymer emulsion, and nano silicon and polymkeric substance achieve Homogeneous phase mixing.Because nano silicon disperse phase has great specific surface area, being combined closely with matrix, having the physical and mechanical property more excellent than conventional composites materials, is desirable enhancement type material.Table 3 and Fig. 3 be preparation acrylic ester polymer/nanometer silica composite and polycarbonate with the mechanical property of mass ratio 2/100 matrix material.Comparative example is the conventional acrylic ester polymer of not nano-silica-containing nano-dispersed and the mechanical property of polycarbonate Alloys, and the toughness reinforcing raising of low temperature is more, but tensile property declines.And the low temperature notched shock strength of the acrylic ester polymer/nanometer silica composite prepared and polycarbonate composite material and tensile strength are obtained for obvious raising, see embodiment 1 ~ 9 and Fig. 3; Wherein the result of embodiment 1 is: the purer polycarbonate of low temperature notched shock strength of matrix material improve 377%, tension set improves 298%, and the purer polycarbonate of the tensile strength of matrix material add 157%.These results suggest that, acrylic ester polymer/nanometer silica composite prepared by the present invention has significant low temperature toughening effect to polycarbonate, and improve the tensile property that polycarbonate uses as engineering plastics, achieve the toughness reinforcing and object that strengthens simultaneously.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. a preparation method for polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles, is characterized by and comprise the steps:
A. the pre-emulsification of seed monomer
According to above proportioning, in reactor, add emulsifying agent and deionized water, and mix and blend; Add acrylic ester monomer and linking agent again, and mix and blend, namely obtain internal layer seed monomer pre-emulsion, for subsequent use;
B. the pre-emulsification of stratum nucleare build phase monomer
Above-mentioned each component is put into a container, mix and blend, namely obtain stratum nucleare build phase monomer pre-emulsion, for subsequent use;
C. the pre-emulsification of outer monomer
Composition mass fraction
Emulsifying agent 0.80 ~ 1.20
Esters of acrylic acid mix monomer 40 ~ 60
Above-mentioned each component is put into another container, mix and blend, namely obtains outer monomer pre-emulsion, for subsequent use;
Described esters of acrylic acid mix monomer is methyl methacrylate and acrylic acid mixture, and wherein vinylformic acid quality accounts for the 1.6%-2.5% of esters of acrylic acid mix monomer;
D. the pre-emulsification of nano silicon
Above-mentioned nano silicon, emulsifying agent and deionized water are put into the 3rd container, mix and blend, namely obtains the pre-emulsion of nano silicon, for subsequent use;
Acrylic ester monomer in described step a, b is acrylic acid-2-ethyl monooctyl ester;
Emulsifying agent used in described step a, b, c, d is anionic emulsifier;
In step a, b, linking agent is 1,4 butanediol diacrylate;
The preparation of e. acrylic ester polymer/nano silicon composite particles
Fill to a step in the reactor of internal layer seed monomer pre-emulsion, vacuumize rear nitrogen replacement three times; Then continue to pass into nitrogen, in condenser, logical water of condensation, is warming up to 78.5 DEG C by reactant under whipped state, and after homo(io)thermism, at the uniform velocity dripped initiator solution 1 at 10 minutes, then continue reaction 50 minutes, the Seeded polymerization stage terminates; Then in reaction system, the obtained stratum nucleare build phase monomer pre-emulsion of b step is dripped with the first continuously and smoothly of identical speed, and then continuously and smoothly drips the obtained outer monomer pre-emulsion of step c, two kinds of pre-emulsions dropwise 180 minutes continuously and smoothlies, and continuously and smoothly drips initiator solution 2 these 180 minutes while; Afterwards, insulation reaction 120 minutes, then be down to room temperature; Nano silicon pre-emulsion Step d obtained joins in the emulsion of above-mentioned preparation and stirs 30 minutes, obtains acrylic ester polymer/nano silicon composite particles; Finally the composite particles of preparation is obtained polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles through freezing, washing, suction filtration, drying and other steps;
Wherein, add material mass ratio be seed monomer pre-emulsion: stratum nucleare build phase monomer pre-emulsion: outer monomer pre-emulsion: nano silicon pre-emulsion=(165.75 ~ 165.95): (126.98 ~ 147.54): (40.80 ~ 61.20): (50.504 ~ 52.520);
Initiator used is persulphate, adds in the mode of the aqueous solution, and concrete proportioning is as follows:
The mass fraction of the mass fraction water of persulphate
Initiator solution 10.3320
Initiator solution 20.2530
Wherein, quality is than initiator solution 1: seed monomer pre-emulsion: initiator solution 2=20.33:(160.75 ~ 160.95): 30.25.
2. the preparation method of polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles as claimed in claim 1, is characterized by anionic emulsifier used in described step a, b, c, d and is dihexyl adipate sodium sulfonate.
3. the preparation method of polycarbonate toughness reinforcing acrylic ester polymer/nano silicon composite particles as claimed in claim 1, it is characterized by initiator used in described step e is Potassium Persulphate.
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