CN105462143B - The preparation method of makrolon toughness reinforcing acrylate polymer/nano-calcium carbonate compound particle - Google Patents
The preparation method of makrolon toughness reinforcing acrylate polymer/nano-calcium carbonate compound particle Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The present invention is a kind of preparation method of makrolon toughness reinforcing acrylate polymer/nano-calcium carbonate compound particle.This method is by selecting emulsifier and nano-calcium carbonate dosage, utilize seeded emulsion polymerization technology, by the in-stiu coating of the preparation of seed stage elastomer, the growth of elastomer particle diameter and plastic outer layer, and adjust the feed postition of initiator, prepare acrylate polymer emulsion, then nano-calcium carbonate pre-emulsion is mixed with aforesaid propylene acid ester polymer emulsion, acrylate polymer/nano-calcium carbonate compound particle is obtained through demulsification.By 1.96% acrylate polymer/nano-calcium carbonate compound particle and polycarbonate blending, the purer makrolon of low temperature notched impact strength of composite improves 3 times, tensile strength purer makrolon adds more than 1 times simultaneously, realizes toughness reinforcing simultaneously and the purpose strengthened.
Description
Technical field
The present invention relates to category polymer modification field, specially makrolon toughness reinforcing acrylate polymer/receive
The preparation method of rice calcium carbonate composite particles.
Background technology
It is study hotspot in recent years particle shape and structure to be designed to assign material specific use.Sandwich construction
The method of emulsion polymerisation particles is more, polymerization such as semi-continuous seed emulsion polymerization, swelling seeding polymerization, micro-emulsion polymerization etc.
Mechanism.The major advantage that acrylic ester impact-resisting hits modifying agent (ACR) has：Good impact modification effect, wider processing
Temperature range, low-shrinkage, product size are stable；Have processing aid feature concurrently, the fusion plastification time of compound can be shortened, changed
Kind co-mixing system moulding processability；And also there is preferable weatherability.One of makrolon category five large-engineering plastics, have resistance to
Heat, creep resistant, it is resistant to chemical etching, electric insulation the features such as, be widely used in actinic material, medicine equipment and food industry, build
Build the fields such as material, electronic apparatus.But makrolon has the shortcomings that easy stress cracking, this will limit it very many
Using.In recent years, research worker and achieves certain with particle having multilayer structure come Toughening Modification of Polycarbonate engineering plastics
Effect.Xiaodong Liu and Hans Bertilsson utilize the nucleocapsid structure of MBS
The PC/ABS blends of anti-impact modifier (MBS) toughness reinforcing recovery.PC/ABS (80/20, mass ratio) adds 5 parts of MBS and can showed
Go out preferable tensile toughness and notch impact toughness, elongation at break improves 5%, and tensile strength have dropped 7.42%, breach
Impact strength is 1.81 times of (Xiaodong Liu, Hans Bertilsson.Recycling of ABS of starting blend
and ABS/PC Blends.Journal of Applied Polymer Science,1999,74:510-515).Chen Jianfei
PC reclaimed materials progress toughening modifying, research are found Deng using hud typed silicon rubber：Silicon rubber is stratum nucleare, the poly- methyl of Surface coating
During the shell of acrylic acid, if other bulking agents are added without, to PC without toughening effect；When 15% epoxy resin of addition (DGEBA)
During bulking agent, there is obvious toughness to improve, notch impact strength is original 3 times, tensile strength decline 11.11% (Chen Jianfei,
What toughness reinforcing and flame-retardant modified research plastics industry of the such as Yadong, Sun Shuanyue " core-shell structure copolymer " the type silicon rubber to makrolon reclaimed materials,
2010,2：19-24).Guo Baohua etc. have studied MBS (MBS) to makrolon
Toughening effect and toughening mechanism, they have studied influence of the different MBS additions to makrolon, find：When MBS contents reach
When 15%, impact strength reaches peak, is the pure PC 3 times of [increasings of the .MBS such as Guo Baohua, Xu Xiaolin, Xu Jun to makrolon
The discussion China Rubber/plastics Technologies of tough effect and its toughening mechanism and equipment, 2006,32 (7)：23-27].
Though MBS, ABS type core-shell particles have certain toughening effect, double bond structure, resistance to atmospheric aging are contained in its main chain
Property is poor.And utilize polyacrylate multi-layer core-shell structure ACR modified polycarbonates, it usually needs larger addition (12wt%
More than), preferable toughening effect can be just played, this will greatly reduce the tensile strength of polycarbonate matrix material.
Nano material can assign high polymer material many special performances, because the yardstick of Nano particles of calcium carbonate is in group
Cluster molecule and the alternate transitional region of macro object, thus show many special natures, correspondingly nano-calcium carbonate and other
The compound use and its physicochemical properties of material turn into the focus of research.It is not big through methyl methacrylate and butyl acrylate
The nano-calcium carbonate of dual MCU system polymerization cladding forms core shell structure toughness reinforcing composite particles, and by 5 parts of modifying agent and makrolon/
ABS(60:40) alloy is blended.Experiment discovery, modified polycarbonate impact strength raising 28%, tensile strength and makrolon/
ABS it is consistent [it is not big, look into Liu Feng, Zeng Xiaofei, wait Nano-meter CaCO3s3Composite particles toughened reinforced PC/ABS [J] is high
Molecular material scientific and engineering, 2007,23 (6):220-223.].
In order to expand use of the engineering plastics in extremely frigid zones, it is necessary to improve the cryogenic property of engineering plastics, be usually added into
Rubber elastomer, such as the CN 101870751A that this group is applied, the butyl polyacrylate elastomer used.Characterize cold tolerance
Index is the glass transition temperature (T of rubber elastomerg)；TgValue is lower, shows that its cold resistance is better.Butyl polyacrylate
TgIt is worth for -23 DEG C (1Hz), but can not still meets requirement in extremely frigid zones.It if is improved, for example, it is single by changing
The methods of body material, it is related to the selection of the materials such as emulsifying agent again, in patent CN 102352002A and CN 102351977A
Dodecyl Biphenyl Ether sodium sulfonate emulsifying agent, but it is water-soluble big, makes condensation product caused by polymerization process excessive, it is impossible to meet
Requirement；And during solving this problem, it is excessive to easily cause instantaneous number of free radical again, makes polymerization system because of local mistake
It is hot and unstable, cause polymerization to fail.If being directly added into not emulsified calcium carbonate water dispersion liquid, such as CN101864120A, often
Can decline the tensile strength of composite.
The content of the invention
It is an object of the invention to for needing to add more than 10% rubber at present to polycarbonate matrix resin toughening
Elastomer modifier, just its notch impact strength can be made to reach requirement, this declines the tensile strength for making makrolon
More than 15%, a kind of deficiency of the poor processability of blend, there is provided makrolon toughness reinforcing acrylate polymer/nanometer
The preparation method of calcium carbonate composite particles.This method utilizes seed by selecting emulsifier and nano-calcium carbonate dosage
Emulsion polymerization technology, by the in-stiu coating of the preparation of seed stage elastomer, the growth of elastomer particle diameter and plastic outer layer, and
And adjustment initiator feed postition, prepare acrylate polymer emulsion, then by nano-calcium carbonate pre-emulsion with it is above-mentioned
Acrylate polymer emulsion is mixed, and is dispersed in by stirring nano-calcium carbonate in emulsion, and propylene is obtained through demulsification
Acid ester polymer/nano-calcium carbonate compound particle.A small amount of compound particle is added in makrolon, is remarkably improved poly- carbonic acid
The low-temperature impact toughness and tensile strength of ester composite.With acrylate polymer/nano-calcium carbonate prepared by the present invention
Compound particle carrys out modified polycarbonate, adds 1.96% acrylate polymer/nano-calcium carbonate compound particle can and shows
The toughness for improving polycarbonate matrix material is write, the purer makrolon of low temperature notched impact strength of composite improves
380%, fracture elongation improves 204%, while tensile strength adds 136%.
The technical scheme is that：
A kind of preparation method of makrolon toughness reinforcing acrylate polymer/nano-calcium carbonate compound particle, including such as
Lower step：
A. the pre-emulsification of seed monomer
Matched more than, emulsifying agent and deionized water are added into reactor, and mix；Add again into reactor
Enter acrylic ester monomer and crosslinking agent, and mix, that is, obtain internal layer seed monomer pre-emulsion, it is standby；
B. the pre-emulsification of stratum nucleare build phase monomer
Above-mentioned each component is put into a container, mixes, that is, obtains stratum nucleare build phase monomer pre-emulsion, it is standby
With；
C. the pre-emulsification of outer layer 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, mixes, that is, obtains outer layer monomer pre-emulsion, it is standby；
Described esters of acrylic acid mix monomer is the mixture of methyl methacrylate and acrylic acid, wherein acrylic acid
Quality accounts for the 1.1%~1.6% of esters of acrylic acid mix monomer；
D. the pre-emulsification of nano-calcium carbonate
Above-mentioned nano-calcium carbonate, emulsifying agent and deionized water are put into the 3rd container, mixes, that is, obtains nanometer
The pre-emulsion of calcium carbonate, it is standby；
Acrylic ester monomer in step a, b is acrylic acid-2-ethyl monooctyl ester；
Emulsifying agent used is anion emulsifier in described step a, b, c, d；
Step a, crosslinking agent is 1,4 butanediol diacrylate in b；
E. the preparation of acrylate polymer/nano-calcium carbonate compound particle
In the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing with nitrogen displacement three times；Then after
It is continuous to be passed through nitrogen, lead to condensed water in condenser, reactant is warming up to 78.5 DEG C under stirring, after temperature is constant,
Initiator solution 1 is at the uniform velocity added dropwise within 10 minutes, then proceedes to reaction 50 minutes, the Seeded polymerization stage terminates；Then to anti-
Answer in system and stratum nucleare build phase monomer pre-emulsion made from b step is added dropwise with identical speed elder generation continuously and smoothly, it is then continuous again
Outer layer monomer pre-emulsion made from step c is at the uniform velocity added dropwise, two kinds of pre-emulsions were added dropwise in 180 minutes continuously and smoothlies, and herein
180 minutes initiator solutions 2 of continuously and smoothly's dropwise addition simultaneously；Afterwards, insulation reaction 120 minutes, then it is down to room temperature；By Step d
Obtained nano-calcium carbonate pre-emulsion is added in the emulsion of above-mentioned preparation and stirred 30 minutes, obtains acrylate polymer/receive
Rice calcium carbonate composite particles；Finally by the compound particle of preparation it is chilled, washing, filter, drying and other steps obtain makrolon
Toughness reinforcing acrylate polymer/nano-calcium carbonate compound particle.
Wherein, the mass ratio for adding material is seed monomer pre-emulsion：Stratum nucleare build phase monomer pre-emulsion：Outer layer list
Body pre-emulsion：Nano-calcium carbonate pre-emulsion=(162.75~162.95)：(129.92~150.51)：(40.80~61.20)：
(50.504~52.520).
Initiator used is persulfate, is added in a manner of the aqueous solution, and specific proportioning is as follows：
Wherein, quality is than initiator solution 1：Seed monomer pre-emulsion：Initiator solution 2=20.33：(162.75
~162.95)：30.25；
The specific quality of above material is not the restriction to invention, in actual production, according to required product amount according to above-mentioned matter
Amount ratio is integrally expanded or shunk.
In preparation method of the above-mentioned modified polycarbonate toughness reinforcing with acrylate polymer/nano-calcium carbonate compound particle,
Anion emulsifier used is dihexyl adipate sodium sulfonate in described step a, b, c, d；
Persulfate used is potassium peroxydisulfate in step e.
The beneficial effects of the invention are as follows：
For fragility and half fragility polar plas, modifying agent of the generally use butyl polyacrylate as rubber phase elastomer
To improve its toughness.In order to expand use of these plastics in extremely frigid zones, it is necessary to improve their resistance to low temperature.Characterize resistance to
The index of cryogenic property is the glass transition temperature (T of rubber phase elastomerg), TgValue is lower, shows that its lower temperature resistance is got over
It is good.The T of butyl polyacrylategIt is worth for -23 DEG C (1Hz), but can not still meets requirement in extremely frigid zones.The present invention uses third
Olefin(e) acid -2- ethyls monooctyl ester is as monomer, its TgValue is lower, is -51 DEG C (1Hz), resistance to low temperature is more preferable.Now, according to ten
Dialkyl group Biphenyl Ether sodium sulfonate because it is water-soluble big, makes condensation product caused by polymerization process (discarded object) excessively as emulsifying agent,
Requirement can not be met.On the basis of many experiments, the present invention uses anion emulsifier dihexyl adipate sodium sulfonate, real
The stabilization of existing emulsion polymerization systems.In previous literature, the water soluble starter that emulsion polymerization uses adds to be disposable,
It is excessive that this easily causes instantaneous number of free radical, makes polymerization system unstable because of hot-spot, causes polymerization to fail.Therefore this hair
It is bright also to have adjusted the initiator concentration of seed latex grain build phase, and be at the uniform velocity added dropwise after being made into initiator solution, last rank
Section be incubated 2 hours again, realize high monomer conversion (>98.5%), and as waste material condensation product content it is low (<0.5%),
I.e. the conversion ratio of monomer improves, and simplifies the last handling process of residual monomer in emulsion polymeric product.The nano-meter characteristic of calcium carbonate,
It is set to be dispersed in after adding water with suspension in acrylate polymer emulsion, obtained modifying agent possesses nano-calcium carbonate
Nano-meter characteristic, acrylate polymer can play significant low temperature toughening effect to polycarbonate matrix, and nano-calcium carbonate
Significant enhancing effect is played to polycarbonate matrix using its nano effect.With the acrylic ester polymerization prepared by the present invention
Thing/nano-calcium carbonate compound particle carrys out modified polycarbonate, add 1.96% acrylate polymer/nano-calcium carbonate it is compound
Particle can significantly improves the toughness of polycarbonate matrix material, the purer poly- carbonic acid of low temperature notched impact strength of composite
Ester improves 380%, and fracture elongation improves 204%, while tensile strength adds 136%, obtains to poly- carbonic acid
The unexpected toughness reinforcing of ester matrix resin and enhancing effect.
Brief description of the drawings：
Fig. 1 is variation diagram of the acrylate polymer preparation process monomer conversion of embodiment 1 with the reaction time.
Fig. 2 is variation diagram of the acrylate polymer preparation process latex particle size of embodiment 1 with the reaction time.
Fig. 3 is that pure makrolon, comparative example and embodiment 1-9 acrylate polymers/nano-calcium carbonate compound particle change
The low temperature notched impact strength and tensile strength graph of a relation of property polycarbonate Alloys.
The present invention is further described with reference to the accompanying drawings and examples.
Embodiment
Embodiment 1
A. the pre-emulsification of seed monomer
First, 0.71g anion emulsifier dihexyl adipate sodium sulfonates are added into 500ml four-hole boiling flasks and 150g is gone
Ionized water, and mix 30 minutes；12g acrylic acid-2-ethyl monooctyl ester monomers and 0.04g crosslinking agents are added into reactor again
BDO diacrylate, and be placed in electromagnetic agitation and mix 20 minutes, that is, seed monomer pre-emulsion is obtained, it is standby
With；
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.85g anion emulsifier dihexyl adipates sodium sulfonate, 140g acrylic acid-2-ethyl monooctyl ester monomers and
0.66g crosslinking agent BDO diacrylates are added in 400ml beakers, are then placed within electromagnetic agitation and are mixed
20 minutes, that is, stratum nucleare build phase monomer pre-emulsion is obtained, it is standby；
C. the pre-emulsification of outer layer monomer
By 0.8g anion emulsifier dihexyl adipates sodium sulfonate, 40g methyl methacrylate monomers and 0.64g propylene
Acid is added in 400ml beakers, is then placed within electromagnetic agitation and is mixed 20 minutes, that is, obtains outer layer monomer pre-emulsion,
It is standby；
D. the pre-emulsification of nano-calcium carbonate
0.5g nano-calcium carbonates (20~30nm), 0.012g dihexyl adipates sodium sulfonate and 50g deionized waters are added
Into 400ml beakers, it is placed in electromagnetic agitation and mixes 60 minutes, that is, obtain the pre-emulsion of nano-calcium carbonate, it is standby；
E. the preparation of acrylate polymer/nano-calcium carbonate compound particle
In the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing with nitrogen displacement three times, to remove
Oxygen, realize the inert atmosphere of system；Then proceed to be passed through nitrogen, lead to condensed water in condenser, will reaction under stirring
Thing is warming up to 78.5 DEG C, and after temperature is constant, constant pressure funnel at the uniform velocity instills 20.33g initiator solutions and dripped for 1,10 minutes
Add complete；After then proceeding to reaction 50 minutes, the Seeded polymerization stage terminates.Then it is first with identical speed into reaction system
Stratum nucleare build phase monomer pre-emulsion made from b step is added dropwise, it is pre- to be added dropwise outer layer monomer made from step c immediately after being added dropwise
Emulsion, two kinds of pre-emulsions were added dropwise in 180 minutes continuously and smoothlies, and 30.25g was added dropwise in continuously and smoothly simultaneously at this 180 minutes
Initiator solution 2；Afterwards, insulation reaction 120 minutes, then it is down to room temperature；Nano-calcium carbonate pre-emulsion made from Step d is existed
It is added under stirring in the emulsion of above-mentioned preparation, stirs 30 minutes, that is, obtain the compound grain of acrylate polymer/nano-calcium carbonate
Son；Finally by the compound particle of preparation it is chilled, washing, filter, drying and other steps obtain the acrylate with hybrid structure
Polymer/nano calcium carbonate composite particles.
Initiator used is potassium peroxydisulfate.Deionized water need to be added with certain proportion when in use, and in magnetic stirrer
Initiator solution is made in 20 minutes in upper stirring and dissolving.Specific proportioning is as follows：
Acrylate polymer to preparation and it is characterized as below with polycarbonate composite material：
(1) acrylate polymer
The present invention samples 2ml in polymer emulsion preparation process, at interval of 30 minutes, and 0.05ml dilutes through deionized water
Afterwards, it is 256nm in Malvern Zetasizer Nano-ZS90 dynamic laser Analyzer testing results latex particle sizes, and not
It is consistent with calculated value with the emulsion particle measured value in reaction time, as shown in Figure 2；In addition, latex particle size profile exponent is
0.036.Therefore, the latex particle size of the emulsion is controllable.
Remaining 1.95ml parts are used for the instantaneous conversion rate and total conversion for determining polymerized monomer, see Fig. 1.After weighing
(note wet combustion cup weight) is put into 80 DEG C of baking oven and dried 24 hours, to mass conservation after be re-weighed (note dry combustion method cup weight).
The measure of solid content
Solid content S is calculated as follows：
In formula：m0To dry the quality of empty bottle, m1To add the quality (wet combustion cup quality) after emulsion, m2For in drying box
Quality (dry combustion method cup quality) after middle drying.
The calculating of monomer conversion
Total conversion OC：
Instantaneous conversion rate IC：
In formula：MiEmulsion gross mass, S when being sampled for ithiSolid content when being sampled for ith, m' are to be sampled to ith
When add initiator gross mass, Δ m be to ith sample when addition emulsifying agent, crosslinking agent gross mass, M0To add monomer
Gross mass, M be to ith sample when addition monomer quality.
Theoretical Grain Size can be calculated by following formula：
Wherein：dsThe particle diameter that particle size values by latex particle at the end of seed stage are surveyed when being the second sub-sampling, MsFor kind
The amount of monomer that sub-stage adds, MtThe amount of monomer added for t, I are the instantaneous conversion rate of t.
Agglomerated thing cubage formula is as follows：
In formula：W' for dry before the gross mass of agglomerated thing and beaker, w for dry after the gross mass of agglomerated thing and beaker, w0
For the gross mass of acrylic ester monomer used in formula.
(2) polycarbonate composite material
By the acrylate polymer of preparation/nano-calcium carbonate compound particle, makrolon and acrylate polymer point
After being dried in vacuo 12 hours not at 80 DEG C, in mass ratio 2:100 mix, through the production of Nanjing Ke Ya extrusion machineries research institute
It is granulated after TE-34 (L/D=28) double screw extruder extrusion, screw speed is 65 turns per minute, and twin-screw temperature control is successively
For：250、258、258、258、258、255℃.The composite material granular of gained is used extensively after being dried in vacuo 12 hours at 80 DEG C
The JPH30 type injection machine injection moldings of Dong Hongli machines Co., Ltd production, injection temperature control are followed successively by：253、253、258、
258 DEG C, 40MPa injection pressures, obtain test bars.Obtained batten carries out tensile property and impact property test, test temperature
Spend for -25 DEG C.
Embodiment 2~9
Other steps are with embodiment 1, but a steps seed stage emulsifying agent used, Step d nano-calcium carbonate in embodiment 2~9
The change of calcareous amount and emulsifying agent quality, it is specific as shown in table 1.
Comparative example
A. the pre-emulsification of seed monomer
First, 0.71g anion emulsifier dihexyl adipate sodium sulfonates are added into 500ml four-hole boiling flasks and 150g is gone
Ionized water, and mix 30 minutes；12g acrylic acid-2-ethyl monooctyl ester monomers and 0.04g crosslinking agents are added into reactor again
BDO diacrylate, and be placed in electromagnetic agitation and mix 20 minutes, that is, seed monomer pre-emulsion is obtained, it is standby
With；
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.85g anion emulsifier dihexyl adipates sodium sulfonate, 140g acrylic acid-2-ethyl monooctyl ester monomers and
0.66g crosslinking agent BDO diacrylates are added in 400ml beakers, are then placed within electromagnetic agitation and are mixed
20 minutes, that is, stratum nucleare build phase monomer pre-emulsion is obtained, it is standby；
C. the pre-emulsification of outer layer monomer
By 0.8g anion emulsifier dihexyl adipates sodium sulfonate, 40g methyl methacrylate monomers and 0.64g propylene
Acid is added in 400ml beakers, is then placed within electromagnetic agitation and is mixed 20 minutes, that is, obtains outer layer monomer pre-emulsion,
It is standby；
D. the preparation of acrylate polymer
In the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing with nitrogen displacement three times, to remove
Oxygen, realize the inert atmosphere of system；Then proceed to be passed through nitrogen, lead to condensed water in condenser, will reaction under stirring
Thing is warming up to 78.5 DEG C, and after temperature is constant, initiator solution 1 was at the uniform velocity added dropwise at 10 minutes, after continuing reaction 50 minutes, kind
Sub- polymerization stage terminates.Then stratum nucleare build phase monomer pre-emulsion made from b step is continuously added dropwise into reaction system
With step c made from outer layer monomer pre-emulsion, two kinds of pre-emulsions are added dropwise in 180 minutes continuously and smoothlies, and at this 180 minutes
Initiator solution 2 is added dropwise in continuously and smoothly simultaneously；Afterwards, insulation reaction 120 minutes, then it is down to room temperature；Finally by the breast of preparation
Liquid is chilled, washs, filter, drying and other steps obtain acrylate polymer.
Initiator used is potassium peroxydisulfate.Deionized water need to be added with certain proportion when in use, and in magnetic stirrer
Initiator solution is made in 20 minutes in upper stirring and dissolving.Specific proportioning is as follows：
The quality of some components in the embodiment 1~9 of table 1
The polymerization parameter of acrylate polymer is listed in Table 2 below in embodiment 1~5.Acrylate polymer/nano-calcium carbonate
The mechanical property that calcium compound particle forms composite with makrolon is listed in Table 3 below.
The polymerization parameter of the acrylate polymer of table 2
The mechanical property of 3 acrylate polymers of table/nano-calcium carbonate compound particle and polycarbonate composite material
Fig. 1 is variation diagram of the acrylate polymer preparation process monomer conversion of embodiment 1 with the reaction time.By Fig. 1
Understand, the instantaneous conversion rate of each stage monomer is all higher than 98% in embodiment 1, and the monomer for illustrating to add largely is polymerize
Reaction, that is, the monomeric species, the addition of initiator and the feed postition that add, polymeric reaction temperature three are matchings,
This is also important to controlling for latex particle size.If in the monomer newly added, unreacted content of monomer is high, easily exists
New micella is formed in emulsion system, the monomer for causing newly to add fails completely in former emulsion particle superficial growth.Fig. 2 is embodiment
1 acrylate polymer preparation process latex particle size with the reaction time variation diagram.It was found from Fig. 2 results, with seed stage
At the end of on the basis of (reaction 60 minutes), during at interval of reaction 30 minutes, the emulsion particle Theoretical Grain Size and the actual measurement grain that are calculated
Footpath is basically identical, illustrates no new micelle formation, and the monomer newly added grows in former emulsion particle surface aggregate；And in monomer
Add into emulsification dosage be also suitable.If newly add monomer in add into emulsification dosage it is too low, emulsion particle is easy
Demulsification, condensation product content is caused to raise；And add into emulsifier content it is too high, then can generate new micella, make the breast of growth
The particle diameter of micelle is uncontrollable.Table 2 is the polymerization parameter of embodiment acrylate polymer.As shown in Table 2, with seed stage breast
The increase of agent dosage, in the case where adding identical seed monomer amount, the micella number of generation increases, and causes the grain of emulsion particle
Footpath diminishes, such as embodiment 1~5.When the inorganic filler in polymeric matrix, which reaches nanometer scale, to be disperseed, the nanometer of formation
The performances such as Compound Material Engineering show the huge difference with traditional material.Nano-calcium carbonate is dispersed in acrylic ester polymerization
When in thing, because nano-calcium carbonate dispersed phase has larger specific surface area, combined closely, showed than routine with matrix
The more excellent mechanical property of composite.Table 3 and Fig. 3 be acrylate polymer/nano-calcium carbonate compound particle for preparing with
Makrolon is with the mechanical property of the composite of mass ratio 2/100.Comparative example is free from the common acrylate of nano-calcium carbonate
The mechanical property of polymer and polycarbonate Alloys, the raising of low temperature notched impact strength is more, but tensile property declines.And make
Standby acrylate polymer/nano-calcium carbonate compound particle forms the low temperature notched impact strength of composite with makrolon
Obvious raising is obtained for tensile strength, sees embodiment 1~9 and Fig. 3；The result of wherein embodiment 1 is：Acrylate gathers
The purer makrolon of low temperature notched impact strength of compound/nano-calcium carbonate and polycarbonate composite material improves 380%,
Fracture elongation improves 204%, and the purer makrolon of tensile strength of composite adds 136%.Result above
Illustrate, acrylate polymer/nano-calcium carbonate compound particle prepared by the present invention has significant low temperature to increase to makrolon
Tough effect, and improve the tensile property that makrolon uses as engineering plastics, is realized while toughness reinforcing and the purpose of enhancing.
Unaccomplished matter of the present invention is known technology.
Claims (1)
1. a kind of makrolon toughness reinforcing preparation method of acrylate polymer/nano-calcium carbonate compound particle, it is characterized in that
Comprise the following steps：
A. the pre-emulsification of seed monomer
Composition mass fraction
Emulsifying agent 0.71 ~ 0.91
Deionized water 150
Acrylic ester monomer 12
Crosslinking agent 0.04
Matched more than, emulsifying agent and deionized water are added into reactor, and mix；Third is added into reactor again
Olefin(e) acid esters monomer and crosslinking agent, and mix, that is, internal layer seed monomer pre-emulsion is obtained, it is standby；
B. the pre-emulsification of stratum nucleare build phase monomer
Composition mass fraction
Emulsifying agent 1.60 ~ 1.85
Acrylic ester monomer 128 ~ 148
Crosslinking agent 0.32 ~ 0.66
Above-mentioned each component is put into a container, mixes, that is, obtains stratum nucleare build phase monomer pre-emulsion, it is standby；
C. the pre-emulsification of outer layer 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, mixes, that is, obtains outer layer monomer pre-emulsion, it is standby；
Described esters of acrylic acid mix monomer is the mixture of methyl methacrylate and acrylic acid, and wherein acrylic acid quality accounts for
The 1.1% ~ 1.6% of esters of acrylic acid mix monomer；
D. the pre-emulsification of nano-calcium carbonate
Composition mass fraction
Nano-calcium carbonate 0.5 ~ 2.5
Emulsifying agent 0.004 ~ 0.020
Deionized water 50
Above-mentioned nano-calcium carbonate, emulsifying agent and deionized water are put into the 3rd container, mixes, that is, obtains nano-calcium carbonate
The pre-emulsion of calcium, it is standby；
Acrylic ester monomer in described step a, b is acrylic acid-2-ethyl monooctyl ester；
Emulsifying agent used is anion emulsifier in described step a, b, c, d；
Step a, crosslinking agent is 1,4 butanediol diacrylate in b；
E. the preparation of acrylate polymer/nano-calcium carbonate compound particle
In the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing with nitrogen displacement three times；Then proceed to lead to
Enter nitrogen, lead to condensed water in condenser, reactant is warming up to 78.5 ° of С under stirring, after temperature is constant, at 10 points
Initiator solution 1 is at the uniform velocity added dropwise in clock, then proceedes to reaction 50 minutes, the Seeded polymerization stage terminates；Then to reactant
Stratum nucleare build phase monomer pre-emulsion made from b step is added dropwise with identical speed elder generation continuously and smoothly in system, then continuously and smoothly again
Outer layer monomer pre-emulsion made from step c is added dropwise, two kinds of pre-emulsions were added dropwise in 180 minutes continuously and smoothlies, and at this 180 points
Initiator solution 2 is added dropwise in continuously and smoothly to clock simultaneously；Afterwards, insulation reaction 120 minutes, then it is down to room temperature；By made from Step d
Nano-calcium carbonate pre-emulsion is added in the emulsion of above-mentioned preparation and stirred 30 minutes, obtains acrylate polymer/nano-calcium carbonate
Calcium compound particle；Finally by the compound particle of preparation it is chilled, washing, filter, drying steps obtain makrolon toughness reinforcing with third
Olefine acid ester polymer/nano-calcium carbonate compound particle；
Wherein, the mass ratio for adding material is seed monomer pre-emulsion：Stratum nucleare build phase monomer pre-emulsion：Outer layer monomer is pre-
Emulsion：Nano-calcium carbonate pre-emulsion=（162.75~162.95）：（129.92~150.51）：（40.80~61.20）：（50.504~
52.520）；
Initiator used is persulfate, is added in a manner of the aqueous solution, and specific proportioning is as follows：
The mass fraction of the mass fraction water of persulfate
Initiator solution 1 0.33 20
Initiator solution 2 0.25 30
Wherein, quality is than initiator solution 1：Seed monomer pre-emulsion：Initiator solution 2=20.33：（162.75~
162.95）：30.25；
Anion emulsifier used is dihexyl adipate sodium sulfonate in described step a, b, c, d；
Persulfate used is potassium peroxydisulfate in described step e.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101864120A (en) * | 2010-07-08 | 2010-10-20 | 河北工业大学 | Preparation method of polyacrylic ester/nanometer CaCO3 composite material |
| CN102702423A (en) * | 2012-06-25 | 2012-10-03 | 河北工业大学 | Preparation method of acrylic ester copolymer latex particle for toughening and modifying polybutylene terephthalate |
| CN104448112A (en) * | 2014-11-11 | 2015-03-25 | 河北工业大学 | Preparation method of functional polyacrylate composite emulsion for modifying low-temperature toughness of nylon 6 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864120A (en) * | 2010-07-08 | 2010-10-20 | 河北工业大学 | Preparation method of polyacrylic ester/nanometer CaCO3 composite material |
| CN102702423A (en) * | 2012-06-25 | 2012-10-03 | 河北工业大学 | Preparation method of acrylic ester copolymer latex particle for toughening and modifying polybutylene terephthalate |
| CN104448112A (en) * | 2014-11-11 | 2015-03-25 | 河北工业大学 | Preparation method of functional polyacrylate composite emulsion for modifying low-temperature toughness of nylon 6 |
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