CN105418836B - The preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle - Google Patents
The preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- 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
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/36—Silica
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- 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 present invention is a kind of preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle.This method is by selecting emulsifier and nano silicon consumption, 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 silicon pre-emulsion is well mixed with aforesaid propylene acid ester polymer emulsion, acrylate polymer/nano silicon compound particle is obtained through demulsification.A small amount of compound particle of the invention is added in makrolon, acrylate polymer/nano silicon compound particle of addition 1.96% can just significantly improve the toughness of polycarbonate matrix material, the purer makrolon of low temperature notched impact strength of composite improves 287%, fracture elongation improves 298%, while tensile strength adds 157%.
Description
Technical field
The present invention relates to category polymer modification field, specially a kind of makrolon toughness reinforcing acrylic ester polymerization
The preparation method of thing/nano silicon compound particle.
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, is swelled 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.Makrolon belongs to one of five large-engineering plastics, with 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, and 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 that anti-impact modifier (MBS) toughness reinforcing is reclaimed.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
Toughening modifying is carried out to PC reclaimed materials Deng using hud typed silicon rubber, research is found：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 Yadong, " core-shell structure copolymer " the type silicon rubber such as Sun Shuanyue to the toughness reinforcing and flame-retardant modified research plastics industries of 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, the 3 times of [increasings of the .MBS such as Guo Baohua, Xu Xiaolin, Xu Jun to makrolon for being pure PC
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.
The Peculiar function of nano material, can assign high polymer material many special performances, due to nanometer titanium dioxide silicon grain
The yardstick of son is in cluster molecule and the alternate transitional region of macro object, thus shows many special natures, correspondingly right
Nano silicon and its focus of the physicochemical properties as research with polyblend and composite.Zhang Zhiyi leads to
Nano-silicon dioxide modified dose that emulsion polymerization is prepared for a small amount of polymethyl methacrylate of Surface coating is crossed, and is changed this
Property agent and makrolon press 10：90 blendings, investigate the performance change of modified polycarbonate.Experiment discovery, modified polycarbonate
Impact strength improves 50%, and for 1.45 times of pure matrix resin, [Zhang Zhiyi, Zhao Ning, Wei Wei wait core shell structures to tensile strength
Preparation with layer structure modifying agent and its influence [J] engineering plastics applications to PC performances, 2007,33 (3):5-8.].Should
The modified polycarbonate tensile strength of material that method is obtained is improved really, but required nano-silicon dioxide modified dose of consumption
It is more to have reached 10%, and toughness improves less only 50%.
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, the CN 101870751A that such as 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 use requirement can not be still met in extremely frigid zones.It is if be improved, such as single by changing
The methods such as body material, are related in the selection of the materials such as emulsifying agent, such as patent CN 102352002A and CN 102351977A again
Dodecyl Biphenyl Ether sodium sulfonate emulsifying agent, but it is water-soluble big, and the condensation product for producing polymerization process is excessive, it is impossible to meet
Use 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
Heat and it is unstable, cause polymerization fail.It is modified if directly nano silicon is directly added into makrolon, such as
CN101759943A and CN102464845A, can be often hard to be uniformly dispersed in because of silica reunion in matrix causes titanium dioxide
Silicon enhancing effect is not good.
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 can make its notch impact strength reach use requirement, and this declines the tensile strength for making makrolon
More than 15%, there is provided a kind of makrolon toughness reinforcing acrylate polymer/nanometer for the deficiency of the poor processability of blend
The preparation method of silica dioxide composite particles.This method is utilized by selecting emulsifier and nano silicon consumption
Seeded emulsion polymerization technology, is wrapped by the original position of the preparation of seed stage elastomer, the growth of elastomer particle diameter and plastic outer layer
Cover, and adjust the feed postition of initiator, prepare acrylate polymer emulsion, then by nano silicon pre-emulsion
Mixed with aforesaid propylene acid ester polymer emulsion, acrylate polymer/nano silicon compound particle is obtained through demulsification.Will
A small amount of compound particle is added in makrolon, and low-temperature impact toughness and the stretching for being remarkably improved polycarbonate composite material are strong
Degree.Acrylate polymer/nano silicon compound particle of addition 1.96% can just significantly improve polycarbonate matrix
The toughness of material, the purer makrolon of low temperature notched impact strength of composite improves 377%, and fracture elongation improves
298%, while tensile strength adds 157%.
The technical scheme is that：
A kind of preparation method of makrolon toughness reinforcing acrylate polymer/nano silicon compound particle, including
Following steps：
A. the pre-emulsification of seed monomer
Matched more than, emulsifying agent and deionized water are added into reactor, and mix；Add acrylate
Class 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
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 matter
Amount 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, mixes, that is, is received
The pre-emulsion of rice silica, 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；
Crosslinking agent is 1,4 butanediol diacrylate in step a, b；
E. the preparation of acrylate polymer/nano silicon compound particle
Nitrogen displacement is used in the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing three times；Then after
Continuous be passed through in nitrogen, condenser leads to condensed water, and reactant is warming up into 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 with stratum nucleare build phase monomer pre-emulsion made from the first continuously and smoothly's dropwise addition b step of identical speed in system, 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 in 180 minutes continuously and smoothly's completion of dropping, and herein
180 minutes initiator solutions 2 of continuously and smoothly's dropwise addition simultaneously；Afterwards, insulation reaction 120 minutes, then be down to room temperature；By Step d
Obtained nano silicon pre-emulsion be added in the emulsion of above-mentioned preparation stir 30 minutes, obtain acrylate polymer/
Nano silicon compound particle；Finally by the compound particle of preparation is chilled, washing, suction filtration, drying and other steps obtain poly- carbon
Acid esters toughness reinforcing acrylate polymer/nano silicon 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 silicon pre-emulsion=(165.75~165.95)：(126.98~147.54)：(40.80~
61.20)：(50.504~52.520).
Initiator used is persulfate, is added in the way 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：(160.75
~160.95)：30.25
The restriction of the specific quality of above material not to invention, in actual production, according to required product amount according to above-mentioned matter
Amount ratio is integrally expanded or shunk.
The preparation method of above-mentioned modified polycarbonate toughness reinforcing acrylate polymer/nano silicon compound particle
In, anion emulsifier used is dihexyl adipate sodium sulfonate in described step a, b, c, d.
The preparation method of above-mentioned modified polycarbonate toughness reinforcing acrylate polymer/nano silicon compound particle
In, initiator used is potassium peroxydisulfate in the step e.
The beneficial effects of the invention are as follows：
For fragility and half fragility polar plas, generally using modifying agent of the 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 use requirement can not be still met in extremely frigid zones.The present invention uses third
Olefin(e) acid -2- ethyls monooctyl ester is used 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 the condensation product (discarded object) that polymerization process is produced excessively as emulsifying agent,
Use 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 is used 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 made into after initiator solution and be at the uniform velocity added dropwise, last rank
Section is 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 is improved, and simplifies the last handling process of residual monomer in emulsion polymeric product.Nano silicon is uniform
It is dispersed in acrylate polymer emulsion, obtained modifying agent had both possessed the nano-meter characteristic of nano silicon to makrolon
Matrix plays significant enhancing effect, and the characteristic but also with acrylate polymer plays significant low temperature to polycarbonate matrix
Toughening effect.With the acrylate polymer prepared by the present invention/nano silicon compound particle come modified polycarbonate, add
The acrylate polymer for plus 1.96%/nano silicon compound particle can just significantly improve polycarbonate matrix material
Toughness, the purer makrolon of low temperature notched impact strength of composite improves 377%, and fracture elongation is improved
298%, while tensile strength adds 157%, obtain and the unexpected toughness reinforcing of polycarbonate matrix resin and enhancing are imitated
Really.
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 pure makrolon, comparative example and embodiment 1-9 acrylate polymers/nano silicon compound particle
The tensile strength and low temperature notched impact strength graph of a relation of modified polycarbonate composite.
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；15g acrylic acid-2-ethyl monooctyl ester monomers and 0.04g crosslinking agents are added into reactor again
BDO diacrylate, and be placed on mixing 20 minutes in electromagnetic agitation, that is, seed monomer pre-emulsion is obtained, it is standby
With；
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.81g anion emulsifier dihexyl adipates sodium sulfonate, 145g acrylic acid-2-ethyl monooctyl ester monomers and
0.73g crosslinking agent BDO diacrylates are added in 400ml beakers, are then placed within electromagnetic agitation and are mixed
20 minutes, that is, second layer 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 1.0g 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 silicon
1.20g nano silicons (10~20nm), 0.012g dihexyl adipates sodium sulfonate and 50g deionized waters are added
Enter into 400ml beakers, be placed in electromagnetic agitation and mix 60 minutes, that is, obtain the pre-emulsion of nano silicon, it is standby
With；
E. the preparation of acrylic acid ester emulsion
Nitrogen displacement is used in the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing three times, to remove
Oxygen, realizes the inert atmosphere of system；Then proceed to be passed through and lead to condensed water in nitrogen, condenser, will reaction under stirring
Thing is warming up to 78.5 DEG C, after temperature is constant, and constant pressure funnel continuously and smoothly instills 1,10 points of 20.33g initiator solutions
Clock completion of dropping；Continue after reacting 50 minutes, the Seeded polymerization stage terminates.Then it is first with identical speed into reaction system
The step c of continuously and smoothly's dropwise addition immediately is added dropwise after stratum nucleare build phase monomer pre-emulsion made from b step, completion of dropping in continuously and smoothly
Obtained outer layer monomer pre-emulsion, two kinds of monomer pre-emulsions are and same at this 180 minutes in 180 minutes continuously and smoothly's completion of dropping
When continuously and smoothly 30.25g initiator solutions 2 are added dropwise；Afterwards, insulation reaction 120 minutes, then be down to room temperature；Step d is made
Nano silicon pre-emulsion be added under agitation in the emulsion of above-mentioned preparation, stir 30 minutes, obtain acrylate gather
Compound/nano silicon compound particle；Finally by the compound particle of preparation is chilled, washing, suction filtration, drying and other steps obtain
Acrylate polymer with hybrid structure/nano silicon compound particle.
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 sampled 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 size, 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 after emulsion (wet combustion cup quality), 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' is to ith sampling
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, MsTo plant
The amount of monomer that sub-stage is added, MtThe amount of monomer added for t, I is the instantaneous conversion rate of t.
Agglomerated thing cubage formula is as follows：
In formula：W' is the gross mass of agglomerated thing and beaker before drying, and w is the gross mass of agglomerated thing and beaker after drying, w0
For the gross mass of acrylic ester monomer used in formula.
(2) polycarbonate composite material
By the acrylate polymer of preparation/nano silicon compound particle, makrolon and acrylate polymer
After being dried in vacuo 12 hours at 80 DEG C respectively, in mass ratio 2:100 mix, and are produced through Nanjing Ke Ya extrusion machineries research institute
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 wide 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 is 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 step be the same as Examples 1, but a step seed stages emulsifying agent 1 used, Step d nanometer two in embodiment 2~9
The change of siliconoxide mass and the mass of emulsifying agent 2, 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；15g acrylic acid-2-ethyl monooctyl ester monomers and 0.04g crosslinking agents are added into reactor again
BDO diacrylate, and be placed on mixing 20 minutes in electromagnetic agitation, that is, seed monomer pre-emulsion is obtained, it is standby
With；
B. the pre-emulsification of stratum nucleare build phase monomer
By 1.81g anion emulsifier dihexyl adipates sodium sulfonate, 145g acrylic acid-2-ethyl monooctyl ester monomers and
0.73g 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 1.0g 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 acrylic acid ester emulsion
Nitrogen displacement is used in the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing three times, to remove
Oxygen, realizes the inert atmosphere of system；Then proceed to be passed through and lead to condensed water in nitrogen, condenser, will reaction under stirring
Thing is warming up to 78.5 DEG C, after temperature is constant, and initiator solution 1 is added dropwise in 10 minutes continuously and smoothlies, continues to react 50 minutes
Afterwards, the Seeded polymerization stage terminates.Then into reaction system, stratum nucleare build phase list made from b step is added dropwise in continuously and smoothly
Outer layer monomer pre-emulsion made from body pre-emulsion and step c, two kinds of monomer pre-emulsions in 180 minutes continuously and smoothly's completion of dropping,
And initiator solution 2 was added dropwise in continuously and smoothly simultaneously at this 180 minutes；Afterwards, insulation reaction 120 minutes, then be down to room temperature；Most
Afterwards by the emulsion of preparation is chilled, washing, suction filtration, 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, these acrylate polymer/nanometers
The mechanical property of silica dioxide composite particles and polycarbonate composite material 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 silicon 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 90% in embodiment 1, illustrate that the monomer added is largely polymerize
Reaction, that is, monomeric species, the addition of initiator and the polymeric reaction temperature three added are matchings, and this is to emulsion particle
The control of particle diameter is also important.If in the monomer newly added, unreacted content of monomer is high, easily in emulsion system
New micella is formed, causes the monomer newly added to fail completely in former emulsion particle superficial growth.Fig. 2 is the acrylate of embodiment 1
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 it is (anti-
Answer 60 minutes) on the basis of, during at interval of reacting 30 minutes, calculate obtained emulsion particle Theoretical Grain Size and actual measurement particle diameter basic one
Cause, illustrate without new micelle formation, the monomer newly added grows in former emulsion particle surface aggregate；And added in monomer into
It is also suitable to emulsify dosage.If newly add monomer in add into emulsification dosage it is too low, emulsion particle is easily demulsified, and causes
Condensation product content is raised；And add into emulsifier content it is too high, then can generate new micella, make the particle diameter of the emulsion particle of growth
It is uncontrollable.Table 2 is the polymerization parameter of each embodiment acrylate polymer.As shown in Table 2, with seed stage emulsifier
Increase, in the case where adding identical seed monomer, the micella number of generation increases, and causes the particle diameter of emulsion particle to diminish, such as
Embodiment 1~5.When the inorganic filler in polymeric matrix reaches that nanometer scale is disperseed, the nano composite material of formation
The performances such as mechanics show the huge difference with traditional material.Nano silicon random dispersion is in acrylate polymer emulsion
In, nano silicon realizes uniform mix with polymer.Greatly compare surface because nano silicon dispersed phase has
Product, is combined closely with matrix, is preferable reinforcing profile with the physical and mechanical property more excellent than conventional composites materials
Material.Table 3 and Fig. 3 are multiple with mass ratio 2/100 for the acrylate polymer/nanometer silica composite and makrolon prepared
The mechanical property of condensation material.Comparative example is free from the conventional acrylic ester polymer and poly- carbonic acid of nano silicon nano-dispersed
The mechanical property of ester blend, low temperature toughness reinforcing improves more, but tensile property declines.And the acrylate polymer prepared/receive
The low temperature notched impact strength and tensile strength of rice silica composite and polycarbonate composite material are obtained for significantly
Improve, see embodiment 1~9 and Fig. 3；The result of wherein embodiment 1 is：The purer poly- carbon of low temperature notched impact strength of composite
Acid esters improves 377%, and fracture elongation improves 298%, and the increasing of the purer makrolon of tensile strength of composite
Add 157%.It these results suggest that, acrylate polymer/nanometer silica composite prepared by the present invention is to poly- carbon
Acid esters has significant low temperature toughening effect, and improves the tensile property that makrolon is used as engineering plastics, realizes same
Shi Zengren and enhanced purpose.
Unaccomplished matter of the present invention is known technology.
Claims (1)
1. a kind of makrolon toughness reinforcing preparation method of acrylate polymer/nano silicon compound particle, its feature
To 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 15
Crosslinking agent 0.04
Matched more than, emulsifying agent and deionized water are added into reactor, and mix；Add esters of acrylic acid list
Body 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 1.56 ~ 1.81
Acrylic ester monomer 125 ~ 145
Crosslinking agent 0.42 ~ 0.73
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 is accounted for
The 1.6%-2.5% of esters of acrylic acid mix monomer；
D. the pre-emulsification of nano silicon
Composition mass fraction
Nano silicon 0.5 ~ 2.5
Emulsifying agent 0.004 ~ 0.020
Deionized water 50
Above-mentioned nano silicon, emulsifying agent and deionized water are put into the 3rd container, mixes, that is, obtains nanometer two
The pre-emulsion of silica, 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；
Crosslinking agent is 1,4 butanediol diacrylate in step a, b；
E. the preparation of acrylate polymer/nano silicon compound particle
Nitrogen displacement is used in the reactor that internal layer seed monomer pre-emulsion is filled to a steps, after vacuumizing three times；Then proceed to lead to
Enter and lead to condensed water in nitrogen, 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 the first continuously and smoothly of identical speed 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 in 180 minutes continuously and smoothly's completion of dropping, and at this 180 points
Initiator solution 2 is added dropwise in continuously and smoothly to clock simultaneously；Afterwards, insulation reaction 120 minutes, then be down to room temperature；By made from Step d
Nano silicon pre-emulsion is added in the emulsion of above-mentioned preparation and stirred 30 minutes, obtains acrylate polymer/nanometer two
Silica compound particle；Finally by the compound particle of preparation is chilled, washing, suction filtration, drying steps obtain makrolon toughness reinforcing
With acrylate polymer/nano silicon 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 silicon pre-emulsion=（165.75~165.95）：（126.98~147.54）：（40.80~61.20）：（50.504
~52.520）；
Initiator used is persulfate, is added in the way 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：（160.75~
160.95）： 30.25；
Anion emulsifier used is dihexyl adipate sodium sulfonate in described step a, b, c, d；
Initiator used is potassium peroxydisulfate in the step e.
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| CN108264765B (en) * | 2018-01-23 | 2020-04-28 | 河北工业大学 | Preparation method of toughened heat-conducting insulating cyanate resin-based composite material |
| CN111057359B (en) * | 2019-12-11 | 2022-03-04 | 宁波多普达聚合物有限公司 | CNT (carbon nanotube) composite branched acrylate with core-shell structure and weather-resistant antistatic low-temperature-resistant polycarbonate material |
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