CN102702423B - The polybutylene terephthalate toughening modifying preparation method of acrylic ester copolymer latex particle - Google Patents
The polybutylene terephthalate toughening modifying preparation method of acrylic ester copolymer latex particle Download PDFInfo
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Abstract
The present invention is a kind of preparation method of polybutylene terephthalate toughening modifying acrylic ester copolymer latex particle, and the method comprises the following steps: the preparation of (a) seed pre-emulsion; The preparation of (b) nuclear layer monomer pre-emulsion; The preparation of (c) shell monomers pre-emulsion; The preparation of (d) acrylic ester emulsion.The method adopts methacrylic acid (MAA) as function monomer, thus a kind of novel nucleocapsid structure copolymer latices particle toughening agent of emulsion synthesize.The present invention adopts redox method to have the latex particle of nucleocapsid structure by the synthesis of seed semi-continuous emulsion polymerization method, function monomer methacrylic acid on latex particle is surface and copolymerized, about 20 DEG C can be reduced with adopting merely polymerization temperature compared with thermal decomposition initiating system, notched Izod impact strength notched Izod impact strength compared with before of the PBT after blended improves about 25%, and notched Izod impact strength improves about 50%.
Description
Technical field
The present invention relates to the preparation method of polybutylene terephthalate toughening modifying acrylic ester copolymer latex particle, belong to engineering plastic modification field.
Background introduction
Polybutylene terephthalate (PBT) is the linear saturated engineering materials of a kind of high crystal type.To take PBT as the thermoplastic polyester engineering plastics of representative be continues the important engineering plastics of the later another class of nylon (PA), yuban (POM), polycarbonate (PC) and polyphenyl ether modified thing (MPPO), PBT realizes industrialization, expects that dominant position is occupied in field in thermoplastic engineering.PBT has outstanding over-all properties, and as good mechanical performance, physical strength is high, creep is less; Weathering resistance is good, excellent fireproof performance; High and the crystallization velocity of degree of crystallinity is fast, and these performances are less by temperatures involved.PBT relies on the performance of these excellences to be widely used in the fields such as electronic apparatus, automotive industry and machinery, instrument and household electrical appliance.But PBT has high crackle as tough matrix causes energy and lower crack growth energy, so its unnotched impact strength is very high, and notched Izod impact strength is lower.But PBT shock strength is low and toughness is not enough, is still a kind of obstacle in actual applying.Not only have high intensity, unnotched impact strength in actual use as structured material, also will have higher restraining effect to the development of indentation, there crackle, this also just requires that PBT will have higher shock strength could meet further requirement of engineering.So carry out to PBT the integral part that toughening modifying is the research contents of its high performance always.
At present, be used for the method for modified PBT be mostly adopt polyolefine or rubber elastomer directly blended with it, the form of PBT/HDPE blend and PBT/HDPE-g-MAH blend and performance as people's comparative studies such as Qi, find when HDPE-g-MAH consumption reaches 10%, the notched Izod impact strength of blend is 6.5KJ/m
2, be approximately 1.3 times of pure PBT/HDPE blend.This directly blended method accomplishes to control the dispersion [QiRR of plasticized modifier in matrix resin, NieJG, ZhouCX, etal.Influenceofhighdensitypolyethylene-g-maleicanhydrid eoncompatibilityandpropertiesofpoly (butyleneterephthalate)/highdensitypolyethyleneblends [J] .JournalofAppliedPolymerScience, 2006,102 (6): 6081-6087].Report is had to adopt the latex particle properties-correcting agent of nucleocapsid structure carry out toughness reinforcing PBT and obtain good toughening effect in recent years, as: the people such as Yang and this laboratory Qu grandness wait the synthesis of people's emulsion polymerization with the positive butyl ester of polyacrylic acid for stratum nucleare, polymethylmethacrylate is shell, and carrys out toughness reinforcing PBT at " core-shell structure copolymer " type properties-correcting agent [ACR (acrylic acid esters co-polymer)-g-GMA] of shell graft glycidyl methacrylate (PBA/PMMA-g-GMA); The people such as the Qu Xiongwei different GMA that utilized oxide-reduction method to investigate and different linking agent add-on are on the impact of the mechanical property of the PBT after blended, and result makes the shock strength of blended rear PBT than pure PBT(2.82kJ/m
2) improve about 20 times and 17 times respectively.[1HYang, KCho.Surfacemodificationeffectsofcore-shellrubberparticl esonthetougheningofpoly (butyleneterephthalate) [J] .JournalofAppliedPolymerScience, 2010,116 (4): 1948-1957; 2 Qus are grand, Li Yanmin, Wang Nongyue, etc. a kind of preparation method [P] of polybutylene terephthalate toughening modifying acrylate copolymer emulsion. Chinese patent: 102351977A, 2012-02-15.].But in emulsion synthesize process, adopt single thermal decomposition initiating, emulsion synthesize temperature is relatively high, and GMA and matrix blended time epoxide group open loop relative consistency play a part very important, previous research and also do not investigate nucleocapsid mass ratio and seed stage emulsifier to the impact of blended rear PBT performance.Today save energy and reduce the cost environmental protection overall situation under, shown its deficiency this class methods day.This patent method not only have employed oxide-reduction method, and sought a kind of novel functional monomer methacrylic acid, and investigate different IPs shell mass ratio and seed stage emulsifier to the impact of blended rear PBT performance, the shock strength of modified PBT is improved greatly.
Summary of the invention
The object of the invention is to for present emulsion synthesis power consumption high, heavy-polluted problem, the preparation method of a kind of novel acrylic ester copolymer latices particle of polybutylene terephthalate toughening modifying is proposed, the process employs methacrylic acid (MAA) as function monomer, thus a kind of novel nucleocapsid structure copolymer latices particle toughening agent (PBMMA) of emulsion synthesize, the method not only reduces synthesis temperature, and the consistency of toughner and PBT is had further raising, different IPs shell mass ratio and seed stage emulsifier are meanwhile investigated to the impact of blended rear PBT performance, result significantly improves the notched Izod impact strength of matrix resin.
Technical scheme of the present invention is:
A preparation method for polybutylene terephthalate toughening modifying acrylic ester copolymer latex particle, comprises the following steps:
A. the preparation of seed pre-emulsion
Material composition and proportioning are:
First, reactor nitrogen purge 20min, in reactor, then add the emulsifying agent of afore mentioned rules quality, oxygenant and deionized water, and mix and blend 20min under nitrogen protection; Add the acrylic ester monomer of afore mentioned rules quality more wherein, and mix and blend 10min, namely obtain seed pre-emulsion, for subsequent use.
B. the preparation of nuclear layer monomer pre-emulsion
Material composition and proportioning are:
Above-mentioned composition is all added in container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain nuclear layer monomer pre-emulsion, for subsequent use.
C. the preparation of shell monomers pre-emulsion
Shell material I forms and proportioning is:
Composition mass fraction
Emulsifying agent 0.13
Methyl methacrylate 10 ~ 50
Above-mentioned composition is all added in another container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain shell monomers pre-emulsion I, for subsequent use;
Shell material II forms and proportioning is:
Above-mentioned composition is all added in another container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain shell monomers pre-emulsion II, for subsequent use.
D. the preparation of acrylic ester emulsion
Carry out in polyreaction reactor under nitrogen protection, temperature controls at 63 DEG C ± 1 DEG C, and stir speed (S.S.) controls at 150 ~ 250 revs/min; First in the seed pre-emulsion of gained in step a, pass into nitrogen, dispersed with stirring 10min under 50 DEG C of water-baths, add the first time reductive agent aqueous solution, wherein quality proportioning seed pre-emulsion: the first time reductive agent aqueous solution=150.37 ~ 150.87:5, regulate temperature to 63 DEG C ± 1 DEG C, enter reaction, in flask, after reaction 30min, add the second time reductive agent aqueous solution of same mass fraction, after continuing reaction 30min, namely obtain seed emulsion; Then in the seed emulsion obtained, at the uniform velocity drip nuclear layer monomer pre-emulsion obtained in step b and the third time reductive agent aqueous solution simultaneously, carry out stratum nucleare growth, add-on is quality proportioning seed pre-emulsion: nuclear layer monomer pre-emulsion: the reductive agent aqueous solution=150.37 ~ 150.87:112.89 ~ 153.49:27.5 ~ 37.5 for the third time; After nuclear layer monomer pre-emulsion dropwises, at the uniform velocity drip obtained shell monomers pre-emulsion I and the 4th time reductive agent aqueous solution of step c in emulsion simultaneously, add-on is quality proportioning is seed pre-emulsion: shell monomers pre-emulsion I: the four the reductive agent aqueous solution=150.37 ~ 150.87:10.13 ~ 50.13:2.5 ~ 12.5, carry out shell growth, so far, 60min when dropping nuclear layer monomer pre-emulsion, shell monomers pre-emulsion I share; Shell monomers pre-emulsion II and the 5th time reductive agent aqueous solution that step c is obtained is at the uniform velocity dripped the while of last, add-on is quality proportioning seed pre-emulsion: shell monomers pre-emulsion II: the five the reductive agent aqueous solution=150.37 ~ 150.87:31.99 ~ 34.02:10, proceed shell to increase, this step needs titration 15min, afterwards, be incubated 1 hour again, be down to 40 DEG C of dischargings, must have poly-(butyl acrylate/methyl methacrylate-co-methacrylic acid) of nucleocapsid structure, i.e. PBMMA latex particle.
E. last refrigerator-freezer of being put into by obtained core-shell polymer carries out breakdown of emulsion in freezing 12 hours, obtains powdery granule after washing, drying.
F. get the copolymer powder that step obtains, then add the PBT resin of its 5 times of quality, blending extrusion on the twin screw extruder under the barrel temperature of 170 DEG C-245 DEG C, screw speed is certain, after pelletizing, drying, and injection moulding on injection moulding machine.
The concrete quality of above material is not limitation of the invention, in actual production, expands according to desired product amount or reduces according to above-mentioned mass ratio entirety.
In above-mentioned steps a, b, c, anionic emulsifier used is dodecyl Biphenyl Ether sodium sulfonate.
In above-mentioned steps b, linking agent used is the mixture of allyl methacrylate(AMA) and 1,4 butanediol diacrylate, and mass ratio is 1:4.
Acrylic ester monomer used in above-mentioned steps a, b is n-butyl acrylate.
Oxygenant used in above-mentioned steps a is Potassium Persulphate, and in steps d, reductive agent used is aqueous solution of sodium bisulfite, and wherein the mass ratio of sodium bisulfite and deionized water is 0.156:60.
The invention has the beneficial effects as follows: adopt redox method to have the latex particle of nucleocapsid structure by the synthesis of seed semi-continuous emulsion polymerization method, function monomer methacrylic acid on latex particle is surface and copolymerized, thus make it carry out melt blending as properties-correcting agent and PBT to reach better consistency, redox initiation system can reduce about 20 DEG C with adopting merely polymerization temperature compared with thermal decomposition initiating system, thus both obtained well toughness while also reach energy-saving and cost-reducing green benefit.Notched Izod impact strength notched Izod impact strength compared with before of the PBT after wherein blended is the highest improves about 50%.
Accompanying drawing explanation
Fig. 1 is the variation diagram of particle diameter with the reaction times of the acrylate copolymer latex of embodiment 1.
Fig. 2 is the dynamic light scattering grain size distribution (the ZetasizerZS90 dynamic light scattering test with Malvern company of Britain) of the final emulsion of embodiment 1.
Fig. 3 is that core-shell structure copolymer is than the influence curve of consumption to PBT/PBMMA blend mechanical property.
Fig. 4 is the influence curve of stratum nucleare emulsifier to PBT/PBMMA blend mechanical property.
Embodiment
Embodiment 1
A. the preparation of seed pre-emulsion
First, in 500ml four-hole boiling flask, first lead to nitrogen purge 20min, add 0.10g anionic emulsifier dodecyl Biphenyl Ether sodium sulfonate, 140g deionized water and 0.27g Potassium Persulphate and mix and blend 20min; 10g n-butyl acrylate is added again in reaction flask, and mix and blend 10min, namely obtain seed pre-emulsion, for subsequent use.
B. the preparation of nuclear layer monomer pre-emulsion
Mixed cross-linker and the 150g n-butyl acrylate of 1.89g anionic emulsifier dodecyl Biphenyl Ether sodium sulfonate, 0.27g allyl methacrylate(AMA) and 1.08g1,4-butylene glycol diacrylate is added in 500ml beaker, and mix and blend 20min; Namely nuclear layer monomer pre-emulsion is obtained; Leave standstill after pre-emulsion is obtained, for subsequent use.
C. the preparation of shell monomers pre-emulsion
Get the beaker of 1 50ml, 0.13g anionic emulsifier dodecyl Biphenyl Ether sodium sulfonate, 10g methyl methacrylate are added in beaker, is then placed on mix and blend 20min on magnetic stirrer, namely obtains shell monomers pre-emulsion I; Leave standstill after pre-emulsion is obtained, for subsequent use;
Get the beaker of 1 50ml, 0.39g anionic emulsifier dodecyl Biphenyl Ether sodium sulfonate, 30g methyl methacrylate and 1.6g methacrylic acid are added in beaker, then be placed on mix and blend 20min on magnetic stirrer, namely obtain shell monomers pre-emulsion II; Leave standstill after pre-emulsion is obtained, for subsequent use.
D. the preparation of acrylic ester emulsion
Sodium bisulfite used is reduction initiator; 0.156g sodium bisulfite is joined in 60g deionized water, and abundant dissolving makes the reductive agent aqueous solution on magnetic stirrer.
Polyreaction is equipped with in the 500ml four-hole boiling flask of agitator, thermometer, constant pressure funnel under nitrogen protection carries out; four-hole boiling flask is placed in water bath with thermostatic control; temperature controls at 63 DEG C ± 1 DEG C by thermostat, and stir speed (S.S.) is by stirring governor control at 150 revs/min.First in the seed pre-emulsion 150.37g of gained in step a, pass into nitrogen, dispersed with stirring 10min under 50 DEG C of water-baths, add the 5g reductive agent aqueous solution and regulate bath temperature to 63 DEG C ± 1 DEG C, enter the seeding polymerization stage, the seeding polymerization stage adds the 5g reductive agent aqueous solution after carrying out 30min in flask, and after continuing reaction 30min, the seeding polymerization stage terminates and obtains seed emulsion.After the seeding polymerization stage terminates, the nuclear layer monomer pre-emulsion 153.39g in the seed emulsion of preparation simultaneously at the uniform velocity obtained by dropping step b and reductive agent aqueous solution 37.5g carries out stratum nucleare growth; After nuclear layer monomer pre-emulsion dropwises, at the uniform velocity drip 10.13g shell monomers pre-emulsion I and the 2.5g reductive agent aqueous solution prepared by step c in emulsion simultaneously, carry out shell growth, 60min when titration nuclear layer monomer pre-emulsion and shell monomers pre-emulsion I share; At the uniform velocity drip the obtained 31.99g shell monomers pre-emulsion II of step c and the 10g reductive agent aqueous solution while of last, proceed shell and increase, this step titration needs to carry out 15min, afterwards, be incubated 1 hour again, be down to 40 DEG C of dischargings, the PBMMA latex particle of nucleocapsid structure must be had.
E. last refrigerator-freezer freezing (-15 DEG C) of being put into by obtained core-shell polymer carries out breakdown of emulsion in 12 hours, obtains powdery granule after washing, drying.
F. the copolymer powder 80g that step obtains is got, add 400gPBT resin again, blending extrusion in the TE-34 type twin-screw mixer extruder group that extrusion machinery institute produces, forcing machine each district temperature is set as 227 DEG C, 235 DEG C, 243 DEG C, 245 DEG C, 245 DEG C, 240 DEG C respectively, screw speed is 245 revs/min, by the injection moulding on injection moulding machine after pelletizing, drying of gained blend, injection moulding machine each section of temperature is 235 DEG C, 240 DEG C, 245 DEG C and 240 DEG C, and screw in injection molding machine rotating speed is 45 revs/min.
Embodiment 2 ~ 6 concrete steps are with embodiment 1, but core-shell structure copolymer is than different in embodiment 2 ~ 6,10g n-butyl acrylate wherein in the middle of a step is constant, and the n-butyl acrylate in the middle of b step becomes 140g, 130g, 120g, 110g, 100g respectively, in c step, methyl methacrylate becomes 20g, 30g, 40g, 50g, 60g respectively, function monomer 1.6g methacrylic acid becomes 2.0g, 2.4g, 2.8g, 3.2g, 3.6g respectively, and its consumption and latex particle polymerization parameter are as table 1.
Embodiment 7 ~ 11 concrete steps are with embodiment 1, and during interim embodiment 7 ~ 11:a walks, stratum nucleare emulsifier becomes 0.2g, 0.3g, 0.4g, 0.5g, 0.6g respectively from 0.1g, and its consumption and latex particle polymerization parameter are as table 2.
The different nucleocapsid of table 1 is than consumption single factor test latex particle polymerization process parameter
Table 2 different emulsifiers consumption latex particle polymerization process parameter
The test of gained latex particle performance:
As can be seen from table 1 and 2: nucleocapsid changes from 80/20 ~ 55/45 than consumption, emulsifier is changed by 0.1 ~ 0.6g, final conversion of monomer is all more than 98%, polydispersity index (PDI) <0.061 of latex particle size, aggregation content <1.06%, this illustrates that letex polymerization monomer conversion is very high, and latex particle system is comparatively stable.
Also can be found out by Fig. 1 and Fig. 2, it is basically identical with theoretical value that the particle diameter of the emulsion particle in example 1 increases measured value, and size distribution is very narrow, and illustrates that particle diameter growth controls better, latex particle does not have offspring to generate in being polymerized.
The test of blend material mechanical property
Carried out stretching and shock test by the balance weight impact testing machine of obtained batten at Shenzhen City Xinsansi Metering Technology Co., Ltd model to be CMT6104 microcomputer controlled electronic universal tester and model be ZBC-4, test-results as shown in Figures 3 and 4.
Fig. 3 is that different nucleocapsid is than the influence curve of consumption to the mechanical property of body material, as can be seen from Figure 3, nucleocapsid ratio is 75/25, and emulsifying agent is 0.1g, when methacrylic acid is 1.6g, the notched Izod impact strength of PBT/PBMMA blend is than pure PBT (2.80KJ/m
2) improve about 25 times.
Fig. 4 is that stratum nucleare different emulsifiers consumption is to the influence curve of the mechanical property of body material, as can be seen from Figure 4, emulsification dosage is 0.3g, when nucleocapsid ratio is 80/20, when methacrylic acid is 1.6g, the notched Izod impact strength of blend reaches maximum value, it is about 30 times of pure PBT, and the tensile strength of blend declines few, show the latex particle better performances of testing synthesis, higher tensile strength can be kept while raising PBT notched Izod impact strength.
Notched Izod impact strength is obtained for obvious raising compared with mentioning in document before, interim blended after the notched Izod impact strength of PBT wait people with the grandness of this laboratory Qu before compared with (with its improve 20 times for benchmark): 1. nucleocapsid ratio is for 75/25, emulsifying agent is 0.1g, when methacrylic acid is 1.6g, notched Izod impact strength improves about 25%; 2. nucleocapsid ratio is 80/20, and emulsifying agent is 0.3g, and when methacrylic acid is 1.6g, notched Izod impact strength improves about 50%.Thus making the over-all properties of PBT more excellent, higher shock strength can meet further requirement of engineering, and PBT is more widely used.
Claims (1)
1. a polybutylene terephthalate toughening modifying preparation method for acrylic ester copolymer latex particle, is characterized by and comprise the following steps:
A. the preparation of seed pre-emulsion
Material composition and proportioning are:
First, reactor nitrogen purge 20min, in reactor, then add the emulsifying agent of afore mentioned rules quality, oxygenant and deionized water, and mix and blend 20min under nitrogen protection; Add the acrylic ester monomer of afore mentioned rules quality more wherein, and mix and blend 10min, namely obtain seed pre-emulsion, for subsequent use;
B. the preparation of nuclear layer monomer pre-emulsion
Material composition and proportioning are:
Above-mentioned composition is all added in container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain nuclear layer monomer pre-emulsion, for subsequent use;
C. the preparation of shell monomers pre-emulsion
Shell material I forms and proportioning is:
Composition mass fraction
Emulsifying agent 0.13
Methyl methacrylate 10 ~ 50
Above-mentioned composition is all added in another container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain shell monomers pre-emulsion I, for subsequent use;
Shell material II forms and proportioning is:
Above-mentioned composition is all added in another container, magnetic stirrer stirs 20 ~ 30min and makes it fully mix, namely obtain shell monomers pre-emulsion II, for subsequent use;
D. the preparation of acrylic ester emulsion
Carry out in polyreaction reactor under nitrogen protection, temperature controls at 63 DEG C ± 1 DEG C, and stir speed (S.S.) controls at 150 ~ 250 revs/min; First in the seed pre-emulsion of gained in step a, pass into nitrogen, dispersed with stirring 10min under 50 DEG C of water-baths, add the first time reductive agent aqueous solution, wherein quality proportioning seed pre-emulsion: the first time reductive agent aqueous solution=150.37 ~ 150.87:5, regulate temperature to 63 DEG C ± 1 DEG C, enter reaction, in flask, after reaction 30min, add the second time reductive agent aqueous solution of same mass fraction, after continuing reaction 30min, namely obtain seed emulsion; Then in the seed emulsion obtained, at the uniform velocity drip nuclear layer monomer pre-emulsion obtained in step b and the third time reductive agent aqueous solution simultaneously, carry out stratum nucleare growth, add-on is quality proportioning seed pre-emulsion: nuclear layer monomer pre-emulsion: the reductive agent aqueous solution=150.37 ~ 150.87:112.89 ~ 153.49:27.5 ~ 37.5 for the third time; After nuclear layer monomer pre-emulsion dropwises, at the uniform velocity drip obtained shell monomers pre-emulsion I and the 4th time reductive agent aqueous solution of step c in emulsion simultaneously, add-on is quality proportioning is seed pre-emulsion: shell monomers pre-emulsion I: the four the reductive agent aqueous solution=150.37 ~ 150.87:10.13 ~ 50.13:2.5 ~ 12.5, carry out shell growth, so far, 60min when dropping nuclear layer monomer pre-emulsion, shell monomers pre-emulsion I share; Shell monomers pre-emulsion II and the 5th time reductive agent aqueous solution that step c is obtained is at the uniform velocity dripped the while of last, add-on is quality proportioning seed pre-emulsion: shell monomers pre-emulsion II: the five the reductive agent aqueous solution=150.37 ~ 150.87:31.99 ~ 34.02:10, proceed shell to increase, this step needs titration 15min, afterwards, be incubated 1 hour again, be down to 40 DEG C of dischargings, must have poly-(butyl acrylate/methyl methacrylate-co-methacrylic acid) of nucleocapsid structure, i.e. PBMMA latex particle;
E. last refrigerator-freezer of being put into by obtained core-shell polymer carries out breakdown of emulsion in freezing 12 hours, obtains powdery granule after washing, drying.；
F. get the copolymer powder that step obtains, then add the PBT resin of its 5 times of quality, blending extrusion on the twin screw extruder under the barrel temperature of 170 DEG C-245 DEG C, screw speed is certain, after pelletizing, drying, and injection moulding on injection moulding machine;
In above-mentioned steps a, b, c, anionic emulsifier used is dodecyl Biphenyl Ether sodium sulfonate;
In above-mentioned steps b, linking agent used is the mixture of allyl methacrylate(AMA) and 1,4 butanediol diacrylate, and mass ratio is 1:4;
Acrylic ester monomer used in above-mentioned steps a, b is n-butyl acrylate;
Oxygenant used in above-mentioned steps a is Potassium Persulphate, and in steps d, reductive agent used is aqueous solution of sodium bisulfite, and wherein the mass ratio of sodium bisulfite and deionized water is 0.156:60.
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| CN105524210B (en) * | 2016-01-12 | 2017-07-11 | 河北工业大学 | The makrolon toughness reinforcing preparation method of multi-layered acrylic ester polymer particle |
| CN105884982B (en) * | 2016-06-27 | 2018-05-18 | 河北工业大学 | PA6/PBT blends are modified the preparation method with acrylate polymer particle |
| CN113087838B (en) * | 2021-04-27 | 2022-08-09 | 巨石集团有限公司 | Acrylate emulsion for glass fiber and preparation method and application thereof |
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