CN101649020B - Method for preparing polyacrylic ester foaming regulator with multi-layer nuclear shell structure - Google Patents
Method for preparing polyacrylic ester foaming regulator with multi-layer nuclear shell structure Download PDFInfo
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Abstract
The invention relates to a method for preparing a polyacrylic ester foaming regulation agent with a multi-layer nuclear shell structure. The method prepares an acrylic ester nuclear shell copolymer with a multi-layer nuclear shell structure, which uses an acrylic ester homopolymer as a nucleus and uses acrylic ester and a modified monomer copolymer as shells. The method comprises the following steps: a. pre-emulsifying a nuclear layer monomer; b. pre-emulsifying a shell layer monomer; c. preparing acrylic ester emulsion; finally obtaining multi-layer nuclear shell acrylic ester copolymer emulsion; freezing, washing, drying and the like to obtain acrylic ester copolymer powder with the multi-layer nuclear shell structure. The method greatly improves the plasticizing time and the fusant strength of rigid low-foaming polyvinyl chloride, is beneficial to the dispersing effect of particles in a polyvinyl chloride set and fully develops the function of plasticizing and improving the fusant strength.
Description
Technical field
Technical scheme of the present invention relates to the foaming control agent that is used for the low foamed polyvinyl chloride of hard, is specially a kind of preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure.
Background technology
The low foamed polyvinyl chloride forming materials of hard is a dynamic foaming process, requires the intensity of outside expansible pressure of gas and abscess to adapt to reach running balance during foaming.(Foaming control agent FCA) is normally made through multi-step emulsion polymerization reaction by acrylic ester monomer foaming control agent, is a kind of extra high molecular polymer, and with polyvinyl chloride good consistency is arranged.FCA can promote plasticizing, the fusion of polyvinyl chloride, improves the intensity and the ductility of foam, make foaming process stable, controlled, thereby it is even, tiny to obtain foam structure, and independence is good, the foaming product that density is lower.Abroad, the synthetic route of foaming control agent mainly contains three: the letex polymerization route of methyl methacrylate and acrylate; The letex polymerization route of vinylbenzene and vinyl cyanide; Emulsion copolymerization route [the Jean-Pierre Disson of methyl methacrylate and vinylbenzene, acrylate, SGirois, Acrylic process aids for PVC:From theoretical concepts to practical use, Journal of Vinyland Additive Technology, 9 (4): 177-187,2003].Wherein, the Blendex-590 of General Electric engineering plastics company (GE) is the multipolymer of methyl methacrylate-styrene-acrylonitrile, higher [the P H Daniels of relative molecular weight, Optimization of plastisol processes by dynamic mechanical analysis, Journal of Vinyl and AdditiveTechnology, 13 (3): 151-154,2007].At home, the foam polyvinyl chloride conditioning agent ACR K-400 of magnificent chemical industry industrial corporation development is moistened by provincial technical evaluation [Liu Zhengxi, Yin Guobao in Wenzhou, the production of foaming control agent ACR K-400 and the application in the hard PVC foaming plate thereof, additives for plastics, (4): 21-22,2004].ACR K-400 adds in the rigid polyvinyl chloride foaming plate, has improved melt strength, makes cell wall bear the bulging force of gas in the free foaming process, avoids occurring the bubble wall and breaks, and forms bulla, reduces pipe performance.But, the polymkeric substance of being studied mostly is the linear chain structure both at home and abroad, be difficult to avoid the shortcoming that foam structure is inhomogeneous and abscess subsides, and the present invention is a crosslinking structure with polymer manufacture one-tenth part, and copolymer is become multi-layer core-shell structure, the processing plasticizing performance of starting with and improving polyvinyl chloride from the polymer architecture aspect improves the melt strength of polyvinyl chloride simultaneously.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiency that the low foamed polyvinyl chloride material foaming control agent of current hard exists, provide a kind of preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure.It is that nuclear, acrylate and modified monomer multipolymer are the acrylate nucleocapsid multipolymer with multi-layer core-shell structure of shell with the Voncoat R 3310 that this method prepares a kind of.This analog copolymer can improve the melt strength of the low foamed polyvinyl chloride blend of hard effectively.
The present invention solves this technical problem the technical scheme that is adopted:
A kind of preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure, concrete steps are as follows:
A. the pre-emulsification of nuclear layer monomer
Composition quality/g
Emulsifying agent 0.5
Deionized water 140
In the 500ml four-hole boiling flask, add the emulsifying agent and the deionized water of afore mentioned rules quality, and mix and stir 20min; In reaction flask, add the acrylic ester monomer of afore mentioned rules quality again, and stir 10min, promptly obtain the nuclear layer monomer pre-emulsion, standby;
B. pre-emulsification of shell monomer
Monomer mass/g emulsifying agent quality/g
The first layer monomer pre-emulsion: 54 0.68
Second layer monomer pre-emulsion: 82 1.03
The 3rd layer of monomer pre-emulsion: 54 0.68
The mix monomer of afore mentioned rules quality and the emulsifying agent of corresponding mass are put into the beaker of 3 300ml respectively, and be placed on and mix to few 20min on the induction stirring, promptly obtain the shell monomers pre-emulsion, standby;
Monomer in the described the first layer pre-emulsion is a methyl methacrylate according to mass ratio: the mixture of butyl acrylate=46: 8; Monomer in the second layer pre-emulsion is a vinylbenzene according to mass ratio: the mixture of vinyl cyanide=54: 28; Monomer in the 3rd layer of pre-emulsion is for being methyl methacrylate according to mass ratio: the mixture of vinylbenzene=24: 30;
Used emulsifying agent is an anionic emulsifier among described step a, the b;
C. preparing acrylate emulsion
To a step fill the nuclear layer monomer pre-emulsion four-hole boiling flask in feed nitrogen, logical water of condensation is warming up to 78 ℃ under whipped state, rotating speed is controlled at 150～250 rev/mins.After treating homo(io)thermism, add initiator solution I; Add initiator solution II behind the 60min rapidly, temperature is transferred to 75 ℃ simultaneously, in reaction system, drip the first layer monomer pre-emulsion, second layer monomer pre-emulsion and the 3rd layer of monomer pre-emulsion that the b step makes then continuously, requirement dropwises from beginning to drip in the monomer pre-emulsion 180min, and add initiator solution III every 60min, the initiator solution III of equivalent adds 3 times, and wherein initiator solution is disposable adding, and the adding speed of three kinds of pre-emulsions is that identical average rate drips; Afterwards, insulation reaction 60min reduces to room temperature again, promptly obtains the multi-layer core-shell acrylate copolymer emulsion.
At last the emulsion of preparation is obtained having the acrylate copolymer powder of multi-layer core-shell structure through freezing, washing, drying and other steps.
Wherein, used initiator is a persulphate.Need in use to add deionized water, and initiator solution is made in abundant dissolving on magnetic stirrer with certain proportion.Concrete proportioning is as follows:
Quality/the g of the quality of persulphate/g water
Initiator solution I 0.44～0.14 20
Initiator solution II 0.12 10
Initiator solution III 0.051 10
The concrete quality of above material is not the qualification to invention, in the actual production, enlarges or dwindles according to above-mentioned mass ratio is whole according to the desired product amount.
Used acrylic ester monomer is a methyl methacrylate among the described step a;
Among the preparation method of above-mentioned polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure, used anionic emulsifier is a dodecyl biphenyl ether sulfonic acid sodium among described step a, the b.
Among the preparation method of above-mentioned polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure, used persulphate is a Potassium Persulphate among the step c.
The invention has the beneficial effects as follows: this method has been prepared into the partial cross-linked acrylate copolymer with multi-layer core-shell structure, has greatly improved the fusion time and the melt strength of the low foamed polyvinyl chloride of hard, and its reason is:
(1) prepares nucleocapsid structure and single particle diameter emulsion of disperseing easily by the seeded emulsion polymerization method, help the dissemination of particle in polyvinyl chloride collective, the effect of giving full play to its plasticizing and improving melt strength;
(2) second-order transition temperature of butyl polyacrylate (56 ℃) is far below room temperature, and under processing temperature, molecular motion at first takes place, and helps the plasticizing of polyvinyl chloride matrix resin;
(3) it is all inequality to have a composition of the stratum nucleare of acrylate copolymer of multi-layer core-shell structure and shell, especially it has added modified monomer in forming, each strata compound all produces different effects to polyvinyl chloride, can improve the performance of two or three contrary of polyvinyl chloride simultaneously.
(4) butyl acrylate contains the tertiary carbon hydrogen atom, in radical polymerization, living radical is easy to form crosslinking structure to the generation chain transfer reaction of butyl polyacrylate macromole, suitable crosslinked (5～8%) help further to improve the molecular weight of acrylate copolymer, thus the melt strength of raising and polyvinyl chloride.But crosslinking degree is unsuitable too high, because too high degree of crosslinking forms grit easily, does not have the effect that increases melt strength.
Description of drawings:
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is that the particle diameter of acrylate copolymer latex of embodiment 1 is with the variation diagram in reaction times.
Fig. 2 is the dynamic light scattering size distribution figure (testing the equal particle diameter of z that obtains this copolymer emulsion with the Zetasizer3000HS type microcosmic particle-size analyzer of Britain Malvern company is 443nm, and the size distribution index is 1.03) of the final emulsion of embodiment 1.
Fig. 3 is for foaming control agent outside the polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure multipolymer that adds embodiment 1 preparation, the acceding state and do not add the plasticizing capacity figure of the polyvinyl chloride blend of foaming control agent.
Embodiment
A. the pre-emulsification of nuclear layer monomer
At first, in the 500ml four-hole boiling flask, add 0.5g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium and 140g deionized water, and mix and stir 20min; In reaction flask, add the 10g methyl methacrylate again, and mix and stir 10min, promptly obtain the nuclear layer monomer pre-emulsion, standby.
B. pre-emulsification of shell monomer
Get the beaker of 3 300ml, 0.68g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 46g methyl methacrylate and 8g butyl acrylate are added in the beaker 1 successively, be placed on then and mix to few 20min on the induction stirring, promptly obtain shell the first layer monomer pre-emulsion; 1.03g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 54g vinylbenzene and 28g vinyl cyanide are added in the beaker 2 successively, place and mix to few 20min on the induction stirring, promptly obtain shell second layer monomer pre-emulsion; 0.68g anionic emulsifier dodecyl biphenyl ether sulfonic acid sodium, 24g methyl methacrylate and 30g vinylbenzene are added in the beaker 3 successively, place and mix to few 20min on the induction stirring, promptly obtain the 3rd layer of monomer pre-emulsion of shell.More than 3 layers of pre-emulsion leave standstill after making, standby.
C. preparing acrylate emulsion
Used initiator is a Potassium Persulphate.Need in use to add deionized water, and initiator solution is made in abundant dissolving on magnetic stirrer with certain proportion.Concrete proportioning is as follows:
Quality/the g of Potassium Persulphate quality/g water
Initiator solution I 0.44 20
Initiator solution II 0.12 10
Initiator solution III 0.051 10
To a step fill the nuclear layer monomer pre-emulsion four-hole boiling flask in feed nitrogen, logical water of condensation is warming up to 78 ℃ under whipped state, rotating speed is controlled at 150～250 to be changeed.After treating homo(io)thermism, add initiator solution I 20.44g; Add initiator solution II 10.12g behind the 60min rapidly, temperature is transferred to 75 ℃ simultaneously.In reaction system, drip the first layer monomer pre-emulsion 54.68g then continuously, wait to dropwise the back and continue to drip second layer monomer pre-emulsion 83.03g, drip the 3rd layer of monomer pre-emulsion 54.68g after dropwising again, require with 180min monomer pre-emulsion to be dropwised from beginning to drip the timing of the first layer monomer pre-emulsion.In the process that drips monomer pre-emulsion, from beginning to drip timing, every 60min excessively adds the initiator solution III of a said ratio, the 10.051g initiator solution III that is equivalent adds 30.153g altogether 3 times, wherein initiator solution is disposable adding, and the adding speed of three kinds of pre-emulsions is that identical average rate drips; Afterwards, insulation reaction 60min reduces to room temperature again, promptly obtains the core-shell acrylic-resin copolymer emulsion.Behind the freezing 12h of emulsion with preparation, obtain having the about 200g of acrylate copolymer powder of multi-layer core-shell structure with deionized water wash, drying at last.
Polymer characterization to preparation is as follows:
(1) latex particle size that records this emulsion with Marvlen Zetasizer 3000HS microcosmic particle size analyzer is 443nm, and the actual measurement latex particle size of differential responses time is consistent with theoretical latex particle size size, as shown in Figure 1; In addition, the latex particle size dispersion index is 1.03, as shown in Figure 2.Therefore, the latex particle particle diameter of this emulsion is controlled, and shows a monodisperse distribution.
(2) be solvent with the butanone, copolymer powder be mixed with the solution of 0.005g/ml.Utilizing the limiting viscosity of this multipolymer of dark type viscometer (one point method) qualitative test then is 1.01dl/g.
(3) press shown in the table 1, the acrylate copolymer powder that the inventive method is prepared joins blend in the low foamed polyvinyl chloride of hard, then blend is done rheology testing.The 68g blend is put into the Polylab R600 of U.S. Thermol company type moment of torsion type Haake torque rheometer, and design temperature is 175 ℃ to be tested.The result as shown in Figure 3, the fusion time of this blend is 62s, balancing torque is 14.0Nm.
Table 1 hard hangs down the foamed polyvinyl chloride mixture recipes
Concrete steps are with embodiment 1, but the concentration of used initiator potassium persulfate aqueous solution I changes among the embodiment 2～6, and are specifically as shown in table 2.
The polyacrylate dispersion of table 2 multi-layer core-shell structure prepares the prescription of initiator I among the embodiment 1～6
The parameter of acrylate polymer emulsion is listed in the table 3 in the foregoing description, these acrylic ester polymers are listed in the table 4 with the intrinsic viscosity value that Ubbelohde viscometer records after the butanone dissolving, list in the table 5 with the plasticizing capacity that records after the low foamed polyvinyl chloride blend of hard.
The parameter of the polyacrylate dispersion of table 3 multi-layer core-shell structure
The intrinsic viscosity value of table 4 multi-layer core-shell structure acrylic ester polymer
The plasticizing capacity of table 5 multi-layer core-shell acrylic ester polymer and polyvinyl chloride blend
As can be seen from Table 3, during with the polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure of this invention preparation, monomeric transformation efficiency all reaches more than 95%, and aggregation content is below 1.5%, visible monomer utilization ratio height, and reaction system is also stable.Used initiator concentration reduces successively in the embodiment of the invention 1～6, so table 4 shows the reduction along with initiator concentration, the intrinsic viscosity of acrylic ester polymer in butanone has the trend of increase.This explanation just can be controlled the molecular weight of the polymkeric substance of reaction generation to a certain extent by the control initiator concentration, thereby improves the plasticizing capacity of polyvinyl chloride blend, and the balancing torque of melt also obviously increases simultaneously.From table 5 result as can be seen, for the polyvinyl chloride blend of the acrylic ester polymer that adds multi-layer core-shell structure, its shortest fusion time can reach 51s, balancing torque reaches 16.9Nm; And we to record the fusion time of the polyvinyl chloride blend of foaming control agent PA600 outside the acceding state under the same conditions be 58s, balancing torque is 15.6Nm.The hard low foaming polypropylene acid esters foaming control agent of this explanation the present invention preparation can greatly improve the melt strength of polyvinyl chloride blend.
Claims (4)
1. the preparation method of a polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure, it is as follows to it is characterized by step:
A. the pre-emulsification of nuclear layer monomer
Composition quality/g
Emulsifying agent 0.5
Deionized water 140
Acrylic ester monomer 10
In the 500ml four-hole boiling flask, add the emulsifying agent and the deionized water of afore mentioned rules quality, and mix and stir 20min; In reaction flask, add the acrylic ester monomer of afore mentioned rules quality again, and stir 10min, promptly obtain the nuclear layer monomer pre-emulsion, standby;
B. pre-emulsification of shell monomer
Monomer mass/g emulsifying agent quality/g
The first layer monomer pre-emulsion: 54 0.68
Second layer monomer pre-emulsion: 82 1.03
The 3rd layer of monomer pre-emulsion: 54 0.68
The mix monomer of afore mentioned rules quality and the emulsifying agent of corresponding mass are put into the beaker of 3 300ml respectively, and be placed on and mix to few 20min on the induction stirring, promptly obtain the shell monomers pre-emulsion, standby;
Monomer in the described the first layer pre-emulsion is a methyl methacrylate according to mass ratio: the mixture of butyl acrylate=46: 8; Monomer in the second layer pre-emulsion is a vinylbenzene according to mass ratio: the mixture of vinyl cyanide=54: 28; Monomer in the 3rd layer of pre-emulsion is for being methyl methacrylate according to mass ratio: the mixture of vinylbenzene=24: 30;
Used emulsifying agent is an anionic emulsifier among described step a, the b;
C. preparing acrylate emulsion
Feed nitrogen in a step fills the four-hole boiling flask of nuclear layer monomer pre-emulsion, logical water of condensation is warming up to 78 ℃ under whipped state, and rotating speed is controlled at 150～250 rev/mins, treat homo(io)thermism after, add initiator solution I; Add initiator solution II behind the 60min rapidly, temperature is transferred to 75 ℃ simultaneously, in reaction system, drip the first layer monomer pre-emulsion, second layer monomer pre-emulsion and the 3rd layer of monomer pre-emulsion that the b step makes then continuously, requirement dropwises from beginning to drip in the monomer pre-emulsion 180min, and add initiator solution III every 60min, the initiator solution III of equivalent adds 3 times, and wherein initiator solution is disposable adding, and the adding speed of three kinds of pre-emulsions is that identical average rate drips; Afterwards, insulation reaction 60min reduces to room temperature again, promptly obtains the multi-layer core-shell acrylate copolymer emulsion,
Emulsion with preparation obtains having the acrylate copolymer powder of multi-layer core-shell structure through freezing, washing, drying and other steps at last,
Wherein, used initiator is a persulphate, adds deionized water, and fully initiator solution is made in dissolving, and proportioning is as follows:
Quality/the g of the quality of persulphate/g water
Initiator solution I 0.44～0.14 20
Initiator solution II 0.12 10
Initiator solution III 0.051 10
The concrete quality of above material is not the qualification to invention, in the actual production, enlarges or dwindles according to above-mentioned mass ratio is whole according to the desired product amount.
2. the preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure according to claim 1, it is characterized by acrylic ester monomer used among the described step a is methyl methacrylate.
3. the preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure according to claim 1 is characterized by that used anionic emulsifier is a dodecyl biphenyl ether sulfonic acid sodium among described step a, the b.
4. the preparation method of polyacrylic ester foaming regulation agent with multi-layer nuclear shell structure according to claim 1, it is characterized by persulphate used among the described step c is Potassium Persulphate.
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| CN101864026B (en) * | 2010-07-08 | 2011-12-14 | 河北工业大学 | Method for preparing functional acrylate copolymer emulsion for toughening nylon 6 |
| CN102417679B (en) * | 2011-11-23 | 2014-05-07 | 山东瑞丰高分子材料股份有限公司 | External lubricant for polyvinyl chloride (PVC) resin forming and processing and production method thereof |
| CN106336478B (en) * | 2016-08-30 | 2019-01-18 | 山东东临新材料股份有限公司 | The preparation method of polyvinyl chloride resin modifying agent |
| CN107674297A (en) * | 2017-09-18 | 2018-02-09 | 安徽环美刷业有限公司 | A kind of environment friendly light brush |
| CN109280123B (en) * | 2018-10-25 | 2020-04-24 | 东莞大宝化工制品有限公司 | Acrylic ester emulsion and preparation method thereof |
| CN114149549A (en) * | 2021-12-31 | 2022-03-08 | 湖南高瑞电源材料有限公司 | Core-shell emulsion and preparation method and application thereof |
| CN116144064B (en) * | 2023-04-18 | 2023-07-28 | 山东昌泰高分子材料股份有限公司 | Preparation method of ultra-high viscosity polyacrylate foaming regulator |
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| CN1944479A (en) * | 2006-10-24 | 2007-04-11 | 河北工业大学 | Poly acrylate composite emulsion for pressure' sensitive adhesive and its preparing and using method |
| CN101190994A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | Ultra-large particle diameter high-fluidity acrylic ester impact-resisting modifier for PVC |
| CN101412783A (en) * | 2008-11-27 | 2009-04-22 | 河北工业大学 | Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive |
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| CN1944479A (en) * | 2006-10-24 | 2007-04-11 | 河北工业大学 | Poly acrylate composite emulsion for pressure' sensitive adhesive and its preparing and using method |
| CN101190994A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | Ultra-large particle diameter high-fluidity acrylic ester impact-resisting modifier for PVC |
| CN101412783A (en) * | 2008-11-27 | 2009-04-22 | 河北工业大学 | Preparation of acrylic ester copolymer emulsion for pressure-sensitive adhesive |
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