CN103613713B - Be applied to the preparation method of transparent PVC goods anti-impact ACR auxiliary agent - Google Patents
Be applied to the preparation method of transparent PVC goods anti-impact ACR auxiliary agent Download PDFInfo
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- CN103613713B CN103613713B CN201310608247.7A CN201310608247A CN103613713B CN 103613713 B CN103613713 B CN 103613713B CN 201310608247 A CN201310608247 A CN 201310608247A CN 103613713 B CN103613713 B CN 103613713B
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Abstract
The invention belongs to ACR auxiliary agent preparation field, be specifically related to a kind of preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent, first prepare the stratum nucleare of ACR particle, coated shell and get final product outside the stratum nucleare of ACR particle.Present invention process is simple to operate, and energy consumption is low, and to environment without substantial pollution, by first preparing a high crosslinked nano level microballoon, duricrust of coated high glass transition temperature outside it, makes the ACR particle of high rubber phase, ensure that the shock resistance of its excellence afterwards; Owing to the addition of function monomer, make it its particle little and have the refractive index close with PVC, there is good impact and weathering resistance, fully meet the demand of outdoor transparent PVC goods.
Description
Technical field
The invention belongs to ACR auxiliary agent preparation field, be specifically related to a kind of preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent.
Background technology
Polyvinyl chloride (PVC) is one of five large resins for universal use, and raw material sources are extensive, with low cost, high comprehensive performance, be widely used, and its output is only second to the second that polyethylene (PE) occupies world's resin yield.Hard PVC has that hardness is large, rigidity and the advantage such as intensity is large, corrosion-resistant, ageing resistance is excellent, electrical insulating property is good, development in recent years is rapid, and wherein hard extruded product such as tubing, sheet material, profiled material etc. are used to replace steel, timber etc. to manufacture pipeline, building structural materials, finishing material.
The degree of crystallinity of PVC is very little, and its transparency is also fine.But it enbrittles, and heating is easily decomposed, and processing temperature, close to decomposition temperature, therefore needs adding assistant and second, third component as toughner, softening agent, stablizer etc.After having added other component like this, the transparency of PVC how is kept to be good problem to study.
Obtain transparent goods, first will have suitable raw material, wherein impurity is few, and after melting, particle is little.After adding second, third component or auxiliary agent, if dissolve each other completely, obtain homogeneous density, homogeneous specific refractory power, isotropic product, then remain transparent.If define two-phase, there are two kinds of situations can keep the transparency: one is the wavelength that the granularity of disperse phase is less than light wave; Two is that the specific refractory power of external phase and disperse phase is equal or relatively.Certainly, suitable auxiliary agent can be utilized to change the coupling of refractive index in the hope of two-phase of two-phase.In addition, require that any surface finish of goods keeps its transmittance to reduce the diffuse-reflectance of light.
Hard transparent PVC high comprehensive performance, cheap, have broad application prospects, but PVC toughness is poor, belong to hard brittle material, its melt viscosity is high simultaneously, processing characteristics is poor, for the Application Areas expanding hard transparent PVC further needs, under the prerequisite ensureing the transparency, to carry out toughening modifying to it.That general is MBS and SBS at present, and both containing double bond, and be not suitable for outdoor use.
ACR anti-impact modifier is typical core/shell polymeric particle.Be made up of different chemical or different component compounds and the composite particles with bilayer or multilayered structure formed.The fifties U.S. RohmandHaasCo. develops ACR core/shell structure type anti-impact modifier first.60 to the seventies, the company such as Japanese, German also studied the core/shell type anti-impact modifier of ACR and MBS class.Early eighties Okubo etc. proposes the new ideas of " particle design ".Up to the present, the polymkeric substance of core/shell structure is the starting point that people study always, all has made great progress in many-sides such as its synthesis, structure, form, performance, the mechanism of action, stress.
Summary of the invention
The object of this invention is to provide a kind of preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent, technological operation is simple, and energy consumption is low, to environment without substantial pollution, obtained auxiliary agent is used for PVC product, when not affecting its transparency, can improve its shock strength and weathering resistance.
The preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent of the present invention, step is as follows:
(1) prepare the stratum nucleare of ACR particle: in reaction vessel, add water, at logical nitrogen, 65-78 DEG C, interval, semicontinuous or continuous print mode add butyl acrylate, function monomer, linking agent and emulsifying agent, add initiator for reaction, preserving heat after reaction ends;
(2) coated shell outside the stratum nucleare of ACR particle: add water in step (1) product, then add methyl methacrylate and emulsifying agent, 65-78 DEG C of fully reaction, takes out breakdown of emulsion, washing, dry, to obtain final product.
Described emulsifying agent is the one in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, two dodecylphenyl ether sodium disulfonate or polyoxyethylene groups ether sodium sulfate.
Described linking agent is the one in Vinylstyrene, Ethylene glycol dimethacrylate, trimethylol propane trimethyl methyl acrylate or triallyl cyanurate.
Described function monomer is 2-phenylthio ethyl acrylate, the p-cumyl-phenoxy group of 2-() one in ethyl propylene acid esters, 2-hydroxyl-3-benzene ethoxycarbonyl propyl acrylate, ethoxyquin tetrabromo-bisphenol (8EO) diacrylate, ethoxylated bisphenol Cong (2EO) diacrylate or adjacent phenylphenoxy ethyl propylene acid esters.
Described initiator is the one in Potassium Persulphate, ammonium persulphate or hydrogen phosphide cumene.
In step (1) by percentage to the quality, in the total mass of water, butyl acrylate, function monomer, linking agent and emulsifying agent for 100%, proportioning is as follows:
The quality of the initiator described in step (1) is the 0.05-0.2% of butyl acrylate and function monomer total mass.
Temperature of reaction described in step (1) is 65-78 DEG C, and holding temperature is 35-50 DEG C, and soaking time is 1-3 hour.
The quality of the methyl methacrylate described in step (2) is the 17.5-23% of butyl acrylate, function monomer and methyl methacrylate total mass, the quality of emulsifying agent is the 0.3-1% of methyl methacrylate quality, and the quality of water is the 230-300% of methyl methacrylate quality.
Step (2) adds water in step (1) product, then add methyl methacrylate, function monomer and emulsifying agent, and 65-78 DEG C of fully reaction, takes out breakdown of emulsion, washing, dry, to obtain final product.
The quality of the methyl methacrylate described in step (2) is the 17.5-23% of butyl acrylate, function monomer and methyl methacrylate total mass, the quality of emulsifying agent is the 0.3-1% of the middle function monomer total mass of methyl methacrylate and step (2), the quality of water is the 230-300% of the middle function monomer total mass of methyl methacrylate and step (2), and the quality of function monomer is the 1-10% of the middle function monomer total mass of methyl methacrylate and step (2).
The preparation of ACR anti-impact modifier adopts the step polymerization of letex polymerization.Its advantage is can according to different needs in synthetic reaction process, control that the composition of particle, size, shell are thick, the ratio, function of surface feature etc. of shell and stratum nucleare radius, and the particle size distribution obtained is more even.
The present invention adopts water to be medium, form good emulsion phase by adding corresponding emulsifying agent, can make monomer can well-proportioned dispersion in media as well, adopt superoxide as initiator, use spraying dry carry out aftertreatment, thus obtain particle, good dispersion ground target compound.
The present invention has obvious core-shell structure copolymer bilayer structure, and outside two-phase interface, have IPN layer to exist.This is the BA containing linking agent because the first step adds, become crosslinked PBA through initiated polymerization, and the MMA that second step adds is better than PBA due to hydrophilic ability, is easy near the water surface, thus carry out on PBA surface permeating, being polymerized and IPN, final formation has the elastomerics of nucleocapsid structure.
The ACR impact modifier of gained of the present invention is typical soft-gravity die structure, " soft " in ACR impact modifying agent for core be rubber phase, " firmly " for shell be high glass transition temperature polymkeric substance, when being subject to impacting, rubber elastomer particle in system becomes stress concentration center, brings out a large amount of silver literary composition and becomes shear zone.A large amount of silver literary composition and the emergence and development of shear zone want lot of energy, absorb a large amount of striking energys and its major part is converted into heat energy to discharge and become ductile rupture, thus raising resistance to impact shock.Shell and polyvinyl chloride resin have suitable consistency, and little on the impact of the mixing effects such as its size, composition, form in the course of processing, and have good dispersiveness.
Between nucleocapsid ACR shell PMMA and PVC, there is good consistency, and between them, there is the connection of hydrogen bond, correspondingly improve the structural stability of PVC molecular chain, in addition because nucleocapsid ACR intramolecule does not exist ultraviosensitive unsaturated strong, itself have good anti-ultraviolet radiation ability, these factors all make ACR significantly improve for anti-photooxidative aging performance during PVC product.
The microcosmic particle size range of ACR impact modifier particle prepared by the inventive method is between 30-100 nanometer, and Granular composite is even.
The present invention compared with prior art, has following beneficial effect:
Present invention process is simple to operate, and energy consumption is low, and to environment without substantial pollution, by first preparing a high crosslinked nano level microballoon, duricrust of coated high glass transition temperature outside it, makes the ACR particle of high rubber phase, ensure that the shock resistance of its excellence afterwards; Owing to the addition of function monomer, make it its particle little and have the refractive index close with PVC, there is good impact and weathering resistance, fully meet the demand of outdoor transparent PVC goods.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
(1) stratum nucleare of ACR particle is prepared: in reaction vessel, add 300g water, at logical nitrogen, intermittent mode adds total amount at 70 DEG C is 160g butyl acrylate, 120g2-phenylthio ethyl acrylate and 2.3g Vinylstyrene, 1.8g sodium lauryl sulphate, add the initiation reaction of 0.22g Potassium Persulphate, reaction terminates rear 50 DEG C of insulations 1 hour;
(2) coated shell outside the stratum nucleare of ACR particle: add 165g water in step (1) product, add the pre-emulsion of 69.3g methyl methacrylate, 0.7g2-phenylthio ethyl acrylate and 0.3g sodium lauryl sulphate, 70 DEG C of fully reactions, take out breakdown of emulsion, washing, drying, both obtained target product 1.
Embodiment 2
(1) stratum nucleare of ACR particle is prepared: in reaction vessel, add 260g water, at logical nitrogen, intermittent mode adds total amount at 72 DEG C is 200g butyl acrylate, the p-cumyl-phenoxy group of 80g2-() ethyl propylene acid esters and 2.8g Ethylene glycol dimethacrylate, 2.0g sodium laurylsulfonate pre-emulsion, add the initiation reaction of 0.25g ammonium persulphate, reaction terminates rear 35 DEG C of insulations 2 hours;
(2) coated shell outside the stratum nucleare of ACR particle: add 180g water in step (1) product, add the pre-emulsion of 60.24g methyl methacrylate, 1.23g2-phenylthio ethyl acrylate and 0.4g sodium laurylsulfonate, 72 DEG C of fully reactions, take out breakdown of emulsion, washing, drying, both obtained target product 2.
Embodiment 3
(1) stratum nucleare of ACR particle is prepared: in reaction vessel, add 320g water, at logical nitrogen, intermittent mode adds total amount at 73 DEG C is 240g butyl acrylate, 40g2-hydroxyl-3-benzene ethoxycarbonyl propyl acrylate and 3.6g trimethylol propane trimethyl methyl acrylate, 2.5g Sodium dodecylbenzene sulfonate pre-emulsion, add the initiation reaction of 0.28g hydrogen phosphide cumene, reaction terminates rear 45 DEG C of insulations 3 hours;
(2) coated shell outside the stratum nucleare of ACR particle: add 200g water in step (1) product, add the pre-emulsion of 76.61g methyl methacrylate, 2.37g2-hydroxyl-3-benzene ethoxycarbonyl propyl acrylate and 0.6g Sodium dodecylbenzene sulfonate, 73 DEG C of fully reactions, take out breakdown of emulsion, washing, drying, both obtained target product 3.
Comparative example 1
Get the product W-300 of the up-to-date transparent anti-impact ACR trade mark of Japanese Zhong Yuan company.
Comparative example 2
Follow the example of the product D-510 of the up-to-date transparent anti-impact ACR trade mark of atropic company of state.
Product test: experiment test formula is in table 1, and the product index of different trade mark ACR is in table 2.
Table 1 experiment test formula
| Composition | Number (weight) |
| PVC | 100 |
| ACR | 7 |
| Processing aid | 1 |
| Organotin stabilizer | 2 |
| Lubricant | 4 |
The product index of the different trade mark ACR of table 2
Although; above the present invention is described in detail with a general description of the specific embodiments; but on basis of the present invention; can to work some amendment and improve; this will be apparent to those skilled in the art; therefore, these done without departing from theon the basis of the spirit of the present invention amendments and improvement, all belong to the scope of protection of present invention.
Claims (9)
1. be applied to a preparation method for transparent PVC goods anti-impact ACR auxiliary agent, it is characterized in that step is as follows:
(1) prepare the stratum nucleare of ACR particle: in reaction vessel, add water, at logical nitrogen, 65-78 DEG C, interval, semicontinuous or continuous print mode add butyl acrylate, function monomer, linking agent and emulsifying agent, add initiator for reaction, preserving heat after reaction ends;
(2) coated shell outside the stratum nucleare of ACR particle: add water in step (1) product, then add methyl methacrylate and emulsifying agent, 65-78 DEG C of fully reaction, takes out breakdown of emulsion, washing, dry, to obtain final product;
Described function monomer is 2-phenylthio ethyl acrylate, the p-cumyl-phenoxy group of 2-() one in ethyl propylene acid esters, 2-hydroxyl-3-benzene ethoxycarbonyl propyl acrylate, ethoxyquin tetrabromo-bisphenol (8EO) diacrylate, ethoxylated bisphenol Cong (2EO) diacrylate or adjacent phenylphenoxy ethyl propylene acid esters.
2. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, is characterized in that described emulsifying agent is the one in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, two dodecylphenyl ether sodium disulfonate or polyoxyethylene groups ether sodium sulfate.
3. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, is characterized in that described linking agent is the one in Vinylstyrene, Ethylene glycol dimethacrylate, trimethylol propane trimethyl methyl acrylate or triallyl cyanurate.
4. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, is characterized in that described initiator is the one in Potassium Persulphate, ammonium persulphate or hydrogen phosphide cumene.
5. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, to it is characterized in that in step (1) by percentage to the quality, in the total mass of water, butyl acrylate, 2-phenylthio ethyl acrylate, Vinylstyrene and sodium lauryl sulphate for 100%, proportioning is as follows:
Water 51.4%
Butyl acrylate 27.4%
Sodium lauryl sulphate 0.3%
Vinylstyrene 0.4%
2-phenylthio ethyl acrylate 20.5%.
6. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, is characterized in that the quality of the initiator described in step (1) is the 0.05-0.2% of butyl acrylate and function monomer total mass.
7. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, it is characterized in that the quality of the methyl methacrylate described in step (2) is the 17.5-23% of butyl acrylate, function monomer and methyl methacrylate total mass, the quality of emulsifying agent is the 0.3-1% of methyl methacrylate quality, and the quality of water is the 230-300% of methyl methacrylate quality.
8. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 1, it is characterized in that step (2) adds water in step (1) product, add methyl methacrylate, function monomer and emulsifying agent again, 65-78 DEG C of fully reaction, take out breakdown of emulsion, washing, dry, to obtain final product.
9. the preparation method being applied to transparent PVC goods anti-impact ACR auxiliary agent according to claim 8, the quality that it is characterized in that the methyl methacrylate described in step (2) is butyl acrylate, the 17.5-23% of function monomer and methyl methacrylate total mass, the quality of emulsifying agent is the 0.3-1% of the middle function monomer total mass of methyl methacrylate and step (2), the quality of water is the 230-300% of the middle function monomer total mass of methyl methacrylate and step (2), the quality of function monomer is the 1-10% of the middle function monomer total mass of methyl methacrylate and step (2).
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| CN104262542A (en) * | 2014-09-30 | 2015-01-07 | 山东瑞丰高分子材料股份有限公司 | Preparation method of ACR |
| CN105085774A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Transparent and environment-friendly PVC (polyvinyl chloride) modifier |
| CN105131458A (en) * | 2015-08-26 | 2015-12-09 | 安徽北马科技有限公司 | Rigid impact modifier for plastics and preparation method thereof |
| CN105086310A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Impact modifier capable of improving polyvinyl chloride processability |
| CN105086312A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Stable modifier capable of improving wear resistance and high temperature resistance of PVC (polyvinyl chloride) |
| CN105086263A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Composite toughening modifier for polyvinyl chloride |
| CN112694692A (en) * | 2020-12-25 | 2021-04-23 | 东莞市悠悠美居家居制造有限公司 | Counterpoint gold-transferring gold-covering printing film and preparation method thereof |
| CN115340637A (en) * | 2022-08-04 | 2022-11-15 | 北京化工大学 | ACR modifier, polyvinyl chloride material, and preparation method and application thereof |
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| CN101190992A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | Transparent acrylic ester impact-resisting modifier for PVC |
| CN101967251A (en) * | 2010-09-21 | 2011-02-09 | 山东日科新材料有限公司 | Polyvinyl chloride mixture with excellent transparency, impact resistance and weatherability |
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| US8986812B2 (en) * | 2007-07-09 | 2015-03-24 | 3M Innovative Properties Company | Thin microstructured optical films |
| TWI428320B (en) * | 2007-11-06 | 2014-03-01 | Sumitomo Chemical Co | Phenyl acrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190992A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | Transparent acrylic ester impact-resisting modifier for PVC |
| CN101967251A (en) * | 2010-09-21 | 2011-02-09 | 山东日科新材料有限公司 | Polyvinyl chloride mixture with excellent transparency, impact resistance and weatherability |
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