CN104693366A - Core-shell structured ACR (Acrylate) latex, modified resin powder material and preparation methods thereof - Google Patents
Core-shell structured ACR (Acrylate) latex, modified resin powder material and preparation methods thereof Download PDFInfo
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Abstract
The invention relates to the technical field of resin and discloses core-shell structured ACR (Acrylate) latex, a modified resin powder material and preparation methods thereof. The core-shell structured ACR latex is prepared from the following raw materials in parts by weight: deionized water, a core-layer comonomer, shell-layer polymer latex, a reaction initiator, a core-layer emulsifier and a cross-linking agent. The modified resin powder material disclosed by the method has the advantages that the notched impact strength, the thermal deformation resisting temperature and the ultraviolet aging resistance are better than those of the high-impact-resistance PVC (Polyvinyl Chloride) in the prior art, the production cost is reduced, and the problems of reactor sticking and coarse particles of the existing modified PVC production processes are solved; by using the PVC reinforcing action of a nano effect, the weather resistance and thermal deformation resistance of the PVC are further improved while the anti-impact modification of the PVC is improved.
Description
Technical field
The present invention relates to resin technology field, is a kind of nucleocapsid structure ACR latex, modified resin powder and preparation method thereof.
Background technology
PVC, because of the flame retardant properties of its cheap, excellent chemical resistance and uniqueness and excellent mechanical property, is widely used in the every field in national economy, its output be only second to polyethylene after second largest Plastic Resin kind.It is poor that the important defect of PVC is exactly cost performance difference and erosion-resisting characteristics, therefore around the above-mentioned shortcoming of PVC, the a lot of Special modifier relevant to PVC of exploitation, the modification of PVC has become a particular study field, wherein most study be also always continuous research be exactly that PVC is processing modified and impact-resistant modified.Current use is at most also be exactly the most successfully adopt emulsion polymerization to prepare the emulsion that stratum nucleare is the hard plastic phase that crosslinked rubber phase shell is polymethylmethacrylate, the acrylate copolymer resin (ACR) then obtained through air stream drying and butadiene-styrene grafting polymethylmethacrylate (MBS).Add at PVC and add the PVC product that ACR or MBS just can obtain having impact-resistance excellence man-hour, be widely used in door and window, tubing and other profiled materials.But because the tap density of ACR and MBS is at present all lower than hard PVC powder, and after super-dry, ACR and MBS particle aggregation, jumping from nano level one is 200 microns, therefore not only there is batch mixing problem of non-uniform man-hour adding, the more important thing is that ACR or MBS and PVC is two-phase polymer, still there is phase interface problem after processing, therefore blending method improves the impact-resistance of PVC often all along with mechanical properties decrease, and this is for being worthless as transport pipe material.The suspension polymerization of the modification of PVC from vinylchlorid is set about again by people for this reason, while needing to expect the problems such as uneven and strength degradation when energy consumption, mixing in solution because of the drying of ACR emulsion, to improving the mechanical property of PVC.The ponding company of the current U.S. and Japan all has product to come out, and current also to realize PVC impact-resistant modified competitively studying in the suspension polymerization at vinylchlorid for domestic Hebei University of Technology and a lot of company.
CN1418898 patent document discloses the preparation method of high-impact polyacrylate composite particles grafting vinyl chloride latex resin, employing acrylate monomer is main raw material, multistep seed latex method, organic agglomerant agglomeration prepare nucleocapsid structure composite particles latex, this latex and vinyl chloride monomer grafting, prepare high rush-resistant polyvinyl chloride resin by latex polymerization method.But this method composite particles latex preparation process is loaded down with trivial details, energy expenditure is large, just will can be obtained the ACR latex of greater particle size by multilayer agglomeration.And latex polymerization legal system is lower for polyvinyl chloride resin proportion, and Application Areas is restricted.As can be seen from the list of patent institute, modified PVC tensile property does not only improve, and declines to some extent on the contrary.
Current employing acrylate copolymer emulsion carries out that original position is suspension modified produces high-impact PVC, Problems existing is: the initial stage is all in the particle design continuing to use ACR emulsion, namely the outside methyl methacrylate for strong hydrophilicity is shell monomers, this emulsion is added in suspension polymerization system, because wetting ability is much larger than vinyl chloride monomer, the polyvinyl chloride resin obtained is all coarse fodders, and it is wide to distribute, cause tap density extremely low, for addressing this problem, domestic have several company then to have employed soft emulsion without hydrophilic stone layer, namely only crosslinked stratum nucleare hydrophobic is by force adopted, the different monooctyl ester of butylacrylate-acrylic acid as crosslinked is that the non-Structure of Core/shell Emulsion of monomer is as modified component, the advantage of the method does not affect suspension polymerization system, obtain particle form good, the impact-resistance of preparation is good, the color of goods is also shallow, but the notched Izod impact strength of goods, tensile strength, microcaloire softening temperature and whiteness change rate variance, it is serious that production process glues still phenomenon.
Summary of the invention
The invention provides a kind of nucleocapsid structure ACR latex, modified resin powder and preparation method thereof, overcome the deficiency of above-mentioned prior art, it effectively can solve existing modified PVC product notched Izod impact strength, tensile strength, microcaloire softening temperature and the whiteness change rate variance obtained by composite particles latex, and production cost height and production process glue the serious problem of still phenomenon.
One of technical scheme of the present invention is realized by following measures: a kind of nucleocapsid structure ACR latex, and raw materials by weight portion comprises deionized water 100 parts, stratum nucleare comonomer 35 parts to 50 parts, 10 parts to 20 parts, sheath polymers latex, reaction initiator 0.3 part to 1.0 parts, stratum nucleare emulsifying agent 0.2 part to 2.0 parts, linking agent 0.1 part to 1.0 parts.
Here is the further optimization and/or improvements to one of foregoing invention technical scheme:
Above-mentioned nucleocapsid structure ACR latex obtains as follows: the first step, in pre-emulsification still, add the stratum nucleare emulsifying agent of the deionized water of 40% to 60% of deionized water quality and 30% to 50% of stratum nucleare emulsifying agent quality and mix, add stratum nucleare comonomer and the linking agent of aequum, after stirring and emulsifying 30min to 60min, obtain pre-emulsion; Second step, in polymeric kettle, add remaining deionized water and remaining stratum nucleare emulsifying agent and mix, be warming up to 82 DEG C to 84 DEG C, the sheath polymers latex of aequum and the reaction initiator of aequum is added successively at temperature is 82 DEG C to 84 DEG C, then in polymeric kettle, drip the pre-emulsion that the first step obtains, the time for adding of pre-emulsion is 2h to 4h, is incubated 1h to 2h after pre-emulsion drips at temperature is 75 DEG C to 85 DEG C; 3rd step, is cooled to 20 DEG C to 45 DEG C after insulation, adjust ph is 7.5 to 8.0, after adjust ph, filters and obtains nucleocapsid structure ACR latex.
Above-mentioned sheath polymers latex obtains as follows: the first step, 40 parts to 60 parts deionized waters, 1.5 parts to 7.5 parts shell emulsifying agents and 30 parts to 40 parts shell comonomers is mixed by weight and obtains pre-latex; Second step, 40 parts to 60 parts deionized waters are added by weight and 3.5 parts to 7.5 parts shell emulsifying agents mix in polymeric kettle, be warming up to 70 DEG C to 90 DEG C, the reaction initiator adding 0.3 part to 1.0 parts at temperature is 70 DEG C to 90 DEG C reacts, in polymeric kettle, drip the pre-latex that the first step obtains simultaneously, the time for adding of pre-latex is 2h to 4h, after dropping, obtains sheath polymers latex after cooling, filtration.
Above-mentioned shell emulsifying agent is Sodium dodecylbenzene sulfonate; Or/and shell comonomer is the mixture that more than one and vinylbenzene in cyclohexyl methacrylate and methyl methacrylate form; Or/and reaction initiator is ammonium persulphate.
Above-mentioned stratum nucleare emulsifying agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate or reactive emulsifier SE-10N or nonionic emulsifier LCN-407; Or/and stratum nucleare comonomer is butyl acrylate or ethyl acrylate; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and linking agent is BDO dimethacrylate or Phthalic acid, diallyl ester; Or/and in the 3rd step prepared by nucleocapsid structure ACR latex, after adjust ph, 500 mesh filter screens filter and obtain nucleocapsid structure ACR latex.
Two of technical scheme of the present invention is realized by following measures: a kind of preparation method of nucleocapsid structure ACR latex, carry out in the steps below: the first step, in pre-emulsification still, add the stratum nucleare emulsifying agent of the deionized water of 40% to 60% of deionized water quality and 30% to 50% of stratum nucleare emulsifying agent quality and mix, add stratum nucleare comonomer and the linking agent of aequum, after stirring and emulsifying 30min to 60min, obtain pre-emulsion; Second step, in polymeric kettle, add remaining deionized water and remaining stratum nucleare emulsifying agent and mix, be warming up to 82 DEG C to 84 DEG C, the sheath polymers latex of aequum and the reaction initiator of aequum is added successively at temperature is 82 DEG C to 84 DEG C, then in polymeric kettle, drip the pre-emulsion that the first step obtains, the time for adding of pre-emulsion is 2h to 4h, is incubated 1h to 2h after pre-emulsion drips at temperature is 75 DEG C to 85 DEG C; 3rd step, is cooled to 20 DEG C to 45 DEG C after insulation, adjust ph is 7.5 to 8.0, after adjust ph, filters and obtains nucleocapsid structure ACR latex.
Here is the further optimization and/or improvements to foregoing invention technical scheme two:
Above-mentioned sheath polymers latex obtains as follows: the first step, 40 parts to 60 parts deionized waters, 1.5 parts to 7.5 parts shell emulsifying agents and 30 parts to 40 parts shell comonomers is mixed by weight and obtains pre-latex; Second step, 40 parts to 60 parts deionized waters are added by weight and 3.5 parts to 7.5 parts shell emulsifying agents mix in polymeric kettle, be warming up to 70 DEG C to 90 DEG C, the reaction initiator adding 0.3 part to 1.0 parts at temperature is 70 DEG C to 90 DEG C reacts, in polymeric kettle, drip the pre-latex that the first step obtains simultaneously, the time for adding of pre-latex is 2h to 4h, after dropping, obtains sheath polymers latex after cooling, filtration.
Above-mentioned shell emulsifying agent is Sodium dodecylbenzene sulfonate; Or/and shell comonomer is the mixture that more than one and vinylbenzene in cyclohexyl methacrylate and methyl methacrylate form; Or/and reaction initiator is ammonium persulphate.
Above-mentioned stratum nucleare emulsifying agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate or reactive emulsifier SE-10N or nonionic emulsifier LCN-407; Or/and stratum nucleare comonomer is butyl acrylate or ethyl acrylate; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and linking agent is BDO dimethacrylate or Phthalic acid, diallyl ester; Or/and in the 3rd step prepared by nucleocapsid structure ACR latex, after adjust ph, 500 mesh filter screens filter and obtain nucleocapsid structure ACR latex.
Three of technical scheme of the present invention is realized by following measures: a kind of modified resin powder, and raw materials by weight portion comprises deionized water 4000 parts to 5000 parts, vinyl chloride monomer 2500 parts to 3000 parts, 330 parts to 660 parts, nucleocapsid structure ACR latex, dispersion agent 5.0 parts to 15.0 parts, polymerization starter 1.25 parts to 3.5 parts, terminator 5 parts to 10 parts.
Here is the further optimization and/or improvements to foregoing invention technical scheme three:
Above-mentioned modified resin powder obtains as follows: add the deionized water of aequum and dispersion agent in a kettle. and mix, pH value is regulated to be 7.5 to 8.0, then add the nucleocapsid structure ACR latex of aequum and polymerization starter and mix, air in nitrogen replacement reactor 1 time to 3 times, add the vinyl chloride monomer of aequum after displaced air and mix and carry out polyreaction, polymerization temperature is 55.5 DEG C to 56.5 DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.
Two or more in the polyvinyl alcohol that the polyvinyl alcohol of above-mentioned dispersion agent to be model be FON-50, model are the polyvinyl alcohol of Alcotex80, model is LL02 and Vltra tears; Or/and polymerization starter is peroxy dicarbonate two (2-ethylhexyl) and the new certain herbaceous plants with big flowers acid esters of dicumyl peroxide is the mixture of 2:1 to 4:1 composition in mass ratio; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and terminator is acetone semicarbazone thiocarbamide; Or/and pressure during nitrogen replacement air in reactor is 0.3MPa.
Four of technical scheme of the present invention is realized by following measures: a kind of preparation method of modified resin powder, carry out as follows: add the deionized water of aequum and dispersion agent in a kettle. and mix, pH value is regulated to be 7.5 to 8.0, then add the nucleocapsid structure ACR latex of aequum and polymerization starter and mix, air in nitrogen replacement reactor 1 time to 3 times, add the vinyl chloride monomer of aequum after displaced air and mix and carry out polyreaction, polymerization temperature is 55.5 DEG C to 56.5 DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.
Here is the further optimization and/or improvements to foregoing invention technical scheme four:
Two or more in the polyvinyl alcohol that the polyvinyl alcohol of above-mentioned dispersion agent to be model be FON-50, model are the polyvinyl alcohol of Alcotex80, model is LL02 and Vltra tears; Or/and polymerization starter is peroxy dicarbonate two (2-ethylhexyl) and the new certain herbaceous plants with big flowers acid esters of dicumyl peroxide is the mixture of 2:1 to 4:1 composition in mass ratio; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and terminator is acetone semicarbazone thiocarbamide; Or/and pressure during nitrogen replacement air in reactor is 0.3MPa.
The modified resin powder that the present invention obtains is better compared with the notched Izod impact strength of prior art high-impact PVC, heat-resistant deformation temperature and anti-ultraviolet ageing performance, reduces production cost, solves sticky still and coarse particle problem in existing modified PVC production process; The present invention utilizes nano effect to the strengthening action of PVC, while raising PVC is impact-resistant modified, the weathering resistance of PVC, heat-resistant deforming ability is improved further again.
Embodiment
The present invention by the restriction of following embodiment, can not determine concrete embodiment according to technical scheme of the present invention and practical situation.
Embodiment 1, this nucleocapsid structure ACR latex, raw materials by weight portion comprises deionized water 100 parts, stratum nucleare comonomer 35 parts to 50 parts, 10 parts to 20 parts, sheath polymers latex, reaction initiator 0.3 part to 1.0 parts, stratum nucleare emulsifying agent 0.2 part to 2.0 parts, linking agent 0.1 part to 1.0 parts.
Embodiment 2, this nucleocapsid structure ACR latex, raw materials by weight portion comprises deionized water 100 parts, stratum nucleare comonomer 35 parts or 50 parts, 10 parts, sheath polymers latex or 20 parts, reaction initiator 0.3 part or 1.0 parts, stratum nucleare emulsifying agent 0.2 part or 2.0 parts, linking agent 0.1 part or 1.0 parts.
Embodiment 3, this nucleocapsid structure ACR latex obtains by following preparation method: the first step, in pre-emulsification still, add the stratum nucleare emulsifying agent of the deionized water of 40% to 60% of deionized water quality and 30% to 50% of stratum nucleare emulsifying agent quality and mix, add stratum nucleare comonomer and the linking agent of aequum, after stirring and emulsifying 30min to 60min, obtain pre-emulsion; Second step, in polymeric kettle, add remaining deionized water and remaining stratum nucleare emulsifying agent and mix, be warming up to 82 DEG C to 84 DEG C, the sheath polymers latex of aequum and the reaction initiator of aequum is added successively at temperature is 82 DEG C to 84 DEG C, then in polymeric kettle, drip the pre-emulsion that the first step obtains, the time for adding of pre-emulsion is 2h to 4h, is incubated 1h to 2h after pre-emulsion drips at temperature is 75 DEG C to 85 DEG C; 3rd step, is cooled to 20 DEG C to 45 DEG C after insulation, adjust ph is 7.5 to 8.0, after adjust ph, filters and obtains nucleocapsid structure ACR latex.The stir speed (S.S.) of stirring and emulsifying is 200 revs/min to 300 revs/min.
Embodiment 4, as the optimization of above-described embodiment, sheath polymers latex obtains as follows: the first step, 40 parts to 60 parts deionized waters, 1.5 parts to 7.5 parts shell emulsifying agents and 30 parts to 40 parts shell comonomers is mixed by weight and obtains pre-latex; Second step, 40 parts to 60 parts deionized waters are added by weight and 3.5 parts to 7.5 parts shell emulsifying agents mix in polymeric kettle, be warming up to 70 DEG C to 90 DEG C, the reaction initiator adding 0.3 part to 1.0 parts at temperature is 70 DEG C to 90 DEG C reacts, in polymeric kettle, drip the pre-latex that the first step obtains simultaneously, the time for adding of pre-latex is 2h to 4h, after dropping, obtains sheath polymers latex after cooling, filtration.
Embodiment 5, as the optimization of above-described embodiment, shell emulsifying agent is Sodium dodecylbenzene sulfonate (SDBS); Or/and shell comonomer is the mixture that more than one and vinylbenzene in cyclohexyl methacrylate (CHMA) and methyl methacrylate (MMA) form; Or/and reaction initiator is ammonium persulphate.
Embodiment 6, as the optimization of above-described embodiment, stratum nucleare emulsifying agent is Sodium dodecylbenzene sulfonate (SDBS) or sodium lauryl sulphate (SDS) or reactive emulsifier SE-10N or nonionic emulsifier LCN-407; Or/and stratum nucleare comonomer is butyl acrylate (BA) or ethyl acrylate (EHA); Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and linking agent is BDO dimethacrylate or Phthalic acid, diallyl ester; Or/and in the 3rd step prepared by nucleocapsid structure ACR latex, after adjust ph, 500 mesh filter screens filter and obtain nucleocapsid structure ACR latex.Wherein ethyl acrylate (EHA) is Isooctyl acrylate monomer again.
Embodiment 7, this modified resin powder, raw materials by weight portion comprises deionized water 4000 parts to 5000 parts, vinyl chloride monomer 2500 parts to 3000 parts, 330 parts to 660 parts, nucleocapsid structure ACR latex, dispersion agent 5.0 parts to 15.0 parts, polymerization starter 1.25 parts to 3.5 parts, terminator 5 parts to 10 parts.
Embodiment 8, this modified resin powder, raw materials by weight portion comprises deionized water 4000 parts or 5000 parts, vinyl chloride monomer 2500 parts or 3000 parts, 330 parts, nucleocapsid structure ACR latex or 660 parts, dispersion agent 5.0 parts or 15.0 parts, polymerization starter 1.25 parts or 3.5 parts, terminator 5 parts or 10 parts.
Embodiment 9, as the optimization of above-described embodiment, modified resin powder is pressed and is stated preparation method and obtain: add the deionized water of aequum and dispersion agent in a kettle. and mix, pH value is regulated to be 7.5 to 8.0, then add the nucleocapsid structure ACR latex of aequum and polymerization starter and mix, air in nitrogen replacement reactor 1 time to 3 times, add the vinyl chloride monomer of aequum after displaced air and mix and carry out polyreaction, polymerization temperature is 55.5 DEG C to 56.5 DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.Feed intake in reactor and react and all carry out under whipped state, stir speed (S.S.) is 200 revs/min to 300 revs/min.The shell of nucleocapsid structure ACR latex of the present invention is cyclohexyl methacrylate hydrophobic is by force the multipolymer of main body, core multipolymer is still the multipolymer of crosslinked butyl acrylate/Isooctyl acrylate monomer hydrophobic by force, and what first prepare is that then sheath polymers latex carry out solubilising polymerization and form the nucleocapsid structure ACR latex of contragradience, the present invention utilizes nano effect to the strengthening action of PVC, while raising PVC is impact-resistant modified, again the weathering resistance of PVC, heat-resistant deforming ability are improved further.The particle diameter of nucleocapsid structure ACR latex of the present invention is 80nm to 100nm, greatly improve the absorption merit of particle surface, and contain a small amount of vinylbenzene segment because of sheath polymers latex, have and can carry out grafting for vinyl chloride monomer and the very high α-H of activity, improve the consistency between rubber-plastic and bonding force, toughening effect is better; The present invention has got rid of the drying process of ACR or MBS, not only reduces facility investment, and reduces energy consumption, and this has adapted to the current urgent policy requiring low-carbon (LC) production process very much.The latex designability with ACR structure is various, by the form (character of sheath polymers of latex particle, the character of stratum nucleare polymkeric substance and the grafting ability of vinylchlorid) and size controlling, can further improve the heat-resistant deformation temperature of PVC, anti-ultraviolet ageing performance.Use reactive emulsifier to mate with conventional emulsifier and can improve seed latex in the dilution stability of resuspension procedure and the swelling stability of resistance to VC.
Embodiment 10, as the optimization of above-described embodiment, dispersion agent is two or more in polyvinyl alcohol (FON-50), polyvinyl alcohol (Alcotex80), polyvinyl alcohol (LL02) and Vltra tears (HPMC); Or/and polymerization starter is peroxy dicarbonate two (2-ethylhexyl) (EHP) and the new certain herbaceous plants with big flowers acid esters (CNP) of dicumyl peroxide is the mixture of 2:1 to 4:1 composition in mass ratio; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and terminator is acetone semicarbazone thiocarbamide (ATSC); Or/and pressure during nitrogen replacement air in reactor is 0.3MPa.
Embodiment 11: this modified resin powder is pressed and stated preparation method and obtain:
(1) preparation of nucleocapsid structure ACR latex
1. the preparation of sheath polymers latex
350g deionized water is added in three mouthfuls of round-bottomed flasks of 3L, 40g Sodium dodecylbenzene sulfonate (SDBS), high-speed stirring 10min, add 165.4g vinylbenzene (St), 165.4g cyclohexyl methacrylate (CHMA), 330.8g methyl methacrylate (MMA), high-speed stirring 30min, obtained pre-latex;
In the four mouthfuls of round-bottomed flasks being connected with spherical reflux condensing tube and stirring, add 714g deionized water, 37.5g Sodium dodecylbenzene sulfonate (SDBS), heating in water bath to temperature is 82 DEG C to 84 DEG C, adds the ammonium persulfate aqueous solution 91g that mass percent is 7% fast, start to drip obtained pre-latex, time for adding is 3h, is added dropwise to complete rear continuation and drips the ammonium persulfate aqueous solution 16.5g that concentration is 7%, time for adding 2h, after dropping, cooling, filtration obtain sheath polymers latex.
2. the preparation of nucleocapsid structure ACR latex
330.0g deionized water is added being furnished with stirring, in three mouthfuls of round-bottomed flasks of 3L that temperature takes into account addition funnel, 7.0g Sodium dodecylbenzene sulfonate (SDBS), add 1.6g allyloxy Nonylphenoxy propyl alcohol polyoxyethylene ether ammonium sulfate (SE-10N), high-speed stirring 10min, then 585.0g butyl acrylate (BA), 58.5g ethyl acrylate (EHA) and 6.5g 1 is added, 4-butyleneglycol methyl methacrylate (BGDMA), stir 30min, obtained pre-emulsion, then in the four mouthfuls of round-bottomed flasks being connected with spherical reflux condensing tube and stirring, add 467.5g deionized water, 773.8g sheath polymers latex (nucleocapsid is than being 7:3), add the sodium bicarbonate aqueous solution that mass percent is 4%, adjust ph is 6 to 8, heating in water bath is 82 DEG C to 84 DEG C to polymerization temperature in the kettle, add the ammonium persulfate aqueous solution 54.0g that mass percent is 7% fast, start to drip pre-emulsion, time for adding is 3h, insulation 1h, 20 DEG C to 45 DEG C are cooled to after being incubated, add the LCN-407 aqueous solution 15.0g that mass percent is 35%, stir 30min, adjust ph is 7.5 to 8.0, filtration obtains nucleocapsid structure ACR latex.
(2) preparation of modified resin powder
In 10L autoclave, add deionized water 5000g, 1.75g PVA (KH20) and 7g L-10 dispersion agent, stir 10min, add 335.0g nucleocapsid structure ACR latex, 3.5g EHP and 3.5g CNP initiator, nitrogen replacement air three times, displacement pressure 0.3MPa, after excluding air, add 2500g vinyl chloride monomer, stir temperature reaction, polymerization temperature controls at 55.5 DEG C to 56.5 DEG C DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds 5g to 10g terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.
Embodiment 12: difference from Example 10 is, in embodiment 11, the add-on of ACR latex is 335.1 g.
Embodiment 13: difference from Example 10 is, in embodiment 11, the add-on of ACR latex is 446.7 g.
Embodiment 14: difference from Example 10 is, in embodiment 11, the add-on of ACR latex is 558.3 g.
Embodiment 15: difference from Example 10 is, in embodiment 11, the add-on of ACR latex is 670.0 g.
Mechanics Performance Testing:
The preparation of Mechanics Performance Testing batten: after modified resin powder the above embodiment of the present invention obtained and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol prepare by table 1, mixing 5min is carried out at fast mixing machine, two rod mill roller temperature is 170 DEG C, thin-pass 12 times, slice thickness is about 1mm, residing sheet material is cut into suitable size, sulfuration is carried out at vulcanizing press, temperature is 180 DEG C, preheating 3min, under pressure 10MPa, insulation 5min, then under 10MPa, room temperature is cooled to, obtain test bars of the present invention, modified resin powder of the present invention and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol combined experiments formula are shown in Table 1.
After prior art high-impact PVC and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol are prepared by table 2, mixing 5min is carried out at fast mixing machine, two rod mill roller temperature is 170 DEG C, thin-pass 12 times, slice thickness is about 1mm, residing sheet material is cut into suitable size, sulfuration is carried out at vulcanizing press, temperature is 180 DEG C, preheating 3min, under pressure 10MPa, insulation 5min, then under 10MPa, room temperature is cooled to, obtain comparative example 1 test bars, prior art high-impact PVC and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol combined experiments formula are shown in Table 2.
Shock strength is tested: above-mentioned made sheet coupon is cut into notch shock batten by GB/T1043-2008 standard universal sampling machine, after at least placing 24h, Ceast. Co. Italy high/low temperature balance weight impact testing machine carries out shock test, and probe temperature is 25 DEG C.
Tensile property is tested: above-mentioned institute panel is cut into dumb-bell shape tensile bars by GB/T1040-2006 standard, at 25 DEG C, build UTM microcomputer controlled electronic universal tester with Chengde gold test its tensile strength, rate of extension is 50 mm/min, and probe temperature is 25 DEG C.
Microcaloire softening temperature measures: measured by GB/T1633-2000 standard by above-mentioned prepared sheet material, loading load is 10N, and thrusting the degree of depth is 1mm, temperature rise rate 50 DEG C/h.Instrument is that Chengde gold builds XRW-300 vicat softening point temperature determinator.
Anti-ultraviolet ageing performance is tested: it is a circulation in 8 hours 18 minutes that ultraviolet aging resistance carries out test condition.The first step temperature 60 C keeps 4 hours, and second step is sprayed water 18 minutes, and the then temperature 40 DEG C of condensations 4 hours of the 3rd step, the test duration is 150h.
The embodiment of the present invention 12 to embodiment 15 nucleocapsid structure ACR latex amounts is shown in Table 3; The performance test results of test bars of the present invention and comparative example 1 test bars is shown in Table 4.As can be seen from Table 4, the notched Izod impact strength of test bars of the present invention, tensile strength, microcaloire softening temperature and whiteness velocity of variation are all improved compared with the notched Izod impact strength of comparative example 1 test bars, tensile strength, microcaloire softening temperature and whiteness velocity of variation, illustrate that the notched Izod impact strength of the modified resin powder that the present invention obtains, heat-resistant deformation temperature and anti-ultraviolet ageing performance are better compared with the notched Izod impact strength of prior art high-impact PVC, heat-resistant deformation temperature and anti-ultraviolet ageing performance.
The present invention uses reverse seed emulsion polymerization, prepare the sheath polymers latex that particle diameter is less, realize the controlled of nucleocapsid structure ACR latex particle size, avoid normally first preparing stratum nucleare latex particle more coated shell multipolymer time, because stratum nucleare latex particle particle diameter is bigger than normal, to after add shell monomers adsorption reduce, size tunable reduces and the problem that broadens of size distribution; The present invention, by chemical modification method, without the need to carrying out a series of processes such as breakdown of emulsion, filtration and drying, reduces production cost; Selected and monomer hydrophilic and oleophilic Sexual behavior mode by the design of latex particle particle diameter, emulsifying agent simultaneously, solve sticky still and coarse particle problem in existing modified PVC production process.
In sum, the modified resin powder that the present invention obtains is better compared with the notched Izod impact strength of prior art high-impact PVC, heat-resistant deformation temperature and anti-ultraviolet ageing performance, reduce production cost, solve sticky still and coarse particle problem in existing modified PVC production process; The present invention utilizes nano effect to the strengthening action of PVC, while raising PVC is impact-resistant modified, the weathering resistance of PVC, heat-resistant deforming ability is improved further again.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can increase and decrease non-essential technical characteristic according to actual needs, meet the demand of different situations.
Table 1 modified resin powder of the present invention and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol combined experiments are filled a prescription
| Component | Modified resin powder of the present invention | Calcium zinc heat stabilizer | Calcium stearate | Stearyl alcohol |
| Parts by weight | 100 | 5 | 0.8 | 0.8 |
Table 2 prior art high-impact PVC and calcium zinc heat stabilizer and calcium stearate and stearyl alcohol combined experiments are filled a prescription
| Component | Prior art high-impact PVC | Calcium zinc heat stabilizer | Calcium stearate | Stearyl alcohol |
| Parts by weight | 100 | 5 | 0.8 | 0.8 |
Table 3 embodiment of the present invention 12 to embodiment 15 nucleocapsid structure ACR latex amounts
| Embodiment | Nucleocapsid structure ACR latex amounts/g of the present invention | Nucleocapsid structure ACR latex of the present invention accounts for vinyl chloride monomer per-cent/% |
| Embodiment 12 | 335.1 | 6 |
| Embodiment 13 | 446.7 | 8 |
| Embodiment 14 | 558.3 | 10 |
| Embodiment 15 | 670.0 | 12 |
The performance test results of table 4 test bars of the present invention and comparative example 1 test bars
| Embodiment | Nucleocapsid structure ACR latex of the present invention accounts for vinyl chloride monomer per-cent/% | Notched Izod impact strength/(kJ/m 2) | Tensile strength/MPa | Microcaloire softening temperature/DEG C | Whiteness velocity of variation/% |
| Embodiment 12 | 6% | 38.78 | 51.4 | 94.5 | 15.3 |
| Embodiment 13 | 8% | 42.65 | 48.3 | 93.2 | 19.4 |
| Embodiment 14 | 10% | 45.77 | 48.1 | 88.1 | 13.8 |
| Embodiment 15 | 12% | 47.98 | 47.7 | 88.30 | 12.89 |
| Comparative example 1 | Prior art high-impact PVC | 35.23 | 46.5 | 87.9 | 19.6 |
Claims (10)
1. a nucleocapsid structure ACR latex, is characterized in that raw materials by weight portion comprises deionized water 100 parts, stratum nucleare comonomer 35 parts to 50 parts, 10 parts to 20 parts, sheath polymers latex, reaction initiator 0.3 part to 1.0 parts, stratum nucleare emulsifying agent 0.2 part to 2.0 parts, linking agent 0.1 part to 1.0 parts.
2. nucleocapsid structure ACR latex according to claim 1, it is characterized in that nucleocapsid structure ACR latex obtains as follows: the first step, in pre-emulsification still, add the stratum nucleare emulsifying agent of the deionized water of 40% to 60% of deionized water quality and 30% to 50% of stratum nucleare emulsifying agent quality and mix, add stratum nucleare comonomer and the linking agent of aequum, after stirring and emulsifying 30min to 60min, obtain pre-emulsion; Second step, in polymeric kettle, add remaining deionized water and remaining stratum nucleare emulsifying agent and mix, be warming up to 82 DEG C to 84 DEG C, the sheath polymers latex of aequum and the reaction initiator of aequum is added successively at temperature is 82 DEG C to 84 DEG C, then in polymeric kettle, drip the pre-emulsion that the first step obtains, the time for adding of pre-emulsion is 2h to 4h, is incubated 1h to 2h after pre-emulsion drips at temperature is 75 DEG C to 85 DEG C; 3rd step, is cooled to 20 DEG C to 45 DEG C after insulation, adjust ph is 7.5 to 8.0, after adjust ph, filters and obtains nucleocapsid structure ACR latex.
3. nucleocapsid structure ACR latex according to claim 1 and 2, it is characterized in that sheath polymers latex obtains as follows: the first step, 40 parts to 60 parts deionized waters, 1.5 parts to 7.5 parts shell emulsifying agents and 30 parts to 40 parts shell comonomers are mixed obtain pre-latex by weight; Second step, 40 parts to 60 parts deionized waters are added by weight and 3.5 parts to 7.5 parts shell emulsifying agents mix in polymeric kettle, be warming up to 70 DEG C to 90 DEG C, the reaction initiator adding 0.3 part to 1.0 parts at temperature is 70 DEG C to 90 DEG C reacts, in polymeric kettle, drip the pre-latex that the first step obtains simultaneously, the time for adding of pre-latex is 2h to 4h, after dropping, obtains sheath polymers latex after cooling, filtration.
4. the nucleocapsid structure ACR latex according to claim 1 or 2 or 3, is characterized in that shell emulsifying agent is Sodium dodecylbenzene sulfonate; Or/and shell comonomer is the mixture that more than one and vinylbenzene in cyclohexyl methacrylate and methyl methacrylate form; Or/and reaction initiator is ammonium persulphate.
5. the nucleocapsid structure ACR latex according to claim 1 or 2 or 3 or 4, is characterized in that stratum nucleare emulsifying agent is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate or reactive emulsifier SE-10N or nonionic emulsifier LCN-407; Or/and stratum nucleare comonomer is butyl acrylate or ethyl acrylate; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and linking agent is BDO dimethacrylate or Phthalic acid, diallyl ester; Or/and in the 3rd step prepared by nucleocapsid structure ACR latex, after adjust ph, 500 mesh filter screens filter and obtain nucleocapsid structure ACR latex.
6. the preparation method of the nucleocapsid structure ACR latex according to claim 1 or 2 or 3 or 4 or 5, it is characterized in that carrying out in the steps below: the first step, in pre-emulsification still, add the stratum nucleare emulsifying agent of the deionized water of 40% to 60% of deionized water quality and 30% to 50% of stratum nucleare emulsifying agent quality and mix, add stratum nucleare comonomer and the linking agent of aequum, after stirring and emulsifying 30min to 60min, obtain pre-emulsion; Second step, in polymeric kettle, add remaining deionized water and remaining stratum nucleare emulsifying agent and mix, be warming up to 82 DEG C to 84 DEG C, the sheath polymers latex of aequum and the reaction initiator of aequum is added successively at temperature is 82 DEG C to 84 DEG C, then in polymeric kettle, drip the pre-emulsion that the first step obtains, the time for adding of pre-emulsion is 2h to 4h, is incubated 1h to 2h after pre-emulsion drips at temperature is 75 DEG C to 85 DEG C; 3rd step, is cooled to 20 DEG C to 45 DEG C after insulation, adjust ph is 7.5 to 8.0, after adjust ph, filters and obtains nucleocapsid structure ACR latex.
7. use a modified resin powder for claim 1 or 2 or 3 or the nucleocapsid structure ACR latex described in 4 or 5, it is characterized in that raw materials by weight portion comprises deionized water 4000 parts to 5000 parts, vinyl chloride monomer 2500 parts to 3000 parts, 330 parts to 660 parts, nucleocapsid structure ACR latex, dispersion agent 5.0 parts to 15.0 parts, polymerization starter 1.25 parts to 3.5 parts, terminator 5 parts to 10 parts.
8. modified resin powder according to claim 7, it is characterized in that obtaining as follows: add the deionized water of aequum and dispersion agent in a kettle. and mix, pH value is regulated to be 7.5 to 8.0, then add the nucleocapsid structure ACR latex of aequum and polymerization starter and mix, air in nitrogen replacement reactor 1 time to 3 times, add the vinyl chloride monomer of aequum after displaced air and mix and carry out polyreaction, polymerization temperature is 55.5 DEG C to 56.5 DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.
9. the modified resin powder according to claim 7 or 8, is characterized in that dispersion agent to be model is the polyvinyl alcohol of FON-50, two or more in polyvinyl alcohol that polyvinyl alcohol that model is Alcotex80, model are LL02 and Vltra tears; Or/and polymerization starter is peroxy dicarbonate two (2-ethylhexyl) and the new certain herbaceous plants with big flowers acid esters of dicumyl peroxide is the mixture of 2:1 to 4:1 composition in mass ratio; Or/and adjust ph pH adjusting agent regulates, pH adjusting agent is sodium bicarbonate or bicarbonate of ammonia or sodium hydroxide or ammoniacal liquor; Or/and terminator is acetone semicarbazone thiocarbamide; Or/and pressure during nitrogen replacement air in reactor is 0.3MPa.
10. the preparation method of the modified resin powder according to claim 7 or 8 or 9, it is characterized in that carrying out as follows: add the deionized water of aequum and dispersion agent in a kettle. and mix, pH value is regulated to be 7.5 to 8.0, then add the nucleocapsid structure ACR latex of aequum and polymerization starter and mix, air in nitrogen replacement reactor 1 time to 3 times, add the vinyl chloride monomer of aequum after displaced air and mix and carry out polyreaction, polymerization temperature is 55.5 DEG C to 56.5 DEG C, the pressure of reactor is 0.85MPa to 0.95MPa, question response still internal pressure adds terminator termination reaction when dropping to 0.2MPa to 0.3MPa, get rid of discharging after unreacted vinyl chloride monomer, material after discharging after filtration, washing, the modified resin powder that percent mass water content is less than 0.5% is obtained after vacuum-drying.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109467646A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride graft copolymer |
| CN113004453A (en) * | 2021-03-08 | 2021-06-22 | 威海金合思化工有限公司 | Optical-grade transparent PMMA toughening agent and preparation method thereof |
| CN116063630A (en) * | 2023-03-22 | 2023-05-05 | 宜春市科远化工有限公司 | Preparation method of ACR impact modifier powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073670A (en) * | 2012-12-24 | 2013-05-01 | 席文峰 | Impact modifier ACR resin and preparation method thereof |
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| CN103073670A (en) * | 2012-12-24 | 2013-05-01 | 席文峰 | Impact modifier ACR resin and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 林润雄 等: ""功能性核/壳结构ACR的分子设计"", 《化工科技》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467646A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride graft copolymer |
| CN109467646B (en) * | 2018-10-10 | 2022-04-08 | 中国石油化工股份有限公司 | Preparation method of vinyl chloride graft copolymer |
| CN113004453A (en) * | 2021-03-08 | 2021-06-22 | 威海金合思化工有限公司 | Optical-grade transparent PMMA toughening agent and preparation method thereof |
| CN116063630A (en) * | 2023-03-22 | 2023-05-05 | 宜春市科远化工有限公司 | Preparation method of ACR impact modifier powder |
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