CN103467663A - Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure - Google Patents
Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure Download PDFInfo
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Abstract
The invention relates to a preparation method of an acrylic ester type processing aid with a multilayer gradient core-shell structure, belonging to the field of modification of functional macromolecular materials. The preparation method comprises the following process steps: (1) under the condition of stirring at 30 DEG C, adding deionized water, an initiator A, an emulsifier, a co-emulsifier, a dispersant, a soft monomer and a crosslinking agent into a reaction kettle, and performing pre-emulsification to obtain a pre-emulsion; (2) heating the pre-emulsion to a temperature less than or equal to 90 DEG C, and performing a thermal reaction to obtain a soft monomer core layer emulsion; and (3) adding an initiator B, alpha olefin and a monomer which has a solubility parameter similar to that of PVC (polyvinyl chloride) into the soft monomer core layer emulsion, and sequentially polymerizing 1-5 layers of rigid polymer shells with a solubility parameter similar to that of polyvinyl chloride to obtain the acrylic ester type processing aid. The obtained PVC processing aid has the advantages of low price, good effect of promoting plasticization, excellent weathering resistance, capability of improving impact properties of a product and the like, and can be widely applied to the fields of PVC building door and window profiles, pipes, wires, cables, small-scale household appliances and the like.
Description
Technical field
The present invention relates to a kind of preparation method of PVC processing aid, specifically, relate to a kind of preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin, belong to the preparation and modification field of functional high molecule material.
Background technology
Polyvinyl chloride (PVC) is one of four large commodity polymer materials, is also the macromolecular material of non-petroleum base route rare in numerous polymers.Because PVC is mainly produced by calcium carbide route, depend on hardly petroleum resources.Its excellent mechanical property, self-extinguishing and relatively cheap price have made it have a wide range of applications in fields such as toy, footwear industry, building, decoration, agriculturals.At present, the global output of PVC has broken through 4,000 ten thousand ton/years.Surpass 50% manufacture that is used to respectively the PVC material of construction and wherein have, also just mean that PVC is in the course of processing, the usage quantity in plasticizing promotor and toughner every year will be over 2,000,000 tons.
ACR is the english abbreviation of esters of acrylic acid rubber, is also the most widely used analog assistant in current PVC field.From chemistry and space structure, ACR is a kind of esters of acrylic acid nano material with nucleocapsid structure.Its current average market price Yue Wei $2 ten thousand/ton.According to the difference of nanoparticle core shell volume ratio, it can be divided into to two kinds of plasticizing promotor (or plasticizing conditioning agent) and toughner.Wherein, when the content of polymethylmethacrylate (PMMA) shell relatively less, and stratum nucleare is called toughner while being the rubber such as lightly crosslinked butyl polyacrylate or polyhutadiene, and this type of ACR toughner can increase substantially the shock resistance of material under the condition that reduces hardly the PVC strength of materials and rigidity; The plasticizing promotor that can be used as PVC when PMMA shell content is higher is used.Because rigidity PMMA has the solubility parameter close with PVC, the two consistency excellence on the one hand; On the other hand, in nanoparticle, the existence of stratum nucleare soft rubber phase can make material can by the deformation of rubber, make impact energy be dissipated when being subject to foreign impacts, thereby reaches the purpose of anti-impact.But regrettably the preparation method of ACR and technique are comparatively complicated, and space structure design is still perfect not, and the larger space of improving is arranged.
Chinese patent CN200510044443.1 discloses the method for one-step synthesis polyvinyl-chloride use acrylic ester impact-resisting modifier, by methyl methacrylate and n-butyl acrylate letex polymerization, formed, under the alkaline condition that to it is characterized in that at pH be 7～10, n-butyl acrylate reacts under 60～80 ℃, when reaction conversion ratio reaches 10～15%, add agglomerant, when reaction conversion ratio reach >=97% the time, add methyl methacrylate, reacted rear discharging spraying drying, the total mass of methyl methacrylate and n-butyl acrylate of wherein take is 100%, methyl methacrylate accounts for 10～50%, n-butyl acrylate accounts for 50～90%, agglomerant is 0.1～1% of n-butyl acrylate amount.Agglomerant can be vinylformic acid, methacrylic acid, sal epsom, sodium-chlor or calcium chloride.The method is simple esters of acrylic acid random copolymers, and space structure is single, complex process, cost costliness.
Above-mentioned defect for traditional ACR, if can adopt and ACR molecular structure and the similar method of space structure design, and the shell of traditional ACR is carried out to gradient design, can when guaranteeing effectively to promote the PVC plasticizing and improving melt strength, reduce to greatest extent the cost of ACR, the remarkable in economical benefits of product.
Summary of the invention
The present invention is intended to provide a kind of preparation method with processing aids acrylic resin of multi-gradient nucleocapsid structure for the deficiencies in the prior art.The present invention is by usining through appropriately crosslinked soft monomer polymkeric substance as kernel, again on the surface of soft kernel on grafting free radical polymerization successively multilayer and PVC there is the rigid polymer shell of close solubility parameter, thereby obtained the gradient core shell structure processing aid that is applicable to PVC.Technique of the present invention is simple, and production cost is relatively low, and the processing aid made has characteristics cheap, toughness reinforcing and that the promotion plasticizing efficiency is high, weathering resistance is good.For achieving the above object, the technical solution used in the present invention is as follows:
A kind of preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin is characterized in that: comprise following processing step:
(1) under 30 ℃ and agitation condition, to adding successively 45～55% deionized water, 0～2.5% initiator A, 0.25～4% emulsifying agent, 0～2% assistant for emulsifying agent, 0.005～0.025% dispersion agent, 40～48% soft monomer and 0～2.5% linking agent in reactor, pre-emulsification is processed after 15 minutes and is obtained the pre-emulsion of particle size range at 100～300 nm;
(2) by pre-emulsion from 30 ℃ be warming up to≤90 ℃, and under agitation condition insulation reaction 1～6 hour, obtain soft monomer stratum nucleare emulsion after being cooled to normal temperature;
(3) add 0.5～5% initiator B in soft monomer stratum nucleare emulsion, and alhpa olefin, with PVC, there is at least one in the monomer of close solubility parameter, stir, at the temperature of 30 ~ 90 ℃ successively after polyreaction 1～5 time, system temperature is cooled to normal temperature, must there are 2～5 layers of gradient core shell structure, and processing aids acrylic resin with close solubility parameter of polymer shell and PVC; The described quality with polymer shell of 2～5 layers of gradient core shell structure accounts for 30～80% of whole polymkeric substance.By internal layer, to outer, the concentration that has the hard monomer of close solubility parameter with PVC is increased to 100% by 0% successively, and outermost layer is all to have the hard monomer of close solubility parameter with PVC.
It should be noted that, per-cent involved in the present invention is mass ratio.
Described initiator A is at least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate or ammonium persulphate.
Described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene (OP, NP, CO), tween or class of department.
Described assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol or lauryl alcohol.
Described dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate or talcum powder.
Described soft monomer is at least one in butyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, N-Hexyl methacrylate, Isooctyl methacrylate, soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, the young oil of rubber, Oleum Verniciae fordii or Viscotrol C.
Described linking agent is at least one in Vinylstyrene, diene acrylate or maleic anhydride.
Described initiator B is radical polymerization initiator, is selected from least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate.
Described alhpa olefin is at least one in methyl acrylate, ethyl propenoate, alkyl vinyl ether, vinyl acetate between to for plastic, vinylbenzene or vinyl cyanide.
The monomer that described and PVC has close solubility parameter is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride or vinylidene chloride.
The PVC material that adopts processing aids acrylic resin of the present invention to process, can be used for processing building doors and windows section bar, tubing, pipe fitting, electric wire, penetration pipe and small household appliances.
Compared with prior art, the outstanding advantages that the present invention has is:
1, the present invention is usingd through appropriately crosslinked soft monomer polymkeric substance as kernel, especially under the reaction system formed at the linking agent of 45～55% deionized water, 0～2.5% initiator A, 0.25～4% emulsifying agent, 0～2% assistant for emulsifying agent, 0.005～0.025% dispersion agent, 40～48% soft monomer and 0～2.5%, pre-emulsification is processed and within 15 minutes, is obtained particle size range after the pre-emulsion of 100～300 nm, be warming up to again≤90 ℃, and insulation reaction 1～6 hour, get final product to obtain soft monomer stratum nucleare emulsion.This processing parameter is reasonable, and technological process simply is easy to realize.
2, the present invention is by adding 0.5～5% initiator B, alhpa olefin and the monomer that has close solubility parameter with PVC in the soft monomer stratum nucleare emulsion making, under the temperature condition of 30 ~ 90 ℃, the surface of soft kernel can be on grafting free radical polymerization successively multilayer and PVC there is the rigid polymer shell of close solubility parameter, thereby obtained the processing aids acrylic resin with 2～5 layers of gradient core shell structure.The method adopts gradient nucleocapsid copolymerization technique, effectively reduce material and process costs by the concentration gradient processing by shell, with PVC, thering is the methyl methacrylate of close solubility parameter, space structure design is reasonable, improve the impact resistance of PVC goods when can meet the existing performance of traditional ACR, and the processing aid made have characteristics cheap, toughness reinforcing and that the promotion plasticizing efficiency is high, weathering resistance is good.
3, the processing aids acrylic resin with multi-gradient nucleocapsid structure that the present invention is prepared can replace traditional processing aid type ACR and anti-impact type ACR, remarkable in economical benefits fully.
The accompanying drawing explanation
The chemical structure schematic diagram that Fig. 1 is multi-gradient nucleocapsid structure processing aids acrylic resin of the present invention
Fig. 2 is the plasticizing capacity correlation curve figure that the present invention has 4 layers of gradient core shell structure ACR and commercially available ACR.
Embodiment
Below by specific embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only for the invention will be further described; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make improvement and the adjustment of some unsubstantialities according to the content of foregoing invention to the present invention.
Embodiment 1
Add successively 100 g deionized waters, 1 g Potassium Persulphate, 6 g tweens, 1 g Sodium dodecylbenzene sulfonate emulsifying agent, 4 g propyl carbinols, 0.1 g polyvinyl alcohol, 100 g soybean oil and 5 g Vinylstyrenes in the four-hole boiling flask that carries heating and whipping appts.Stir 15 minutes under 30 ℃, obtain the soybean oil pre-emulsion; Then, the temperature of reaction system is risen to 75 ℃, insulation reaction is cooled to normal temperature and obtains processing aid kernel (being stratum nucleare) emulsion after 2 hours.
Add successively 1.5 g Potassium Persulphates, 6 g vinylbenzene and 20 g methyl methacrylates in above-mentioned 100g processing aid kernel emulsion.After stirring, system temperature is increased to 75 ℃ gradually, insulation reaction continues to add 1.5 g Potassium Persulphates, 4 g vinylbenzene and 30 g methyl methacrylates in system after 30 minutes, insulation reaction adds 1.5 g Potassium Persulphates and 50 g methyl methacrylates after 30 minutes again in reactor, after insulation reaction 2 hours, system temperature further is increased to 82 ℃.The continuation insulation reaction after 1 hour is cooled to system normal temperature and obtains the processing aids acrylic resin with 3 layers of gradient core shell structure.
Embodiment 2
Add successively 120 g deionized waters, 1 g ammonium persulphate, 1.5 g alkylphenol polyoxyethylene polyoxyethylene nonylphenol ethers, 1 g sodium lauryl sulphate, 0.1 g carboxy cellulose, 100 g butyl acrylates and 8 g diene acrylate in the four-hole boiling flask that carries heating and whipping appts.Stir 15 minutes under 30 ℃, obtain the butyl acrylate pre-emulsion.Then, rising temperature of reaction system to 70 ℃, insulation reaction is cooled to normal temperature and obtains processing aid kernel (being stratum nucleare) emulsion after 2 hours.
In above-mentioned 20g processing aid kernel emulsion, order adds 1 g ammonium persulphate, 4 g vinylbenzene and 10 g methyl methacrylates.After stirring, system temperature is increased to 70 ℃ gradually, insulation reaction added 1 g ammonium persulphate, 3 g vinylbenzene and 20 g methyl methacrylates after 30 minutes in system, insulation reaction adds 1 g ammonium persulphate, 2 g vinylbenzene and 30 g methyl methacrylates after 30 minutes again in reactor, insulation reaction adds 1 g ammonium persulphate, 1 g vinylbenzene and 40 g methyl methacrylates again after 30 minutes, continue insulation reaction 30 minutes.And then adding 1g ammonium persulphate and 50 g methyl methacrylates in reactor, insulation reaction, after 2 hours, further is increased to 82 ℃ by system temperature.Continue insulation reaction 1 hour, must there is the processing aids acrylic resin of 5 layers of gradient core shell structure.
Embodiment 3
Add successively 1000 g deionized waters, 10 g ammonium persulphates, 25 g alkylphenol polyoxyethylene emulsifying agent NP, 10 g sodium lauryl sulphate, 5 g hydroxypropylcelluloses, 5 g polyvinyl alcohol, the different ester suffering of 1000 g vinylformic acid and 50 g Vinylstyrenes in the stainless steel pressure reactor of jacketed and whipping appts.Stir 15 minutes under 30 ℃, obtain the Isooctyl acrylate monomer pre-emulsion.Then, rising temperature of reaction system to 50 ℃, insulation reaction is cooled to normal temperature and obtains processing aid kernel emulsion after 2 hours.
Add successively 100 g peroxy dicarbonates, 2000 g vinyl cyanide, 3000 g vinylchlorid in above-mentioned 20000g processing aid kernel emulsion, after stirring, system temperature is increased to 50 ℃ gradually, heat-insulation pressure keeping reaction 30 minutes.With peristaltic meatering pump, the mixed solution of 200 g peroxy dicarbonates, 1000 g vinyl cyanide and 6000 g vinylchlorid is squeezed into to reactor fast, be controlled in 15 minutes mixed solution is all pumped into to reactor; After heat-insulation pressure keeping reacts and obviously Pressure Drop occurs to system, continue reaction 30 minutes.System temperature is cooled to normal temperature, must there is the processing aid of 3 layers of gradient core shell structure.
Embodiment 4
Add successively 500 g deionized waters, 5 g ammonium persulphates, 10 g alkylphenol polyoxyethylene emulsifying agent CO, 5 g sodium lauryl sulphate, 3 g hydroxypropylcelluloses, 3 g polyvinyl alcohol, 500 g Oleum Verniciae fordiis and 50 g diene acrylate in the stainless steel pressure reactor of jacketed and whipping appts.Stir 15 minutes under 30 ℃, obtain the Oleum Verniciae fordii pre-emulsion.Then, rising temperature of reaction system to 90 ℃, insulation reaction is cooled to normal temperature and obtains processing aid kernel emulsion after 2 hours.
Add successively 50 g peroxy dicarbonates, 1000 g vinyl cyanide, 200 g vinylchlorid in above-mentioned 2000g processing aid kernel emulsion, after stirring, system temperature is increased to 50 ℃ gradually, heat-insulation pressure keeping reaction 30 minutes.With peristaltic meatering pump, the mixed solution of 50 g peroxy dicarbonates, 800 g vinyl cyanide and 300 g vinylchlorid is squeezed into to reactor fast, be controlled in 15 minutes mixed solution is all pumped into to reactor; The heat-insulation pressure keeping reaction is squeezed into reactor with peristaltic pump by the mixed solution of 50 g peroxy dicarbonates, 400 g vinyl cyanide and 700 g vinylchlorid after 30 minutes again fast; The heat-insulation pressure keeping reaction is squeezed into reactor with peristaltic pump by the mixed solution of 50 g peroxy dicarbonates and 1000 g vinylchlorid after 30 minutes again fast, after heat-insulation pressure keeping reacts and obviously Pressure Drop occurs to system, continues reaction 30 minutes.System temperature is cooled to normal temperature, must there is the processing aid of 4 layers of gradient core shell structure.
Experimental example 1 plasticizing capacity contrast experiment
Take embodiment 4 as example, will there is 4 layers of gradient core shell structure ACR and commercially available ACR and be contrasted on plasticizing capacity, the results are shown in accompanying drawing 2.
Conclusion: can find out from accompanying drawing 2: the same amount condition, 4 layers of gradient core shell structure ACR have the similar processing plasticizing performance with commercially available ACR; But the plasticizing moment of torsion from flow curve, the commercially available ACR's of plasticizing torque ratio of 4 layers of gradient core shell structure ACR is lower slightly.Show the energy consumption of 4 layers of gradient core shell structure ACR in can when guaranteeing effectively to promote the PVC plasticizing, suitably reducing the course of processing.
Claims (10)
1. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin is characterized in that: comprise following processing step:
(1) under 30 ℃ and agitation condition, to adding successively 45～55% deionized water, 0～2.5% initiator A, 0.25～4% emulsifying agent, 0～2% assistant for emulsifying agent, 0.005～0.025% dispersion agent, 40～48% soft monomer and 0～2.5% linking agent in reactor, pre-emulsification is processed after 15 minutes and is obtained the pre-emulsion of particle size range at 100～300 nm;
(2) by pre-emulsion from 30 ℃ be warming up to≤90 ℃, and under agitation condition insulation reaction 1～6 hour, obtain soft monomer stratum nucleare emulsion after being cooled to normal temperature;
(3) add 0.5～5% initiator B in soft monomer stratum nucleare emulsion, and alhpa olefin, with PVC, there is at least one in the monomer of close solubility parameter, stir, at the temperature of 30 ~ 90 ℃ successively after polyreaction 1～5 time, system temperature is cooled to normal temperature, must there are 2～5 layers of gradient core shell structure, and processing aids acrylic resin with close solubility parameter of polymer shell and PVC; The described quality with polymer shell of 2～5 layers of gradient core shell structure accounts for 30～80% of whole polymkeric substance.
2. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described initiator A is the graft polymerization initiator, is selected from least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate or ammonium persulphate.
3. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1 is characterized in that: described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene OP, alkylphenol polyoxyethylene NP, alkylphenol polyoxyethylene CO, tween or class of department.
4. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol or lauryl alcohol.
5. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate or talcum powder.
6. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1 is characterized in that: described soft monomer is at least one in butyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, N-Hexyl methacrylate, Isooctyl methacrylate, soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, the young oil of rubber, Oleum Verniciae fordii or Viscotrol C.
7. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described linking agent is at least one in Vinylstyrene, diene acrylate or maleic anhydride.
8. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described initiator B is radical polymerization initiator, is selected from least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate.
9. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described alhpa olefin is at least one in methyl acrylate, ethyl propenoate, alkyl vinyl ether, vinyl acetate between to for plastic, vinylbenzene or vinyl cyanide.
10. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1 is characterized in that: the monomer that described and PVC have close solubility parameter is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride or vinylidene chloride.
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| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN106366234B (en) * | 2016-08-30 | 2019-12-20 | 山东东临新材料股份有限公司 | Acrylate copolymer, preparation method and application thereof |
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| 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 |
| CN118459674A (en) * | 2024-07-10 | 2024-08-09 | 山东广源化工材料有限公司 | Acrylic ester processing aid and preparation method and application thereof |
| CN118459674B (en) * | 2024-07-10 | 2024-09-06 | 山东广源化工材料有限公司 | Acrylic ester processing aid and preparation method and application thereof |
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