CN103570882A - ASA (acrylonitrile styrene acrylate) graft copolymerization resin rubber powder and preparation method thereof - Google Patents
ASA (acrylonitrile styrene acrylate) graft copolymerization resin rubber powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ASA (acrylonitrile styrene acrylate) graft copolymerization resin rubber powder. The ASA graft copolymerization resin rubber powder comprises the following components by parts by weight: 5-30 parts of butyl acrylate, 50-70 parts of styrene, 20-25 parts of acrylonitrile, 0.08-0.35 part of initiator, 0.05-0.5 part of emulgator, 150-500 parts of deionized water H2O, 0.025-0.15 part of diacrylic acid poly butylene terephthalate, 0.025-0.15 part of functionality monomer, 0.002-0.02 part of 1-dodecanethiol, 0.25-0.5 part of dispersing agent, and 0.01-0.05 part of sodium hydrosulfite. According to the ASA graft copolymerization resin rubber powder and the preparation method, the comprehensive properties of the resin can be remarkably improved, steps of amplifying grain size of latex and condensing are omitted, dosage of additives and water is reduced, the technological processes are shortened, the production efficiency is improved, and the manufacture cost is lowered by 30% compared with that of similar foreign products.
Description
Technical field
The present invention relates to the technical field of synthesis of polymer material, be specifically related to a kind of ASA graft copolymer resin rubber powder and preparation method thereof.
Background technology
ASA resin is as new variety in the large series of ABS resin, the graft copolymer being comprised of acrylonitrile-styrene-acrylic ester (Acrylonitrile-Styrene-Acrylate), it is " island structure " that external phase, rubber are disperse phase that its structure presents resin.Compare with ABS, owing to introducing not double bond containing acrylic elastomer, replace double bond containing polybutadiene rubber, make the weathering resistance of ASA have basic change, than ABS, exceed 10 times of left and right; And it is also obviously better than ABS resin aspect chemical resistant properties, has greatly improved ABS resin long-term revealing and put outdoor rear physical strength and significantly decline, be subject to the dayligth effect color shortcoming such as flavescence gradually.
Therefore, as a kind of high performance plastics with excellent weather resistance, ageing resistance, thermotolerance, erosion resistance and shock resistance, at home and abroad use in a large number in recent years, and be widely used in every profession and trade and the fields such as automobile, building, electrical equipment, motorway, environmental sanitation.Meanwhile, as the properties-correcting agent of a kind of good resin or plastics, ASA resin also can be made multiple high performance alloys with blend such as PV, PC, PA.Because ASA resin has the characteristic of all excellences, widely applicable, comprise as outdoor products such as the external component of the various forms of transport such as automobile, motorcycle, electrical appliance, material of construction, bath articles, solar base plate carriers, have a good application prospect.
ASA resin is successfully developed by German BASF AG as far back as nineteen sixty-eight, and first realizes and see industrialization, and commodity are called Lurans.The producer of the ASA resin of producing in the world at present mainly contains: German BASF AG, FDAC change into company, Deng Jiujia manufacturer of ,Dow company of GE.It is more late that the research work that China's ASA resin is relevant is carried out, from the early 1990s till now, the theoretical investigation work that the units such as Beijing University of Chemical Technology, ,Lan Hua research institute of Zhejiang University are correlated with excessively, but equal unrealized suitability for industrialized production, each side research all needs further deeply to be carried out.Therefore, domestic up to now still do not have own synthetic ASA resin to appear on the market, and rely on import to obtain rubber powder raw material completely, then it is semi-synthetic to add SAN resin, auxiliary material etc. to carry out, and prepares the modified ASA resin that meets different demands.As the patent No. patent of invention (denomination of invention: a kind of ASA resin with excellent appearance performance and preparation method thereof that is ZL201110100800.7, applying date 2011.04.21) in disclosed composition prescription, the ASA rubber powder raw material of using during the cross-linking modified graft copolymer of preparation ASA, from Korea S's brocade lake import.
The producer of the ASA resin of current production in the world, its production technique adopts emulsion graft polymerization blending method (GUNTHERBERG N conventionally, WEBER M, LINDENSCHMIDT G etc., < < Thermoplastic molding compositions based on acrylonitrile-styrene-acrylate polymers > >, US6531543 ［ P ］), be divided into three steps: the 1. preparation of acrylate latex; 2. vinyl cyanide and vinylbenzene are to acrylate latex graft copolymerization; 3. by the product of graft copolymerization and resinous blending.Its technological process is generally: cross linked acrylic (PBA) latex is synthetic → agglomeration process → emulsion graft copolymerization closes → condense → wash → be dried → with SAN(AS) resin alloy granulation → ASA resin finished product.The weak point of this technical scheme is: 1. for preparing the acrylate latex of large particle diameter, adopt agglomeration process to make synthetic latex amplify particle diameter, to improve the anti-stampability of ASA resin, virtually extended reaction time, reaction cost improves greatly; When 2. emulsion graft copolymerization closes, be graft resin phase on rubber phase, form core (soft) shell (firmly) structure; After graft reaction, latex must, through flocculate and break emulsion, washing, the operation such as dry, just can obtain the grafting material that can be used as modifier or directly use, technical process is loaded down with trivial details, the consumption of auxiliary agent and deionized water increases greatly, improves raw materials cost, reduces production efficiency; 3. adopt oil-soluble initiator, as benzoyl peroxide (BPO) etc. reacts, be unfavorable for blending modification, reduced the weathering resistance of finished product ASA.
In sum, how breaking external blockade on new techniques, the ASA rubber powder that a kind of reaction time is short, production cost is low, weathering resistance is higher raw material is provided, is that those skilled in the art are badly in need of the technical barrier solving.
Summary of the invention
The present invention looks for another way, a kind of ASA graft copolymer resin rubber powder and preparation method thereof is provided, by adding emulsifying agent to synthesize one step ahead the acrylate latex of large particle diameter, and then prepare ASA rubber powder raw material by the mode that suspension method is carried out graft copolymerization, broken external blockade on new techniques, break external blockade on new techniques, for domestic, provide ASA rosin products of high quality and at a reasonable price, and solved the related defects of the prior art of mentioning in above-mentioned background technology.
The technical solution adopted in the present invention is specific as follows:
A graft copolymer resin rubber powder, the component comprising and the weight fraction of each component are as follows:
Butyl acrylate: 5～30 parts, vinylbenzene: 50～70 parts, vinyl cyanide: 20～25 parts, initiator: 0.08～0.35 part, emulsifying agent: 0.05～0.5 part, deionized water H2O:150～500 part, diacrylate fourth diester: 0.025～0.15 part, functional monomer: 0.025～0.15 part, Dodecyl Mercaptan: 0.002～0.02 part, dispersion agent: 0.25～0.5 part, sodium hydrosulfite: 0.01～0.05 part;
Wherein, initiator is the combination of oil-soluble initiator and water soluble starter; Functional monomer is one or more the combination in propyl methacrylate, methacrylic acid, vinylformic acid ethylene glycol fat.
In preferred technical scheme, oil-soluble initiator is one or more the combination in hydrogen phosphide cumene, lauroyl peroxide, peroxidized t-butyl perbenzoate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, Wickenol 111 (IPP), NBP (NBP).
In preferred technical scheme, water soluble starter is one or more the combination in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide.In the present invention, adopt the shared compound system of oil-soluble initiator and water soluble starter, be conducive to blending modification, greatly improved the weathering resistance of finished product ASA resin.
In preferred technical scheme, emulsifying agent is one or more the combination in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate.
In preferred technical scheme, dispersion agent is the combination of organic dispersing agent and inorganic dispersant, and wherein organic dispersing agent is selected from one or more the combination in hydroxypropylcellulose, methylcellulose gum, Natvosol, polyvinyl alcohol, polyethylene oxide fatty acid ester; Inorganic dispersant is selected from one or more the combination in sal epsom, magnesiumcarbonate, aluminium hydroxide, diatomite.
In preferred technical scheme, ASA graft copolymer resin rubber powder, the component comprising and the weight fraction of each component are as follows:
Butyl acrylate: 20～30 parts, vinylbenzene: 60～70 parts, vinyl cyanide: 20～25 parts, initiator: 0.25～0.35 part, emulsifying agent: 0.3～0.5 part, deionized water H
2o:350～500 part, diacrylate fourth diester: 0.1～0.15 part, functional monomer: 0.12～0.15 part, Dodecyl Mercaptan: 0.002～0.01 part, dispersion agent: 0.25～0.5 part, sodium hydrosulfite: 0.03～0.05 part.
In the present invention, adopting diacrylate fourth diester is linking agent, for being cross-linked of the hot and cold curing system of resin, to improve intensity and the elasticity of resin.Certainly, the present invention is not limited to aforesaid linking agent, also comprise esters of acrylic acids such as Ethylene glycol dimethacrylate, TAC, butyl acrylate, HEA, HPA, HEMA, HPMA, MMA, and tetraethoxy, methyl silicate, Trimethoxy silane etc. are silicone based, and the vinyl monomer such as vinylformic acid, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methacrylic acid, hydroxyethyl methylacrylate, Rocryl 410, and the polyalcohols such as polyoxyethylene glycol, polypropylene glycol, TriMethylolPropane(TMP).
In the present invention, employing Dodecyl Mercaptan is chain-transfer agent, for regulating the relative molecular mass of graft copolymer.Certainly, the present invention is not limited to aforesaid chain-transfer agent, also comprises this class chain-transfer agent that is carried out radical polymerization by aliphatics mercaptan and lauryl mercaptan.
In the present invention, employing sodium hydrosulfite is activator, can increase auxiliary material activity after allocating sizing material into, for improving sulphidity and the thermotolerance of graft copolymer.
The present invention also provides a kind of preparation method of ASA graft copolymer resin rubber powder, and concrete technical scheme, mainly comprises the steps:
(1) in reactor, add H
2o, stir on limit, limit adds emulsifying agent to dissolving; Add initiator, continue to add while stirring functional monomer, butyl acrylate and diacrylate fourth diester, polyase 13 hour at 40～80 ℃, obtains emulsion, standby;
(2) in being dissolved with the reactor of emulsifying agent, add the emulsion of sodium hydrosulfite 90min and step (1) gained, heat up in limit, limit drips butyl acrylate and the diacrylate fourth diester that is dissolved with initiator, reacts 2 hours at 25～90 ℃; Then drip vinylbenzene and the vinyl cyanide that is dissolved with initiator, Dodecyl Mercaptan, continue reaction 2.5 hours, obtain latex, standby;
(3) in the latex of step (2) gained, add and be dissolved with the vinylbenzene of initiator, Dodecyl Mercaptan and vinyl cyanide, H
2o, stirring, add dispersion agent, and intensification polymerization 4 hours forms graft copolymer; After polymerization finishes, put into aftertreatment still, washing, centrifugal, dry, obtains granular ASA resin rubber powder.
In preferred technical scheme, in step (1), the butyl acrylate adding and diacrylate fourth diester, account for 95～99% of whole butyl acrylates and diacrylate fourth diester group component; In described step (2), the butyl acrylate adding and diacrylate fourth diester, account for 1～5% of whole butyl acrylates and diacrylate fourth diester group component.
In preferred technical scheme, in step (3), stir speed (S.S.) is 60～600 revs/min, and the ASA Resin adhesive powder footpath making is 0.2～0.4 μ m.The present invention finds through experimental verification, the ASA resin rubber powder under this particle size range, and the performance index such as its anti-stampability, tensile strength, flexural strength not only meet the external production standard such as Europe, Korea S, but also are slightly better than the like product of external manufacturer production.
ASA graft copolymer resin rubber powder provided by the invention, both can be used as raw material and had sold, and also can be applicable to the preparation of ASA modified resin.Due to the ASA graft copolymer resin rubber powder that adopts preparation method of the present invention to obtain, the ASA rubber powder of the external manufacturer production such as its performance and Korea S Jin Hu is suitable, therefore can be used as alternative materials completely, with AS blend granulation, or with other modification auxiliary material couplings such as anti-impact agent, oxidation inhibitor, photostabilizer, prepare the ASA modified resin finished product of many kinds, polytypic, to meet different market demands.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention adopts single stage method synthesizing propylene acid butyl ester latex, then carries out graft copolymerization by suspension method, makes like this synthetic route of whole ASA resin rubber powder shorten, simple process, flexible operation, steady quality.The present invention adopts butyl acrylate to add monomer when emulsification, a small amount of linking agent carries out letex polymerization jointly, can obtain the latex containing greater particle size, makes ASA resin rubber powder have better impact property.The present invention adopts organic and inorganic composite dispersing agent system when graft copolymerization, makes the narrow diameter distribution of graft copolymer, evenly, is conducive to further blending modification; Also adopt water-soluble, oil soluble composite initiator system, use multistage step-by-step polymerization technology, make ASA graft copolymer resin rubber powder there is complete nucleocapsid structure.
In a word, ASA graft copolymer resin rubber powder provided by the invention and preparation method thereof, can significantly improve the over-all properties of resin, and save the operations such as latex particle size amplification, cohesion, reduce the consumption of auxiliary agent and deionized water, shortened process, enhance productivity, and manufacturing cost to reduce by 30% than external like product.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of ASA graft copolymer resin rubber powder of the present invention.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further elaborated, but following content is not intended to limit the scope of the invention.
Embodiment 1
Composition of raw materials: (by weight)
5 parts of Butyl acrylates, 70 parts of vinylbenzene, 25 parts of vinyl cyanide, 0.08 part of initiator (hydrogen phosphide cumene, Sodium Persulfate), 0.05 part of emulsifying agent (Sodium dodecylbenzene sulfonate), 0.025 part of linking agent (diacrylate fourth diester), 0.025 part of functional monomer's (methacrylic acid), 0.02 part of chain-transfer agent (Dodecyl Mercaptan), 0.25 part of dispersion agent (hydroxypropylcellulose, sal epsom), 0.01 part, activator (sodium hydrosulfite), deionized water H
2o150 part.
Preparation process: (as shown in Figure 1)
First, by deionized water H
2o adds in the reactor of band stirring, start that stir on reactor limit, limit adds emulsifying agent until dissolve, add again initiator, continue that stir on limit, limit adds butyl acrylate, linking agent, functional monomer (wherein butyl acrylate and linking agent, account for whole butyl acrylates and linking agent group component 95～99%), polyase 13 hour at 40～80 ℃ of temperature, obtains emulsion, standby;
Then, by deionized water H
2o adds in the reactor that is dissolved with emulsifying agent, add sodium hydrosulfite, a small amount of formaldehyde and the foregoing polymerized emulsion of 1/3 amount, heat up in limit, limit drips butyl acrylate, linking agent (butyl acrylate and the linking agent that is dissolved with initiator, account for whole butyl acrylates and linking agent group component 1～5%), drip off, at 25～80 ℃, react 2 hours, drip again vinylbenzene and the vinyl cyanide that part is dissolved with initiator, Dodecyl Mercaptan, drip off and continue reaction 2.5 hours, temperature of reaction is 25～90 ℃, cooling drips Adlerika, obtains latex, standby;
Then, at foregoing latex, add deionized water H
2o, adds vinylbenzene and the vinyl cyanide that is dissolved with initiator, Dodecyl Mercaptan under fully stirring, and continues to stir, and adds dispersion agent, intensification polymerization 4 hours, and stirring velocity is carried to 600 revs/min from 60 revs/min, and temperature of reaction is carried to 90 ℃ from 60 ℃, forms graft copolymer;
Finally, after polymerization finishes, put into aftertreatment still, fully washing, then centrifugal, dry, obtain the ASA resin rubber powder of fine particle shape, rubber powder particle diameter is 20～120 orders.
Material property:
Adopt above-mentioned preparation method's gained ASA resin good rigidly, thermotolerance is high.Each performance data detects as follows: notched Izod impact strength 10KJ/m
2, tensile strength 40MPa, elongation at break 25%, flexural strength 61Mpa, modulus in flexure 2300Mpa, 90 ℃ of heat-drawn wires.
Embodiment 2
Composition of raw materials: (by weight)
30 parts of Butyl acrylates, 50 parts of vinylbenzene, 20 parts of vinyl cyanide, 0.35 part of initiator (Diisopropyl azodicarboxylate, Potassium Persulphate, Sodium Persulfate), 0.5 part of emulsifying agent (sodium lauryl sulphate, sodium laurylsulfonate), 0.15 part of linking agent (diacrylate fourth diester), 0.15 part of functional monomer's (propyl methacrylate, vinylformic acid ethylene glycol fat), 0.5 part of dispersion agent (methylcellulose gum, polyvinyl alcohol, magnesiumcarbonate), 0.05 part, activator (sodium hydrosulfite), 0.002 part of chain-transfer agent (Dodecyl Mercaptan), deionized water H
2o500 part.
Preparation process: identical with the preparation method described in embodiment 1, obtain the ASA resin rubber powder of fine particle shape, rubber powder particle diameter is 20～120 orders.
Material property:
Adopt above-mentioned preparation method's gained ASA resin good toughness, processibility is good, and elongation at break is high, and ductility is good, has well weather-proof, ageing-resistant performance.Each performance data detects as follows: notched Izod impact strength 45KJ/ ㎡, tensile strength 30Mpa, elongation at break 100%, flexural strength 51Mpa, modulus in flexure 1600Mpa, 82 ℃ of heat-drawn wires.
Embodiment 3
Composition of raw materials: (by weight)
20 parts of Butyl acrylates, 60 parts of vinylbenzene, 20 parts of vinyl cyanide, 0.25 part of initiator (peroxidized t-butyl perbenzoate, hydrogen peroxide), 0.3 part of emulsifying agent (sodium laurylsulfonate), 0.10 part of linking agent (diacrylate fourth diester), 0.12 part of functional monomer's (propyl methacrylate), 0.01 part of chain-transfer agent (Dodecyl Mercaptan), 0.3 part of dispersion agent (Natvosol, diatomite), 0.03 part, activator (sodium hydrosulfite), deionized water H2O350 part.
Preparation process: identical with the preparation method described in embodiment 1, obtain the ASA resin rubber powder of fine particle shape, rubber powder particle diameter is 20～120 orders.
Material property:
Adopt above-mentioned preparation method's gained ASA resin good combination property, applied widely, can be used for preparing various outdoor plastics.Each performance data detects as follows: notched Izod impact strength 35KJ/m
2, tensile strength 35Mpa, elongation at break 60%, flexural strength 54Mpa, modulus in flexure 1700Mpa, 88 ℃ of heat-drawn wires.
Claims (10)
1. an ASA graft copolymer resin rubber powder, is characterized in that, the component comprising and the weight fraction of each component are as follows:
Butyl acrylate: 5～30 parts, vinylbenzene: 50～70 parts, vinyl cyanide: 20～25 parts, initiator: 0.08～0.35 part, emulsifying agent: 0.05～0.5 part, deionized water H
2o:150～500 part, diacrylate fourth diester: 0.025～0.15 part, functional monomer: 0.025～0.15 part, Dodecyl Mercaptan: 0.002～0.02 part, dispersion agent: 0.25～0.5 part, sodium hydrosulfite: 0.01～0.05 part;
Wherein, described initiator is the combination of oil-soluble initiator and water soluble starter; Described functional monomer is one or more the combination in propyl methacrylate, methacrylic acid, vinylformic acid ethylene glycol fat.
2. ASA graft copolymer resin rubber powder according to claim 1, it is characterized in that, described oil-soluble initiator is one or more the combination in hydrogen phosphide cumene, lauroyl peroxide, peroxidized t-butyl perbenzoate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Diisopropyl azodicarboxylate, Wickenol 111, NBP.
3. ASA graft copolymer resin rubber powder according to claim 1, is characterized in that, described water soluble starter is one or more the combination in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, hydrogen peroxide.
4. ASA graft copolymer resin rubber powder according to claim 1, is characterized in that, described emulsifying agent is one or more the combination in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate.
5. ASA graft copolymer resin rubber powder according to claim 1, is characterized in that; Described dispersion agent is the combination of organic dispersing agent and inorganic dispersant, and wherein organic dispersing agent is selected from one or more the combination in hydroxypropylcellulose, methylcellulose gum, Natvosol, polyvinyl alcohol, polyethylene oxide fatty acid ester; Inorganic dispersant is selected from one or more the combination in sal epsom, magnesiumcarbonate, aluminium hydroxide, diatomite.
6. according to the ASA graft copolymer resin rubber powder described in claim 1～5, it is characterized in that, the component comprising and the weight fraction of each component are as follows:
Butyl acrylate: 20～30 parts, vinylbenzene: 60～70 parts, vinyl cyanide: 20～25 parts, initiator: 0.25～0.35 part, emulsifying agent: 0.3～0.5 part, deionized water H
2o:350～500 part, diacrylate fourth diester: 0.1～0.15 part, functional monomer: 0.12～0.15 part, Dodecyl Mercaptan: 0.002～0.01 part, dispersion agent: 0.25～0.5 part, sodium hydrosulfite: 0.03～0.05 part.
7. a method of preparing the ASA graft copolymer resin rubber powder as described in claim 1～5, is characterized in that, comprises the steps:
(1) in reactor, add H
2o, stir on limit, limit adds emulsifying agent to dissolving; Add initiator, continue to add while stirring functional monomer, butyl acrylate and diacrylate fourth diester, polyase 13 hour at 40～80 ℃, obtains emulsion, standby;
(2) in being dissolved with the reactor of emulsifying agent, add the emulsion of sodium hydrosulfite 90min and step (1) gained, heat up in limit, limit drips butyl acrylate and the diacrylate fourth diester that is dissolved with initiator, reacts 2 hours at 25～90 ℃; Then drip vinylbenzene and the vinyl cyanide that is dissolved with initiator, Dodecyl Mercaptan, continue reaction 2.5 hours, obtain latex, standby;
(3) in the latex of step (2) gained, add and be dissolved with the vinylbenzene of initiator, Dodecyl Mercaptan and vinyl cyanide, H
2o, stirring, add dispersion agent, and intensification polymerization 4 hours forms graft copolymer; After polymerization finishes, put into aftertreatment still, washing, centrifugal, dry, obtains granular ASA resin rubber powder.
8. the preparation method of ASA graft copolymer resin rubber powder according to claim 7, it is characterized in that, in described step (1), the butyl acrylate adding and diacrylate fourth diester, account for 95～99% of whole butyl acrylates and diacrylate fourth diester group component; In described step (2), the butyl acrylate adding and diacrylate fourth diester, account for 1～5% of whole butyl acrylates and diacrylate fourth diester group component.
9. the preparation method of ASA graft copolymer resin rubber powder according to claim 7, is characterized in that, in described step (3), stir speed (S.S.) is 60～600 revs/min, and the ASA Resin adhesive powder footpath making is 20～120 orders.
10. as weighed the ASA graft copolymer resin rubber powder as described in 1～9, be applied to the preparation of ASA modified resin.
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