CN101633769B - Polyacrylate resin composition and preparation method thereof - Google Patents
Polyacrylate resin composition and preparation method thereof Download PDFInfo
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- CN101633769B CN101633769B CN2008101171098A CN200810117109A CN101633769B CN 101633769 B CN101633769 B CN 101633769B CN 2008101171098 A CN2008101171098 A CN 2008101171098A CN 200810117109 A CN200810117109 A CN 200810117109A CN 101633769 B CN101633769 B CN 101633769B
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Abstract
The invention discloses a polyacrylate resin composition and a preparation method thereof. The polyacrylate resin composition comprises the following components (based on 100 mass portions of composition): 30 to 60 portions of aryl vinyl monomer-nitrile vinyl monomer graft copolymer A, 35 to 65 portions of vinyl benzene-acrylonitrile copolymer B, and 0 to 8 portions of one or more of butyronitrile rubber powder, butylbenzene rubber powder and polybutadiene powder C, wherein the aryl vinyl unit in the copolymer accounts for 65 to 78 percent, and the nitrile vinyl unit accounts for 22 to 35 percent; the aryl vinyl monomer-nitrile vinyl monomer graft copolymer A is a graft copolymer which uses polyacrylate and polydiene as mixed graft core (A1) and uses aryl vinyl monomer and nitrile vinyl monomer as graft shell (A2); and the latex particle diameter of the polyacrylate graft core is 200 to 600 nanometers, the content of gel is 88 to 93 percent, the polyacrylate unit in the graft copolymer A accounts for 25 to 70 percent by weight, the polydiene unit accounts for 0.5 to 10 percent by weight, the aryl vinyl unit accounts for 15 to 65 percent by weight, and the nitrile vinyl unit accounts for 1.5 to 35 percent by weight.
Description
Technical field
The present invention relates to a kind of polyacrylate resin composition and preparation method thereof.
Background technology
In the resins for universal use field, ABS resin is because excellent property, use comparatively extensive, be applied to automobile, household electrical appliance and exterior material, but also have drawback simultaneously: there is unsaturated link(age) in its grafting trunk thing divinyl on main chain after the polymerization, be subjected to the effect of extraneous factors such as daylight, oxygen, activate two keys easily, it is poor to show as weathering resistance, easily aging, has been subjected to considerable restraint as exterior material.Therefore, the various countries technical specialist once sought surrogate, polyacrylate resin composition thereby the birth of ABS resin.
CN96113082.2 relates to the moulded products of thermoplastic molding materials, a kind of moulded products that is made by the thermoplastic molding materials that contains following component: A) 0%～99.8% weight styrene and/or (methyl) acrylate, (methyl) vinyl cyanide and other monomeric thermoplastic polymer; B) 0.1%～70% weight average particle diameter d50 is less than the graftomer of 700nm, and this polymkeric substance has the shell copolymers of acrylate, cross-linking monomer and other monomeric multipolymer core and vinylbenzene and/or (methyl) acrylate, (methyl) vinyl cyanide; C) 0.1%～70% weight is as the granulated polymer of matting agent.
The preparation method of CN98121931.4 a vinyl cyanide, vinylbenzene and graft copolymers of polyacrylates, this preparation method is: carry out the copolymerization of the superoxide of acrylate monomer and the two keys of band earlier, obtain having peroxide side group polyacrylate elastomer, then with vinylbenzene and acrylonitrile graft copolymer; Change the superoxide add-on, can regulate the grafting density of polyacrylate elastomer, change the add-on of grafted monomer, can regulate total percentage of grafting, thereby realize controllable graft polymerization.Wherein, acrylate monomer: the superoxide of the two keys of band is (95～99.7): (5～0.3); Initiator and emulsifying agent are adopted once and are added in the grafting process; Grafted monomer: polyacrylate elastomer=(10～80): (90～20).The AAS resin of preparation method's gained thus, resistance to impact shock a little less than.
Shortcomings such as the disclosed polyacrylate resin composition of prior art exists resistance to impact shock lower, and weathering resistance is relatively poor.
Summary of the invention
At above-mentioned shortcoming, the invention provides a kind of polyacrylate resin composition and preparation method thereof.
Resin combination disclosed in this invention is made up of aryl ethylene monomer and itrile group vinyl monomer graft copolymer, and specifically, its composition contains following component, is 100 mass fractions in composition:
30～60 parts of aryl ethylene monomers of A-itrile group vinyl monomer graft copolymer,
35～65 parts of styrene-acrylonitrile copolymers of B, styrene units accounts for 65～78% (wt) in the multipolymer, and acrylonitrile unit accounts for 22～35% (wt),
0～8 part of C is selected from one or more in Powdered acrylonitrile-butadiene rubber, powder styrene butadiene rubber, the powder polyhutadiene,
Wherein aryl ethylene monomer-itrile group vinyl monomer graft copolymer A is mixed grafting core (A1) and is the graft copolymer of graft shell (A2) with aryl ethylene monomer and itrile group vinyl monomer with polyacrylic ester and polydiolefin, the latex particle size of polyacrylate grafting core is 200～600nm, gel content 88%～93%, the polyacrylic acid ester units accounts for 25%～70% (wt) among the graft copolymer A, the polydiolefin unit accounts for 0.5%～10% (wt), the aryl ethylene unit accounts for 15%～65% (wt), and the itrile group vinyl units accounts for 1.5%～35% (wt).
Composition disclosed in this invention, the preferred 300～500nm of the latex particle size of polyacrylate grafting core among the graft copolymer A.
Composition disclosed in this invention, the polyacrylic acid ester units is preferred 30%～65% among the graft copolymer A, and the polydiolefin unit accounts for 0.5%～10% (wt), and the aryl ethylene unit is preferred 25%～40%, itrile group vinyl units preferred 2%～30%.
Composition disclosed in this invention, preferred 2～8 parts of C component.
Polyacrylic ester of the present invention can be C
4～C
9The homopolymer of alkyl acrylate in a kind of, specifically, polyacrylic ester of the present invention can be a kind of in polymethyl acrylate, polyethyl acrylate, butyl polyacrylate, the polyacrylic acid monooctyl ester, optimization polypropylene acid butyl ester, polyacrylic acid monooctyl ester.
Polydiolefin of the present invention can be a kind of in polyhutadiene, polyprene, poly-hexadiene, the polycyclopentadiene.
Aryl ethylene monomer of the present invention is the compound that contains aryl hydrocarbon or substituted arene in the vinyl monomer.The aryl ethylene monomer mainly contains: vinylbenzene, right/adjacent/-vinyl toluene (being also referred to as Vinyl toluene), 2, the 4-dimethyl styrene, ethyl styrene is to tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, Alpha-Methyl p-methylstyrene, halogenated styrenes, haloalkyl vinylbenzene, vinyl naphthalene or the like.Can select a kind of in these monomers for use, optimization styrene wherein, Vinyl toluene.
Itrile group vinyl monomer of the present invention is the compound of nitrile group-containing in the vinyl monomer.The itrile group vinyl monomer mainly contains: vinyl cyanide, methacrylonitrile.
The invention discloses a kind of preparation method of polyacrylate resin composition: grafting aryl ethylene monomer and itrile group vinyl monomer on polyacrylic ester and polydiolefin mixing latex, the graft latex that obtains condenses, washing is dry, the grafting powder of gained and styrene-acrylonitrile copolymer blending, granulation.Concrete preparation process is as follows:
(1) preparation of aryl ethylene monomer-itrile group vinyl monomer graft copolymer is 100 mass parts in the summation of polyacrylic ester latex, polydiolefin latex, aryl ethylene class monomer and itrile group vinyl monomer, and wherein latex is in butt:
(a) basic latex
Add 0.5～10 part in 25～70 parts of polyacrylic ester latexs and polydiolefin latex in polymeric kettle, form basic latex, wherein the polyacrylic ester latex particle diameter is 200～600nm, gel content 88%～93%.
In basic latex preparation, the particle diameter of polydiolefin latex of the present invention is not done special restriction, can adopt the polydiolefin latex of 200～400nm.
(b) comonomer grafting basis latex
Comonomer is made up of aryl ethylene monomer and itrile group vinyl monomer, and wherein the aryl ethylene monomer is 15～65 parts, and the itrile group vinyl monomer is 1.5～35 parts; 0.1～1.5 part of emulsifying agent, 0.05～1.0 part of water soluble starter, 0.03～0.6 part of oil-soluble initiator, 0.005～0.1 part of molecular weight regulator, 25～250 parts in water;
Emulsifying agent, water soluble starter are used water dissolution respectively, form homogeneous mixed solution (i) respectively, (ii); Aryl ethylene monomer, itrile group vinyl monomer, oil-soluble initiator, molecular weight regulator are made mix monomer;
35～60 ℃ of basis latex heating, add 20%～40% mix monomer and 30%～50% homogeneous mixed solution (ii), reacted 0.5～1.5 hour, add 30～50% homogeneous mixed solution (i), begin to add remaining mixed monomer, remaining homogeneous mixed solution (i) and (ii), 1.5～2.5 hours joining days, monomer adopts the mode that drips, homogeneous mixed solution (i) (ii) divides 2 times to add last time or to drip continuously, adds preferred 2～6 times in batches; After dropwising, 65～80 ℃ were reacted 2～4 hours down, were cooled to 50～60 ℃ of dischargings, obtained graft latex.
(c) graft latex is condensed, wash drying again and make aryl ethylene monomer-itrile group vinyl monomer graft copolymer grafting powder;
The present invention does not do special requirement to the agglomeration process of graft latex, can adopt calcium chloride general in the prior art, sal epsom, sodium-chlor, potassium aluminium sulfate, polymeric flocculant etc. to condense, preferably sulfuric acid magnesium, cohesion process adopts general processing condition.
Agglomeration process can for: sal epsom: the graft latex in butt is (5～10): 100, sal epsom is made into 7%～10% solution, when being heated to 50～60 ℃, add graft latex, continue to be warming up to 80～95 ℃, slaking 15～30 minutes, agglomeration process finishes.Afterwards, wash, be dried into the grafting powder, standby.
(2) grafting powder and styrene-acrylonitrile copolymer blending, granulation are 100 mass fractions in composition:
Grafting powder after the oven dry is aryl ethylene monomer-itrile group vinyl monomer graft copolymer.30～60 parts of aryl ethylene monomer-itrile group vinyl monomer graft copolymer grafting powders, 35～65 parts of styrene-acrylonitrile copolymers, 0～8 part is selected from one or more in Powdered acrylonitrile-butadiene rubber, powder styrene butadiene rubber, the powder polyhutadiene, carry out blending, blend is extruded through twin screw extruder can obtain the polyacrylate resin composition product.
The described grafting of the present invention (b) step is shell N of grafting on basic latex, wherein, N be by two kinds with certain proportion blended comonomer, the present invention adopts aryl ethylene monomer and itrile group vinyl monomer.For grafting on the grafting trunk, forming,, adopt oil-soluble initiator and water soluble starter coupling to use among the preparation method disclosed in this invention to improve percentage of grafting.Use the higher outer grafting that is easy to get of traditional water soluble starter, be difficult for grafting in the inner initiation of basic latex, therefore, adopt oil-soluble initiator and water soluble starter coupling to use, interior grafting and outer grafting had both been guaranteed, percentage of grafting is improved, thereby increases the consistency of resin phase and rubber phase, cause the shock strength of polyacrylate resin composition and over-all properties to be improved.
Emulsifying agent adopts the mode that in batches adds in the graft latex preparation, prevent in polymerization emulsifying agent moment concentration to surpass critical latex concentration CMC and produce new micella and cause latex particle size to reduce, and reduced the aryl ethylene monomer and the copolymerization of itrile group vinyl monomer generates copolymer.Adopt the big latex of particle diameter can make the polyacrylate resin of high impact, latex particle size reduces, and the polyacrylate resin shock strength that then makes decreases.Water soluble starter adds in batches, is to prevent that reaction heat moment is too big, causes reaction heat to be difficult for withdrawing from, and causes danger; Reaction heat moment also can cause the latex stability variation during Datong District very much, thereby produces the more glue of analysing.Therefore in graft latex preparation of the present invention the adding of emulsifying agent and water soluble starter must emulsifying agent and the adding of water soluble starter must be divided into and adding more than 3 times or adding continuously, add fashionable preferred 3～6 times in batches, otherwise can not reach effect disclosed in this invention.
The present invention in the grafting process employing polyacrylic ester BA and polydiolefin mixing latex as the grafting core, common grafting aryl ethylene monomer and itrile group vinyl monomer, polyacrylic ester and polydiolefin two components are mixed more evenly in this process, can improve the over-all properties of polyacrylate resin composition, especially shock strength; Can synthesize plastic emitting content and be 40%～75% grafting powder; Be easy to control the ratio of polyacrylic ester BA and polydiolefin in the graftomer; Simple to operate, flow process shortens, and raises the efficiency.
Grafting core among the present invention can not adopt latex after acrylate, the diolefine copolymerization as the grafting core: when acrylate and diolefine copolymerization, reactivity ratio constant r1 is greater than 1, the ability of its homopolymerization is greater than copolymerized ability, and homopolymerization can only take place for it, is unfavorable for copolyreaction.In addition, acrylic ester polymerization must add linking agent in order to improve its gel content, makes the polyacrylic ester latex that obtains can carry out graft copolymerization; And diolefine itself has crosslinked ability, need not add linking agent when polymerization.If after adding linking agent during with acrylate, diolefine copolymerization, will make that the gel content of diolefine is too high to cause final resin property to descend.
Polyacrylic ester is 25～70 parts among the present invention, and polyhutadiene is 0.5～10 part, and the polyacrylic acid ester content can not be too high or too low.After the polyacrylic acid ester content is too low, the weathering resistance of final resin is descended greatly, the processing characteristics that causes mobile decline to have influence on goods descends thereby melting index also can descend; Too highly will cause final polymkeric substance shock strength relatively poor.
Styrene-acrylonitrile copolymer can adopt commercially available product or utilize mature industrial technology to obtain in the present invention, can take methods such as CN1455786, CN85101103 to obtain; Perhaps use commercially available product at present, for example BHF, CHF, APH, APN, HH, the HF etc. of Lanzhou Petrochemical Company production.Styrene units accounts for 65～78% (wt) in the styrene-acrylonitrile copolymer, and acrylonitrile unit accounts for 22～35% (wt), and molecular weight is preferably in 60000～120000.
Do not get rid of during the composition blending among the present invention and add other common agent, as oxidation inhibitor, lubricant, static inhibitor, fire retardant, colorant, white dyes or the like.Oxidation inhibitor can be in phenols, phosphorous acid ester, the monothioester one or more, preferred 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol) (2246), β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecanol ester of propionic acid (1076); Lubricant can be in ethylene bis stearamide (EBS), Magnesium Stearate, the silicone oil one or more; Auxiliary dosage and ratio are all same as the prior art, to kind, add-on the present invention of auxiliary agent and have no special requirements.The consumption of various common agents is generally 0.1～1.0 part, is 0.2～0.5 part as oxidation inhibitor, and lubricant is 0.15～0.6 part.
Polyacrylic ester latex of the present invention can adopt the commercially available prod, also can adopt prior preparation method: for example described method preparation of CN00101339.4, as long as can reach particle diameter 200～600nm, the requirement of gel content 88%～93% gets final product.
The present invention also provides a kind of preparation method of polyacrylic ester latex, is 100 mass parts in acrylate monomer:
Water: acrylate monomer is (100～150): 100, preferred (120～140): 100; Emulsifying agent: acrylate monomer is (0.6～1.4): 100; Water soluble starter: acrylate monomer is (0.3～1.0): 100; Linking agent: acrylate monomer is (0.5～3.0): 100, preferred (0.8～1.5): 100;
Emulsifying agent, water soluble starter are used water dissolution respectively, and 1., 2. each form the homogeneous phase mixed solution, linking agent joined in the acrylate monomer form the homogeneous phase monomer mixed solution 3.;
1. and surplus water in polymeric kettle, add 0.5%～15% homogeneous phase mixed solution, when being heated to 50～65 ℃, 3. 2. join in the polymeric kettle with 30%～50% homogeneous phase mixed solution 20%～40% acrylate monomer mixed solution, reacted 0.5～1.5 hour, add 30～50% homogeneous phase mixed solutions 1., 1. and 2. begin to add remaining mix monomer, remaining homogeneous mixed solution, 1.5～2.5 hours joining days, monomer adopts the mode that drips, 1., 2. homogeneous mixed solution divides and adds or adding continuously preferred 2～6 times more than 2 times; After dropwising, 65～80 ℃ were reacted 2～4 hours down, were cooled to 50～60 ℃ of dischargings, obtained polyacrylic ester latex.
Emulsifying agent adds in batches, is to prevent that emulsifying agent moment concentration surpasses critical latex concentration CMC and produces new micella in polymerization, causes latex particle size to reduce.Water soluble starter adds in batches, mainly be because this polyreaction heat release is very concentrated, polymerization temperature will rise to about 90 degree in short several minutes even cause and emit warm phenomenon, there is certain potential safety hazard, add initiator controlled polymerization intensification well in batches, be to prevent that the reaction heat that reaction heat moment causes too greatly is difficult for withdrawing from, thereby polymerization exotherm is controlled in the safety range.
The linking agent that the present invention uses is meant contract in basic benzene, tirethylene glycol dimethacrylate, monoene propyl group maleic acid ester, the diallyl phthalate (DAP) one or more of triallyl cyanurate, Ethylene glycol dimethacrylate, Vinylstyrene (DVB), two, preferred diallyl phthalate (DAP) and/or Vinylstyrene (DVB).Among the preparation method disclosed in this invention, must add linking agent, to improve the gel content of acrylate latex, to form crosslinked rubber phase, help polyacrylate resin when being subjected to foreign impacts, can absorb extraneous anti-impact energy more, cause the product shock strength to improve.
The water soluble starter that the present invention uses is meant a class material of initiated polymerization that can be water-soluble, can be persulphate, hydrogen peroxide, hydroperoxide; Preferred persulphate, specifically can for Potassium Persulphate (KPS), ammonium persulphate, Sodium Persulfate, in a kind of, preferred Potassium Persulphate (KPS).
The oil-soluble initiator that the present invention uses is a kind of as dilauroyl peroxide (LPO), dibenzoyl peroxide (BPO), Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Cellmic C 121, preferred dilauroyl peroxide (LPO).
The molecular weight regulator that the present invention uses is meant a kind of in positive mercaptan, branched mercaptan, unsaturated fatty acids, neopentanoic acid, ethylene glycol, Virahol, the alkiodide, mercaptan can be that carbonatoms is 5 to 14 mercaptan, unsaturated fatty acids can be cis-9-octadecenoic acid and suitable 9, suitable 12-diene stearic acid etc., preferred tertiary lauryl mercaptan (RSH).
The emulsifying agent that the present invention uses is meant one or more in the anion surfactants such as sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, sodium oleate, potassium oleate, preferably sodium dodecyl sulfate (SDS) and/or Sodium dodecylbenzene sulfonate.
Polyacrylate resin composition disclosed in this invention, have excellent in cushion effect (150～300J/m), good weatherability (than about 10 times of the good weatherability of ABS resin).
The preparation method of polyacrylate resin composition disclosed in this invention, simple to operate, aryl ethylene monomer and itrile group vinyl monomer-grafted rate height.
Embodiment
Further demonstrate the present invention below, but the present invention is not limited to these embodiment.
Main analytical procedure or analytical instrument that the present invention adopts
(1) polyacrylic ester latex particle diameter
90Plus particle diameter instrument with Brookhaven company is measured
(2) polyacrylic ester latex gel content
After the emulsion condensation oven dry, be solvent with the butanone, use the Soxhlet extractor extracting, go out ratio of expansion by the swollen incremental computations, gel content is obtained in the oven dry of swollen gel.
The gel content X1 (weight %) of latex is calculated as follows:
X1＝m
2/m
0×100
In the formula: m
0-sample mass, gram; m
2-swollen gel dries quantity, gram.
(3) resin object property testing standard:
Tensile strength: with 150 * 4 * 10 sample preparations, the ISO527 test.
Flexural strength: with 80 * 10 * 4 (mm) sample preparation, the ISO178 test.
Shock strength: with 63.5 * 12.7 * 3.2 (mm) sample preparation, the ISO180/4A test.
Vicat softening point: with 10 * 10 * 4 (mm) sample preparation, ISO 306 tests.
Melting index: ISO1133,220 ℃/10Kg test.
Density: ISO1183 test.
The preparation of embodiment 1 butyl polyacrylate (PBA) latex
Prescription
100 parts of butyl acrylates (BA)
0.5 part of Potassium Persulphate (KPS)
0.64 part of sodium lauryl sulphate (SDS)
1.2 parts of diallyl phthalates (DAP)
135 parts in water
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, DAP is joined form the homogeneous phase monomer mixed solution among the BA.In polymeric kettle, add homogeneous phase mixed solution and the surplus water that contains 0.2 part of SDS, when being heated to 60 ℃, 25 parts of homogeneous phase monomer mixed solutions are joined in the polymeric kettle, add the homogeneous phase mixed solution that contains 0.25 part of KPS again, reacted 1 hour, and added the homogeneous phase mixed solution that contains 0.2 part of SDS, begin to drip the homogeneous phase monomer mixed solution, the dropping time is 2 hours, drips and adds the homogeneous phase mixed solution that contains 0.21 part of SDS, the homogeneous phase mixed solution that contains 0.125 part of KPS after 1 hour; When dropwising soon, will contain the homogeneous phase mixed solution that remains SDS, the homogeneous phase mixed solution that contains KPS joins in the polymeric kettle.After dropwising, isothermal reaction 4 hours, obtaining particle diameter is that 410.8nm, gel content are 90.36% PBA latex.
The preparation of embodiment 2 polyethyl acrylate latex
Prescription
100 parts of ethyl propenoates
0.41 part of Potassium Persulphate (KPS)
0.69 part of sodium lauryl sulphate (SDS)
0.69 part of dimethacrylate second diester
0.3 part of potassium oleate
124 parts in water
Prepare polyethyl acrylate latex by patent ZL00101339.4 embodiment 5 described methods.Obtaining particle diameter is that 380nm, gel content are 89.16% polyethyl acrylate latex.
The preparation of embodiment 3 polyacrylic acid monooctyl ester latex
Prescription
100 parts of Octyl acrylates
0.9 part of Potassium Persulphate (KPS)
1.0 parts of sodium lauryl sulphate (SDS)
0.3 part of Sodium dodecylbenzene sulfonate (SDBS)
1.5 parts of Vinylstyrenes (DVB)
150 parts in water
At first water is with SDS, KPS, SDBS dissolving, and each forms the homogeneous phase mixed solution, DVB is joined form the homogeneous phase monomer mixed solution in the Octyl acrylate.In polymeric kettle, add homogeneous phase mixed solution and the surplus water that contains 0.10 part of SDS, when being heated to 50 ℃, 35 parts of homogeneous phase monomer mixed solutions are joined in the polymeric kettle, add the homogeneous phase mixed solution that contains 0.45 part of KPS again, reacted 0.5 hour, add the homogeneous phase mixed solution that contains 0.3 part of SDS, the homogeneous phase mixed solution that contains 0.1 part of SDBS, begin to drip the homogeneous phase monomer mixed solution, the dropping time is 2 hours, will contain the homogeneous phase mixed solution of 0.6 part SDS, the homogeneous phase mixed solution that contains 0.45 part of KPS, the homogeneous phase mixed solution that contains 0.2 part of SDBS and be divided into 5 equal portions.Monomer dropping add respectively after 0.4 hour, 0.8 hour, 1.2 hours, 1.6 hours and 2 hours 1 equal portions contain the homogeneous phase mixed solution of SDS and contain KPS the homogeneous phase mixed solution, contain the homogeneous phase mixed solution of SDBS.After dropwising, isothermal reaction 3 hours, obtaining particle diameter is that 510.8nm, gel content are 90.16% polyacrylic acid monooctyl ester latex.
The preparation of embodiment 4 butyl polyacrylates (PBA) latex
Prescription
100 parts of butyl acrylates (BA)
0.5 part of Potassium Persulphate (KPS)
0.64 part of sodium lauryl sulphate (SDS)
0.1 part of potassium stearate
1.2 parts of Vinylstyrenes (DVB)
135 parts in water
At first water is with SDS, KPS, potassium stearate dissolving, and each forms the homogeneous phase mixed solution, DVB is joined form the homogeneous phase monomer mixed solution among the BA.In polymeric kettle, add the homogeneous phase mixed solution that contains 0.02 part of SDS, the homogeneous phase mixed solution and the surplus water that contain 0.03 part of potassium stearate, when being heated to 50 ℃, 25 parts of homogeneous phase monomer mixed solutions are joined in the polymeric kettle, add the homogeneous phase mixed solution that contains 0.25 part of KPS again, reacted 1 hour, add the homogeneous phase mixed solution that contains 0.2 part of SDS, the homogeneous phase mixed solution that contains 0.03 part of potassium stearate, begin to drip the homogeneous phase monomer mixed solution, the dropping time is 2 hours, adds the homogeneous phase mixed solution that once contains 0.21 part of SDS when dripping 0.3 hour, the homogeneous phase mixed solution that contains 0.125 part of KPS, the homogeneous phase mixed solution that contains 0.03 part of potassium stearate; When dropwising soon, will contain the homogeneous phase mixed solution that remains SDS, the homogeneous phase mixed solution that contains KPS joins in the polymeric kettle.After dropwising, isothermal reaction 3.5 hours, obtaining particle diameter is that 320.8nm, gel content are 90.06% PBA latex.
The preparation of embodiment 5 polymethyl acrylate latex
Prescription
100 parts of methyl acrylates
0.5 part of Potassium Persulphate (KPS)
0.64 part of sodium lauryl sulphate (SDS)
1.2 parts of diallyl phthalates (DAP)
135 parts in water
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, DAP is joined form the homogeneous phase monomer mixed solution in the methyl acrylate.In polymeric kettle, add homogeneous phase mixed solution and the surplus water that contains 0.02 part of SDS, when being heated to 55 ℃, 25 parts of homogeneous phase monomer mixed solutions are joined in the polymeric kettle, add the homogeneous phase mixed solution that contains 0.25 part of KPS again, reacted 0.8 hour, and added the homogeneous phase mixed solution that contains 0.2 part of SDS, begin to drip the homogeneous phase monomer mixed solution, the dropping time is 2 hours, drips and adds the homogeneous phase mixed solution that once contains 0.21 part of SDS, the homogeneous phase mixed solution that contains 0.125 part of KPS after 1 hour; When dropwising soon, will contain the homogeneous phase mixed solution that remains SDS2, the homogeneous phase mixed solution that contains KPS joins in the polymeric kettle.After dropwising, isothermal reaction 4 hours, obtaining particle diameter is that 410.8nm, gel content are 90.36% polymethyl acrylate latex.
The preparation of embodiment 6 butyl polyacrylates (PBA) latex
Prescription
100 parts of butyl acrylates (BA)
0.5 part of Potassium Persulphate (KPS)
0.64 part of sodium lauryl sulphate (SDS)
1.2 parts of diallyl phthalates (DAP)
125 parts in water
At first water is with SD, KPS dissolving, and each forms the homogeneous phase mixed solution, DAP is joined form the homogeneous phase monomer mixed solution among the BA.In polymeric kettle, add homogeneous phase mixed solution and the surplus water that contains 0.02 part of SDS, when being heated to 58 ℃, 40 parts of homogeneous phase monomer mixed solutions are joined in the polymeric kettle, add the homogeneous phase mixed solution that contains 0.25 part of KPS again, reacted 0.5 hour, and added the homogeneous phase mixed solution that contains 0.2 part of SDS, begin to drip the homogeneous phase monomer mixed solution, the dropping time is 2 hours, drips and adds the homogeneous phase mixed solution that once contains 0.21 part of SDS, the homogeneous phase mixed solution that contains 0.125 part of KPS after 1 hour; When dropwising soon, will contain the homogeneous phase mixed solution that remains SDS, the homogeneous phase mixed solution that contains KPS joins in the polymeric kettle.After dropwising, isothermal reaction 3.5 hours, obtaining particle diameter is that 400.2nm, gel content are 90.36% PBA latex.
The preparation of embodiment 7 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
56.5 parts in embodiment 1PBA latex (butt)
5.5 parts of polybutadiene latexs (Lanzhou Petrochemical Company production)
38 parts of ST+AN (75: 25)
0.35 part of KPS
0.4 part of SDS
0.1 part of LPO
0.02 part of RSH
H
275 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add PBA latex, polybutadiene latex and surplus water among the embodiment 1, the beginning heat temperature raising.Add 30 parts of mix monomers when treating 60 ℃, the homogeneous phase mixed solution that contains 0.11 part of KPS, reacted 1 hour, add the homogeneous phase mixed solution that contains 0.12 part of SDS, begin to drip mix monomer, the dropping time is 2.5 hours, when monomer dropping is added the homogeneous phase mixed solution that once contains 0.12 part of SDS, the homogeneous phase mixed solution that contains 0.11 part of KPS after 1.2 hours; When dropwising soon, SDS will be remained, KPS joins in the polymeric kettle.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 483nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
45 parts
500 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The preparation of embodiment 8 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
63 parts in embodiment 2 PEA latex (butt)
2 parts in poly-hexadiene latex (Lanzhou Petrochemical Company production)
35 parts of ST+AN (95: 5)
0.25 part of KPS
0.35 part of SDS
0.04 part of potassium stearate
0.1 part of LPO
0.02 part of RSH
H
290 parts of O
At first water is with SDS, KPS, potassium stearate dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add PEA latex among the embodiment 2, poly-hexadiene latex and surplus water, the beginning heat temperature raising.Add 20 parts of mix monomers when treating 45 ℃, the homogeneous phase mixed solution that contains 0.09 part of KPS, reacted 1.5 hours, add the homogeneous phase mixed solution that contains 0.12 part of SDS, the homogeneous phase mixed solution that contains 0.01 part of potassium stearate, begin to drip mix monomer, the dropping time is 2 hours, will contain the homogeneous phase mixed solution of 0.24 part of SDS, the homogeneous phase mixed solution that contains 0.025 part of potassium stearate, the homogeneous phase mixed solution that contains 0.18 part of KPS and be divided into 4 equal portions.Add the homogeneous phase mixed solution contain 1 part of SDS after 0.5 hour, 1.0 hours, 1.5 hours and 2 hours respectively at monomer dropping, contain the homogeneous phase mixed solution of potassium stearate and contain the homogeneous phase mixed solution of KPS.After dropwising, isothermal reaction 2.5 hours obtains the graft latex that particle diameter is 323.1nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
45 parts
500 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
Implement the preparation of 9 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
43 parts in embodiment 3 polyacrylic acid monooctyl ester latex (butt)
3 parts of polybutadiene latexs (Lanzhou Petrochemical Company production)
54 parts of ST+AN (55: 45)
0.5 part of KPS
0.5 part of SDS
0.16 part of Sodium dodecylbenzene sulfonate (SDBS)
0.16 part of LPO
0.03 part of RSH
H
290 parts of O
At first water is with SDS, KPS, SDBS dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add latex, polybutadiene latex and surplus water among the embodiment 3, the beginning heat temperature raising.Add 20 parts of mix monomers when treating 40 ℃, the homogeneous phase mixed solution that contains 0.2 part of KPS, reacted 1 hour, add the homogeneous phase mixed solution that contains 0.2 part of SDS, the homogeneous phase mixed solution that contains 0.06 part of SDBS, begin to drip mix monomer, the dropping time is 1.5 hours, and the remaining homogeneous phase mixed solution that contains 0.3 part of SDS, the homogeneous phase mixed solution that contains 0.1 part of SDBS, the homogeneous phase mixed solution that contains 0.3 part of KPS are divided into 3 equal portions.Add 1 portion of homogeneous phase mixed solution that contains the homogeneous phase mixed solution of SDS and contain KPS after 0.5 hour, 1.0 hours and 1.5 hours respectively at monomer dropping.After dropwising, isothermal reaction 3.5 hours obtains the graft latex that particle diameter is 553.9nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up and stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 94 ℃ of slakings 10 minutes, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The preparation of embodiment 10 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
45 parts in embodiment 3 polyacrylic acid monooctyl ester latex (butt)
3 parts in polyprene latex
52 parts of ethyl styrene+methacrylonitriles (60: 40)
0.5 part of KPS
0.5 part of SDS
0.2 part of LPO
0.03 part of RSH
H
2100 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and ethyl styrene, methacrylonitrile, LPO, RSH are made mix monomer.In polymeric kettle, add embodiment 3 latex, polyprene latex and surplus water, the beginning heat temperature raising.Add 20 parts of mix monomers when treating 55 ℃, the homogeneous phase mixed solution that contains 0.17 part of KPS, reacted 0.6 hour, add the homogeneous phase mixed solution that contains 0.17 part of SDS, begin to drip mix monomer, the dropping time is 1.5 hours, and the remaining homogeneous phase mixed solution that contains 0.33 part of SDS, the homogeneous phase mixed solution that contains 0.33 part of KPS are divided into 3 equal portions.Add 1 portion of homogeneous phase mixed solution that contains the homogeneous phase mixed solution of SDS and contain KPS after 0.5 hour, 1.0 hours and 1.5 hours respectively at monomer dropping.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 553.9nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up and stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 94 ℃ of slakings 10 minutes, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The preparation of embodiment 11 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
57 parts in embodiment 1PBA latex (butt)
5 parts of polybutadiene latexs
38 parts of Vinyl toluene+AN (70: 30)
0.35 part of KPS
0.4 part of SDS
0.1 part of LPO
0.02 part of RSH
H
275 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and Vinyl toluene, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add PBA latex, polybutadiene latex and surplus water among the embodiment one, the beginning heat temperature raising.Add 30 parts of mix monomers when treating 55 ℃, the homogeneous phase mixed solution that contains 0.11 part of KPS, reacted 0.5 hour, add the homogeneous phase mixed solution that contains 0.12 part of SDS, begin to drip mix monomer, the dropping time is 2.5 hours, when monomer dropping is added the homogeneous phase mixed solution that once contains 0.14 part of SDS, the homogeneous phase mixed solution that contains 0.12 part of KPS after 1.2 hours; When dropwising soon, the homogeneous phase mixed solution of the remaining SDS of containing, the homogeneous phase mixed solution that contains KPS are joined in the polymeric kettle.After dropwising, isothermal reaction 3 hours obtains the graft latex that particle diameter is 483nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The preparation of embodiment 12 aryl ethylenes monomer-itrile group vinyl monomer graft copolymer
The grafting prescription
63 parts in embodiment 2PEA latex (butt)
2 parts of polybutadiene latexs
35 parts of bromostyrene+methacrylonitriles (95: 5)
0.3 part of KPS
0.35 part of SDS
0.1 part of LPO
0.02 part of RSH
H
290 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and bromostyrene, methacrylonitrile, LPO, RSH are made mix monomer.In polymeric kettle, add PEA latex, polybutadiene latex and surplus water among the embodiment 2, the beginning heat temperature raising.Add 20 parts of mix monomers when treating 50 ℃, the homogeneous phase mixed solution that contains 0.1 part of KPS, reacted 1.2 hours, add the homogeneous phase mixed solution that contains 0.12 part of SDS, begin to drip mix monomer, the dropping time is 2 hours, will contain the homogeneous phase mixed solution of remaining 0.23 part of SDS, the homogeneous phase mixed solution that contains 0.2 part of KPS is divided into 4 equal portions.Add the homogeneous phase mixed solution that contains the homogeneous phase mixed solution of 1 part of SDS and contain 1 part of KPS after 0.5 hour, 1.0 hours, 1.5 hours and 2 hours respectively at monomer dropping.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 323.1nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
48 parts
80 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
Embodiment 13 blending, granulation system polyacrylate resin composition
Prescription
55 parts of embodiment 7 grafting powders
SAN pearl material (Lanzhou petrochemical industry APN) 39 parts
5 parts of Powdered acrylonitrile-butadiene rubber
0.45 part of antioxidant 2246
0.25 part of EBS
0.25 part of Magnesium Stearate
0.05 part of silicone oil
By prescription various components are carried out weighing, mixed 6 minutes in super mixer afterwards, extruding pelletization prepares resin combination on the twin screw extruder that is warming up to 220 ℃ of embodiment 7 again, and its test result is seen table 1.
Embodiment 14 blending, granulation system polyacrylate resin composition
Prescription
46 parts of embodiment 7 grafting powders
46 parts of high shock resistance type substance law SAN pellets (Lanzhou petrochemical industry HH)
7 parts of powder styrene butadiene rubbers
0.1 part of EBS
0.05 part of Magnesium Stearate
0.85 part of silicone oil
Operation is with embodiment 13.The test result of polyacrylate resin composition is seen table 1.
Embodiment 15 blending, granulation system polyacrylate resin composition
Prescription
31 parts of embodiment 8 grafting powders
62 parts of SAN (Lanzhou petrochemical industry APH)
6 parts in polyhutadiene powder
0.5 part of antioxidant 2246
0.2 part of EBS
0.2 part of Magnesium Stearate
0.10 part of silicone oil
Operation is with embodiment 13.The test result of polyacrylate resin composition is seen table 1.
Embodiment 16 blending, granulation system polyacrylate resin composition
Prescription
33 parts of embodiment 7 grafting powders
SAN pearl material (Lanzhou petrochemical industry APH) 66 parts
0.3 part of antioxidant 1076
0.1 part of EBS
0.1 part of Magnesium Stearate
0.5 part of silicone oil
Operation is with embodiment 13.The test result of polyacrylate resin composition is seen table 1.
Comparative Examples 1
Graft polymerization, cohesion:
The grafting prescription
60 parts in embodiment 1PBA latex (butt)
40 parts of vinylbenzene ST+ vinyl cyanide AN (75: 25)
0.25 part of Potassium Persulphate (KPS)
0.4 part of sodium lauryl sulphate (SDS)
0.05 part of RSH
H
280 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, RSH are made mix monomer.The PBA latex and the surplus water that in polymeric kettle, add embodiment 1, the beginning heat temperature raising.Add 25 parts of mix monomers when treating 60 ℃, contain the homogeneous phase mixed solution of KPS, reacted 1 hour, add the homogeneous phase mixed solution that contains SDS, begin to drip mix monomer, the dropping time is 2 hours.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 460.8nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
45 parts
500 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The grafting powder carries out blending granulation system polyacrylate resin by embodiment 13.Its test result is seen table 1.
Comparative Examples 2
Graft polymerization, cohesion:
The grafting prescription
47 parts in embodiment 2PEA latex (butt)
53 parts of ST+AN (70: 30)
0.2 part of KPS
0.3 part of SDS
0.02 part of RSH
H
280 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add PEA latex and surplus water among the embodiment 2, the beginning heat temperature raising.Add 25 parts of mix monomers and the homogeneous phase mixed solution that contains KPS when treating 55 ℃, after polyreaction begins, add the homogeneous phase mixed solution that contains SDS, begin to drip mix monomer, the dropping time is 2 hours.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 290.1nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
45 parts
500 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The grafting powder carries out blending granulation system polyacrylate resin by embodiment 14, and its test result sees Table 1.
Comparative Examples 3
Graft polymerization, cohesion:
The grafting prescription
50 parts in embodiment 3 polyacrylic acid monooctyl ester latex (butt)
50 parts of ST+AN (60: 40)
0.15 part of KPS
0.6 part of SDS
0.03 part of RSH
H
2125 parts of O
At first water is with SDS, KPS dissolving, and each forms the homogeneous phase mixed solution, and vinylbenzene ST, vinyl cyanide AN, LPO, RSH are made mix monomer.In polymeric kettle, add misery ester gum breast of embodiment tripropylene and surplus water, the beginning heat temperature raising.Add 25 parts of mix monomers and the homogeneous phase mixed solution that contains KPS when treating 60 ℃, reacted 1 hour, add the homogeneous phase mixed solution that contains SDS, begin to drip mix monomer, the dropping time is 1.5 hours.After dropwising, isothermal reaction 4 hours obtains the graft latex that particle diameter is 569.1nm.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
48 parts
80 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
Carry out blending granulation system polyacrylate resin by embodiment 15, its test result sees Table 1:
Comparative Examples 4
Blending, granulation system polyacrylate resin composition
Prescription
33 parts of Comparative Examples one grafting powders
66 parts of SAN (Lanzhou petrochemical industry APN)
0.1 part of antioxidant 1076
0.1 part of EBS
0.3 part of Magnesium Stearate
0.5 part of silicone oil
Operation is with embodiment 13.The test result of polyacrylate resin composition sees Table 1.
By Comparative Examples 1～4 as can be seen, adopt simple polyacrylic ester latex to carry out grafting in graft polymerization, the grafting powder of gained and SAN, lubricant carry out blending, granulation, obtain the poor-performing of polyacrylate composition.
Comparative Examples 5
With the latex after acrylate, the diolefine copolymerization as the grafting core, graft reaction, blending, granulation system polyacrylate resin composition.
The basis latex formulations
100 parts of butyl acrylates (BA)
15 parts of divinyl
0.5 part of Potassium Persulphate (KPS)
0.64 part of sodium lauryl sulphate (SDS)
1.2 parts of diallyl phthalates (DAP)
135 parts in water
Operation makes basic latex with embodiment 1.
The grafting prescription
60 parts in basis latex
40 parts of Vinyl toluene+AN (70: 30)
0.35 part of KPS
0.4 part of SDS
0.15 part of LPO
0.02 part of RSH
H
280 parts of O
Operation is with embodiment 11.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The blending granulating formula
46 parts of grafting powders
46 parts of high shock resistance type substance law SAN pellets (Lanzhou petrochemical industry HH)
7 parts of powder styrene butadiene rubbers
0.1 part of EBS
0.05 part of Magnesium Stearate
0.85 part of silicone oil
Operation is with embodiment 14.The test result of polyacrylate resin composition sees Table 1.
As seen, the latex after acrylate, the diolefine copolymerization being carried out the final resin combination performance that grafting, cohesion, blending granulation make again as the grafting core will descend a lot.
Comparative Examples 6
With the grafting respectively of polyacrylic ester BA and polydiolefin in the grafting core, blending, granulation system polyacrylate resin composition.
Grafting prescription 1
60 parts in embodiment 1PBA latex (butt)
40 parts of Vinyl toluene+AN (70: 30)
0.35 part of KPS
0.4 part of SDS
0.15 part of LPO
0.02 part of RSH
H
280 parts of O
Operation is with embodiment 11.
Grafting prescription 2
60 parts of polybutadiene latexs
40 parts of Vinyl toluene+AN (70: 30)
0.35 part of KPS
0.4 part of SDS
0.15 part of LPO
0.02 part of RSH
H
280 parts of O
Operation is with embodiment 11.
The cohesion prescription
100 parts of graft latex 1+ graft latexes 2 (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The blending granulating formula
46 parts of grafting powders
46 parts of high shock resistance type substance law SAN pellets (Lanzhou petrochemical industry HH)
7 parts of powder styrene butadiene rubbers
0.1 part of EBS
0.05 part of Magnesium Stearate
0.85 part of silicone oil
Operation is with embodiment 14.The test result of polyacrylate resin composition sees Table 1.
As seen, with the grafting respectively of polyacrylic ester BA and polydiolefin in the grafting core, blending, granulation system polyacrylate resin poor-performing.
Comparative Examples 7
With polyacrylic ester: polydiolefin be 15: 150 o'clock mixing latex as the mixed grafting core, grafting, blending, granulation system polyacrylate resin composition.
The grafting prescription
5.5 parts in embodiment 1PBA latex (butt)
56.5 parts of polybutadiene latexs
38 parts of Vinyl toluene+AN (70: 30)
0.35 part of KPS
0.4 part of SDS
0.1 part of LPO
0.02 part of RSH
H
280 parts of O
Operation is with embodiment 11.
The cohesion prescription
100 parts of graft latexes (butt)
Sal epsom MgSO
410 parts
130 parts in water
With load weighted MgSO
4Soluble in water, heat up to stir, when treating that temperature rises to 60 ℃, slowly add graft latex, and continue to heat up, in 90 ℃ of slaking half an hour, cooling discharge afterwards.Washing, bake drying become the grafting powder.
The blending granulating formula
46 parts of grafting powders
46 parts of high shock resistance type substance law SAN pellets (Lanzhou petrochemical industry HH)
7 parts of powder styrene butadiene rubbers
0.1 part of EBS
0.05 part of Magnesium Stearate
0.85 part of silicone oil
Operation is with embodiment 14.The test result of polyacrylate resin composition sees Table 1.
Table 1 composition properties
Claims (19)
1. a polyacrylate resin composition is characterized in that composition contains following component, is 100 mass fractions in composition:
30～60 parts of aryl ethylene monomers of A-itrile group vinyl monomer graft copolymer,
35～65 parts of styrene-acrylonitrile copolymers of B, styrene units accounts for 65～78% (wt) in the multipolymer, and acrylonitrile unit accounts for 22～35% (wt),
0～8 part of C is selected from one or more in Powdered acrylonitrile-butadiene rubber, powder styrene butadiene rubber, the powder polyhutadiene,
Wherein aryl ethylene monomer-itrile group vinyl monomer graft copolymer A is mixed grafting core (A1) and is the graft copolymer of graft shell (A2) with aryl ethylene monomer and itrile group vinyl monomer with polyacrylic ester and polydiolefin, the latex particle size of polyacrylate grafting core is 200～600nm, gel content 88%～93%, the polyacrylic acid ester units accounts for 25%～70% (wt) among the graft copolymer A, the polydiolefin unit accounts for 0.5%～10% (wt), the aryl ethylene unit accounts for 15%～65% (wt), and the itrile group vinyl units accounts for 1.5%～35% (wt); The aryl ethylene monomer is selected from vinylbenzene, Vinyl toluene, 2, the 4-dimethyl styrene, ethyl styrene, to tert-butylbenzene ethene, alpha-methyl styrene, α-ethyl styrene, the Alpha-Methyl p-methylstyrene, halogenated styrenes, in haloalkyl vinylbenzene and the vinyl naphthalene one or more, polyacrylic ester is selected from polymethyl acrylate, polyethyl acrylate, in butyl polyacrylate and the polyacrylic acid monooctyl ester one or more, polydiolefin is selected from polyhutadiene, polyprene, a kind of in poly-hexadiene and the polycyclopentadiene, the itrile group vinyl monomer is vinyl cyanide and/or methacrylonitrile.
2. a kind of polyacrylate resin composition according to claim 1 is characterized in that the preferred 300～500nm of latex particle size of polyacrylate grafting core among the graft copolymer A.
3. a kind of polyacrylate resin composition according to claim 1, it is characterized in that the polyacrylic acid ester units accounts for 30%～65% among the graft copolymer A, the polydiolefin unit accounts for 0.5%～10% (wt), and the aryl ethylene unit accounts for 25%～40%, and the itrile group vinyl units accounts for 2%～30%.
4. a kind of polyacrylate resin composition according to claim 1 is characterized in that 2～8 parts of C components.
5. a kind of polyacrylate resin composition according to claim 1 is characterized in that polyacrylic ester is one or more in butyl polyacrylate, the polyacrylic acid monooctyl ester.
6. a kind of polyacrylate resin composition according to claim 1 is characterized in that the aryl ethylene monomer is vinylbenzene and/or Vinyl toluene.
7. the preparation method of a kind of polyacrylate resin composition according to claim 1 is characterized in that the concrete preparation process of composition is:
(1) preparation of aryl ethylene monomer-itrile group vinyl monomer graft copolymer is 100 mass parts in the summation of polyacrylic ester latex, polydiolefin latex, aryl ethylene class monomer and itrile group vinyl monomer, and wherein latex is in butt:
(a) basic latex
Add 0.5～10 part in 25～70 parts of polyacrylic ester latexs and polydiolefin latex in polymeric kettle, form basic latex, wherein the polyacrylic ester latex particle diameter is 200～600nm, gel content 88%～93%;
(b) comonomer grafting basis latex
Comonomer is made up of aryl ethylene monomer and itrile group vinyl monomer, wherein the aryl ethylene monomer is 15～65 parts, the itrile group vinyl monomer is 1.5～35 parts, 0.1～1.5 part of emulsifying agent, 0.05～1.0 part of water soluble starter, 0.03～0.6 part of oil-soluble initiator, 0.005～0.1 part of molecular weight regulator, 25～250 parts in water;
Emulsifying agent, water soluble starter are used water dissolution respectively, form homogeneous mixed solution (i) respectively, (ii); Aryl ethylene monomer, itrile group vinyl monomer, oil-soluble initiator, molecular weight regulator are made mix monomer;
35～60 ℃ of basis latex heating, add 20%～40% mix monomer and 30%～50% homogeneous mixed solution (ii), reacted 0.5～1.5 hour, the homogeneous mixed solution (i) of adding 30%～50%, begin to add remaining mixed monomer, remaining homogeneous mixed solution (i) and (ii), 1.5～2.5 hours joining days, monomer adopts the mode that drips, homogeneous mixed solution (i) (ii) divides 2 times to add last time or to drip continuously; After dropwising, 65～80 ℃ were reacted 2～4 hours down, were cooled to 50～60 ℃ of dischargings, obtained graft latex;
(c) graft latex is condensed, washing, drying are made aryl ethylene monomer-itrile group vinyl monomer graft copolymer grafting powder again;
(2) grafting powder and styrene-acrylonitrile copolymer blending, granulation are 100 mass fractions in composition:
30～60 parts of aryl ethylene monomer-itrile group vinyl monomer graft copolymer grafting powders, 35～65 parts of styrene-acrylonitrile copolymers and 0～8 part are selected from one or more in Powdered acrylonitrile-butadiene rubber, powder styrene butadiene rubber, the powder polyhutadiene, carry out blending, blend is extruded through twin screw extruder can obtain the polyacrylate resin composition product.
8. the preparation method of a kind of polyacrylate resin composition according to claim 7 is characterized in that water soluble starter is a kind of in Potassium Persulphate, ammonium persulphate, the Sodium Persulfate.
9. the preparation method of a kind of polyacrylate resin composition according to claim 8 is characterized in that water soluble starter is a Potassium Persulphate.
10. want the preparation method of 7 described a kind of polyacrylate resin compositions according to right, it is characterized in that oil-soluble initiator is a kind of of dilauroyl peroxide, dibenzoyl peroxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), Cellmic C 121.
11. the preparation method of a kind of polyacrylate resin composition according to claim 10 is characterized in that oil-soluble initiator is a dilauroyl peroxide.
12. the preparation method of a kind of polyacrylate resin composition according to claim 7 is characterized in that molecular weight regulator is a kind of in positive mercaptan, branched mercaptan, unsaturated fatty acids, neopentanoic acid, ethylene glycol, Virahol, the alkiodide.
13. the preparation method of a kind of polyacrylate resin composition according to claim 12 is characterized in that molecular weight regulator is uncle's lauryl mercaptan.
14. the preparation method of a kind of polyacrylate resin composition according to claim 7 is characterized in that emulsifying agent is to be in sodium lauryl sulphate, dodecyl sulphate potassium, Sodium dodecylbenzene sulfonate, Potassium dodecylbenzenesulfonate, potassium stearate, synthetic fatty acid potassium, sodium oleate, the potassium oleate one or more.
15. the preparation method of a kind of polyacrylate resin composition according to claim 14 is characterized in that emulsifying agent is sodium lauryl sulphate and/or Sodium dodecylbenzene sulfonate.
16. the preparation method of a kind of polyacrylate resin composition according to claim 7 is characterized in that the preparation method of polyacrylic ester latex is, is 100 mass parts in acrylate monomer:
Water: acrylate monomer is (100～150): 100, and emulsifying agent: acrylate monomer is (0.6～1.4): 100, water soluble starter: acrylate monomer is (0.3～1.0): 100, linking agent: acrylate monomer is (0.5～3.0): 100;
Emulsifying agent, water soluble starter are used water dissolution respectively, and 1., 2. each form the homogeneous phase mixed solution, linking agent joined in the acrylate monomer form monomer mixed solution 3.;
1. and surplus water in polymeric kettle, add 0.5%～15% homogeneous phase mixed solution, when being heated to 50～65 ℃, 2. 3. 20%～40% monomer mixed solution joined in the polymeric kettle with 30%～50% homogeneous phase mixed solution, reacted 0.5～1.5 hour, add 30～50% homogeneous phase mixed solutions 1.; 1. and 2. begin to add remaining mixed monomer, remaining homogeneous mixed solution, 1.5～2.5 hours joining days, monomer adopts the mode that drips, and 1., 2. homogeneous mixed solution divides 2 times to add last time or continuously; After dropwising, 65～80 ℃ were reacted 2～4 hours down, were cooled to 50～60 ℃ of dischargings, obtained polyacrylic ester latex.
17. the preparation method of a kind of polyacrylate resin composition according to claim 16 is characterized in that linking agent: acrylate monomer is (0.5～3.0): 100.
18. the preparation method of a kind of polyacrylate resin composition according to claim 16 is characterized in that linking agent is contract in basic benzene, tirethylene glycol dimethacrylate, monoene propyl group maleic acid ester, the diallyl phthalate one or more of triallyl cyanurate, Ethylene glycol dimethacrylate, Vinylstyrene, two.
19. the preparation method of a kind of acrylate composition according to claim 16 is characterized in that linking agent is diallyl phthalate and/or Vinylstyrene.
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| CN1156736A (en) * | 1995-10-04 | 1997-08-13 | 巴斯福股份公司 | Shaped articles comprising thermoplastic molding materials |
| CN1404506A (en) * | 2000-02-23 | 2003-03-19 | 拜尔公司 | ABS moulding material with improved workability and a high lustre |
| CN1760254A (en) * | 2005-06-03 | 2006-04-19 | 中化国际余杭高分子材料研发设计有限公司 | Composition of cinnamene resin with good light sensation and plasticity |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156736A (en) * | 1995-10-04 | 1997-08-13 | 巴斯福股份公司 | Shaped articles comprising thermoplastic molding materials |
| CN1404506A (en) * | 2000-02-23 | 2003-03-19 | 拜尔公司 | ABS moulding material with improved workability and a high lustre |
| CN1760254A (en) * | 2005-06-03 | 2006-04-19 | 中化国际余杭高分子材料研发设计有限公司 | Composition of cinnamene resin with good light sensation and plasticity |
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| Publication number | Publication date |
|---|---|
| CN101633769A (en) | 2010-01-27 |
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