CN102911318B - Graft copolymer and thermoplastic resin composition - Google Patents
Graft copolymer and thermoplastic resin composition Download PDFInfo
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- CN102911318B CN102911318B CN201210272486.5A CN201210272486A CN102911318B CN 102911318 B CN102911318 B CN 102911318B CN 201210272486 A CN201210272486 A CN 201210272486A CN 102911318 B CN102911318 B CN 102911318B
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Abstract
The present invention relates to graft copolymer and thermoplastic resin composition, described graft copolymer is by obtaining the monomer graft polymerizes containing at least one be selected from the group that is made up of aromatic vinyl system monomer and vinyl cyanide system monomer of 20 ~ 95 weight parts to the rubber polymer of 5 ~ 80 weight parts, wherein, rubber polymer has the cis-1 of 21 ~ 30%, 4 keys, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1,2-vinyl bonds is as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35.
Description
Technical field
The present invention relates to use the excellent rubber polymer of polymerization stability, shock-resistance and the excellent graft copolymer of mobility and the thermoplastic resin composition that obtained by this graft copolymer.
Background technology
ABS resin is the resin that the balance of shock-resistance and mobility is excellent, is used to the shell of the interior exterior member of the vehicles such as automobile, various household appliances or OA equipment, other groceries fields etc. widely in field.Present rapid growth at Asian market (particularly China), it utilizes field more and more to expand.On the other hand, as being representative with automotive field, requiring lighting, developing the thin-walled property of parts.Therefore, in order to further thin-walled property, require than now more excellent shock-resistance and mobility.
As improvement shock-resistance and the method for mobility, to propose and with the two or more rubber polymer (Japanese Unexamined Patent Publication 11-130825 publication) at peak with different tan δ.But, two or more rubber polymers must be prepared, there is less economical problem.
In addition, as the resin combination that the balance of tint permanence, gloss, rigidity and impact strength is excellent, propose the reinforcing rubber aromatic mono-vinyl resin combination (Japanese Laid-Open Patent Publication 60-233116 publication) using and there is the rubber polymer of specific microstructure.But, insufficient as the physical property required now.
Summary of the invention
The object of the invention is to, provide use the excellent rubber polymer of polymerization stability, shock-resistance and the excellent graft copolymer of mobility and the thermoplastic resin composition that obtained by this graft copolymer.
The present inventor conducts in-depth research to solve the problem of prior art, found that, be conceived to microstructure and the swelling capacity of rubber polymer, rubber polymer use there is the cis-Isosorbide-5-Nitrae key of 21 ~ 30%, the anti-form-1 of 47 ~ 60%, 4 keys, 16 ~ 23% 1,2-vinyl bonds is as microstructure and swelling capacity is the rubber polymer of 13 ~ 35, thus, not only the polymerization stability of rubber polymer is excellent, and can obtain shock-resistance and the excellent graft copolymer of mobility.
Namely, the thermoplastic resin composition that the present invention relates to graft copolymer and obtained by this graft copolymer, described graft copolymer is by obtaining at least one monomer graft polymerizes be selected from aromatic vinyl system monomer and vinyl cyanide system monomer of 20 ~ 95 weight parts to the rubber polymer of 5 ~ 80 weight parts, it is characterized in that, rubber polymer has the cis-1 of 21 ~ 30%, 4 keys, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1,2-vinyl bonds is as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35.
According to the present invention, can provide use the excellent rubber polymer of polymerization stability, shock-resistance and the excellent graft copolymer of mobility and use have the thermoplastic resin composition of this graft copolymer.
Embodiment
Below, be described in detail with regard to the preferred embodiment of the present invention.But the present invention is not limited to embodiment below.
Graft copolymer of the present invention, to be selected from aromatic vinyl system monomer, vinyl cyanide system monomer and can with at least one monomer graft polymerizes in other vinyl monomers of these monomer copolymerizations to having cis-1,4 keys are 21 ~ 30%, anti-form-1,4 keys to be 47 ~ 60%, 1,2-vinyl bonds be 16 ~ 23% microstructure and swelling capacity be 13 ~ 35 rubber polymer on the graft copolymer that obtains.
The graft copolymer of present embodiment is by obtaining the monomer graft polymerizes containing at least one be selected from aromatic vinyl system monomer and vinyl cyanide system monomer of 20 ~ 95 weight parts to the rubber polymer of 5 ~ 80 weight parts, rubber polymer has the cis-1 of 21 ~ 30%, 4 keys, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1,2-vinyl bonds is as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35.
As rubber polymer, can enumerate: polybutadiene rubber, styrene butadiene rubbers (SBR), styrene-butadiene-styrene (SBS) segmented copolymer, vinylbenzene-(ethylene-butylene)-vinylbenzene (SEBS) segmented copolymer, acrylonitrile-butadiene rubber (NBR), acrylonitrile-styrene-divinyl rubber, methyl methacrylate butadiene rubber.Particularly preferably polybutadiene rubber, styrene butadiene rubbers, acrylonitrile-butadiene rubber.
Importantly the microstructure of rubber polymer is cis-Isosorbide-5-Nitrae key 21 ~ 30%, anti-form-1,4 key 47 ~ 60%, 1,2-vinyl bonds 16 ~ 23%, and the swelling capacity of rubber polymer is 13 ~ 35.Cis-Isosorbide-5-Nitrae key 21 ~ 30% extraneous situation and the extraneous situation of 1,2-vinyl bonds 16 ~ 23% under, polymerization stability significantly reduces.At anti-form-1,4 keys are in the extraneous situation of 47 ~ 60%, and shock-resistance and mobility reduce.In the extraneous situation of swelling capacity 13 ~ 35, the cross-linking density of rubber polymer is not best, and shock-resistance reduces.The swelling capacity of preferred rubber matter polymkeric substance is 15 ~ 30, is more preferably 17 ~ 25.
The microstructure of rubber polymer can by the vinylbenzene used by infrared absorption spectrometry and cis-1,4 keys, anti-form-1, the absorbancy of the characteristic absorbance of 4 keys, 1,2-vinyl bonds and by Hampton method (reference: R.R.Hampton; Ana1.Chem., the formula of the specific absorbance of each key of 21,923 (1949)) trying to achieve is obtained.
With regard to the mensuration of the swelling capacity of rubber polymer, the solid matter of rubber polymer is flooded 48 hours in 100m1 toluene at 25 DEG C, with 300 object metal mesh filters, (weight a) and to the composition being insoluble to toluene carries out the weight (weight b) after vacuum-drying to the mensuration weight being insoluble to the composition of toluene now, obtains swelling capacity by following formula.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/vacuum-drying after weight (weight b)
The weight average particle diameter of rubber polymer is not particularly limited, and from the view point of physical property balance, is preferably 0.1 ~ 0.9 μm, is more preferably 0.2 ~ 0.5 μm, more preferably 0.34 ~ 0.5 μm, is particularly preferably 0.38 ~ 0.45 μm.In addition, the adjustment of the weight average particle diameter of rubber polymer can use known method, also can use by manufacture the smaller rubber polymer latex of particle diameter in advance and make its condense expand and formed target weight median size cohesion expand rubber polymer.
As the adjustment microstructure of rubber polymer and the method for swelling capacity, can be any method, the method for kind and amount etc. of the kind that such as changes polymerization starter and the use of amount, free radical catalyst or base metal catalysts, polymerization temperature, chain-transfer agent can be enumerated.Particularly the impact of polymerization temperature is comparatively large, and the ratio regular meeting of cis-Isosorbide-5-Nitrae key occurs significantly to change because polymerization temperature is different.Swelling capacity can occur significantly to change because the cross-linking density of rubber polymer composition is different.
Rubber polymer can be obtained by known polymerization.Now, the reagent and additive in polymerization such as common tensio-active agent, initiator, molecular weight regulator, ionogen can be used.As tensio-active agent, can enumerate: an alkali metal salt etc. of the alkylsulphonic acids such as an alkali metal salt of the carboxylic acids such as an alkali metal salt of the higher fatty acid such as an alkali metal salt of nilox resin acid potassium or nilox resin acid such as nilox resin acid sodium etc., potassium oleate or sodium oleate and Sodium dodecylbenzene sulfonate.
As initiator, can enumerate: make the reducto oxydative system etc. that the persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate or the organo-peroxide such as tertbutyl peroxide, isopropyl benzene hydroperoxide and reductive agent composition combine.As molecular weight regulator, can enumerate: thio-alcohol (tertiary lauryl mercaptan, n-dodecyl mercaptan etc.), terpinolene, alpha-methyl styrene dimer etc.
As ionogen, can enumerate: the alkaline matters such as sodium hydroxide, potassium hydroxide, ammonium hydroxide; Sodium-chlor, potassium sulfate, sodium-acetate, sodium sulfate, potassiumphosphate, tetrapotassium pyrophosphate etc.These reagent and additive in polymerization can be used alone or mix two or more use.
The consumption of these reagent and additive in polymerization is not also limited, generally, form every 100 weight parts monomers of rubber polymer, use tensio-active agent 0.5 ~ 5.0 weight part, initiator 0.1 ~ 3.0 weight part, molecular weight regulator 0 ~ 1 weight part, ionogen 0.02 ~ 1 weight part.In addition, the addition means forming the monomer of rubber polymer, tensio-active agent and reagent and additive in polymerization is also not particularly limited, the initial stage can be used to add in the lump or monomer and/or tensio-active agent continuously or successively any one method such as interpolation.Polymerization temperature is also not particularly limited, from the view point of the ratio controlling cis-Isosorbide-5-Nitrae key, the preferably scope of 50 ~ 80 DEG C.
The graft copolymer of present embodiment obtains by making at least one monomer graft polymerizes that is selected from aromatic vinyl system monomer and vinyl cyanide system monomer under the existence of rubber polymer.In addition, can be used together can with other vinyl monomers of aromatic vinyl system monomer and vinyl cyanide system monomer copolymerization.
As the aromatic vinyl system monomer forming graft copolymer, can enumerate: vinylbenzene, alpha-methyl styrene, p-methylstyrene, bromstyrol etc., can use a kind of or two or more.Particularly preferably vinylbenzene, alpha-methyl styrene.
As vinyl cyanide system monomer, can enumerate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, anti-maleic nitrile etc., can use a kind of or two or more.Particularly preferably vinyl cyanide.
As can other vinyl monomers of copolymerization, can enumerate: (methyl) acrylic ester monomer, maleimide system monomer, acid amides system monomer etc., can use a kind of or two or more.As (methyl) acrylic ester monomer, can illustrate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, 2-EHA, (methyl) phenyl acrylate, (methyl) vinylformic acid 4-tertiary butyl phenyl ester, (methyl) vinylformic acid dibromo phenyl ester, (methyl) vinylformic acid chlorobenzene ester etc.As maleimide system monomer, can illustrate: N-phenylmaleimide, N-N-cyclohexylmaleimide etc.As acid amides system monomer, can illustrate: acrylamide, Methacrylamide etc.
The composition ratio of the above-mentioned monomer that grafting is aggregated on rubber polymer is not particularly limited, preferably: aromatic vinyl system monomer 60 ~ 90 % by weight, vinyl cyanide system monomer 10 ~ 40 % by weight and can the composition ratio of other vinyl monomers 0 ~ 30 % by weight of copolymerization; The composition ratio of aromatic vinyl system monomer 30 ~ 80 % by weight and (methyl) acrylic ester monomer 20 ~ 70 % by weight; Aromatic vinyl system monomer 20 ~ 70 % by weight, (methyl) acrylic ester monomer 20 ~ 70 % by weight, vinyl cyanide system monomer 10 ~ 60 % by weight and can the composition ratio of other vinyl monomers 0 ~ 30 % by weight of copolymerization.
With regard to the ratio of the rubber polymer in graft copolymer and monomer, from physical property balance aspect, need for rubber polymer 5 ~ 80 weight part, monomer 20 ~ 95 weight part, be preferably rubber polymer 30 ~ 70 weight part, monomer 30 ~ 70 weight part.The percentage of grafting of graft copolymer is not particularly limited, but when percentage of grafting is too low, there is the trend that shock-resistance reduces, when percentage of grafting is too high, there is the trend that mobility reduces, therefore, be preferably 25 ~ 85%, be more preferably 30 ~ 60%.
Be not particularly limited the swelling capacity of graft copolymer, from the view point of shock-resistance, swelling capacity is preferably 3 ~ 9, is more preferably 4 ~ 8.As the method for the swelling capacity of adjustment graft copolymer, can be any method, but there is the tendency of the molecular weight relying on percentage of grafting and graft side chain significantly.
The percentage of grafting of graft copolymer can be that graft copolymer is separated into soluble ingredient and insoluble composition and is obtained by following formula by solvent with acetone.
Weight × 100 of the rubber polymer in percentage of grafting (%)=(being insoluble to the weight of the rubber polymer in the weight-graft copolymer of the composition of acetone)/graft copolymer
The swelling capacity of graft copolymer can be obtained as follows: by graft copolymer dipping in acetone, take out its insoluble composition, after vacuum-drying one night, the composition being insoluble to acetone of the graft copolymer after vacuum-drying is flooded 48 hours in 100m1 toluene at 25 DEG C, with 300 object metal mesh filters, (weight a) and to the composition being insoluble to toluene carries out the weight (weight b) after vacuum-drying to the mensuration weight being insoluble to the composition of toluene now, and is tried to achieve by following formula.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/vacuum-drying after weight (weight b)
Being not particularly limited for the method making graft copolymer be polymerized of present embodiment, can use emulsion polymerization, suspension polymerization, mass polymerization etc.When use emulsion polymerization, by by above-mentioned monomer graft polymerizes on above-mentioned rubber polymer, the latex of graft copolymer can be obtained.With regard to the latex of graft copolymer, by solidifying via utilizing known method to carry out, cleaning, dewater, drying process, the powder of graft copolymer can be obtained.
In addition, the graft copolymer obtained can be used alone, also can be used in combination with other thermoplastic resins as required.As other such thermoplastic resins, can enumerate such as: styrene-acrylonitrile resin (AS resin), alpha-methyl styrene-acrylonitrile resin, styrene-acrylonitrile-methyl-methacrylate resin (MAS resin), N-phenylmaleimide-styrene resin, N-phenylmaleimide-styrene-acrylonitrile resin, polycarbonate resin, polybutylene terephthalate resin, pet resin, polyamide resin, rubber-reinforced polystyrene resin (HIPS resin), acrylonitrile-butadiene rubber-styrene resin (ABS resin), vinyl cyanide-terpolymer EP rubber-styrene resin (AES resin), methyl methacrylate butadiene rubber-styrene resin (MBS resin), acrylonitri Ie-acrylic rubber-styrene resin (AAS resin) etc.
The thermoplastic resin composition of present embodiment contains above-mentioned graft copolymer and other thermoplastic resins.
Thermoplastic resin composition can also be contained as required further: the antioxidants such as hindered phenol system, organic compounds containing sulfur system, organic phosphorus compound system; The thermo-stabilizers such as phenol system, acrylic ester; The UV light absorber of benzotriazole system, benzophenone series, salicylate system; The lubricants such as organic nickel system, higher fatty acid amides class; The softening agent such as phosphoric acid ester; The halogen-containing based compounds such as many bromophenyls ether, tetrabromobisphenol-A, brominated epoxy oligomer, bromination; Fire retardant/the flame retardant such as phosphorus series compound, ANTIMONY TRIOXIDE SB 203 99.8 PCT; Odor masking agent; Carbon black; Titanium oxide; Pigment and dyestuff etc.And then, also can add strengthening agent or the weighting agents such as talcum, calcium carbonate, aluminium hydroxide, glass fibre, glass flake, granulated glass sphere, carbon fiber, steel fiber.
Thermoplastic resin composition in present embodiment can be obtained by mixing mentioned component.In order to mix, the known kneading devices such as such as forcing machine, roller, closed mixing machine, kneading machine can be used.
According to the present embodiment, above-mentioned graft copolymer or thermoplastic resin composition can be used to make the products formed of excellent impact resistance.
[embodiment]
Illustrate that embodiment illustrates the present invention below, but the present invention is not by any restriction of these embodiments.It should be noted that, " part " and " % " of illustrating in an embodiment is weight standard.In addition, the evaluation of each physical property in embodiment and comparative example is carried out by method below.Measurement result and evaluation result are shown in table 1 and table 2.
(mensuration of the weight average particle diameter of rubber polymer latex)
Osmium dyeing is carried out to rubber polymer latex, use transmission electron microscope (NEC manufacture: JEM-1400) to take 800 photographs, use image analysis apparatus (Asahi Chemical Industry manufactures: IP-1000C type) to try to achieve weight average particle diameter.
(sample making for microstructure measures)
Adding acetone and place in graft copolymer or the thermoplastic resin composition that obtained by this graft copolymer makes it dissolve a night.Centrifugation (12000rpm × 30 minute) is carried out to the sample after dissolving.In centrifuge tube, residual being insoluble in the composition of acetone adds acetone, again carries out centrifugation under the same conditions.After centrifugation, discarded acetone-insoluble composition, fully cleans with methyl alcohol while carry out suction filtration to the composition being insoluble to acetone.And then in order to remove impurity, adding Virahol above-mentioned being insoluble in the composition of acetone and making with mantle heater it reflux more than 7 hours.After backflow terminates, with glass filter, suction filtration is carried out to the composition being insoluble to acetone, fully clean with Virahol.Composition vacuum-drying one night of acetone will be insoluble to.Being insoluble in the composition of acetone after vacuum drying adds normal hexane, makes it reflux more than 5 hours with mantle heater.With filter paper, extracting solution is filtered, with vaporizer concentrate solid after, carry out vacuum-drying.This vacuum-drying thing is dissolved in chloroform.
(mensuration of absorbancy)
As above the sample obtained is coated on plate that thallium bromo-iodide (KRS-5) makes, makes chloroform dry, use Fourier transform infrared light-dividing device (perkin elmer manufactures Spectrum One) to measure absorbancy.
(calculating of microstructure)
Cinnamic characteristic absorbance is apparent in 699cm
-1, the cis of divinyl-Isosorbide-5-Nitrae key, anti-form-1, the characteristic absorbance of 4 keys and 1,2-vinyl bonds is apparent in 724cm separately
-1, 967cm
-1, 911cm
-1.Tried to achieve the containing ratio (%) of each key by Hampton formula by the absorbancy obtained.
S＝0.374A
699-0.260A
724-0.014A
911
C＝-0.025A
699+1.834A
724-0.027A
911-0.004A
967
V=-0.007A
699-0.015A
724+0.314A
911-0.007A
967
T=-0.007A
699-0.036A
724-0.011A
911+0.394A
967
Cis-Isosorbide-5-Nitrae key (%)=C/ (C+V+T) × 100
Anti-form-1,4 keys (%)=T/ (C+V+T) × 100
1,2-vinyl bonds (%)=V/ (C+V+T) × 100
At this, A
λfor the absorbancy at respective wave number place.
(swelling capacity of rubber polymer measures)
The solid matter of rubber polymer is flooded 48 hours in 100m1 toluene at 25 DEG C, with 300 object metal mesh filters, (weight a) and to the composition being insoluble to toluene carries out the weight (weight b) after vacuum-drying to the mensuration weight being insoluble to the composition of toluene now, tries to achieve swelling capacity by following formula.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/vacuum-drying after weight (weight b)
(swelling capacity of graft copolymer measures)
By graft copolymer dipping in acetone, take out its insoluble composition, carry out vacuum-drying one night.The composition being insoluble to acetone of the graft copolymer after vacuum-drying is flooded 48 hours in 100m1 toluene at 25 DEG C, with 300 object metal mesh filters, (weight a) and to the composition being insoluble to toluene carries out the weight (weight b) after vacuum-drying to the mensuration weight being insoluble to the composition of toluene now, tries to achieve swelling capacity by following formula.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/vacuum-drying after weight (weight b)
(evaluation of polymerization stability)
The evaluation of the polymerization stability of rubber polymer, filters the rubber polymer latex obtained after rubber polymer polymerization with 300 object wire nettings, judges with the amount of the condensation product obtained.Evaluation result is shown in table 2.
A: lower than 0.01 (%)
More than B:0.01 and lower than 0.05 (%)
More than C:0.05 and lower than 0.10 (%)
More than D:0.10
(manufacture of rubber polymer latex (a-1))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 90 weight part, vinylbenzene 10 weight part, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight part, sodium hydroxide 0.15 weight part, deionized water 163 weight part, carry out stirring and make it react 41 hours at 70 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 70 DEG C while continue stirring 6 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-1) thus.With regard to the microstructure of this rubber polymer latex (a-1), cis-Isosorbide-5-Nitrae key is 25%, anti-form-1, and 4 keys are 56%, 1,2-vinyl bonds is 19%, and weight average particle diameter is 420nm.In addition, swelling capacity is 15.
(manufacture of rubber polymer latex (a-2))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 95 weight part, vinylbenzene 5 weight part, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight part, sodium hydroxide 0.15 weight part, deionized water 163 weight part, carry out stirring and make it react 45 hours at 65 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 75 DEG C while continue stirring 6 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-2) thus.With regard to the microstructure of this rubber polymer latex (a-2), cis-Isosorbide-5-Nitrae key is 27%, anti-form-1, and 4 keys are 53%, 1,2-vinyl bonds is 20%, and weight average particle diameter is 389nm.In addition, swelling capacity is 28.
(manufacture of rubber polymer latex (a-3))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 98 weight part, vinyl cyanide 2 weight part, n-dodecyl mercaptan 0.35 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 2.1 weight part, sodium hydroxide 0.18 weight part, deionized water 200 weight part, carry out stirring and make it react 48 hours at 55 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 70 DEG C while continue stirring 5 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-3) thus.With regard to the microstructure of this rubber polymer latex (a-3), cis-Isosorbide-5-Nitrae key is 23%, anti-form-1, and 4 keys are 55%, 1,2-vinyl bonds is 22%, and weight average particle diameter is 390nm.In addition, swelling capacity is 23.
(manufacture of rubber polymer latex (a-4))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 95 weight part, vinylbenzene 5 weight part, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 2.5 weight part, nilox resin acid sodium 2.9 weight part, sodium hydroxide 0.15 weight part, deionized water 188 weight part, carry out stirring and make it react 51 hours at 38 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 52 DEG C while continue stirring 9 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-4) thus.With regard to the microstructure of this rubber polymer latex (a-4), cis-Isosorbide-5-Nitrae key is 23%, anti-form-1, and 4 keys are 48%, 1,2-vinyl bonds is 29%, and weight average particle diameter is 375nm.In addition, swelling capacity is 19.
(manufacture of rubber polymer latex (a-5))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 90 weight part, vinylbenzene 10 weight part, n-dodecyl mercaptan 0.5 weight part, Potassium Persulphate 1.7 weight part, nilox resin acid sodium 2.5 weight part, sodium hydroxide 0.2 weight part, deionized water 200 weight part, carry out stirring and make it react 50 hours at 45 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 55 DEG C while continue stirring 6 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-5) thus.With regard to the microstructure of this rubber polymer latex (a-5), cis-Isosorbide-5-Nitrae key is 31%, anti-form-1, and 4 keys are 53%, 1,2-vinyl bonds is 16%, and weight average particle diameter is 375nm.In addition, swelling capacity is 30.
(manufacture of rubber polymer latex (a-6))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 99 weight part, vinylbenzene 1 weight part, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight part, sodium hydroxide 0.15 weight part, deionized water 163 weight part, carry out stirring and make it react 42 hours at 89 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 90 DEG C while continue stirring 9 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-6) thus.With regard to the microstructure of this rubber polymer latex (a-6), cis-Isosorbide-5-Nitrae key is 21%, anti-form-1, and 4 keys are 63%, 1,2-vinyl bonds is 16%, and weight average particle diameter is 333nm.In addition, swelling capacity is 19.
(manufacture of rubber polymer latex (a-7))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 90 weight part, vinylbenzene 10 weight part, Potassium Persulphate 0.7 weight part, nilox resin acid sodium 1.9 weight part, sodium hydroxide 0.15 weight part, deionized water 163 weight part, carry out stirring and make it react 43 hours at 65 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 70 DEG C while continue stirring 6 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-7) thus.With regard to the microstructure of this rubber polymer latex (a-7), cis-Isosorbide-5-Nitrae key is 23%, anti-form-1, and 4 keys are 59%, 1,2-vinyl bonds is 18%, and weight average particle diameter is 333nm.In addition, swelling capacity is 10.
(manufacture of rubber polymer latex (a-8))
After the inside nitrogen replacement of the pressure vessel of 10 liters, load 1,3-divinyl 93 weight part, vinylbenzene 7 weight part, n-dodecyl mercaptan 0.8 weight part, Potassium Persulphate 0.8 weight part, nilox resin acid sodium 1.9 weight part, sodium hydroxide 0.15 weight part, deionized water 170 weight part, carry out stirring and make it react 42 hours at 80 DEG C.Then, nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight part is added.And then while temperature is maintained 82 DEG C while continue stirring 9 hours and complete reaction.Then, carry out reducing pressure to remove residual 1,3-butadiene, obtain rubber polymer latex (a-8) thus.With regard to the microstructure of this rubber polymer latex (a-8), cis-Isosorbide-5-Nitrae key is 20%, anti-form-1, and 4 keys are 65%, 1,2-vinyl bonds is 15%, and weight average particle diameter is 360nm.In addition, swelling capacity is 40.
(manufacture of graft copolymer (A-1))
In the polymerization reactor of resistance to compacting, load polywater 148 parts, rubber polymer latex (a-1) 45 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 63 DEG C in groove, adding and Potassium Persulphate 0.35 weight part is dissolved in the aqueous solution obtained in deionized water 11 weight part.After reaching 65 DEG C, with the mixed solution of the monomer shown in 4 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.20 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.5 weight part in deionized water 20 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 98%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-1).Measure the percentage of grafting of the graft copolymer (A-1) obtained, result percentage of grafting is 50%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-1) is 4.9.
(manufacture of graft copolymer (A-2))
In the polymerization reactor of resistance to compacting, load polywater 150 parts, rubber polymer latex (a-2) 50 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 65 DEG C in groove, adding and Potassium Persulphate 0.30 weight part is dissolved in the aqueous solution obtained in deionized water 12 weight part.After reaching 68 DEG C, with the mixed solution of the monomer shown in 4.4 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.25 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.35 weight part in deionized water 19 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 98%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-2).Measure the percentage of grafting of the graft copolymer (A-2) obtained, result percentage of grafting is 45%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-2) is 5.3.
(manufacture of graft copolymer (A-3))
In the polymerization reactor of resistance to compacting, load polywater 152 parts, rubber polymer latex (a-1) 45 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 58 DEG C in groove, adding and Potassium Persulphate 0.55 weight part is dissolved in the aqueous solution obtained in deionized water 15 weight part.After reaching 60 DEG C, with the mixed solution of the monomer shown in 4.5 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.05 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.32 weight part in deionized water 15 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 97%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-3).Measure the percentage of grafting of the graft copolymer (A-3) obtained, result percentage of grafting is 79%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-3) is 2.4.
(manufacture of graft copolymer (A-4))
In the polymerization reactor of resistance to compacting, load polywater 155 parts, rubber polymer latex (a-3) 50 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 63 DEG C in groove, adding and Potassium Persulphate 0.35 weight part is dissolved in the aqueous solution obtained in deionized water 13 weight part.After reaching 65 DEG C, with the mixed solution of the monomer shown in 6.0 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.20 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.21 weight part in deionized water 16 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 97%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-4).Measure the percentage of grafting of the graft copolymer (A-4) obtained, result percentage of grafting is 60%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-4) is 5.0.
(manufacture of graft copolymer (A-5))
In the polymerization reactor of resistance to compacting, load polywater 167 parts, rubber polymer latex (a-4) 45 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 54 DEG C in groove, adding and Potassium Persulphate 0.35 weight part is dissolved in the aqueous solution obtained in deionized water 14 weight part.After reaching 56 DEG C, with the mixed solution of the monomer shown in 5.5 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.21 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.51 weight part in deionized water 17 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 97%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-5).Measure the percentage of grafting of the graft copolymer (A-5) obtained, result percentage of grafting is 35%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-5) is 5.2.
(manufacture of graft copolymer (A-6))
In the polymerization reactor of resistance to compacting, load polywater 170 parts, rubber polymer latex (a-5) 50 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 54 DEG C in groove, adding and Potassium Persulphate 0.25 weight part is dissolved in the aqueous solution obtained in deionized water 14 weight part.After reaching 56 DEG C, with the mixed solution of the monomer shown in 5.5 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.45 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.51 weight part in deionized water 17 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 97%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-6).Measure the percentage of grafting of the graft copolymer (A-6) obtained, result percentage of grafting is 29%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-6) is 6.7.
(manufacture of graft copolymer (A-7))
In the polymerization reactor of resistance to compacting, load polywater 168 parts, rubber polymer latex (a-6) 45 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 70 DEG C in groove, adding and Potassium Persulphate 0.60 weight part is dissolved in the aqueous solution obtained in deionized water 18 weight part.After reaching 72 DEG C, with the mixed solution of the monomer shown in 4.0 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.25 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.50 weight part in deionized water 17 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 98%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-7).Measure the percentage of grafting of the graft copolymer (A-7) obtained, result percentage of grafting is 86%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-7) is 3.1.
(manufacture of graft copolymer (A-8))
In the polymerization reactor of resistance to compacting, load polywater 165 parts, rubber polymer latex (a-7) 45 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 65 DEG C in groove, adding and Potassium Persulphate 0.40 weight part is dissolved in the aqueous solution obtained in deionized water 16 weight part.After reaching 68 DEG C, with the mixed solution of the monomer shown in 4.0 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.27 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.35 weight part in deionized water 16 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 98%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-8).Measure the percentage of grafting of the graft copolymer (A-8) obtained, result percentage of grafting is 59%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-8) is 4.8.
(manufacture of graft copolymer (A-9))
In the polymerization reactor of resistance to compacting, load polywater 167 parts, rubber polymer latex (a-8) 50 weight part (solids component), carry out nitrogen replacement, when making to be warming up to 62 DEG C in groove, adding and Potassium Persulphate 0.35 weight part is dissolved in the aqueous solution obtained in deionized water 14 weight part.After reaching 64 DEG C, with the mixed solution of the monomer shown in 4.0 hours continuous interpolation tables 1 and n-dodecyl mercaptan 0.35 weight part and the emulsifier aqueous solution being dissolved with potassium oleate 1.25 weight part in deionized water 16 weight part.Then, polymerization is terminated in the moment of polymerisation conversion more than 98%.Then, carry out saltouing, dewatering and drying, obtain the powder of graft copolymer (A-9).Measure the percentage of grafting of the graft copolymer (A-9) obtained, result percentage of grafting is 47%.In addition, the swelling capacity being insoluble to the composition of acetone of graft copolymer (A-9) is 7.3.
(manufacture of AS resin)
In glass reactor after nitrogen replacement, load deionized water 155 parts, vinylbenzene 7.1 parts, vinyl cyanide 2.9 parts, Sodium dodecylbenzene sulfonate 0.25 part (solids component conversion) and Potassium Persulphate 0.75 part, be polymerized 1 hour at 65 DEG C.Then, the mixing solutions be made up of vinylbenzene 63.9 parts, vinyl cyanide 26.1 parts and the emulsifier aqueous solution 30 parts containing Sodium dodecylbenzene sulfonate 1.5 parts (solids component conversion) was dripped continuously with 3 hours respectively.Keep 3 hours after dripping, obtain the copolymer emulsion of AS resin.Then, carry out saltouing, dewatering and drying, obtain the powder of AS resin.
< embodiment 1 ~ 5 and comparative example 1 ~ 6>
After graft copolymer (A-1) ~ (A-9) shown in mixture table 2 and AS resin, use 40mm twin screw extruder to carry out melting mixing at 240 DEG C, obtain particle.By the particle obtained, with being set as that the injection moulding machine of 250 DEG C carries out shaping to various products formed, and carry out evaluation of physical property.Evaluation result is shown in table 2.It should be noted that, respective evaluation method is as follows.
(shock-resistance)
Use the particle obtained in each embodiment and comparative example, according to ISO-294 to test film carry out shaping after, according to ISO-179, with 4mm thickness measurement breach Charpy impact value.Unit: kJ/m
2.
(mobility)
Use the particle obtained in each embodiment and comparative example, according to ISO-1133,220 DEG C, measure melt volume-flow rate under the condition of load 10kg.Unit: cm
3/ 10 minutes.
Table 1
Table 2
As shown in table 2, embodiment 1 ~ 5 is the example of the thermoplastic resin composition of the present application, and polymerization stability, shock-resistance and mobility are excellent.
As shown in table 2,1,2-vinyl bonds of the microstructure of the rubber polymer of comparative example 1 is outer in scope, the cis-Isosorbide-5-Nitrae key of comparative example 2 and 3 outside scope, therefore, obtain the result of polymerization stability difference.The anti-form-1 of the microstructure of the rubber polymer of comparative example 4,4 keys, outside scope, therefore, obtain the result of poor impact resistance.The swelling capacity of the rubber polymer of comparative example 5, outside scope, therefore, obtains the result of poor impact resistance.The microstructure of the rubber polymer of comparative example 6 and swelling capacity, outside scope, therefore, obtain the result of polymerization stability and poor impact resistance.
The rubber polymer that graft copolymer of the present invention uses polymerization stability excellent, shock-resistance and mobility excellent, therefore, use has the thermoplastic resin composition of graft copolymer to be preferably applied to require with the shock-resistance of lighting and the product etc. of excellent mobility.
Claims (3)
1. a graft copolymer, by the monomer graft polymerizes containing at least one be selected from aromatic vinyl system monomer and vinyl cyanide system monomer of 20 ~ 95 weight parts is obtained to the rubber polymer of 5 ~ 80 weight parts, the feature of described graft copolymer is
Rubber polymer has the cis-Isosorbide-5-Nitrae key of 21 ~ 30%, the anti-form-1 of 47 ~ 60%, 4 keys, 16 ~ 23% 1,2-vinyl bonds as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35,
Described graft copolymer is obtained by emulsion polymerization.
2. graft copolymer according to claim 1, wherein, the swelling capacity of graft copolymer is 3 ~ 9.
3. a thermoplastic resin composition, is obtained by the graft copolymer described in claim 1 or 2 and other thermoplastic resin.
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