CN102911318A - Graft copolymer and thermoplastic resin composition - Google Patents
Graft copolymer and thermoplastic resin composition Download PDFInfo
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- CN102911318A CN102911318A CN2012102724865A CN201210272486A CN102911318A CN 102911318 A CN102911318 A CN 102911318A CN 2012102724865 A CN2012102724865 A CN 2012102724865A CN 201210272486 A CN201210272486 A CN 201210272486A CN 102911318 A CN102911318 A CN 102911318A
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Abstract
The present invention relates to a graft copolymer and a thermoplastic resin composition. The graft copolymer is obtained by graft polymerization of 20-95 parts by weight of at least one monomer selected from the group consisting of aromatic vinyl monomers and cyanide vinyl monomer and 5-80 parts by weight of a rubbery polymer, wherein the rubbery polymer has 21-30% of cis 1,4 bond, 47-60% of trans 1,4 bond, and 16-23% of 1,2-vinyl bond as a micro-structure, and the swelling degree of the rubber polymer is 13-35.
Description
Technical field
The present invention relates to use the good rubber polymer of polymerization stability, shock-resistance and mobile good graft copolymer and the thermoplastic resin composition who is obtained by this graft copolymer.
Background technology
ABS resin is shock-resistance and the mobile good resin of balance, is used to the vehicle such as automobile with the shell of interior exterior member, various household appliances or OA equipment, other groceries fields etc. widely in the field.(particularly China) presents rapid growth at Asian market, and it utilizes the field more and more to enlarge.On the other hand, as take automotive field as representative, require lighting, developing the thin-walled property of parts.Therefore, for further thin-walled property, require than present better shock-resistance and flowability.
As improvement shock-resistance and mobile method, proposed and used the two or more rubber polymer (Japanese kokai publication hei 11-130825 communique) at the peak with different tan δ.But, must prepare two or more rubber polymers, there is less economical problem.
In addition, as the good resin combination of the balance of tint permanence, gloss, rigidity and impact strength, proposed to use the reinforcing rubber aromatic series list acetate resin composition (Japanese kokai publication sho 60-233116 communique) of the rubber polymer with specific microstructure.But, also insufficient as the physical property of present requirement.
Summary of the invention
The object of the invention is to, provide use the good rubber polymer of polymerization stability, shock-resistance and mobile good graft copolymer and the thermoplastic resin composition who is obtained by this graft copolymer.
The inventor conducts in-depth research for the problem that solves prior art, found that, be conceived to microstructure and the swelling capacity of rubber polymer, rubber polymer uses has 21 ~ 30% cis-Isosorbide-5-Nitrae key, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1, the 2-vinyl bonds is 13 ~ 35 rubber polymer as microstructure and swelling capacity, thus, not only the polymerization stability of rubber polymer is good, and can obtain shock-resistance and mobile good graft copolymer.
Namely, the thermoplastic resin composition who the present invention relates to graft copolymer and obtained by this graft copolymer, described graft copolymer is that monomer and vinyl cyanide are that at least a monomer-grafted in the monomer is aggregated on the rubber polymer of 5 ~ 80 weight parts and obtains by the aromatic vinyl that is selected from 20 ~ 95 weight parts, it is characterized in that, rubber polymer has 21 ~ 30% cis-1,4 keys, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1, the 2-vinyl bonds is as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35.
According to the present invention, can provide and use the thermoplastic resin composition good rubber polymer of polymerization stability, that shock-resistance and mobile good graft copolymer and use have this graft copolymer.
Embodiment
Below, at length describe with regard to preferred implementation of the present invention.But the present invention is not limited to following embodiment.
Graft copolymer of the present invention, be will be selected from aromatic vinyl be monomer, vinyl cyanide be monomer and can with other vinyl monomers of these monomer copolymerizations at least a monomer-grafted being aggregated to have cis-1,4 keys are 21 ~ 30%, anti-form-1,4 keys are 47 ~ 60%, 1, and the 2-vinyl bonds is that 16 ~ 23% microstructure and swelling capacity are the graft copolymer that obtains on 13 ~ 35 the rubber polymer.
The graft copolymer of present embodiment is that monomer and vinyl cyanide are that at least a monomer-grafted in the monomer is aggregated on the rubber polymer of 5 ~ 80 weight parts and obtains by being selected from aromatic vinyl containing of 20 ~ 95 weight parts, rubber polymer has 21 ~ 30% cis-1,4 keys, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1, the 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-(ethene-divinyl)-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 keys 47 ~ 60%, 1, and 2-vinyl bonds 16 ~ 23%, and the swelling capacity of rubber polymer is 13 ~ 35.In the extraneous situation and 1,2-vinyl bonds extraneous situation 16 ~ 23% of cis-Isosorbide-5-Nitrae key 21 ~ 30%, polymerization stability significantly reduces.At anti-form-1,4 keys are in 47 ~ 60% extraneous situation, and shock-resistance and flowability 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, more preferably 17 ~ 25.
The microstructure of rubber polymer can be by using vinylbenzene by infrared absorption spectrometry and cis-Isosorbide-5-Nitrae key, anti-form-1,4 keys, 1, the absorbancy of the characteristic absorbance of 2-vinyl bonds and by Hampton method (reference: R.R.Hampton; The formula of the specific absorbance of each key of Ana1.Chem., 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 was flooded 48 hours under 25 ℃ in 100m1 toluene, with 300 purpose metal mesh filters, (weight a) and to the composition that is insoluble to toluene is carried out weight (weight b) after the vacuum-drying, obtains swelling capacity by following formula to measure the weight of the composition that is insoluble to toluene of this moment.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/weight (weight b) after the vacuum-drying
The weight average particle diameter of rubber polymer is not particularly limited, and from the viewpoint of physical property balance, is preferably 0.1 ~ 0.9 μ m, 0.2 ~ 0.5 μ m more preferably, and more preferably 0.34 ~ 0.5 μ m is particularly preferably 0.38 ~ 0.45 μ m.In addition, the adjusting of the weight average particle diameter of rubber polymer can be used known method, also can use by making in advance the smaller rubber polymer latex of particle diameter and making its cohesion enlarge the cohesion that forms the target weight median size to enlarge rubber polymer.
As the microstructure of regulating rubber polymer and the method for swelling capacity, any method can be, the method such as the kind of the kind that changes polymerization starter and amount, free radical catalyst or base metal catalysts use, polymerization temperature, chain-transfer agent and amount etc. can be enumerated.Particularly the impact of polymerization temperature is larger, and the ratio regular meeting of cis-Isosorbide-5-Nitrae key occurs significantly to change because polymerization temperature is different.Swelling capacity can significantly change because of different generation of the cross-linking density of rubber polymer composition.
Rubber polymer can obtain by known polymerization.At this moment, can use the reagent and additive in polymerization such as common tensio-active agent, initiator, molecular weight regulator, ionogen.As tensio-active agent, can enumerate: an alkali metal salt of the alkylsulphonic acids such as an alkali metal salt of the carboxylic acids such as an alkali metal salt of the senior lipid acid such as an alkali metal salt, potassium oleate or sodium oleate of the nilox resin acid such as nilox resin acid potassium or nilox resin acid sodium and Sodium dodecylbenzene sulfonate etc.
As initiator, can enumerate: make reducto oxydative system that the organo-peroxides such as the persulphates such as Potassium Persulphate, Sodium Persulfate, ammonium persulphate or tertbutyl peroxide, isopropyl benzene hydroperoxide and reductive agent composition combine etc.As molecular weight regulator, can enumerate: thio-alcohol (uncle's 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, vitriolate of tartar, sodium-acetate, sodium sulfate, potassiumphosphate, tetrapotassium pyrophosphate etc.These reagent and additive in polymerization can use separately or mix two or more the use.
To the consumption of these reagent and additive in polymerization also without limits, generally speaking, consist of per 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 of the monomer, tensio-active agent and the reagent and additive in polymerization that consist of rubber polymer also is not particularly limited, the initial stage of can using adds or monomer and/or tensio-active agent any one method such as interpolation continuously or successively in the lump.Polymerization temperature also is not particularly limited, from the viewpoint of ratio of control cis-Isosorbide-5-Nitrae key, preferred 50 ~ 80 ℃ scope.
To be selected from aromatic vinyl be that monomer and vinyl cyanide are that at least a monomer-grafted polymerization in the monomer obtains to the graft copolymer of present embodiment by making in the presence of rubber polymer.In addition, may be used to be that monomer and vinyl cyanide are other vinyl monomers of monomer copolymerization with aromatic vinyl.
Aromatic vinyl as the formation graft copolymer is monomer, 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.
Be monomer as vinyl cyanide, can enumerate: vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, anti-maleic nitrile etc., can use a kind of or two or more.Vinyl cyanide particularly preferably.
But as other vinyl monomers of copolymerization, can enumerate: (methyl) acrylic ester monomer, maleimide are that monomer, acid amides are monomer etc., can use a kind of or two or more.As (methyl) acrylic ester monomer, can illustration: (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.Be monomer as maleimide, can illustration: N-phenylmaleimide, N-N-cyclohexylmaleimide etc.Be monomer as acid amides, can illustration: acrylamide, Methacrylamide etc.
The composition ratio that grafting is aggregated to the above-mentioned monomer on the rubber polymer is not particularly limited, and is preferred: be the composition ratio of other vinyl monomer 0 ~ 30 % by weight of monomer 10 ~ 40 % by weight and copolymerization but aromatic vinyl is monomer 60 ~ 90 % by weight, vinyl cyanide; Aromatic vinyl is the composition ratio of monomer 30 ~ 80 % by weight and (methyl) acrylic ester monomer 20 ~ 70 % by weight; Aromatic vinyl be monomer 20 ~ 70 % by weight, (methyl) but acrylic ester monomer 20 ~ 70 % by weight, vinyl cyanide are the composition ratio of other vinyl monomer 0 ~ 30 % by weight of monomer 10 ~ 60 % by weight and copolymerization.
With regard to the ratio of the rubber polymer in the graft copolymer and monomer, from physical property balance aspect, need to be rubber polymer 5 ~ 80 weight parts, monomer 20 ~ 95 weight parts, be preferably rubber polymer 30 ~ 70 weight parts, monomer 30 ~ 70 weight parts.Percentage of grafting to graft copolymer is not particularly limited, but percentage of grafting cross when low, when percentage of grafting is too high, there is the mobile trend that reduces in the trend that exists shock-resistance to reduce, and therefore, is preferably 25 ~ 85%, more preferably 30 ~ 60%.
Swelling capacity to graft copolymer is not particularly limited, and from the viewpoint of shock-resistance, swelling capacity is preferably 3 ~ 9, and more preferably 4 ~ 8.Method as the swelling capacity of regulating graft copolymer can be any method, but has the tendency of the molecular weight that relies on significantly percentage of grafting and graft side chain.
The percentage of grafting of graft copolymer can be take acetone as solvent be separated into graft copolymer solvable composition and insoluble composition and obtains by following formula.
The weight of the rubber polymer in percentage of grafting (%)=(being insoluble to the weight of the rubber polymer in the weight-graft copolymer of composition of acetone)/graft copolymer * 100
The swelling capacity of graft copolymer can followingly be obtained: graft copolymer is immersed in the acetone, take out its insoluble composition, after one night of vacuum-drying, the composition that is insoluble to acetone of the graft copolymer after the vacuum-drying was flooded 48 hours under 25 ℃ in 100m1 toluene, with 300 purpose metal mesh filters, (weight a) and to the composition that is insoluble to toluene is carried out weight (weight b) after the vacuum-drying, and tries to achieve by following formula to measure the weight of the composition that is insoluble to toluene of this moment.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/weight (weight b) after the vacuum-drying
Being used for of present embodiment is not particularly limited the method for graft copolymer polymerization, can use emulsion polymerization, suspension polymerization, mass polymerization etc.In the situation of using emulsion polymerization, by with above-mentioned monomer-grafted being aggregated on the above-mentioned rubber polymer, can obtain the latex of graft copolymer.With regard to the latex of graft copolymer, by known method is solidified via utilizing, cleaning, dehydration, drying process, can obtain the powder of graft copolymer.
In addition, resulting graft copolymer can use separately, also can mix use with other thermoplastic resins as required.As other such thermoplastic resins, for example can enumerate: 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, the 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), vinyl cyanide-acrylic rubber-styrene resin (AAS resin) etc.
The thermoplastic resin composition of present embodiment is contained above-mentioned graft copolymer and other thermoplastic resins.
The thermoplastic resin composition can also further be contained as required: 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; The smell screening 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 the present embodiment can obtain by mixing mentioned component.In order to mix, can use known kneading devices such as forcing machine, roller, closed mixing machine, kneading machine.
According to present embodiment, can use above-mentioned graft copolymer or thermoplastic resin composition to make the products formed of excellent impact resistance.
[embodiment]
The below illustrates embodiment and specifies the present invention, but the present invention is not subjected to any restriction of these embodiment.Need to prove that " part " and " % " that illustrate in an embodiment are weight standards.In addition, carry out the evaluation of each physical property in embodiment and the comparative example by following method.Measurement result and evaluation result are shown in table 1 and the table 2.
(mensuration of the weight average particle diameter of rubber polymer latex)
Rubber polymer latex is carried out osmium dyeing, and (the NEC manufacturing: JEM-1400) take 800 photographs, (Asahi Chemical Industry makes: the IP-1000C type) try to achieve weight average particle diameter to use image analysis apparatus to use transmission electron microscope.
(being used for the sample making that microstructure is measured)
In graft copolymer or the thermoplastic resin composition that obtained by this graft copolymer, add acetone and place and make its dissolving a night.Sample after the dissolving is carried out centrifugation (12000rpm * 30 minute).In centrifuge tube, add acetone in the residual composition that is insoluble to acetone, again carry out under the same conditions centrifugation.After the centrifugation, discarded acetone-insoluble composition, with methyl alcohol fully clean on one side the composition that be insoluble to acetone carried out suction filtration on one side.And then in order to remove impurity, in the above-mentioned composition that is insoluble to acetone, add Virahol and make its backflow more than 7 hours with hood-shaped well heater.Reflux after the end, with glass filter the composition that is insoluble to acetone is carried out suction filtration, fully clean with Virahol.One night of composition vacuum-drying of acetone will be insoluble to.Add normal hexane in the composition that is insoluble to acetone after vacuum-drying, make it reflux more than 5 hours with hood-shaped well heater.With filter paper extracting solution is filtered, with vaporizer concentrated solid after, carry out vacuum-drying.This vacuum-drying thing is dissolved in the chloroform.
(mensuration of absorbancy)
The sample that as above obtains is coated on the plate of thallium bromo-iodide (KRS-5) system, makes chloroform dry, use Fourier transform infrared light-dividing device (perkin elmer is made 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
-1Tried to achieve the containing ratio (%) of each key by the Hampton formula by the absorbancy that obtains.
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
λAbsorbancy for separately wave number place.
(swelling capacity of rubber polymer is measured)
The solid matter of rubber polymer was flooded 48 hours under 25 ℃ in 100m1 toluene, with 300 purpose metal mesh filters, (weight a) and to the composition that is insoluble to toluene is carried out weight (weight b) after the vacuum-drying, tries to achieve swelling capacity by following formula to measure the weight of the composition that is insoluble to toluene of this moment.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/weight (weight b) after the vacuum-drying
(swelling capacity of graft copolymer is measured)
Graft copolymer is immersed in the acetone, takes out its insoluble composition, carry out one night of vacuum-drying.The composition that is insoluble to acetone of the graft copolymer after the vacuum-drying was flooded 48 hours under 25 ℃ in 100m1 toluene, with 300 purpose metal mesh filters, (weight a) and to the composition that is insoluble to toluene is carried out weight (weight b) after the vacuum-drying, tries to achieve swelling capacity by following formula to measure the weight of the composition that is insoluble to toluene of this moment.
The weight of swelling capacity=the be insoluble to composition of toluene (weight a)/weight (weight b) after the vacuum-drying
(evaluation of polymerization stability)
The evaluation of the polymerization stability of rubber polymer, the rubber polymer latex that obtains after to the rubber polymer polymerization with 300 purpose wire nettings filters, and judges with the amount of the condensation product that obtains.Evaluation result is shown in table 2.
A: be lower than 0.01 (%)
B:0.01 is above and be lower than 0.05 (%)
C:0.05 is above and be lower than 0.10 (%)
More than the D:0.10
(manufacturing of rubber polymer latex (a-1))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 90 weight parts, vinylbenzene 10 weight parts, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 163 weight parts make it 70 ℃ of lower reactions 41 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 70 ℃ of one side continuation stirrings 6 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-1).With regard to the microstructure of this rubber polymer latex (a-1), cis-Isosorbide-5-Nitrae key is 25%, and anti-form-1,4 keys are that 56%, 1,2-vinyl bonds is 19%, and weight average particle diameter is 420nm.In addition, swelling capacity is 15.
(manufacturing of rubber polymer latex (a-2))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 95 weight parts, vinylbenzene 5 weight parts, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 163 weight parts make it 65 ℃ of lower reactions 45 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 75 ℃ of one side continuation stirrings 6 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-2).With regard to the microstructure of this rubber polymer latex (a-2), cis-Isosorbide-5-Nitrae key is 27%, and anti-form-1,4 keys are that 53%, 1,2-vinyl bonds is 20%, and weight average particle diameter is 389nm.In addition, swelling capacity is 28.
(manufacturing of rubber polymer latex (a-3))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 98 weight parts, vinyl cyanide 2 weight parts, n-dodecyl mercaptan 0.35 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 2.1 weight parts, sodium hydroxide 0.18 weight part, deionized water 200 weight parts make it 55 ℃ of lower reactions 48 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 70 ℃ of one side continuation stirrings 5 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-3).With regard to the microstructure of this rubber polymer latex (a-3), cis-Isosorbide-5-Nitrae key is 23%, and anti-form-1,4 keys are that 55%, 1,2-vinyl bonds is 22%, and weight average particle diameter is 390nm.In addition, swelling capacity is 23.
(manufacturing of rubber polymer latex (a-4))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 95 weight parts, vinylbenzene 5 weight parts, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 2.5 weight parts, nilox resin acid sodium 2.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 188 weight parts make it 38 ℃ of lower reactions 51 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 52 ℃ of one side continuation stirrings 9 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-4).With regard to the microstructure of this rubber polymer latex (a-4), cis-Isosorbide-5-Nitrae key is 23%, and anti-form-1,4 keys are that 48%, 1,2-vinyl bonds is 29%, and weight average particle diameter is 375nm.In addition, swelling capacity is 19.
(manufacturing of rubber polymer latex (a-5))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 90 weight parts, vinylbenzene 10 weight parts, n-dodecyl mercaptan 0.5 weight part, Potassium Persulphate 1.7 weight parts, nilox resin acid sodium 2.5 weight parts, sodium hydroxide 0.2 weight part, deionized water 200 weight parts make it 45 ℃ of lower reactions 50 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 55 ℃ of one side continuation stirrings 6 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-5).With regard to the microstructure of this rubber polymer latex (a-5), cis-Isosorbide-5-Nitrae key is 31%, and anti-form-1,4 keys are that 53%, 1,2-vinyl bonds is 16%, and weight average particle diameter is 375nm.In addition, swelling capacity is 30.
(manufacturing of rubber polymer latex (a-6))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 99 weight parts, vinylbenzene 1 weight part, n-dodecyl mercaptan 0.3 weight part, Potassium Persulphate 0.5 weight part, nilox resin acid sodium 1.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 163 weight parts make it 89 ℃ of lower reactions 42 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 90 ℃ of one side continuation stirrings 9 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-6).With regard to the microstructure of this rubber polymer latex (a-6), cis-Isosorbide-5-Nitrae key is 21%, and anti-form-1,4 keys are that 63%, 1,2-vinyl bonds is 16%, and weight average particle diameter is 333nm.In addition, swelling capacity is 19.
(manufacturing of rubber polymer latex (a-7))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 90 weight parts, vinylbenzene 10 weight parts, Potassium Persulphate 0.7 weight part, nilox resin acid sodium 1.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 163 weight parts make it 65 ℃ of lower reactions 43 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 70 ℃ of one side continuation stirrings 6 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-7).With regard to the microstructure of this rubber polymer latex (a-7), cis-Isosorbide-5-Nitrae key is 23%, and anti-form-1,4 keys are that 59%, 1,2-vinyl bonds is 18%, and weight average particle diameter is 333nm.In addition, swelling capacity is 10.
(manufacturing of rubber polymer latex (a-8))
With the inside of 10 liters pressure vessels with nitrogen replacement after, pack 1 into, 3-divinyl 93 weight parts, vinylbenzene 7 weight parts, n-dodecyl mercaptan 0.8 weight part, Potassium Persulphate 0.8 weight part, nilox resin acid sodium 1.9 weight parts, sodium hydroxide 0.15 weight part, deionized water 170 weight parts make it 80 ℃ of lower reactions 42 hours while stir.Then, add nilox resin acid sodium 0.2 weight part, sodium hydroxide 0.1 weight part and deionized water 5 weight parts.And then temperature is maintained 82 ℃ of one side continuation stirrings 9 hours on one side and finish reaction.Then, reduce pressure to remove residual 1,3-butadiene, obtain thus rubber polymer latex (a-8).With regard to the microstructure of this rubber polymer latex (a-8), cis-Isosorbide-5-Nitrae key is 20%, and anti-form-1,4 keys are that 65%, 1,2-vinyl bonds is 15%, and weight average particle diameter is 360nm.In addition, swelling capacity is 40.
(manufacturing of graft copolymer (A-1))
In the polymerization reactor of withstand voltage system, pack into 148 parts of polywaters, rubber polymer latex (a-1) 45 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 63 ℃, add that Potassium Persulphate 0.35 weight part is dissolved in deionized water 11 weight parts and the aqueous solution that obtains.After reaching 65 ℃, with the mixed solution of the monomer shown in 4 hours continuous adding tables 1 and n-dodecyl mercaptan 0.20 weight part with in deionized water 20 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.5 weight parts.Then, surpass moment of 98% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-1).The percentage of grafting of the graft copolymer that mensuration obtains (A-1), percentage of grafting is 50% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-1) is 4.9.
(manufacturing of graft copolymer (A-2))
In the polymerization reactor of withstand voltage system, pack into 150 parts of polywaters, rubber polymer latex (a-2) 50 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 65 ℃, add that Potassium Persulphate 0.30 weight part is dissolved in deionized water 12 weight parts and the aqueous solution that obtains.After reaching 68 ℃, with the mixed solution of the monomer shown in 4.4 hours continuous adding tables 1 and n-dodecyl mercaptan 0.25 weight part with in deionized water 19 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.35 weight parts.Then, surpass moment of 98% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-2).The percentage of grafting of the graft copolymer that mensuration obtains (A-2), percentage of grafting is 45% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-2) is 5.3.
(manufacturing of graft copolymer (A-3))
In the polymerization reactor of withstand voltage system, pack into 152 parts of polywaters, rubber polymer latex (a-1) 45 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 58 ℃, add that Potassium Persulphate 0.55 weight part is dissolved in deionized water 15 weight parts and the aqueous solution that obtains.After reaching 60 ℃, with the mixed solution of the monomer shown in 4.5 hours continuous adding tables 1 and n-dodecyl mercaptan 0.05 weight part with in deionized water 15 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.32 weight parts.Then, surpass moment of 97% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-3).The percentage of grafting of the graft copolymer that mensuration obtains (A-3), percentage of grafting is 79% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-3) is 2.4.
(manufacturing of graft copolymer (A-4))
In the polymerization reactor of withstand voltage system, pack into 155 parts of polywaters, rubber polymer latex (a-3) 50 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 63 ℃, add that Potassium Persulphate 0.35 weight part is dissolved in deionized water 13 weight parts and the aqueous solution that obtains.After reaching 65 ℃, with the mixed solution of the monomer shown in 6.0 hours continuous adding tables 1 and n-dodecyl mercaptan 0.20 weight part with in deionized water 16 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.21 weight parts.Then, surpass moment of 97% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-4).The percentage of grafting of the graft copolymer that mensuration obtains (A-4), percentage of grafting is 60% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-4) is 5.0.
(manufacturing of graft copolymer (A-5))
In the polymerization reactor of withstand voltage system, pack into 167 parts of polywaters, rubber polymer latex (a-4) 45 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 54 ℃, add that Potassium Persulphate 0.35 weight part is dissolved in deionized water 14 weight parts and the aqueous solution that obtains.After reaching 56 ℃, with the mixed solution of the monomer shown in 5.5 hours continuous adding tables 1 and n-dodecyl mercaptan 0.21 weight part with in deionized water 17 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.51 weight parts.Then, surpass moment of 97% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-5).The percentage of grafting of the graft copolymer that mensuration obtains (A-5), percentage of grafting is 35% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-5) is 5.2.
(manufacturing of graft copolymer (A-6))
In the polymerization reactor of withstand voltage system, pack into 170 parts of polywaters, rubber polymer latex (a-5) 50 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 54 ℃, add that Potassium Persulphate 0.25 weight part is dissolved in deionized water 14 weight parts and the aqueous solution that obtains.After reaching 56 ℃, with the mixed solution of the monomer shown in 5.5 hours continuous adding tables 1 and n-dodecyl mercaptan 0.45 weight part with in deionized water 17 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.51 weight parts.Then, surpass moment of 97% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-6).The percentage of grafting of the graft copolymer that mensuration obtains (A-6), percentage of grafting is 29% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-6) is 6.7.
(manufacturing of graft copolymer (A-7))
In the polymerization reactor of withstand voltage system, pack into 168 parts of polywaters, rubber polymer latex (a-6) 45 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 70 ℃, add that Potassium Persulphate 0.60 weight part is dissolved in deionized water 18 weight parts and the aqueous solution that obtains.After reaching 72 ℃, with the mixed solution of the monomer shown in 4.0 hours continuous adding tables 1 and n-dodecyl mercaptan 0.25 weight part with in deionized water 17 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.50 weight parts.Then, surpass moment of 98% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-7).The percentage of grafting of the graft copolymer that mensuration obtains (A-7), percentage of grafting is 86% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-7) is 3.1.
(manufacturing of graft copolymer (A-8))
In the polymerization reactor of withstand voltage system, pack into 165 parts of polywaters, rubber polymer latex (a-7) 45 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 65 ℃, add that Potassium Persulphate 0.40 weight part is dissolved in deionized water 16 weight parts and the aqueous solution that obtains.After reaching 68 ℃, with the mixed solution of the monomer shown in 4.0 hours continuous adding tables 1 and n-dodecyl mercaptan 0.27 weight part with in deionized water 16 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.35 weight parts.Then, surpass moment of 98% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-8).The percentage of grafting of the graft copolymer that mensuration obtains (A-8), percentage of grafting is 59% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-8) is 4.8.
(manufacturing of graft copolymer (A-9))
In the polymerization reactor of withstand voltage system, pack into 167 parts of polywaters, rubber polymer latex (a-8) 50 weight parts (solids component), carry out nitrogen replacement, when in making groove, being warming up to 62 ℃, add that Potassium Persulphate 0.35 weight part is dissolved in deionized water 14 weight parts and the aqueous solution that obtains.After reaching 64 ℃, with the mixed solution of the monomer shown in 4.0 hours continuous adding tables 1 and n-dodecyl mercaptan 0.35 weight part with in deionized water 16 weight parts, be dissolved with the emulsifier aqueous solution of potassium oleate 1.25 weight parts.Then, surpass moment of 98% at polymerisation conversion and finish polymerization.Then, saltout, dewater and drying, obtain the powder of graft copolymer (A-9).The percentage of grafting of the graft copolymer that mensuration obtains (A-9), percentage of grafting is 47% as a result.In addition, the swelling capacity of the composition that is insoluble to acetone of graft copolymer (A-9) is 7.3.
(manufacturing of AS resin)
In the glass reactor behind nitrogen replacement, 0.75 part of 155 parts of the deionized waters of packing into, 7.1 parts of vinylbenzene, 2.9 parts of vinyl cyanide, Sodium dodecylbenzene sulfonate 0.25 part (solids component conversion) and Potassium Persulphate were 65 ℃ of lower polymerizations 1 hour.Then, respectively with dripping continuously by 63.9 parts of vinylbenzene, 26.1 parts of mixing solutionss that consist of of vinyl cyanide in 3 hours and containing 30 parts of the emulsifier aqueous solutions of 1.5 parts of Sodium dodecylbenzene sulfonatees (solids component conversion).Kept 3 hours after dripping, obtain the copolymer emulsion of AS resin.Then, saltout, dewater and drying, obtain the powder of AS resin.
＜embodiment 1 ~ 5 and comparative example 1 ~ 6 〉
Behind graft copolymer shown in the mixture table 2 (A-1) ~ (A-9) and the AS resin, use the 40mm twin screw extruder under 240 ℃, to carry out melting mixing, obtain particle.By the particle that obtains, with the injection moulding machine that is set as 250 ℃ various products formeds are carried out moulding, and carry out evaluation of physical property.Evaluation result is shown in table 2.Need to prove that evaluation method separately is as follows.
(shock-resistance)
Use the particle that obtains in each embodiment and the comparative example, according to ISO-294 test film is carried out moulding after, according to ISO-179, with 4mm thickness measurement breach Charpy impact value.Unit: kJ/m
2
(flowability)
Use the particle that obtains in each embodiment and the comparative example, according to ISO-1133, under 220 ℃, the condition of load 10kg, measure melt volume-flow rate.Unit: cm
3/ 10 minutes.
Table 1
Table 2
As shown in table 2, embodiment 1 ~ 5 is the thermoplastic resin composition's of the present application example, polymerization stability, shock-resistance and mobile good.
As shown in table 2,1 of the microstructure of the rubber polymer of comparative example 1,2-vinyl bonds outside scope, comparative example 2 and 3 cis-Isosorbide-5-Nitrae key outside scope, therefore, obtained the poor result of polymerization stability.Therefore the anti-form-1 of the microstructure of the rubber polymer of comparative example 4,4 keys, have obtained the result of poor impact resistance outside scope.Therefore the swelling capacity of the rubber polymer of comparative example 5, has obtained the result of poor impact resistance outside scope.Therefore the microstructure of the rubber polymer of comparative example 6 and swelling capacity, have obtained the result of polymerization stability and poor impact resistance outside scope.
Graft copolymer of the present invention uses the good rubber polymer of polymerization stability, shock-resistance and mobile good, therefore, use the thermoplastic resin composition that graft copolymer is arranged to be preferably applied to require to follow the shock-resistance of lighting and the product of good flowability etc.
Claims (3)
1. graft copolymer, be that monomer and vinyl cyanide are that at least a monomer-grafted in the group of monomer composition is aggregated on the rubber polymer of 5 ~ 80 weight parts and obtains by containing of 20 ~ 95 weight parts being selected from by aromatic vinyl, described graft copolymer is characterised in that
Rubber polymer has 21 ~ 30% cis-Isosorbide-5-Nitrae key, 47 ~ 60% anti-form-1,4 keys, 16 ~ 23% 1, the 2-vinyl bonds is as microstructure, and the swelling capacity of rubber polymer is 13 ~ 35.
2. graft copolymer according to claim 1, wherein, the swelling capacity of graft copolymer is 3 ~ 9.
3. a thermoplastic resin composition is contained claim 1 or 2 described graft copolymers and other thermoplastic resin.
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| JP2011230694A JP5436517B2 (en) | 2011-08-01 | 2011-10-20 | Graft copolymer and thermoplastic resin composition |
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| CN1466601A (en) * | 2001-07-30 | 2004-01-07 | LG��ѧ��ʽ���� | Acrylonitrile-butadiene-styrene (ABS) thermoplastic transparent resin |
| CN1727375A (en) * | 2004-12-27 | 2006-02-01 | 上海华谊本体聚合技术开发有限公司 | Technique of continuous bulk polymerization for preparing compound body of ABS polymer in high shock resistant |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1466601A (en) * | 2001-07-30 | 2004-01-07 | LG��ѧ��ʽ���� | Acrylonitrile-butadiene-styrene (ABS) thermoplastic transparent resin |
| CN1727375A (en) * | 2004-12-27 | 2006-02-01 | 上海华谊本体聚合技术开发有限公司 | Technique of continuous bulk polymerization for preparing compound body of ABS polymer in high shock resistant |
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