CN101058622B - Method of preparing extinction injection moulding level ACS polymer based on continuous noumenon method - Google Patents
Method of preparing extinction injection moulding level ACS polymer based on continuous noumenon method Download PDFInfo
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- CN101058622B CN101058622B CN2007100993175A CN200710099317A CN101058622B CN 101058622 B CN101058622 B CN 101058622B CN 2007100993175 A CN2007100993175 A CN 2007100993175A CN 200710099317 A CN200710099317 A CN 200710099317A CN 101058622 B CN101058622 B CN 101058622B
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Abstract
The invention discloses a delustring injection moulding ACS polymer preparing method based on the continuous body method, which comprises the following steps: regarding the chlorinated polyvinyl chloride(CPE) rubber solution dissolving in monoalkyl vinyl aromatic hydrocarbons monomer, unsaturated nitrile monomer mixture as the main material for the polymerization reaction; mixing the outcome yield that the same or the different rubber solution proceeding the polymerization reaction in the specific condition; making a double or polymodal particle diameters ACS product suitable for plastic working by controlling the rubber particle diameters and the distributions, the variety of the rubber, the content of the rubber, the input ratio of the materials in the process of shaping the product; getting the specific property delustring injection moulding ABS resin product. The invention has a good impacting strength and a good property, which is fit for manufacturing the electric, the toy, the household electrical appliance,and so on.
Description
Technical field
The present invention relates to chemical field, specifically, relate to a kind of based on continuous basis
The extinction injection moulding level abs polymer preparation method of body method.
Background technology
The abs polymer material is knownly to have been found that for a long time it can be used in many Application Areass.Wherein the injection moulding workpiece is the of paramount importance Application Areas of ABS resin.
ABS is when the crust etc. of shell, leather trunk and the fascia that be used for tame electrical article, must satisfy shock-resistant and characteristic such as low gloss.
Generally speaking, common shock-resistant AB S resin of healing high, glossiness is lower, in other words, the rubber content of ABS resin is higher, rubber particles is healed, and big glossiness is just lower, EP 201,099 provides a kind of two-step approach polymerization technique to prepare the method for low gloss ABS (acrylonitrile-styrene-divinyl) resin; The approach that vinylbenzene and acrylonitrile grafting is prepared the ABS graft copolymer on polybutadiene rubber has been described among the EP 129,796; US 3,928, and patent such as 494, DE2,057,935 has further described the preparation technology of high-impact AB S.But improve tensile strength deterioration that the glue weight phenylethylene is a resin, increase the needed synthetic technology of particle diameter more complicated relatively again, although these two kinds of methods reduce glossy effect arranged, obtain that actual required glossiness has great difficulty under different field, occasion.
Patent JP 58-93711 has disclosed a kind of preparation process of low gloss ABS thermoplastic resin, and its method is that polystyrene is sneaked in the ABS latex, utilizes the difference of its consistency difference and two kinds of material contracts rates, reduces gloss.But this method effect on reduction resin surface gloss is not remarkable, and has therefore lost the shock strength of product.
Can prepare the low gloss ABS resin with a kind of specific emulsion polymerisation process, its characteristics are to add the carboxylic-acid monomer in polymerization process, and the polymer beads that utilizes polycondensation to generate reduces surface luster.But because the low productive rate of polycondensation, so it is very little to glossy reduction contribution, its production circulation ratio is bad still more.
Patent KP 93-6912 makes the low gloss ABS resin with suspending or body-suspension two-step approach polymerization technique.This ABS has limited its range of application along with the difference of injecting condition occurs some again such as problems such as serious contraction, gloss skewness, hardness reductions.
Low gloss ABS resin described in the patent WO 99/03904 is to add polymkeric substance gloss properties-correcting agent in ABS, reaches the purpose that reduces surface luster.This polymkeric substance gloss properties-correcting agent is to add in the ABS emulsion condensation stage to be no more than 25% PBD or SBR or NBR latex and to make.Though its defective is the gloss of prepared ABS composition and has obtained effectively reducing, and does not look after the balance of shock strength, tensile strength over-all properties, during practical application, when needing frequent the adjustment, gloss seems very inconvenient again especially.
In addition, in resin combination, add matting agent, also can play extinction effect as materials such as zinc oxide, titanium dioxide, tripoli; Another kind of method commonly used is to improve processing technology.But these two kinds of methods all cause negative impact to some performance such as mechanical property, the dyeing behavior etc. of material, and have improved the cost of the finished product.
Therefore, how to prepare a kind of ABS resin composition that has shock-resistance, high-tensile and low glossization simultaneously easily, be the problem that the people in the industry studies for a long time always.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who has the abs polymer of shock-resistance, high-tensile and low glossization simultaneously.
In order to realize purpose of the present invention, the invention provides a kind of extinction injection moulding level abs polymer preparation method based on continuous bulk, comprise
1) rubber is dissolved in monoalkyl vinyl aromatic monomer and the unsaturated nitrile monomer mixture and forms rubber solutions, and with after solvent and initiator mix, add as main charging and carry out graft polymerization reaction in first reactor.
Main charging polyreaction solids content to the polymerisate in first reactor is preferably 20-30%, inlet amount is preferably 1200-2000ml/h, temperature of reaction is preferably 90-115 ℃, and reaction pressure is preferably 5-12 normal atmosphere, and stirring velocity is preferably 50-200rpm.
Wherein, described rubber is that second-order transition temperature is not more than 85 ℃ conjugation 1, and 3-dience rubber or second-order transition temperature are not more than 85 ℃ conjugation 1, but the monoene of 3-dience rubber and copolymerization belongs to the multipolymer and/or the segmented copolymer of unsaturated monomer; Be preferably to poly-1, wherein contain the cis-isomeride of weight percentage 30-98% and the trans-isomer(ide) of weight percentage 2-70%; More preferably butylbenzene block rubber or polybutadiene rubber.
Described monoalkyl vinyl aromatic monomer structure is shown below:
Wherein, Ar is preferably one or more in phenyl, halogenophenyl, alkyl phenyl or the halogenated alkyl phenyl; X is preferably hydrogen, methyl or ethyl; Vinylbenzene more preferably.
Described unsaturated nitrile monomer is preferably one or more in vinyl cyanide, methacrylonitrile or the ethyl acrylonitrile, more elects vinyl cyanide as.
Gross weight in rubber solutions is 100%, and described mono-alkenyl aromatic monomer content is preferably 40-60%, more preferably 50-55%; Described unsaturated nitrile is preferably 5-20%, 15-20% more preferably, and all the other are rubber, and rubber content is no more than 25%.
The ratio that described solvent is preferably weight is 8:2-7: 3 aromatic hydrocarbon and alkenolic mixture, and wherein: described aromatic hydrocarbon is preferably benzene, ethylbenzene or toluene; Described aliphatic ketone is preferably acetone, methyl ethyl ketone or methyl propyl ketone.
Described weight of solvent is preferably the 10-20% of rubber solutions weight, more preferably 12-20%.
Described initiator is preferably one or more of following substances; T-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester or cross the neodecanoic acid tertiary butyl ester.
Described initiator weight is preferably the 0.001-3.0% of rubber solutions weight, more preferably the 0.005-1.0% of rubber solutions weight.
2) polymerisate of main charging in first reactor in the described step 1) added second reactor, optional with additional monomer, carry out the phase-inversion polymerization reaction, rubber weight average particle diameter 0.3-1.7 micron after second reactor is finished phase reversion.
Described additional monomer is one or more of following substances: vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid and corresponding ester, acrylamide, Methacrylamide, vinylchlorid, bromine ethene, inclined to one side sym-dibromoethane, vinyl-acetic ester, vinyl propionate base ester, the toxilic acid dimethyl esters, the toxilic acid diethyl ester, dibutyl maleinate, maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-xylyl maleimide or N-2,4-xylyl maleimide.
The add-on of additional monomer is the 1-20% of rubber solutions weight.
Main charging polyreaction solids content to the polymerisate in second reactor is preferably 30-45%, and temperature of reaction is preferably 100-125 ℃, and reaction pressure is preferably 5-12 normal atmosphere, and stirring velocity is preferably 50-200rpm.
3) with step 2) polymerisate that makes adds in follow-up two reactors proceed polyreaction at least.
Carry out polyreaction solids content to the polymerisate and be preferably 45-75%, temperature of reaction is preferably 120-170 ℃, and reaction pressure is preferably 5-12 normal atmosphere, and stirring velocity is preferably 5-70rpm.
4) material that will from final reactor, discharge, devolatilization separates, extruding pelletization, obtain the extinction injection moulding level abs polymer, wherein the rubber weight average particle diameter is not more than 1.7 microns, and rubber phase distribution Dw/Dn is 2.2 at the most, rubber content is 10-18%, monomer conversion 65-85%.
Temperature when devolatilization separates is preferably 190-220 ℃, and pressure is preferably 2-200mmHg.
The method of the invention also comprises rubber is dissolved in the monoalkyl vinyl aromatic monomer, form rubber solutions in the unsaturated nitrile monomer mixture, and with solvent and initiator after mixing, make time charging, add and to carry out grafting and phase-inversion polymerization in the graft reaction device and react that solids content is 38-45% to the polymerisate, inlet amount is 150-450ml/h, temperature of reaction is 90-115 ℃, stirring velocity is 50-200rpm, polymerisate that makes and described step 2) polymerisate that makes mixes by static mixer, adds in follow-up at least two reactors and proceed polyreaction;
Wherein, described rubber is that second-order transition temperature is not more than 85 ℃ conjugation 1,3-dience rubber or second-order transition temperature are not more than 85 ℃ conjugation 1, but the monoene of 3-dience rubber and copolymerization belongs to the multipolymer and/or the segmented copolymer of unsaturated monomer, be preferably and be poly-1, the 3-divinyl rubber wherein contains the cis-isomeride of weight percentage 30-98% and the trans-isomer(ide) of weight percentage 2-70%; More preferably butylbenzene block rubber or polybutadiene rubber.
Described monoalkyl vinyl aromatic monomer structure is shown below:
Wherein, Ar is preferably one or more in phenyl, halogenophenyl, alkyl phenyl or the halogenated alkyl phenyl; X is preferably hydrogen, methyl or ethyl; Vinylbenzene more preferably.
Described unsaturated nitrile monomer is preferably one or more in vinyl cyanide, methacrylonitrile or the ethyl acrylonitrile, more elects vinyl cyanide as.
Gross weight in rubber solutions is 100%, and described mono-alkenyl aromatic monomer content is preferably 40-60%, more preferably 50-55%; Described unsaturated nitrile is preferably 5-20%, 15-20% more preferably, and all the other are rubber, and rubber content is no more than 25%.
The ratio that described solvent is preferably weight is 8: 2-7: 3 aromatic hydrocarbon and alkenolic mixture, and wherein: described aromatic hydrocarbon is preferably benzene, ethylbenzene or toluene; Described aliphatic ketone is preferably acetone, methyl ethyl ketone or methyl propyl ketone.
Described weight of solvent is preferably the 10-20% of rubber solutions weight, more preferably 12-20%.
Described initiator is preferably one or more of following substances; T-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester or cross the neodecanoic acid tertiary butyl ester.
Described initiator weight is preferably the 0.001-3.0% of rubber solutions weight, more preferably the 0.005-1.0% of rubber solutions weight.
Preferred chain-transfer agent, softening agent and the oxidation inhibitor of adding in the described step 1), its kind and consumption all can use with reference to standard of the prior art.
Described step 1), 2) or 3) in the preferred molecular weight regulator that adds, be about as much as the 0.001-1.0% of rubber solutions weight, the molecular weight regulator of introducing can be mercaptan, halogenide and terpenes etc.
In the method for the invention, preferably introduce the formed useful cavitation of silicone oil.To those skilled in the art, well-known is that cavitation is a process, forms the space owing to be subjected to the effect of tensile stress in rubber grain in view of the above.The ability of ACS cavitation like this is made us to hoping, discharges hydrostatic tension force and allows cracking in the rubber matrix around under low tensile stress because the hole turns to rubber.In other words, cavitation has reduced stretching yield stress, the raising of flexible and tensile elongation simultaneously, and cavitation does not reduce the modulus of material.
In the preparation according to rubber that can cavitation of the present invention, the preferred silicone oil that adds with respect to about 0.05-0.4% of rubber solutions weight.Suitable silicone oil is the segmented copolymer of siloxane blocks, for example polyether-polysiloxane and the polydialkysiloxane that comprises the viscosity with about 100-1000000 centipoise (cs), preferably polydimethylsiloxane.
The moment that silicone oil joins in the abs polymer is not a most critical, can be in described step 1), 2), 3) or 4) add in arbitrary process.
In preparation method shown in the present, all reactors are preferably the plunger tpe reactor, to improve monomeric transformation efficiency.
In the present invention, rubber size can be measured by sedimentation-light scattering technique.The second-order transition temperature of rubber can pass through the assay determination of differential scanning calorimetric (DSC) method.The product cl content can be measured by the cl content chemical analysis.The molecular weight of matrix is measured by the gel permeation chromatography (GPC) that oneself is calibrated to proper A N content.Residual oligopolymer (dipolymer and trimer) content can by with the gas chromatograph for determination of mass spectrograph associating.The bioassay standard of measuring tensile modulus and elongation at break is ASTM D648.The Izod shock strength is according to the ASTMD256 standard test.
In described step 1), 2), 3) or 4) in add silicone oil.
The product that adopts the method for the invention to make has rubber content 12-18%, and presents the ABS product of the suitable injection moulding processing of two or multimodal footpath size distribution.Two or the multimodal footpath size distribution that product had, make prepared polymkeric substance have high shock strength on the one hand, its processing characteristics is good on the other hand, and rubber phase has the particle diameter more much bigger than emulsion method simultaneously, so its elongation is much higher than traditional ABS product.
Description of drawings
Fig. 1 the method for the invention process flow sheet.
Embodiment
Embodiment 1:
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs and will cut
Become the Asahi AsapreneTM 610AX rubber 10kg of 10*10mm, add the rubber dissolving tank by adding Jiao Kou, stirring and dissolving is 8 hours under the normal temperature.Add vinyl cyanide 17.9kg, 4.1g then and cross neodecanoic acid tertiary butyl ester, 0.62Kg softening agent mineral oil, 0.11Kg antioxidant 1076,0.17Kg chain-transfer agent mercaptan and 40g silicone oil, continue dispersed with stirring 30rain, as main charging.
Add l9kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM756A rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 8 hours under the normal temperature.Add vinyl cyanide 17.9kg then, and 4.1g crosses the neodecanoic acid tertiary butyl ester, 0.62Kg softening agent mineral oil, the 0.1lKg antioxidant 1076,0.17Kg chain-transfer agent mercaptan and 40g silicone oil continue dispersed with stirring 30min, as inferior charging.
Main inlet amount is 1540mL/h; System pressure is controlled at 1.0MPa; The temperature of reaction of 4 reactors is followed successively by 100 ℃; 108 ℃; 116 ℃; 132 ℃; The mixing speed of reactor is followed successively by 150/150/40/15rpm; The reactor volume that is adopted is 3.9L
Inferior inlet amount is 400mL/h, and employed temperature of reaction is 100 ℃, and mixing speed is 150rpm.It is the reactor of 2.1L that inferior charging adds a volume earlier, through after the abundant grafting, adds the 3rd reactor and the material thorough mixing by the static mixer and second reactor at glue.
The 3rd strand of material is that inlet amount is 60mL/h through the conditioning agent NDM of ethylbenzene dilution, and the content of conditioning agent NDM is 700ppm, adds second reactor inlet continuously.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 1.
The analytical results of table 1, embodiment 1
Embodiment 2:
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM 610AX rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 10 hours under the normal temperature.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as main charging.
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM756A rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 10 hours under the normal temperature.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as inferior charging.
Main inlet amount is 1540mL/h; System pressure is controlled at 1.1MPa; The temperature of reaction of 4 reactors is followed successively by 106 ℃; 113 ℃; 125 ℃; L54 ℃; The mixing speed of reactor is followed successively by 100/100/40/15rpm; The reactor volume that is adopted is 3.9L.
Inferior charging is 400mL/h, and employed temperature of reaction is 100 ℃, and mixing speed is 150rpm.It is the reactor of 2.1L that inferior charging adds a volume earlier, through after the abundant grafting, adds the 3rd reactor and the material thorough mixing by the static mixer and second reactor at glue.
The 3rd strand of material is that inlet amount is 60mL/h through the conditioning agent NDM of ethylbenzene dilution, and the content of conditioning agent NDM is 700ppm.Add second reactor inlet continuously.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 2.
The analytical results of table 2, embodiment 2
Embodiment 3:
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM 610AX rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 11 hours under the normal temperature.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as main charging.
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM756A rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 11 hours under the normal temperature.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as inferior charging.
Main inlet amount is 1540mL/h; System pressure is controlled at 1.2MPa; The temperature of reaction of 4 reactors is followed successively by 103 ℃; 110 ℃; 120 ℃; 140 ℃; The mixing speed of reactor is followed successively by 70/70/40/15rpm; The reactor volume that is adopted is 3.9L.
Inferior charging is 400mL/h, and employed temperature of reaction is 100 ℃, and mixing speed is 100rpm.It is the reactor of 2.1L that inferior charging adds a volume earlier, through after the abundant grafting, adds the 3rd reactor and the material thorough mixing by the static mixer and second reactor at glue.
The 3rd strand of material is that inlet amount is 60mL/h through the conditioning agent NDM of ethylbenzene dilution, and the content of conditioning agent NDM is 700ppm.Add second reactor inlet continuously.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 3.
The analytical results of table 3, embodiment 3
Embodiment 4:
Add 19kg ethylbenzene in the rubber dissolving tank, 50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM756A rubber 10kg that will be cut into 10*10mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 9 hours under the normal temperature.Add vinyl cyanide l7.9kg then, 0.3Kg crosses sad tertiary butyl ester, 0.28Kg softening agent mineral oil, and the 0.05Kg antioxidant 1076,0.19Kg chain-transfer agent mercaptan continues dispersed with stirring 30min.
The inlet amount of reactor is 1540mL/h; System pressure is controlled at 1.0MPa; The temperature of reaction of 4 reactors is followed successively by 105 ℃; 1113 ℃; 125 ℃; 145 ℃; The mixing speed of reactor is followed successively by 100/100/40/15rpm; The reactor volume that is adopted is 3.9L.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization injection moulding machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 4.
The analytical results of table 4, embodiment 4
Embodiment 5:
Adding the 19kg weight ratio in the rubber dissolving tank is ethylbenzene and the acetone mixture of 8:2,50.95kg vinylbenzene, start and stir the Asahi AsapreneTM610AX rubber 10kg that will be cut into 10*10mm, add the rubber dissolving tank by adding Jiao Kou, stirring and dissolving is 10 hours under the normal temperature.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as main charging.
Adding the 19kg weight ratio in the rubber dissolving tank is ethylbenzene and the acetone mixture of 8:2,50.95kg vinylbenzene, start to stir the Asahi AsapreneTM756A rubber 10kg that will be cut into 10*10mm, add the rubber dissolving tank, under the normal temperature stirring and dissolving lO hour by adding Jiao Kou.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as inferior charging.
Main inlet amount is 1300mL/h; System pressure is controlled at 1.1MPa; The temperature of reaction of 4 reactors is followed successively by 100 ℃; 110 ℃; 125 ℃; 145 ℃; The mixing speed of reactor is followed successively by 100/100/40/15rpm; The reactor volume that is adopted is 3.9L.
Inferior charging is 250mL/h, and employed temperature of reaction is 90 ℃, and mixing speed is 150rpm.It is the reactor of 2.1L that inferior charging adds a volume earlier, through after the abundant grafting, adds the 3rd reactor and the material thorough mixing by the static mixer and second reactor at glue.
The 3rd strand of material is that inlet amount is 45mL/h through the conditioning agent NDM of ethylbenzene dilution, and the content of conditioning agent NDM is 650ppm.Add second reactor inlet continuously.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 5.
The analytical results of table 5, embodiment 5
Embodiment 6:
Adding the 19kg weight ratio in the rubber dissolving tank is toluene and the methylethyl alcohol/ketone mixtures of 3:1,50.95kg vinylbenzene starts and stirs the Asahi AsapreneTM610AX rubber 10kg that will be cut into 1 0*1 0mm, adds the rubber dissolving tank by adding Jiao Kou, and stirring and dissolving is 10 hours under the normal temperature.Add vinyl cyanide 17.9kg then, the 0.4Kg t-butyl perbenzoate, 0.44Kg softening agent mineral oil, the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as main charging.
Adding the 19kg weight ratio in the rubber dissolving tank is toluene and the methylethyl alcohol/ketone mixtures of 3:1,50.95kg vinylbenzene, start to stir the AsahiAsapreneTM756A rubber 10kg that will be cut into 10*10mm, add the rubber dissolving tank, under the normal temperature stirring and dissolving l0 hour by adding Jiao Kou.Add vinyl cyanide 17.9kg then, 0.4Kg crosses sad tertiary butyl ester, 0.44Kg softening agent mineral oil, and the 0.08Kg antioxidant 1076,0.12Kg chain-transfer agent mercaptan continues dispersed with stirring 30min, as inferior charging.
Main inlet amount is 1800mL/h; System pressure is controlled at 0.8MPa; The temperature of reaction of 4 reactors is followed successively by 110 ℃; 115 ℃; 135 ℃; 155 ℃; The mixing speed of reactor is followed successively by 100/100/40/15rpm; The reactor volume that is adopted is 3.9L.
Inferior charging is 450mL/h, and employed temperature of reaction is 105 ℃, and mixing speed is 150rpm.It is the reactor of 2.1L that inferior charging adds a volume earlier, through after the abundant grafting, adds the 3rd reactor and the material thorough mixing by the static mixer and second reactor at glue.
The 3rd strand of material is that inlet amount is 80mL/h through the conditioning agent NDM of ethylbenzene dilution, and the content of conditioning agent NDM is 500ppm.Add second reactor inlet continuously.
Reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTMD standard analysis test products to see Table 6.
The analytical results of table 6, embodiment 6
Though the present invention discloses as above with preferred embodiment; but it is not in order to qualification the present invention, any person of ordinary skill in the field, without departing from the spirit and scope of the present invention; can do a little change and improvement, protection scope of the present invention is worked as with being as the criterion that claim was defined.
Claims (9)
1. the preparation method based on the extinction injection moulding level abs polymer of continuous bulk comprises the steps:
1) rubber is dissolved in monoalkyl vinyl aromatic monomer and the unsaturated nitrile monomer mixture and forms rubber solutions, and with after solvent and initiator mix, add as main charging and carry out graft polymerization reaction in first reactor;
Wherein, described rubber is that second-order transition temperature is not more than 85 ℃ conjugation 1, and 3-dience rubber or second-order transition temperature are not more than 85 ℃ conjugation 1, but the monoene of 3-dience rubber and copolymerization belongs to the multipolymer and/or the segmented copolymer of unsaturated monomer;
2) polymerisate of main charging in first reactor in the described step 1) added second reactor, carry out the phase-inversion polymerization reaction, rubber weight average particle diameter 0.3-1.7 micron after second reactor is finished phase reversion;
3) rubber is dissolved in monoalkyl vinyl aromatic monomer, the unsaturated nitrile monomer mixture and forms rubber solutions, and with solvent and initiator after mixing, make time charging, add and to carry out grafting and phase-inversion polymerization in the graft reaction device and react that solids content is 38-45% to the polymerisate, inlet amount is 150-450ml/h, temperature of reaction is 90-115 ℃, stirring velocity is 50-200rpm, polymerisate that makes and described step 2) polymerisate that makes mixes by static mixer, adds in follow-up at least two reactors and proceed polyreaction;
Wherein, described rubber is that second-order transition temperature is not more than 85 ℃ conjugation 1, and 3-dience rubber or second-order transition temperature are not more than 85 ℃ conjugation 1, but the monoene of 3-dience rubber and copolymerization belongs to the multipolymer and/or the segmented copolymer of unsaturated monomer;
4) material that will from final reactor, discharge, devolatilization separates, extruding pelletization, obtain the extinction injection moulding level abs polymer, wherein the rubber weight average particle diameter is not more than 1.7 microns, and rubber phase distribution Dw/Dn is 2.2 at the most, rubber content is 10-18%, monomer conversion 65-85%.
2. the method for claim 1 is characterized in that, the polymerisate of main charging in first reactor in the described step 1) added second reactor, carries out the phase-inversion polymerization reaction with additional monomer,
Wherein, described additional monomer is one or more of following substances: vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid and corresponding ester, acrylamide, Methacrylamide, vinylchlorid, bromine ethene, inclined to one side sym-dibromoethane, vinyl-acetic ester, vinyl propionate base ester, the toxilic acid dimethyl esters, the toxilic acid diethyl ester, dibutyl maleinate, maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-xylyl maleimide or N-2,4-xylyl maleimide;
The add-on of additional monomer is the 1-20% of rubber solutions weight.
3. the method for claim 1 is characterized in that,
In the described step 1):
Main charging polyreaction solids content to the polymerisate in first reactor is 20-30%, and inlet amount is 1200-2000ml/h, and temperature of reaction is 90-115 ℃, and reaction pressure is a 5-12 normal atmosphere, and stirring velocity is 50-200rpm;
Described step 2) in:
Main charging polyreaction solids content to the polymerisate in second reactor is 30-45%, and temperature of reaction is 100-125 ℃, and reaction pressure is a 5-12 normal atmosphere, and stirring velocity is 50-200rpm;
In the described step 3):
Carrying out polyreaction solids content to the polymerisate is 45-75%, and temperature of reaction is 120-170 ℃, and reaction pressure is a 5-12 normal atmosphere, and stirring velocity is 5-70rpm.
4. as the arbitrary described method of claim 1-3, it is characterized in that, is 100% in the gross weight of rubber solutions, and mono-alkenyl aromatic monomer content is 40-60%, and unsaturated nitrile content is 15-20%, and all the other are rubber, and rubber content is no more than 25%;
Described weight of solvent is the 10-20% of rubber solutions weight;
Described initiator weight is the 0.001-3.0% of rubber solutions weight.
5. method as claimed in claim 4 is characterized in that, is 100% in the gross weight of rubber solutions, and mono-alkenyl aromatic monomer content is 50-55%, and unsaturated nitrile content is 5-20%, and all the other are rubber, and rubber content is no more than 25%;
Described weight of solvent is the 12-20% of rubber solutions weight;
Described initiator weight is the 0.005-1.0% of rubber solutions weight.
6. as the arbitrary described method of claim 1-3, it is characterized in that,
Described rubber wherein contains the cis-isomeride of weight percentage 30-98% and the trans-isomer(ide) of weight percentage 2-70% for poly-1;
Described monoalkyl vinyl aromatic monomer structure is shown below:
Wherein, Ar is one or more in phenyl, halogenophenyl, alkyl phenyl or the halogenated alkyl phenyl; X is hydrogen, methyl or ethyl;
Described unsaturated nitrile monomer is one or more in vinyl cyanide, methacrylonitrile or the ethyl acrylonitrile;
Described solvent is aromatic hydrocarbon and alkenolic mixture, and the ratio of aromatic hydrocarbon and alkenolic weight is 8: 2-7: 3;
Described initiator is one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester or cross the neodecanoic acid tertiary butyl ester.
7. method as claimed in claim 6 is characterized in that,
Described rubber is butylbenzene block rubber or polybutadiene rubber;
It is vinylbenzene that described monoene belongs to unsaturated monomer;
Described vinyl unsaturated nitrile monomer is a vinyl cyanide;
Aromatic hydrocarbon in the described solvent is benzene, ethylbenzene or toluene; Aliphatic ketone in the described solvent is acetone, methyl ethyl ketone or methyl propyl ketone.
8. as the arbitrary described method of claim 1-3, it is characterized in that,
Add chain-transfer agent, softening agent and oxidation inhibitor in the described step 1),
Described step 1), 2) or 3) in add molecular weight regulator;
In described step 1), 2), 3) or 4) in add silicone oil.
9. as the arbitrary described method of claim 1-3, it is characterized in that described reactor is the plunger tpe reactor.
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| CN102086254B (en) * | 2010-04-08 | 2012-08-22 | 上海领智化工科技有限公司 | Method for preparing high impact resistant ACS polymer |
| CN102675815A (en) * | 2012-05-22 | 2012-09-19 | 苏州新区华士达工程塑胶有限公司 | Formula of reinforced ABS (acrylonitrile-butadiene-styrene) |
| CN103232679B (en) * | 2013-04-18 | 2015-03-04 | 苏州旭光聚合物有限公司 | Low-glossiness ABS (acrylonitrile-butadiene-styrene) resin |
| CN103275452A (en) * | 2013-06-07 | 2013-09-04 | 曹广文 | Environmentally-friendly weather and aging resistant flame-retardant resin composition and preparation method thereof |
| CN111748170A (en) * | 2020-07-16 | 2020-10-09 | 雷丽 | Modified ABS resin and production process thereof |
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