CN101914178B - Preparation method of dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer - Google Patents
Preparation method of dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer Download PDFInfo
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Abstract
The invention relates to a preparation method of a dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer, which is characterized by comprising the following steps of: mixing and dispersing 2-15 percent of cyclones, 35-75 percent of dutrex monomer, 15-50 percent of acrylonitrile and 0.001-2.0 percent of evocating agent into 1.0-10.0 percent of solvent in the total weight percentage of a monomer; mixing; polymerizing at the temperature of 85-300 DEG C and atmospheric pressure of 0.1-10.0Mpa; stopping polymerizing until the solid content is 50-99 percent in a polymerized product; and obtaining the dutrex-unsaturated nitrile-cyclenes heat-resistant copolymer after the solvent is removed. Compared with the prior art, the prepared product of the invention has higher thermal deformation temperature, excellent mechanical property, forming property and high product quality; meanwhile, the reaction conversion rate is greatly increased and reaches above 95 percent. The prepared heat-resistant copolymer can be widely used for the fields of electronic instruments, automotive industry, household electrical appliance parts, packaging materials, general merchandises, and the like which have a certain requirement for material heat resistance.
Description
Technical field
The present invention relates to the preparation field of superpolymer, specifically refer to the preparation method of a kind of aromatic hydrocarbon-unsaturated nitrile-cycloolefin heat-resistant copolymer.
Background technology
Styrene copolymer except PS, important and large-scale industrial production styrene-acrylonitrile copolymer (SAN) and acrylonitrile-butadiene-styrene copolymer (ABS) arranged in addition.Wherein the SAN resin is the colourless or little yellow thermoplastics of non-crystalline state; On dimensional stability, weathering resistance, thermotolerance, oil-proofness and chemicalstability, has good performance; Apolar substances such as ability gasoline, kerosene, aromatic hydrocarbon; Water-fast, sour, alkali, washing composition and halogenated hydrocarbon solvent, but be dissolved in ketone, can be by the organic solvent swelling.The little Huang of ABS resin outward appearance is opaque, has good dimensional stability, and outstanding shock-resistance, thermotolerance, dielectricity, wear resistance and surface luster property etc. are prone to application and painted.
Along with developing of automobile industry, and the technical progress in fields such as electronics, household electrical appliances, the demand of heat resistant type plastics has been presented the trend that increases gradually, the research of heat resistant type SAN and heat resistant type ABS has become an important topic in this field.With respect to universal SAN resin, heat resistant type SAN resin is under the prerequisite that guarantees other each item indexs, and heat-drawn wire and Vicat softening point have raising by a relatively large margin, and is also few as the heat resistant type SAN resin of commodity selling in the market.
Though improve ABS or SAN thermotolerance can through with other heat stable resin component alloy such as PC or add means such as mineral filler for example, more efficient methods is still through copolymerization introduction stiff molecule.Research and development show, (α-MS), p-methylstyrene (P-MS), maleic anhydride (MA) or ammonia substituted maleimide amine is N-phenylmaleimide etc. for example, can improve the resistance toheat of polymkeric substance for alpha-methyl styrene in grafting on the molecular chain of SAN.But concerning some special dimensions or particular requirement; More than the thermotolerance of existing these graft modification products can't meet the demands; Also need further to improve; And existing ABS or SAN have sacrificed the tensile strength and the breach resistance to impact shock of a part of mechanical property, particularly material when improving resistance toheat; Simultaneously, because methyl substituted vinylbenzene reactive behavior is lower, so conversion rate of products is low.
Summary of the invention
Technical problem to be solved by this invention is the preparation method that aromatic hydrocarbon-unsaturated nitrile that a kind of thermotolerance is further enhanced and the product mechanical property is good, conversion rate of products is high-cycloolefin heat-resistant copolymer is provided to the present situation of prior art.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of this aromatic hydrocarbon-unsaturated nitrile-cycloolefin heat-resistant copolymer; It is characterized in that the unsaturated nitrile of the cycloolefin of monomer 2～15%, 35～75% aromatic hydrocarbon monomer and 15～50% and the initiator blending dispersion that accounts for monomer total amount 0.001-2.0% in monomer total amount 1.0-10.0% solvent; Stir; Polymerization under 85-300 ℃, 0.1-10.0Mpa; Stop polymerization when solid content is for 50-99% to polymerisate, promptly obtain aromatic hydrocarbon-unsaturated nitrile-cycloolefin heat-resistant copolymer after removing solvent;
Wherein, described cycloolefin is selected from one or more in cyclopentenes, methyl cyclopentene, dimethylcyclopentene, ethyl cyclopentenes, tetrahydrobenzene, tetrahydrotoluene, dimethyl-tetrahydrobenzene or the ethyl-cyclohexene;
Described aromatic hydrocarbon be selected from vinylbenzene, alpha-methyl styrene, α-ethyl styrene, neighbour-vinyl toluene ,-vinyl toluene, p-methylstyrene, 2; 4-dimethyl styrene, right-t-butyl styrene, α-ethyl p-methylstyrene, neighbour-chloro-styrene ,-chloro-styrene, right-chloro-styrene, neighbour-bromstyrol, 2; 4-Dowspray 9,2-methyl-4-chloro-styrene or 2,6-two chloro-4-vinyl toluenes;
Described unsaturated nitrile is selected from vinyl cyanide, Alpha-Methyl vinyl cyanide or ethyl acrylonitrile;
Said initiator is selected from one or more in peroxide initiator or the azo-initiator;
Described solvent is selected from one or more in straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, aromatic hydrocarbons or the halohydrocarbon;
Above-mentioned each content is weight percentage.
Preferably; The consumption of said aromatic hydrocarbon monomer is 50～75%, and the consumption of said unsaturated nitrile monomer is 15～35%, and the consumption of said cycloolefin is 4～10%; The consumption of said solvent is monomer total amount 3.0-8.0%, and the consumption of said initiator is monomer total amount 0.01-2.0%.
Described straight chain aliphatic hydrocarbon can be selected from one or more in normal hexane, Skellysolve A, normal heptane, octane or the whiteruss hydrocarbon; Described cyclic aliphatic hydrocarbon can be selected from one or more in hexanaphthene, pentamethylene, methylcyclopentane, dimethylcyclopentane, trimethyl cyclopentane, ethyl cyclopentane, diethylammonium pentamethylene or the cyclooctane, and described aromatic hydrocarbons can be selected from one or more in benzene, toluene, ethylbenzene, YLENE or the trimethylbenzene; Described halohydrocarbon can be selected from one or more in methylene dichloride, chlorobenzene or the dichlorobenzene.Preferred normal hexane of above-mentioned solvent and/or ethylbenzene.
Preferably,, the processing fluidity of polymkeric substance is met the demands, adding a certain amount of molecular weight regulator to reaction system usually for the molecular weight of telo merization product; In order to delay the photooxidation droping speed of polymkeric substance, prolong the work-ing life of polymkeric substance simultaneously, in polymkeric substance, add a certain amount of oxidation inhibitor usually.Before polyreaction, also in said solvent, add molecular weight regulator and/or oxidation inhibitor as required.The consumption of wherein said molecular weight regulator is for accounting for total monomer weight 0.01-3.0%; The consumption of said oxidation inhibitor is the 0.05-2.0% that accounts for monomer weight, so that product obtains better properties.
Described molecular weight regulator can be selected from one or more in the linear dimer of n-dodecyl mercaptan, uncle's lauryl mercaptan or alpha-methyl styrene; Described oxidation inhibitor is selected from one or more in Hinered phenols antioxidant or the phosphite ester kind antioxidant.
Described Hinered phenols antioxidant can be selected from antioxidant 1010 or antioxidant 1076, and described phosphite ester kind antioxidant is an oxidation inhibitor 168.
Better, described oxidation inhibitor can adopt antioxidant 1010 and oxidation inhibitor 168 to be used, and the two is used has synergistic effect.
In the above-mentioned scenarios, described stirring velocity can be 20-200rpm.
Above-mentioned polyreaction can be carried out in the complete mixing flow tower reactor, and monomer conversion is higher; Remove solvent and can in devolatilizer, carry out the devolatilization separation; The product that obtains can also carry out extruding pelletization as required, to make things convenient for following process.
Compared with prior art, the invention provides a kind of preparation method of heat-resistant copolymer of brand-new aromatic hydrocarbon-unsaturated nitrile-cycloolefin, auxiliary dosage is few in this method; Product has higher heat-drawn wire; Heat-drawn wire reaches more than 94 ℃, has excellent mechanical property and moulding processability simultaneously concurrently, and its tensile strength reaches more than the 75Mpa; Izod breach resistance to impact shock is greater than 20J/m, good product quality; Reaction conversion ratio also improves greatly, all reach more than 95%, and the transformation efficiency in the existing technology has only 85%, and the tensile strength of common heat-resisting SAN reaches generally at 40～60Mpa, and the breach resistance to impact shock is generally at 12～18J/m.The heat-resistant copolymer that makes with present method can be widely used in electronic instrument, automotive industry, household electrical appliances accessory, wrapping material, general merchandise etc. to the material thermal resistance field that can have certain requirements.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Embodiment 1
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, the 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum, adds 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.2% oxidation inhibitor 168 of monomer weight, mixes 30min under the normal temperature.Be heated to 85 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.5MPa, 85 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.5 hours, obtained solid content and be 92.0% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Carry out the forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.ASTM D256 standard, sample thickness 3.2mm are adopted in the test of Izod breach resistance to impact shock; ASTM D638 standard, test speed 50mm/min are adopted in the tensile strength test; ASTM D648 standard, sample thickness 6.4mm, test load 1.82MPa are adopted in the heat-drawn wire test; ASTM D1525 standard, test load 10N are adopted in the Vicat softening point test.
Embodiment 2
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, the 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum, adds 1.0% Lucidol, 0.05% n-dodecyl mercaptan, 0.4% oxidation inhibitor 168 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 120 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.0 hours, and obtaining solid content is 92.6% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 3
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, the 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum, adds 1.0% Lucidol, 0.05% n-dodecyl mercaptan, 0.2% antioxidant 1076 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 100 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.0 hours, and obtaining solid content is 90.6% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 4
Get 1.2kg vinylbenzene, the 0.35kg vinyl cyanide, the 0.10kg tetrahydrobenzene, 0.10kg ethylbenzene is put into reactor drum, adds 0.02% t-butyl perbenzoate, 0.05% n-dodecyl mercaptan, 0.2% antioxidant 1010 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 100 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.0 hours, and obtaining solid content is 93.3% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 5
Get 1.5kg vinylbenzene, the 0.75kg vinyl cyanide, the 0.18kg tetrahydrobenzene, 0.15kg toluene is put into reactor drum, adds 1.0% Lucidol, 0.05% n-dodecyl mercaptan, 0.2% antioxidant 1076 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 95 ℃ of temperature of reaction, stirring velocity 80rpm reacted 2.0 hours, and obtaining solid content is 91.8% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 6
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, the 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum, adds 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.2% antioxidant 1010 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 90 ℃ of temperature of reaction, stirring velocity 80rpm reacted 2.5 hours, and obtaining solid content is 91.5% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 7
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, the 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum, adds 1.5% Lucidol, 0.03% alpha-methyl styrene, 0.2% antioxidant 1076 of monomer weight, mixes 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.5 hours, and obtaining solid content is 91.8% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 8
Get the 1.6kg alpha-methyl styrene; 0.50kg vinyl cyanide; 0.15kg tetrahydrobenzene, 0.15kg ethylbenzene is put into reactor drum; Add 0.05% t-butyl perbenzoate, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1076,0.1% oxidation inhibitor 168 of monomer weight, mix 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 95 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.5 hours, and obtaining solid content is 93.4% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 9
Get vinyl toluene between 1.5kg; 0.75kg ethyl acrylonitrile; 0.15kg the dimethyl-tetrahydrobenzene, 0.15kg toluene is put into reactor drum; Add 1.0% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1076,0.1% oxidation inhibitor 168 of monomer weight, mix 30min under the normal temperature.Be heated to 95 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 95 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.5 hours, and obtaining solid content is 90.2% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 10
Get the 1.5kg alpha-methyl styrene; 0.50kg vinyl cyanide; 0.15kg tetrahydrotoluene, 0.15kg ethylbenzene is put into reactor drum; Add 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 2.5 hours, and obtaining solid content is 89.5% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 11
Get the 1.5kg alpha-methyl styrene; 0.50kg vinyl cyanide; 0.15kg tetrahydrotoluene, 0.15kg toluene is put into reactor drum; Add 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 91.4% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 12
Get monomer 1.5kg α-ethyl styrene, 0.50kg Alpha-Methyl vinyl cyanide, 0.15kg cyclopentenes and solvent mixture 0.1kg normal hexane and 0.05kg ethylbenzene; Put into reactor drum; Add 1.9% Diisopropyl azodicarboxylate, 0.05% α-vinyl toluene linear dimeric, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 90.3% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 13
Get monomer 1.5kg p-methylstyrene, 0.50kg ethyl acrylonitrile, 0.15kg methyl cyclopentene and solvent mixture 0.15kg hexanaphthene; Put into reactor drum; Add 0.001% t-butyl perbenzoate, 0.05% uncle's lauryl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 90.9% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 14
Get monomer 1.5kg to chloro-styrene, 0.50kg vinyl cyanide, 0.15kg ethyl-cyclohexene and solvent mixture 0.15kg chlorobenzene; Put into reactor drum; Add 1.5% Lucidol, uncle's lauryl mercaptan of 0.05% and mixture, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of n-dodecyl mercaptan of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 91.2% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 15
Get monomer 1.5kg right-t-butyl styrene, 0.50kg vinyl cyanide, 0.15kg dimethylcyclopentene and solvent mixture 0.1kg normal hexane, 0.05kg ethylbenzene; Put into reactor drum; Add 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 90.5% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 16
Get monomer 1.5kg2; 4-Dowspray 9,0.50kg vinyl cyanide, 0.15kg ethyl cyclopentenes and solvent mixture 0.1kg normal hexane, 0.05kg ethylbenzene; Put into reactor drum; Add 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 91.6% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Embodiment 17
Get monomer 1.5kg2-methyl-4-chloro-styrene, 0.50kg vinyl cyanide, 0.15kg cyclopentenes and solvent mixture 0.1kg normal hexane, 0.05kg ethylbenzene; Put into reactor drum; Add 1.5% Lucidol, 0.05% n-dodecyl mercaptan, 0.15% antioxidant 1010,0.1% oxidation inhibitor 168 of total monomer weight, mix 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.4MPa, 105 ℃ of temperature of reaction, stirring velocity 100rpm reacted 3.0 hours, and obtaining solid content is 91.4% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
Comparative Examples
Get 1.5kg vinylbenzene, the 0.50kg vinyl cyanide, 0.15kg ethylbenzene is put into reactor drum, adds 1.0% Lucidol, 0.05% n-dodecyl mercaptan, 0.2% antioxidant 1076 of monomer weight, mixes 30min under the normal temperature.Be heated to 105 ℃ with reactor drum external jacket electric heater then, control reaction pressure 0.3MPa, 95 ℃ of temperature of reaction, stirring velocity 80rpm reacted 3.0 hours, and obtaining solid content is 91.2% polymkeric substance glue.The polymkeric substance glue gets into devolatilizer and removes unreacted monomer and solvent then, and the temperature when devolatilization separates is controlled at 230 ℃, and pressure is 3mmHg.Forcing machine granulation after the melt devolatilization separating treatment.Use the performance of corresponding ASTM standard analysis test products to see table 1.
The test result of each embodiment of table 1
The test result of continuous each embodiment of table 1
Continuous table 2
| Performance | Unit | Embodiment 15 | Embodiment 16 | Embodiment 17 | Comparative Examples |
| Izod breach resistance to impact shock | J/m | 33 | 32 | 35 | 16 |
| Tensile strength | MPa | 78.2 | 79.0 | 77.3 | 68.0 |
| Heat-drawn wire | ℃ | 98.8 | 98.0 | 99.7 | 91.7 |
| Vicat softening point | ℃ | 124.2 | 122.2 | 125.0 | 104.7 |
Claims (9)
1. the preparation method of aromatic hydrocarbon-unsaturated nitrile-cycloolefin heat-resistant copolymer; It is characterized in that the unsaturated nitrile of the cycloolefin of monomer 2～15%, 35～75% aromatic hydrocarbon monomer and 15～50% and the initiator blending dispersion that accounts for monomer total amount 0.001-2.0% in accounting for monomer total amount 1.0-10.0% solvent; Stir; Polymerization under 85-300 ℃, 0.1-10.0Mpa; Stop polymerization when solid content is for 50-99% to polymerisate, promptly obtain aromatic hydrocarbon-unsaturated nitrile-cycloolefin heat-resistant copolymer after removing solvent;
Wherein, described cycloolefin is selected from one or more in cyclopentenes, methyl cyclopentene, dimethylcyclopentene, ethyl cyclopentenes, tetrahydrobenzene, tetrahydrotoluene, dimethyl-tetrahydrobenzene or the ethyl-cyclohexene;
Described aromatic hydrocarbon be selected from vinylbenzene, alpha-methyl styrene, α-ethyl styrene, neighbour-vinyl toluene ,-vinyl toluene, p-methylstyrene, 2; 4-dimethyl styrene, right-t-butyl styrene, α-ethyl p-methylstyrene, neighbour-chloro-styrene ,-chloro-styrene, right-chloro-styrene, neighbour-bromstyrol, 2; 4-Dowspray 9,2-methyl-4-chloro-styrene or 2,6-two chloro-4-vinyl toluenes;
Described unsaturated nitrile is selected from vinyl cyanide, Alpha-Methyl vinyl cyanide or ethyl acrylonitrile;
Said initiator is selected from one or more in peroxide initiator or the azo-initiator;
Described solvent is selected from one or more in straight chain aliphatic hydrocarbon, cyclic aliphatic hydrocarbon, aromatic hydrocarbons or the halohydrocarbon;
Above-mentioned each content is weight percentage.
2. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 1-cycloolefin heat-resistant copolymer; The consumption of said aromatic hydrocarbon monomer is 50～75%; The consumption of said unsaturated nitrile monomer is 15～35%, and the consumption of said cycloolefin is 4～10%, and the consumption of said solvent is monomer total amount 3.0-8.0%; The consumption of said initiator is monomer total amount 0.01-2.0%, and each monomer consumption summation is 100%.
3. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 1-cycloolefin heat-resistant copolymer is characterized in that said straight chain aliphatic hydrocarbon is selected from one or more in normal hexane, Skellysolve A, normal heptane, octane or the whiteruss hydrocarbon; Described cyclic aliphatic hydrocarbon is selected from one or more in hexanaphthene, pentamethylene, methylcyclopentane, dimethylcyclopentane, trimethyl cyclopentane, ethyl cyclopentane, diethylammonium pentamethylene or the cyclooctane, and described aromatic hydrocarbons is selected from one or more in benzene, toluene, ethylbenzene, YLENE or the trimethylbenzene; Described halohydrocarbon is selected from one or more in methylene dichloride, chlorobenzene or the dichlorobenzene.
4. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 1-cycloolefin heat-resistant copolymer is characterized in that said solvent is normal hexane and/or ethylbenzene.
5. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 1-cycloolefin heat-resistant copolymer is characterized in that before polyreaction, also in said solvent, adding molecular weight regulator and/or oxidation inhibitor; The consumption of wherein said molecular weight regulator is for accounting for total monomer weight 0.01-3.0%; The consumption of said oxidation inhibitor is the 0.05-2.0% that accounts for monomer weight.
6. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 5-cycloolefin heat-resistant copolymer is characterized in that described molecular weight regulator is selected from one or more in the linear dimer of n-dodecyl mercaptan, uncle's lauryl mercaptan or alpha-methyl styrene; Described oxidation inhibitor is selected from one or more in Hinered phenols antioxidant or the phosphite ester kind antioxidant.
7. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 6-cycloolefin heat-resistant copolymer is characterized in that described Hinered phenols antioxidant is selected from antioxidant 1010 or antioxidant 1076, and described phosphite ester kind antioxidant is an oxidation inhibitor 168.
8. the preparation method of aromatic hydrocarbon-unsaturated nitrile according to claim 7-cycloolefin heat-resistant copolymer is characterized in that described oxidation inhibitor adopts antioxidant 1010 and oxidation inhibitor 168 to be used.
9. according to the preparation method of the described aromatic hydrocarbon-unsaturated nitrile of the arbitrary claim of claim 1 to 8-cycloolefin heat-resistant copolymer, it is characterized in that described stirring velocity is 20-200rpm, the reaction times is 2～10 hours.
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| CN102382228B (en) * | 2011-09-02 | 2012-12-19 | 宁波镇洋化工发展有限公司 | SAN (styrene-acrylonitrile copolymer) preparation method |
| CN102702638B (en) * | 2012-05-30 | 2014-04-16 | 宁波镇洋化工发展有限公司 | Glass fiber-reinforced styrene-acrylonitrile-cycloolefin (SAN) copolymer composition |
| CN104119659A (en) * | 2014-06-06 | 2014-10-29 | 宁波浙铁大风化工有限公司 | High-fluidity PC (polycarbonate) composition and preparation method thereof |
| CN105693928B (en) * | 2016-03-17 | 2017-08-08 | 宁波工程学院 | Norborneol alkenes, hexafluoropropene and acrylonitrile ternary polymerization catalyst and method for ternary polymerization |
| CN111534073B (en) * | 2020-05-06 | 2022-08-16 | 宁波浙铁大风化工有限公司 | Glass fiber reinforced PC material capable of being welded by ultrasonic waves and preparation method thereof |
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