CN102993350B - Styrene/maleic anhydride compound and preparation method thereof - Google Patents
Styrene/maleic anhydride compound and preparation method thereof Download PDFInfo
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- -1 Styrene/maleic anhydride compound Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 43
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 239000003607 modifier Substances 0.000 claims description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 15
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000002171 ethylene diamines Chemical class 0.000 claims description 3
- 150000002240 furans Chemical group 0.000 claims description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 abstract description 27
- 229920005604 random copolymer Polymers 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000006757 chemical reactions by type Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005453 pelletization Methods 0.000 description 11
- 238000010008 shearing Methods 0.000 description 11
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a styrene/maleic anhydride compound and a preparation method thereof. The preparation method of the styrene/maleic anhydride compound comprises the following steps: dissolving maleic anhydride, a polarity regulator accounting for 0.1-1 percent of the total weight of the styrene/maleic anhydride compound and a radical initiator to a styrene monomer, and controlling a screw barrel of a double-screw extruder to 30-280 DEG C to carry out extrusion and granulation in the reactive-type double-screw extruder to obtain the styrene/maleic anhydride compound. The preparation method is implemented by adopting a reactive extrusion bulk method without using a large number of solvents, therefore the problems of overhigh energy consumption and heavy environmental pollution caused by the adoption of a large number of solvents in a solution method are solved, and the copolymerization reaction can be controlled due to the addition of the polarity regulator so as to promote to generate random copolymers by the reaction; and the styrene/maleic anhydride compound produced by synthesis is high in rigidity, heat resistance and toughness and accords with the requirements of SMA (Styrene Maleic Anhydride) materials for vehicles.
Description
Technical field
The present invention relates to field of polymer technology, particularly a kind of Styrene/maleic anhydride compound and preparation method thereof.
Background technology
Simple polystyrene material is more crisp, poor heat resistance, and its range of application is restricted.Carry out random copolymerization by maleic anhydride and styrene monomer, novel thermoplastic engineering plastics random styrene maleic anhydride copolymer (SMA) resin can be prepared, the thermotolerance of polystyrene resin can be improved thus.SMA resin is succeeded in developing by Arco company of the U.S., and introduces to the market with the trade(brand)name of Dylark, and at present, external existing a lot of SMA resin new grades, as Cypress, Styromol etc.
The main range of application of SMA resin is the aspects such as automobile making, household electrical appliance, material of construction, office facility, instrument manufacture, at present, industrialized maleic anhydride and cinnamic random copolymerization react main under the initiation of radical initiator, be polymerized in polar solvent, but, solution method needs to consume a large amount of solvents, causes energy consumption too high too large with environmental pollution, does not meet the low stain of current industrial development, the requirement of less energy-consumption.For automobile SMA, there is certain requirement to the tensile strength of SMA, modulus in flexure, toughness and thermotolerance, and adopt different SMA preparation methods, all need to select suitable technique that the SMA obtained just can be made to meet above-mentioned performance requriements.
Summary of the invention
Goal of the invention of the present invention, being to overcome the deficiencies in the prior art, providing a kind of preparation method of Styrene/maleic anhydride compound.
Another object of the present invention is to provide the Styrene/maleic anhydride compound prepared by described preparation method.
Above-mentioned purpose of the present invention is achieved by following technical solution:
A kind of preparation method of Styrene/maleic anhydride compound, maleic anhydride, the polar modifier accounting for Styrene/maleic anhydride compound gross weight 0.1 ~ 1%, radical initiator is comprised the steps: to dissolve in styrene monomer, in response type twin screw extruder, control double-screw extruding machine barrel temperature to extrude at 30 ~ 280 DEG C, granulation, obtains described Styrene/maleic anhydride compound;
Described polar modifier is one in furans, ethylenediamines and ether material or its mixture.
The advantage that reactive extrursion prepares high molecular polymer can not add any solvent to react, and therefore overcomes the shortcoming that solvent method needs to consume a large amount of solvent.
But, contriver finds, in the process of reactive extrursion, obvious competing reaction is there is in styrene monomer with being polymerized of maleic anhydride monomer, when not adding polar modifier, in the Styrene/maleic anhydride compound that reactive extrursion obtains, the ratio of alternating copolymer is higher, and its toughness is poor, is difficult to the requirement meeting automobile SMA material.When adding appropriate polar modifier in raw material, styrene monomer can be controlled and be polymerized with the mode of maleic anhydride monomer according to random copolymerization.The toughness of the Styrene/maleic anhydride compound product of gained significantly improves, and all makes moderate progress in rigidity and thermotolerance, meets the requirement of automobile SMA material.
Wherein, the length-to-diameter ratio of the screw rod of described response type twin screw extruder is 48 ~ 68:1.The length-to-diameter ratio of screw rod has material impact to polymerization single polymerization monomer transformation efficiency and side reaction in product, if length-to-diameter ratio is too short, then transformation efficiency is lower, and the rigidity of product, thermotolerance and toughness there will be decline; If length-to-diameter ratio is long, then polymkeric substance in an extruder the residence time longer, side reaction increases, and product may be deepened by color and luster, and the rigidity of product, thermotolerance and toughness also there will be decline in addition.
Wherein, the length-to-diameter ratio of the screw rod of described response type twin screw extruder is 64:1.
Wherein, described response type twin screw extruder is omnidistance sealed reaction type twin screw extruder.
Wherein, the temperature in each district of described double-screw extruding machine barrel is: the temperature that described double-screw extruding machine barrel is each section is: material section temperature is 30 ~ 180 DEG C, conversion zone temperature is 150 ~ 220 DEG C, homogenizing zone temperature 180 ~ 220 DEG C, transportation section temperature 200 ~ 220 DEG C.
Those skilled in the art carry out subregion according to the length of double-screw extruder screw length-to-diameter ratio to barrel usually, general is a district with the length-to-diameter ratio velocity of variation of 3:1 or 4:1, usually, the length-to-diameter ratio of response type twin screw extruder is at more than 45:1, for response type twin screw extruder described in the application, with length-to-diameter ratio be 64:1 be example, be a district with the length-to-diameter ratio velocity of variation of 4:1, be material section from the first district ~ bis-district, three ~ 11 districts are conversion zone, 12 ~ 14 districts are homogenizing zone, more than 14th district are transportation section.
The Main Function of material section is to various material pre-mixing;
The Main Function of conversion zone has been polyreaction, makes transformation efficiency complete;
The Main Function of homogenizing zone is that the polymkeric substance composition distribution that reaction is generated is more homogeneous;
The Main Function of transportation section sets up head pressure, makes polymer-extruded mouth model grain.
Wherein, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.
Wherein, described radical initiator is any one or its mixture in azo-compound, peroxide radical initiator.
Wherein, the molecular weight of described polar modifier is 50 ~ 300.
Wherein, described polar modifier is one in furans, ethylenediamines and ether material or its mixture.
Wherein, described polar modifier is tetrahydrofuran (THF), Tetramethyl Ethylene Diamine or diethylene glycol dimethyl ether.
Wherein, the rotating speed of described twin screw extruder is 30 ~ 300 revs/min.
In described Styrene/maleic anhydride compound, the ratio by mass percentage ratio of each raw material calculates as follows:
Vinylbenzene 67 ~ 94.8%;
Maleic anhydride 5 ~ 30%;
Polar modifier 0.1 ~ 1%;
Radical initiator 0.1 ~ 2%.
A kind of Styrene/maleic anhydride compound prepared by described preparation method.The Styrene/maleic anhydride compound that described preparation method obtains, its tensile strength>=35MPa, modulus in flexure>=2000Mpa, 23 DEG C of notched Izod impact strength>=3.5KJ/m
2, heat-drawn wire (1.80Mpa)>=100 DEG C, meets the performance requriements of automobile SMA material completely.
Compared with prior art, the present invention has following beneficial effect:
The preparation method of Styrene/maleic anhydride compound of the present invention, reactive extrursion substance law is adopted to carry out, avoid the use of a large amount of solvent, therefore solution method is overcome owing to needing to adopt a large amount of solvent to cause the problem that energy consumption is too high and environmental pollution is too large, adding by polar modifier, the carrying out of copolyreaction can be controlled, impel reaction to generate random copolymers; Synthesize according to described preparation method the Styrene/maleic anhydride compound obtained and there is high rigidity, thermotolerance and toughness, meet the requirement of automobile SMA material.
Embodiment
Below in conjunction with some embodiments, Styrene/maleic anhydride compound of the present invention is described further.Specific embodiment is for further describing the present invention, non-limiting protection scope of the present invention.
Embodiments of the invention adopt following raw material:
Vinylbenzene, Qilu Petrochemical;
Maleic anhydride, Hensel is graceful;
Diisopropyl azodicarboxylate (AIBN), Changzhou one ploughs Chemical Co., Ltd.;
Benzoyl peroxide (BPO), the permanent safe chemical industry in Zouping, Shandong;
Dicumyl peroxide (DCP), the permanent safe chemical industry in Zouping, Shandong;
Tetrahydrofuran (THF), Wuxi City Yinke chemical plant;
Tetramethyl Ethylene Diamine, Jiangsu Qiangsheng Chemical Co., Ltd.;
Diethylene glycol dimethyl ether, Shanghai Si Mantai Chemical Industry Science Co., Ltd;
Material performance test method:
(1) tensile strength: test by ISO527/2-93;
(2) modulus in flexure: test by ISO178/2-93;
(3) heat-drawn wire (1.80Mpa): test by ISO75/1-93;
(4) 23 DEG C of Izod notched impact strength: by ISO179/2-93 test, A type breach;
Embodiment 1
5 kilograms of maleic anhydride monomers, 0.1 kilogram of polar modifier tetrahydrofuran (THF) (THF), 0.1 kilogram of radical initiator AIBN are dissolved in 94.8 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, carry out vacuum removal to residual polar modifier, the melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 2
15 kilograms of maleic anhydride monomers, 0.5 kilogram of polar modifier Tetramethyl Ethylene Diamine (TMEDA), 0.5 kilogram of radical initiator BPO are dissolved in 84 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 3
25 kilograms of maleic anhydride monomers, 1 kilogram of polar modifier diethylene glycol dimethyl ether, 1 kilogram of radical initiator DCP are dissolved in 73 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 4
30 kilograms of maleic anhydride monomers, 1 kilogram of polar modifier diethylene glycol dimethyl ether, 1 kilogram of radical initiator DCP are dissolved in 67 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 48:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 5
30 kilograms of maleic anhydride monomers, 1 kilogram of polar modifier diethylene glycol dimethyl ether, 1 kilogram of radical initiator DCP are dissolved in 67 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 68:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 6
5 kilograms of maleic anhydride monomers, 0.1 kilogram of polar modifier tetrahydrofuran (THF) (THF), 0.1 kilogram of radical initiator AIBN are dissolved in 94.8 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 300 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Embodiment 7
5 kilograms of maleic anhydride monomers, 0.1 kilogram of polar modifier tetrahydrofuran (THF) (THF), 0.1 kilogram of radical initiator DCP are dissolved in 94.8 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 30 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Comparative example 1
5 kilograms of maleic anhydride monomers, 0.1 kilogram of radical initiator AIBN are dissolved in 94.9 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Comparative example 2
25 kilograms of maleic anhydride monomers, 1 kilogram of radical initiator DCP are dissolved in 74 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 64:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Comparative example 3
30 kilograms of maleic anhydride monomers, 1 kilogram of polar modifier diethylene glycol dimethyl ether, 1 kilogram of radical initiator DCP are dissolved in 67 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 28:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
Comparative example 4
30 kilograms of maleic anhydride monomers, 1 kilogram of polar modifier diethylene glycol dimethyl ether, 1 kilogram of radical initiator DCP are dissolved in 67 kilograms of styrene monomers, the omnidistance sealed reaction type twin screw extruder that length-to-diameter ratio is 80:1 is injected by high-pressure plunger volume pump, the temperature that extruding machine barrel is each section is: material section temperature is 150 DEG C, conversion zone temperature is 200 DEG C, homogenizing zone temperature 200 DEG C, transportation section temperature 200 DEG C.
The rotating speed of screw rod is 100 revs/min.
Under forcing machine internal high temperature and under the shearing dissemination of screwing element, random copolymerization reaction is there is in vinylbenzene, maleic anhydride under the effect of radical initiator and polar modifier, react completely and form SMA random copolymers, between the outlet and the entrance of transportation section of homogenizing zone, vacuum removal is carried out to residual polar modifier.Melt after devolatilization is by obtaining finished product after extruding dies extruding pelletization.
The performance test of embodiment 1 ~ 7 and comparative example 1 ~ 4 is as shown in table 1:
As can be seen from comparative example 1 and 2, when in preparation process, do not add polar modifier, the toughness properties of gained Styrene/maleic anhydride compound obviously declines, and can not meet the requirement of automobile SMA.As can be seen from comparative example 3, if the screw rod of forcing machine is too short, then transformation efficiency is lower, and the toughness of product declines to some extent, and modulus in flexure and physical strength are obviously not enough; As can be seen from comparative example 4, if major diameter is long, then polymer's heat history is longer, and side reaction increases, and the toughness of product declines to some extent, and modulus in flexure and physical strength are obviously not enough.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. the preparation method of a Styrene/maleic anhydride compound, it is characterized in that, maleic anhydride, the polar modifier accounting for Styrene/maleic anhydride compound gross weight 0.1 ~ 1%, radical initiator is comprised the steps: to dissolve in styrene monomer, in response type twin screw extruder, control double-screw extruding machine barrel temperature to extrude at 30 ~ 280 DEG C, granulation, obtains described Styrene/maleic anhydride compound;
Described polar modifier is one in ethylenediamines and ether material or its mixture, can control styrene monomer and be polymerized with the mode of maleic anhydride monomer according to random copolymerization;
The length-to-diameter ratio of the screw rod of described response type twin screw extruder is 48 ~ 68:1;
Wherein preparing vinylbenzene in each raw material of Styrene/maleic anhydride compound is 67 ~ 94.8%; Maleic anhydride is 5 ~ 30%.
2. preparation method as claimed in claim 1, described polar modifier is furans.
3. preparation method as claimed in claim 1, it is characterized in that, the length-to-diameter ratio of the screw rod of described response type twin screw extruder is 64:1.
4. preparation method as claimed in claim 1, it is characterized in that, the temperature that described double-screw extruding machine barrel is each section is: material section temperature is 30 ~ 180 DEG C, and conversion zone temperature is 150 ~ 220 DEG C, homogenizing zone temperature 180 ~ 220 DEG C, transportation section temperature 200 ~ 220 DEG C.
5. preparation method as claimed in claim 4, is characterized in that, between the outlet and the entrance of transportation section of homogenizing zone, carry out vacuum removal to residual polar modifier.
6. preparation method as claimed in claim 1, is characterized in that, described radical initiator is any one or its mixture in azo-compound, peroxide radical initiator.
7. preparation method as claimed in claim 1, it is characterized in that, the molecular weight of described polar modifier is 50 ~ 300.
8. preparation method as claimed in claim 1, it is characterized in that, described polar modifier is tetrahydrofuran (THF), Tetramethyl Ethylene Diamine or diethylene glycol dimethyl ether.
9. preparation method as claimed in claim 1, is characterized in that, the ratio by mass percentage ratio of described each raw material calculates as follows:
10. one kind by the Styrene/maleic anhydride compound that in claim 1 ~ 9, described in any one claim, preparation method prepares.
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| CN201210376694.XA CN102993350B (en) | 2012-09-28 | 2012-09-28 | Styrene/maleic anhydride compound and preparation method thereof |
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| CN1103408A (en) * | 1993-12-02 | 1995-06-07 | 中国石油化工总公司 | Synthesis of random styrene-maleic anhydride copolymer |
| CN101717555A (en) * | 2009-12-02 | 2010-06-02 | 华东理工大学 | Reactive extrusion polymerizing method for styrene/alkadiene segmented copolymers |
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| CN1103408A (en) * | 1993-12-02 | 1995-06-07 | 中国石油化工总公司 | Synthesis of random styrene-maleic anhydride copolymer |
| CN101717555A (en) * | 2009-12-02 | 2010-06-02 | 华东理工大学 | Reactive extrusion polymerizing method for styrene/alkadiene segmented copolymers |
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