CN104497218A - Synthetic method and device capable of improving performance of MBS (methacrylate-butadiene-styrene copolymer) - Google Patents
Synthetic method and device capable of improving performance of MBS (methacrylate-butadiene-styrene copolymer) Download PDFInfo
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- CN104497218A CN104497218A CN201410808323.3A CN201410808323A CN104497218A CN 104497218 A CN104497218 A CN 104497218A CN 201410808323 A CN201410808323 A CN 201410808323A CN 104497218 A CN104497218 A CN 104497218A
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Abstract
The invention discloses a synthetic method and device capable of improving the performance of an MBS (methacrylate-butadiene-styrene copolymer). According to the scheme, reaction is maintained under an ultrasonic action in two steps, so that the synthetic reaction speed and efficiency of the MBS are relatively high, and the MBS is easily synthesized; the consumption of an utilized initiator is greatly reduced, so that the product cost is lowered, the thermal stability of the synthesized MBS is relatively high, the yellowing of the product can be avoided, the toughness to the strength of low-impact-strength products is improved, a stress whitening phenomenon can be reduced, the transparency is good, the fog scale is low, and a comprehensive application effect is excellent. The synthetic method is simple and easy to implement; and the utilized device is simple in structure, low in cost and good in utilization effect.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of synthetic method and device improving MBS performance.
Background technology
In PVC, add appropriate methyl methacrylate-divinyl-styrol copolymer (MBS) shock strength raising 4-15 can be improved doubly, also can improve winter hardiness and the processing fluidity of goods simultaneously.Therefore, MBS resin is widely applied as the impact modified material of PVC.In recent years research shows: MBS can significantly improve the low-temperature impact toughness of PC, PA, PET etc.
Existing domestic patent or document show, the synthesis of MBS is roughly divided into two steps: the first step is the synthesis of styrene-butadiene latex; Second step is that styrene-butadiene latex and methyl methacrylate reactive grafting obtain MBS.Wherein, the particle diameter of the styrene-butadiene latex of the first step synthesis, gel content are difficult to control, initiator remnants etc. has very important impact to the toughness reinforcing performance of MBS and thermostability etc., and the product that the MBS toughening PVC that the styrene-butadiene latex of less particle diameter synthesizes preparation further obtains comparatively is less likely to occur stress whitening phenomenon.In addition, MBS also has material impact to the transparency of toughening effect and goods with by the consistency of toughness reinforcing phase.Therefore, synthesize particle diameter undoubtedly less, and be conducive to toughening effect with polar group compatability good MBS material, reduce stress whitening phenomenon and improve the transparency of toughness reinforcing transparent material, reduce mist degree.
Summary of the invention
The object of the invention is: the synthetic method and the device that improve MBS performance, its speed of response and efficiency higher, be easier to synthesize MBS, the large minimizing of initiator amount of use, the MBS thermostability of synthesis is better, product can be avoided to turn to be yellow, toughening effect is good, can reduce stress whitening phenomenon, and the transparency is good, mist degree is little, to overcome the deficiencies in the prior art.
The present invention is achieved in that the synthetic method improving MBS performance, comprises the steps:
1) calculate according to the mass fraction, by 25-35 part divinyl, 65-75 part vinylbenzene, 1-2 part initiator and 1-2 part crylic acid ester mixture, reacting by heating 18-22h under ultrasonication, obtains styrene-butadiene latex;
2) styrene-butadiene latex prepared in step 1) is mixed with 70-80 part vinylbenzene, then 0.7-0.8 part glycidyl methacrylate is added, 70-80 part methyl methacrylate and 1-3 part initiator, continue to react 2-4h under ultrasonication, finally add 2-4 part antioxidant again, stir discharging after 20-40 minute under ultrasonication, cohesion is dry obtains finished product.
In step 1) ultrasonication adopt power be 400W impulse ultrasound; Step 2) in ultrasonication adopt power be the impulse ultrasound of 700W.
Initiator described in step 1) is Diisopropyl azodicarboxylate, benzoyl peroxide or 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane; Step 2) described in initiator be superoxide or azo-initiator.
Described antioxidant is antioxidant 1010 or anti-oxidant DLTP.
Step 1) and step 2) in the temperature of reacting by heating be 65-75 DEG C.
Improve the synthesizer of MBS performance, comprise first order reaction still, second order reaction still, is characterized in that: first order reaction still and second order reaction still are jacket structured; One-level opening for feed is provided with at the top of first order reaction still, one-level ultrasonic transducer is provided with in the bottom of first order reaction still, one-level ultrasonic transducer is connected with one-level ultrasonic frequency power supply, be provided with one-level heating medium inlet in the lower sidewall of first order reaction still, be provided with one-level Crude product input in the side wall upper part of first order reaction still; The bottom of first order reaction still is communicated with by the top of pipeline with second order reaction still, and is connected with pump on pipeline; Secondary opening for feed is provided with at the top of second order reaction still, secondary ultrasonic transducer is provided with in the bottom of second order reaction still, secondary ultrasonic transducer is connected with secondary ultrasonic frequency power supply, secondary heating medium inlet is provided with in the lower sidewall of second order reaction still, be provided with secondary Crude product input in the side wall upper part of second order reaction still, be provided with outlet in the bottom of second order reaction still; Agitator is equipped with in first order reaction still and second order reaction still.
Described one-level opening for feed and secondary opening for feed are 3.For the charging simultaneously respectively of different materials.
Described one-level ultrasonic transducer and secondary ultrasonic transducer are more than 3.Make ultrasonic effect evenly.
Owing to have employed technique scheme, compared with prior art, under the present invention all makes reaction remain on ultrasonication in two steps of synthesis MBS, such scheme make MBS synthesising reacting speed and efficiency higher, be easier to synthesize MBS, and the large minimizing of initiator amount used, reduce product cost, the MBS thermostability of synthesis is better, product can be avoided to turn to be yellow, improve the toughness to low shock strength goods, stress whitening phenomenon can be reduced, the transparency is good, and mist degree is little, and integrated application effect is more excellent.The inventive method is simple, easily implements, and the apparatus structure used is simple, and with low cost, result of use is good.
Accompanying drawing explanation
Accompanying drawing 1 is structural representation of the present invention.
Embodiment
Embodiments of the invention: the synthetic method improving MBS performance, comprises the steps:
1) calculate according to the mass fraction, by 30 parts of divinyl, 70 parts of vinylbenzene, 1 part of initiator (Diisopropyl azodicarboxylate) and 1 part of crylic acid ester mixture, reacting by heating 21h under ultrasonication, ultrasonication adopt power be 400W impulse ultrasound, obtain styrene-butadiene latex;
2) styrene-butadiene latex prepared in step 1) is mixed with 75 parts of vinylbenzene, then 0.75 part of glycidyl methacrylate is added, 75 parts of methyl methacrylates and 2 parts of DCP, continue to react for 3 times under ultrasonication, finally add 2 parts of antioxidant 1010s again, under ultrasonication, stir discharging after 30 minutes, cohesion is dry obtains finished product; Step 2) in ultrasonication adopt power be the impulse ultrasound of 700W; Step 1) and step 2) in heating all adopt heating employing 70 DEG C of hot water as circulating-heating medium.
Improve the structure of the synthesizer of MBS performance as shown in Figure 1, comprise first order reaction still 1, second order reaction still 2, is characterized in that: first order reaction still 1 and second order reaction still 2 are jacket structured; 3 one-level opening for feeds 3 are provided with at the top of first order reaction still 1,3 one-level ultrasonic transducers 4 are provided with in the bottom of first order reaction still 1, one-level ultrasonic transducer 4 is connected with one-level ultrasonic frequency power supply 5, be provided with one-level heating medium inlet 6 in the lower sidewall of first order reaction still 1, be provided with one-level Crude product input 7 in the side wall upper part of first order reaction still 1; The bottom of first order reaction still 1 is communicated with the top of second order reaction still 2 by pipeline 8, and is connected with pump 9 on pipeline 8; 3 secondary opening for feeds 10 are provided with at the top of second order reaction still 2,3 secondary ultrasonic transducers 11 are provided with in the bottom of second order reaction still 2, secondary ultrasonic transducer 11 is connected with secondary ultrasonic frequency power supply 12, secondary heating medium inlet 13 is provided with in the lower sidewall of second order reaction still 2, be provided with secondary Crude product input 14 in the side wall upper part of second order reaction still 2, be provided with outlet 16 in the bottom of second order reaction still 2; Agitator 15 is equipped with in first order reaction still 1 and second order reaction still 2.
In order to verify experiment effect of the present invention, finished product embodiment prepared and commercially available MBS carry out Application comparison.
1, by blended with PVC respectively for the QIM-03 being the product MBS1 of embodiment and Qilu Petrochemical, the mass ratio of the ratio MBS:PVC of material is 15:85, in 155 ~ 165 DEG C of mixing 7min bottom sheet on open type plastic purificating set, then 175 DEG C, under the condition of 20MPa, the thick test film of lamination 4mm respectively, at 25 DEG C, test the impact property of the sample of preparation, the shock strength of the MBS/PVC blend adopting the product MBS1 of embodiment to obtain is 41.0KJ/m
2, and the shock strength of the MBS/PVC blend adopting the QIM-03 of Qilu Petrochemical to obtain is 32.5KJ/m
2.
2, MBS1 embodiment synthesized and the QIM-03 of Qilu Petrochemical is blended at 200 DEG C with PMMA and AS respectively, and blending ratio is PMMA45.9%, AS44.1%, MBS10%, and through impact mechanical performance test after injection moulding, the results obtained are as follows in transmittance test:
Show according to contrast experiment: adopt MBS product good mechanical performance prepared by the present invention, can improve the transparency of transparent article, product appearance is more excellent.
Claims (8)
1. improve a synthetic method for MBS performance, it is characterized in that: comprise the steps:
1) calculate according to the mass fraction, by 25-35 part divinyl, 65-75 part vinylbenzene, 1-2 part initiator and 1-2 part crylic acid ester mixture, reacting by heating 18-22h under ultrasonication, obtains styrene-butadiene latex;
2) styrene-butadiene latex prepared in step 1) is mixed with 70-80 part vinylbenzene, then 0.7-0.8 part glycidyl methacrylate is added, 70-80 part methyl methacrylate and 1-3 part initiator, continue to react 2-4h under ultrasonication, finally add 2-4 part antioxidant again, under ultrasonication, stir discharging after 20-40 minute, cohesion is dry obtains finished product.
2. the synthetic method of raising MBS performance according to claim 1, is characterized in that: in step 1) ultrasonication adopt power be 400W impulse ultrasound; Step 2) in ultrasonication adopt power be the impulse ultrasound of 700W.
3. the synthetic method of raising MBS performance according to claim 1, is characterized in that: the initiator described in step 1) is Diisopropyl azodicarboxylate, benzoyl peroxide or 2,5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane; Step 2) described in initiator be superoxide or azo-initiator.
4. the synthetic method of raising MBS performance according to claim 1, is characterized in that: described antioxidant is antioxidant 1010 or anti-oxidant DLTP.
5. the synthetic method of raising MBS performance according to claim 1, is characterized in that: step 1) and step 2) in the temperature of reacting by heating be 65-75 DEG C.
6. adopt the device improving the synthetic method of MBS performance as claimed in claim 1, comprise first order reaction still (1), second order reaction still (2), is characterized in that: first order reaction still (1) and second order reaction still (2) are jacket structured; One-level opening for feed (3) is provided with at the top of first order reaction still (1), one-level ultrasonic transducer (4) is provided with in the bottom of first order reaction still (1), one-level ultrasonic transducer (4) is connected with one-level ultrasonic frequency power supply (5), be provided with one-level heating medium inlet (6) in the lower sidewall of first order reaction still (1), be provided with one-level Crude product input (7) in the side wall upper part of first order reaction still (1); The bottom of first order reaction still (1) is communicated with the top of second order reaction still (2) by pipeline (8), and is connected with pump (9) on pipeline (8); Secondary opening for feed (10) is provided with at the top of second order reaction still (2), secondary ultrasonic transducer (11) is provided with in the bottom of second order reaction still (2), secondary ultrasonic transducer (11) is connected with secondary ultrasonic frequency power supply (12), secondary heating medium inlet (13) is provided with in the lower sidewall of second order reaction still (2), be provided with secondary Crude product input (14) in the side wall upper part of second order reaction still (2), be provided with outlet (16) in the bottom of second order reaction still (2); Agitator (15) is equipped with in first order reaction still (1) and second order reaction still (2).
7. device according to claim 6, is characterized in that: described one-level opening for feed (3) and secondary opening for feed (10) are 3.
8. device according to claim 7, is characterized in that: described one-level ultrasonic transducer (4) and secondary ultrasonic transducer (11) are more than 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849349A (en) * | 2003-09-10 | 2006-10-18 | 西巴特殊化学品控股有限公司 | Stabilization of methylmethacrylate-butadiene-styrene graft copolymers against thermal oxidation |
| CN101492519A (en) * | 2008-01-25 | 2009-07-29 | 中国石油天然气集团公司 | Impact modifier MBS resin of polyvinyl chloride |
| CN104211858A (en) * | 2014-09-17 | 2014-12-17 | 珠海金鸡化工有限公司 | Carboxylic butadiene-styrene latex and preparation method thereof |
| CN204395939U (en) * | 2014-12-23 | 2015-06-17 | 贵州一当科技有限公司 | Realize the device of continuous ultrasound synthesis MBS |
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- 2014-12-23 CN CN201410808323.3A patent/CN104497218B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1849349A (en) * | 2003-09-10 | 2006-10-18 | 西巴特殊化学品控股有限公司 | Stabilization of methylmethacrylate-butadiene-styrene graft copolymers against thermal oxidation |
| CN101492519A (en) * | 2008-01-25 | 2009-07-29 | 中国石油天然气集团公司 | Impact modifier MBS resin of polyvinyl chloride |
| CN104211858A (en) * | 2014-09-17 | 2014-12-17 | 珠海金鸡化工有限公司 | Carboxylic butadiene-styrene latex and preparation method thereof |
| CN204395939U (en) * | 2014-12-23 | 2015-06-17 | 贵州一当科技有限公司 | Realize the device of continuous ultrasound synthesis MBS |
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Effective date of registration: 20190215 Address after: 561000 Xiayun Industrial Park, Pingba District, Anshun City, Guizhou Province Patentee after: Guizhou Tianhai Industrial Co., Ltd. Address before: 550025 College Students Pioneer Park A-319, Guiyang National New Technology Development Zone, Guizhou Province Patentee before: GUIZHOU YIDANG TECHNOLOGY CO., LTD. |
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Effective date of registration: 20190717 Address after: 650000 Songhua Road 500, Chenggong District, Kunming City, Yunnan Province, with No. 6 Patentee after: Kun Tomorrow Hai Industrial Co., Ltd. Address before: 561000 Xiayun Industrial Park, Pingba District, Anshun City, Guizhou Province Patentee before: Guizhou Tianhai Industrial Co., Ltd. |
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Effective date of registration: 20190722 Address after: 561000 Xiayun Industrial Park, Pingba District, Anshun City, Guizhou Province Patentee after: Guizhou Tianhai Industrial Co., Ltd. Address before: 650000 Songhua Road 500, Chenggong District, Kunming City, Yunnan Province, with No. 6 Patentee before: Kun Tomorrow Hai Industrial Co., Ltd. |