CN1392169A - Thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent - Google Patents
Thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent Download PDFInfo
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- CN1392169A CN1392169A CN 02112385 CN02112385A CN1392169A CN 1392169 A CN1392169 A CN 1392169A CN 02112385 CN02112385 CN 02112385 CN 02112385 A CN02112385 A CN 02112385A CN 1392169 A CN1392169 A CN 1392169A
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Abstract
The present invention provides a thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent. It features that inside one high pressure reactor, polyethylene resin, maleic anhydride, dispersant, initiator and conjugated monomer are dissolved in solvent and reacted at certain temperature for certain period, and the product is then washed and dried to obtain grafted polyvinyl-maleic anhydride copolyer. The copolymer may be used as adhesive for composite polyethylene and metal pipe or plate; compatibilizer for polymer alloy to raise its compatibility and compatizier for polyethylene and inorganic communication material to raise the tensile strength without change in compact toughness. The process is simple, high in grafting rate and suitable for large-scale production.
Description
Technical field:
The present invention relates to a kind of method for preparing polyethylene (PE)-maleic anhydride graft copolymer (PE-g-MAH), related in particular to a kind of solvent thermal synthesis method that in autoclave, adopts and prepare the poly novel method of functionalization.The invention belongs to the polymer science field.
Background technology:
Polyethylene is the extremely wide general-purpose plastics of a kind of purposes, and is little because of its molecular polarity, degree of crystallinity is high, advantage such as cheap, easy to process is widely used in doing various plastics.But the adhesive power of nonpolar polyethylene and other material is low, and is poor with the polar polymer consistency, and thermotolerance is not high, makes its range of application receive restriction.In order to enlarge the performance of its range of application and the original material of raising, can carry out grafting by polyethylene and other polar monomer, the polyethylene of preparation functionalization.These polar monomers mainly contain: (Moad G. such as maleic anhydride (MAH), dibutyl maleinate (DBE), vinylformic acid (AA), methacrylic acid (MAA), glycidyl methacrylate (GMA), acrylamide (AM), fumaric acid (FA), vinylbenzene (St) and vinyl alkoxy silane, Prog.Polym.Sci., 24,1999,81-142).Wherein maleic anhydride (MAH) has the two key groups and the stronger carboxylic acid anhydride group of polarity that can react, and copolymerization and be not easy autohemagglutination easily under free radical causes, and becomes the important monomer of non-polar polymer graft modification such as polyethylene.The method that maleic anhydride monomer is grafted on the sub polyethylene subchain is a lot, extrude fusion-grafting, solution graft copolymerization, solid phase grafting, radiation grafting, plasma grafting (Hegazy ES.A. as reaction, Abd E1-RehimH.A., Khalifa N.A.and El-Hag Ali A., Radiation Physics and Chemistry, 55,1999,219-229) etc.The easy continuous production of fusion-grafting, technology are simple, but percentage of grafting is lower, and crosslinking side reaction takes place more seriously, have influenced processibility; The percentage of grafting of solution graft copolymerization is higher, but waste liquid amount is big, and is difficult for scale operation; Solid phase grafting technology is simple, but percentage of grafting is not high, and only is applicable to pulverous polymkeric substance; Radiation and plasma body all need light source, the equipment complexity.
Summary of the invention:
The objective of the invention is to above-mentioned defective at prior art, a kind of novel polyethylene-maleic anhydride graft copolymer thermal synthesis production method of solvent is provided, the percentage of grafting height that the functional poly ethylene copolymer of preparation is obtained, crosslinked less, and solvent load is few, equipment is simple, is convenient to scale operation.
For realizing such purpose, in technical scheme of the present invention, the preparation method's reaction mechanism that adopts is different from solution method in the past, scorification, the solid phase grafting method, radiation and plasma method prepare graft copolymer, polyvinyl resin and reactant are dissolved in a small amount of solvent, more than being higher than the boiling point of solvent, react, system is in (is similar under the postcritical state) under the solvent ebullient state and react, reaction is to carry out under the state of gas-liquid coexistence, make PE fully to contact like this with reactant, react completely, thereby the percentage of grafting height of the functional poly ethylene copolymer of preparation.
The present invention adopts autoclave, in autoclave, put into and be equivalent to PE resin 1-30 PE good solvent doubly, adding weight percent is the PE resin of 40.00-99.99%, the maleic anhydride of 0.10-60.00%, the dispersion agent of 0.00-30.00%, the common monomer of the initiator of 0.01-20.00% and 0.00-60%, put into 80-280 ℃ baking oven after the autoclave lid tightened, placed 0.5-50 hour, use water cooling then, open autoclave, solution is poured in the flocculation agent that is equivalent to its volume 1-10 times, on magnetic stirring apparatus, stirred (rotating speed 5-1000 rev/min) 0.1-10 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 40-200 ℃ of vacuum drying oven dry 5-30 hour promptly obtains grafted polyvinyl-maleic anhydride copolymer (PE-g-MAH).
Solvent of the present invention is toluene, dimethylbenzene, naphthane, perhydronaphthalene, kerosene, whiteruss, is the good solvent of PE.
Flocculation agent of the present invention is ethanol, methyl alcohol, acetone, butanone, distilled water, is the poor solvent of PE.
Dispersion agent of the present invention is toluene, dimethylbenzene naphthane, perhydronaphthalene, kerosene, whiteruss, can with initiator, reaction monomers and PE can both be compatible a class material.
Monomer altogether of the present invention is vinylformic acid, α-Jia Jibingxisuan, third rare acid amides, vinylbenzene, hexanolactam, vinyl pyrrolidone, but is the response type monomer of a class electron donor.
Initiator of the present invention is azo-bis-isobutyl cyanide (AIBN), dicumyl peroxide (DCP), benzamide (BPO), t-butyl peroxide (TBP).
The present invention's method for preparing the PE-g-MAH multipolymer different from the past, conversion unit is simple, because reaction is to be under the supercritical state, so graft copolymer percentage of grafting height (weight percent is not less than 2%wt) that obtains, and than solution method, solvent load is few, is convenient to scale operation.The PE-g-MAH of the present invention's preparation is used for the tackiness agent of aluminum-plastic laminated tube, the expanding material of polymer alloy and the compatilizer of polyethylene and composite material of inorganic matter, and over-all properties is better, and wide application prospect is arranged.
Embodiment:
Following embodiment further specifies of the present invention, rather than limits the scope of the invention.The preparation of embodiment 1:PE-g-MAH graft copolymer
In autoclave, put into the dimethylbenzene of 50ml, add 10gPE resin, 0.6g maleic anhydride, 150mgBPO, the autoclave lid tightened put into 160 ℃ baking oven, placed 8 hours, use water cooling then, open autoclave, solution is poured in the acetone of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the PE-g-MAH graft copolymer of 2.2%wt.The preparation of embodiment 2:PE-g-MAH graft copolymer
In autoclave, put into the dimethylbenzene of 50ml, add 8gPE resin, 2g maleic anhydride, 120mgDCP and acrylamide 0.5g, the autoclave lid tightened put into 180 ℃ baking oven, placed 10 hours, use water cooling then, open autoclave, solution is poured in the acetone of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the PE-g-MAH graft copolymer of 2.7%wt.The preparation of embodiment 3:PE-g-MAH graft copolymer
In autoclave, put into the perhydronaphthalene of 50ml, add 1 milliliter of 5gPE resin, 1.5g maleic anhydride, 150mgDCP and dimethylbenzene, the autoclave lid tightened put into 180 ℃ baking oven, placed 10 hours, use water cooling then, open autoclave, solution is poured in the acetone of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the PE-g-MAH graft copolymer of 3.1%wt.The preparation of embodiment 4:ABS-maleic anhydride graft copolymer
In autoclave, put into the dimethylbenzene of 50ml, add 6gPE resin, 1.8g maleic anhydride, 200mgTBP, vinylformic acid 0.6g and toluene 2ml, the autoclave lid tightened put into 200 ℃ baking oven, placed 8 hours, use water cooling then, open autoclave, solution is poured in the acetone of 300ml, on magnetic stirring apparatus, stirred (200 rev/mins of rotating speeds) 1 hour, to remove unreacted matters, suction filtration then, the powder that suction filtration is obtained in 80 ℃ of vacuum drying ovens dry 12 hours, promptly obtaining percentage of grafting is the PE-g-MAH graft copolymer of 3.4%wt.
The PE-g-MAH of the present invention's preparation is as the tackiness agent of aluminum-plastic laminated tube or plate, and cementability is good, stripping strength is high; The PE-g-MAH of preparation is used for the expanding material of polymer alloy, blend alloy as polyethylene and nylon-6, improved consistency greatly, make the snappiness of polymer alloy, dimensional stability all is better than nylon-6, intensity and barrier obviously are better than polyethylene: the PE-g-MAH of preparation is as the compatilizer of polyethylene and composite material of inorganic matter, makes the significantly increase and impelling strength remains unchanged of poly tensile strength.
Claims (6)
1, a kind of polyethylene-maleic anhydride graft copolymer thermal synthesis production method of solvent, it is characterized in that: in autoclave, put into and be equivalent to polythene PE resin 1-30 PE good solvent doubly, adding weight percent is the PE resin of 40.00-99.99%, the maleic anhydride of 0.10-60.00%, the dispersion agent of 0.00-30.00%, the common monomer of the initiator of 0.01-20.00% and 0.00-60%, autoclave put into 80-280 ℃ baking oven, placed 0.5-50 hour, use water cooling then, open autoclave, solution is poured in the flocculation agent that is equivalent to its volume 1-10 times, on magnetic stirring apparatus, stirred 0.1-10 hour, rotating speed 5-1000 rev/min, remove suction filtration after the unreacted matters, the powder that suction filtration is obtained in 40-200 ℃ of vacuum drying oven dry 5-30 hour promptly obtains grafted polyvinyl-maleic anhydride copolymer PE-g-MAH.
2,, it is characterized in that the polyethylene good solvent is toluene, dimethylbenzene, naphthane, perhydronaphthalene, kerosene, whiteruss as the said polyethylene of claim 1-maleic anhydride graft copolymer thermal synthesis production method of solvent.
3,, it is characterized in that flocculation agent is ethanol, methyl alcohol, acetone, butanone, distilled water as the said polyethylene of claim 1-maleic anhydride graft copolymer thermal synthesis production method of solvent.
4,, it is characterized in that dispersion agent is toluene, dimethylbenzene naphthane, perhydronaphthalene, whiteruss, kerosene as the said polyethylene of claim 1-maleic anhydride graft copolymer thermal synthesis production method of solvent.
5,, it is characterized in that common monomer is vinylformic acid, α-Jia Jibingxisuan, third rare acid amides, vinylbenzene, hexanolactam, vinyl pyrrolidone as the said polyethylene of claim 1-maleic anhydride graft copolymer thermal synthesis production method of solvent.
6,, it is characterized in that initiator is azo-bis-isobutyl cyanide AIBN, dicumyl peroxide DCP, benzamide BPO, t-butyl peroxide TBP as the said polyethylene of claim 1-maleic anhydride graft copolymer thermal synthesis production method of solvent.
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| CNB021123853A CN1160390C (en) | 2002-07-04 | 2002-07-04 | Thermal synthesis process for preparing grafted polyvinyl-maleic anhydride copolymer in solvent |
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| CN1160390C CN1160390C (en) | 2004-08-04 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362032C (en) * | 2006-02-23 | 2008-01-16 | 上海交通大学 | Heat synthesis preparation method for maleic anhydride grafted ethene-octylen copolymer |
| CN100453574C (en) * | 2007-03-15 | 2009-01-21 | 上海交通大学 | Prepn process of grafted ethylene-butylene-dibutyl maleic anhydride copolymer |
| CN101284897B (en) * | 2008-06-05 | 2010-06-02 | 上海交通大学 | Dissolvant hot preparation process for inarching polyisobutene co-polymer with maleic anhydride |
| CN101396888B (en) * | 2007-09-27 | 2013-01-09 | 比亚迪股份有限公司 | Metal composite board and preparation method thereof |
| CN103224693A (en) * | 2013-05-22 | 2013-07-31 | 文安东都嘉诚再生资源有限公司 | Polyester/polyethylene alloy material and preparation method thereof |
| CN112608413A (en) * | 2020-11-25 | 2021-04-06 | 成都金发科技新材料有限公司 | Maleic anhydride grafted polypropylene with low free maleic anhydride content and low-emission glass fiber reinforced polypropylene composite material prepared from maleic anhydride grafted polypropylene |
| CN116375392A (en) * | 2023-04-07 | 2023-07-04 | 广东长鑫环保科技有限公司 | Preparation process of material using nano carbonized plant modification and activation technology |
-
2002
- 2002-07-04 CN CNB021123853A patent/CN1160390C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100362032C (en) * | 2006-02-23 | 2008-01-16 | 上海交通大学 | Heat synthesis preparation method for maleic anhydride grafted ethene-octylen copolymer |
| CN100453574C (en) * | 2007-03-15 | 2009-01-21 | 上海交通大学 | Prepn process of grafted ethylene-butylene-dibutyl maleic anhydride copolymer |
| CN101396888B (en) * | 2007-09-27 | 2013-01-09 | 比亚迪股份有限公司 | Metal composite board and preparation method thereof |
| CN101284897B (en) * | 2008-06-05 | 2010-06-02 | 上海交通大学 | Dissolvant hot preparation process for inarching polyisobutene co-polymer with maleic anhydride |
| CN103224693A (en) * | 2013-05-22 | 2013-07-31 | 文安东都嘉诚再生资源有限公司 | Polyester/polyethylene alloy material and preparation method thereof |
| CN103224693B (en) * | 2013-05-22 | 2016-12-28 | 北京市第五建筑工程集团有限公司 | Polyester/polyethylealloy alloy material and preparation method thereof |
| CN112608413A (en) * | 2020-11-25 | 2021-04-06 | 成都金发科技新材料有限公司 | Maleic anhydride grafted polypropylene with low free maleic anhydride content and low-emission glass fiber reinforced polypropylene composite material prepared from maleic anhydride grafted polypropylene |
| CN116375392A (en) * | 2023-04-07 | 2023-07-04 | 广东长鑫环保科技有限公司 | Preparation process of material using nano carbonized plant modification and activation technology |
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