CN1300201C - Process for preparing polyolefin and vinyl monomer graft copolymer - Google Patents
Process for preparing polyolefin and vinyl monomer graft copolymer Download PDFInfo
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- CN1300201C CN1300201C CNB200510033535XA CN200510033535A CN1300201C CN 1300201 C CN1300201 C CN 1300201C CN B200510033535X A CNB200510033535X A CN B200510033535XA CN 200510033535 A CN200510033535 A CN 200510033535A CN 1300201 C CN1300201 C CN 1300201C
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Abstract
The present invention relates to a synthesizing method for polyolefin and vinyl monomer graft copolymers, which comprises: polyolefin, vinyl monomers, an initiating agent and are water are uniformly mixed; under the action of microwaves within a radiation power range of 100 to 2000 watts, a water phase suspension grafting reaction is carried out for 10 to 150 minutes to prepare graft copolymers of the polyolefin and the vinyl monomers. A water phase suspension method is used by the present invention, and a microwave auxiliary synthesizing technology is used for preparing the graft copolymers of the polyolefin and the vinyl monomer, which enables polymerization reaction speed to be obviously enhanced, a reaction period to be obviously shortened, and cost to be obviously reduced. The defects of high reaction temperature, low reaction speed, long reaction time, large energy consumption of production processes, environment pollution, etc. when the polyolefin and the vinyl monomers have a graft modification reaction at present are overcome. Moreover, the graft ratio of the graft copolymers is high, and the properties of polarity, hydrophilicity/hydrophobicity, reactivity, etc. are obviously improved. Thus, the graft copolymers are suitable for solubilizing agents, surface interface modifying agents and adhesive agents.
Description
Technical field
The present invention relates to the microwave-assisted synthesis field, be specifically related to the synthetic method of polyolefine and vinyl monomer graft copolymer.
Background technology
Polyolefine---for example modal big kind plastics polypropylene (PP) and polyethylene (PE), have advantages such as inexpensive, good combination property, applied range, its chemical constitution and molecular structure have determined PP and PE to be non-polar material, cause painted, the printing, plating of such material, poor performance and bad such as hydrophilic, antistatic, thereby make its application be subjected to certain limitation with blend, filling, the adhesiveproperties of other material.Existing polyolefin plastics kind is carried out modification, make that this output is big, the material of wide application meets or exceeds the performance index of some engineering plastics at aspects such as mechanical property, thermal characteristics or other performances, will produce tremendous influence the development that promotes polymer material science and engineering and related industries.The grafting of polyolefine and vinyl monomer is exactly one of polyolefinic important modification method.The synthetic of existing polyolefine and vinyl monomer graft copolymer generally all adopted the long scorification grafting of monomer high temperature under protection of nitrogen gas, solid phase method grafting or grafting solution method polymerization preparation.The relative merits of these synthetic methods are as follows:
1, synthesis device is simple, general, and synthetic technology and technical process comparative maturity adopt common heating power type of heating to obtain the required heat of reaction, and this is the great advantage of polyolefine and the present synthetic technology of vinyl monomer graft copolymer.
2, the reaction conditions of fusion-grafting or solid phase grafting is comparatively harsh, reaction process needs high temperature, when using common heating power type of heating, heat must just can reach reactive material by the process of progressively transmitting, and heat-up rate is slow, and capacity usage ratio is low, energy consumption is big, and temperature of reaction system is inhomogeneous, easily causes local temperature overheated and make polyolefine take place crosslinked or degraded, influences quality product.
Though 3, the grafting solution method temperature of reaction is lower, owing to need to use a large amount of solvents, therefore, make the production of product originally higher, in building-up process, also can pollute simultaneously environment.
4, the speed of response of these synthetic methods is slow, and technical process is long, causes production efficiency low, and production cost increases.
Summary of the invention
The objective of the invention is to above-mentioned shortcoming at existing polyolefine and vinyl monomer graft copolymer synthetic method, the synthetic method of a kind of polyolefine and vinyl monomer graft copolymer is provided, adopt water phase suspension to utilize the microwave-assisted synthetic technology to prepare polyolefine and vinyl monomer graft copolymer, its outstanding feature is: (1) utilizes microwave radiation to replace traditional heating power heating to react energy needed, it directly transfers energy on the material by dipole rotation and two kinds of effects of ionic conduction of polar molecule, the temperature of reactive material can be risen in moment, speed of response is accelerated, and the temperature of whole reaction system is even; (2) electromagnetic field of microwave generation causes " non-thermal effect " further again fast reaction speed to the direct effect of behavior between reaction molecular; (3) reaction system adopts cheap water as reaction medium, neither needs very high temperature of reaction, can not pollute environment again.Therefore, the new synthetic method that adopts the present invention to propose can make the generated time of polyolefine and vinyl monomer graft copolymer shorten to 10～150 minutes by original 2～6 hours, synthesis cycle significantly shortens, production efficiency obviously improves, and has reduced energy consumption, has reduced production cost.The present invention has overcome existing polyolefine and vinyl monomer graft copolymer temperature of reaction height, slow, the long reaction time of speed of response when synthetic, and the production process energy consumption is greatly and to shortcomings such as environment pollute.
The synthetic method of polyolefine of the present invention and vinyl monomer graft copolymer comprises the steps:
(1) polyolefine, vinyl monomer, initiator, water are mixed;
(2) under the radiation power scope is 100～2000 watts microwave radiation, carry out the aqueous-phase suspending graft reaction 10～150 minutes, make the graft copolymer of polyolefine and vinyl monomer;
The weight fraction consumption of said components is as follows:
100 parts of polyolefine
10～100 parts of vinyl monomers
0.05～2.5 part of initiator
200～600 parts in water
Wherein:
Polyolefine is selected from polypropylene, high density polyethylene(HDPE), new LDPE (film grade), LLDPE, ultrahigh molecular weight polyethylene(UHMWPE), ethylene-vinyl acetate copolymer or chlorinatedpolyethylene;
Vinyl monomer be selected from polar functionalities vinyl monomer, contain in the vinyl monomer of non-polar group one or more;
Initiator is a radical polymerization initiator.
In the step (2), be to carry out the aqueous-phase suspending graft reaction 20～120 minutes under 100～1500 watts the microwave radiation in radiation power, make polyolefine and vinyl monomer graft copolymer.
The weight fraction consumption of component is as follows in the step (1):
100 parts of polyolefine
20～75 parts of vinyl monomers
0.1～1.5 part of initiator
250～500 parts in water
The vinyl monomer of described polar functionalities comprises one or more mixtures in vinylformic acid, methyl acrylate, butyl acrylate, glycidyl acrylate, propenoic acid beta-hydroxy propyl ester, methacrylic acid, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, Jia Jibingxisuanβ-Qiang Yizhi, vinyl cyanide, acrylonitrile derivative, oleic acid, linolic acid, undecylenic acid, maleic anhydride, maleic acid ester, fumaric acid anhydride, the fumarate.
The described vinyl monomer that contains non-polar group comprises one or more mixtures in vinylbenzene, alpha-methyl styrene, the Vinylstyrene.
Described radical polymerization initiator comprises dibenzoyl peroxide or Diisopropyl azodicarboxylate.
The polyolefine of the present invention's preparation and graft copolymerization of vinyl monomer product only need it is separated from reaction medium water, washing, drying can be used then, need not further refiningly again purify, its Application Areas mainly comprises: (1) is as polyolefine and other polymkeric substance, the particularly expanding material of polar polymer blend; (2) as the coupling agent or the interface modifier of polyolefine and various weighting agent infill system and various fiber reinforcement systems; (3) as polyolefinic surface-modifying agent with character such as the polarity of improving polyolefin surfaces, hydrophilic and hydrophobic, reactivities, thereby improve bonding, the printing of polyolefin surfaces, painted, covering with paint, plating, performance such as antistatic.(4) be used for tackiness agent etc. between polyolefine/other plastics, polyolefine/metal, polyolefine/paper and other materials and the other materials as hot melt adhesive.
The microwave-assisted synthetic technology that the present invention adopts prepares polyolefine with vinyl monomer graft copolymer compared with prior art has following advantage: (1) employing polyolefine and vinyl monomer carry out the aqueous-phase suspending grafting, and to obtain with the polyolefine be main chain, be the polyolefin graft copolymer that side chain, percentage of grafting significantly improve with the polymers of vinyl monomers; (2) utilize microwave radiation to substitute traditional heating power heating after, not only energy-conservation but also cleaning also made graft reaction speed obviously improve, the production cycle significantly shortens, production cost reduces; (3) the present invention has overcome that existing polyolefine and vinyl monomer graft copolymer temperature of reaction height when synthetic, speed of response are slow, long reaction time, production process energy consumption be greatly and to shortcomings such as environment pollute.
Embodiment
Embodiment 1
The weight fraction consumption of each component is as follows:
Polyethylene powder 100 grams
Methyl methacrylate 10 grams
Dibenzoyl peroxide 0.05 gram
Water 250 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 2000 watts microwave irradiation power, carried out the aqueous-phase suspending graft reaction 10 minutes, make polycthylene grafted methylmethacrylate copolymer.And under same recipe, when adopting traditional heating power heating method to carry out synthetic this graft copolymer of aqueous-phase suspending grafting, need 100 ℃ of reactions 4 hours down, product property is to such as table 1:
Table 1
| Index | The product of microwave-assisted synthesis method | The product of heating power heating method |
| Transformation efficiency | 81.0％ | 67.2％ |
| Percentage of grafting | 6.8％ | 4.8％ |
| Grafting efficiency | 84.0％ | 71.4％ |
As seen, adopt the polycthylene grafted methylmethacrylate copolymer of microwave-assisted synthetic technology preparation of the present invention, reaction times can reduce to 10 minutes from 4 hours of traditional heating power heating method, shortened more than three hour, efficient improves 24 times, energy consumption obviously reduces, and the indicators of overall performance of product obviously improves.
Embodiment 2
The weight fraction consumption of each component is as follows:
High density polyethylene(HDPE) 100 grams
Methyl methacrylate 50 grams
Glycidyl methacrylate 50 grams
Dicumyl peroxide 2.5 grams
Water 600 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 150 watts microwave irradiation power, carry out the aqueous-phase suspending graft reaction 120 minutes, and made polycthylene grafted methyl methacrylate and glycidyl methacrylate copolymer.And under same recipe, when adopting traditional heating power heating method to carry out synthetic this graft copolymer of solid phase grafting, need 100 ℃ of reactions 3 hours down, product property is to such as table 2:
Table 2
| Index | The product of microwave-assisted synthesis method | The product of tradition solid phase grafting |
| Transformation efficiency | 61.5％ | 50.8％ |
| Percentage of grafting | 34.0％ | 23.4％ |
| Grafting efficiency | 55.3％ | 46.1％ |
As seen, adopt the polycthylene grafted methyl methacrylate and the glycidyl methacrylate copolymer of microwave-assisted synthetic technology preparation of the present invention, reaction times can reduce to 2 hours from 3 hours of traditional solid phase grafting method, shortened 1 hour, energy consumption obviously reduces, and the transformation efficiency of vinyl monomer, percentage of grafting obviously improve.
Embodiment 3
The weight fraction consumption of each component is as follows:
New LDPE (film grade) 100 grams
Methyl methacrylate 50 grams
Maleic anhydride 25 grams
Dibenzoyl peroxide 1.5 grams
Water 500 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 100 watts microwave irradiation power, carry out the aqueous-phase suspending graft reaction 150 minutes, and made polycthylene grafted methyl methacrylate and copolymer-maleic anhydride.And under same recipe, when adopting traditional heating power heating method to carry out synthetic this graft copolymer of solid phase grafting, need 100 ℃ of reactions 2.5 hours down, product property is to such as table 3:
Table 3
| Index | The product of microwave-assisted synthesis method | The product of tradition solid phase grafting |
| Transformation efficiency | 41.0％ | 33.3％ |
| Percentage of grafting | 19.4％ | 12.3％ |
| Grafting efficiency | 63.1％ | 49.2％ |
As seen, adopt the polycthylene grafted methyl methacrylate and the copolymer-maleic anhydride of microwave-assisted synthetic technology preparation of the present invention, though the reaction times is identical with the time of traditional solid phase grafting method, energy consumption still can significantly reduce, and the indicators of overall performance of product obviously improves.
Embodiment 4
The weight fraction consumption of each component is as follows:
Polyethylene 100 grams
Methyl methacrylate 20 grams
Glycidyl methacrylate 20 grams
Vinylbenzene 10 grams
Dibenzoyl peroxide 1.0 grams
Water 400 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 750 watts microwave irradiation power, carry out the aqueous-phase suspending graft reaction 30 minutes, and made polycthylene grafted methyl methacrylate, glycidyl methacrylate and styrol copolymer.And under same recipe, when adopting traditional heating power heating method to carry out synthetic this graft copolymer of aqueous-phase suspending grafting, need 100 ℃ of reactions 2 hours down, product property is to such as table 4:
Table 4
| Index | The product of microwave-assisted synthesis method | The product of heating power heating method |
| Transformation efficiency | 74.2％ | 67.5％ |
| Percentage of grafting | 28.2％ | 21.3％ |
| Grafting efficiency | 76.0％ | 63.1％ |
As seen, adopt polycthylene grafted methyl methacrylate, glycidyl methacrylate and the styrol copolymer of microwave-assisted synthetic technology preparation of the present invention, reaction times can reduce to 30 minutes from 2 hours of traditional heating power heating method, shortened more than one hour, production efficiency improves 4 times, energy consumption obviously reduces, and the indicators of overall performance of product obviously improves.
Embodiment 5
The weight fraction consumption of each component is as follows:
Polyethylene 100 grams
Maleic anhydride 20 grams
Diisopropyl azodicarboxylate 0.1 gram
Water 200 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 1500 watts microwave irradiation power, carried out the aqueous-phase suspending graft reaction 20 minutes, make polycthylene grafted copolymer-maleic anhydride, percentage of grafting states 4.5%, can not pollute environment, and under same recipe, when adopting synthetic this graft copolymer of traditional solution grafting 140 ℃ of reactions 30 minutes in dimethylbenzene, percentage of grafting only is 1.5%, and the dimethylbenzene environmental pollution is serious in the last handling process after reaction finishes.
Embodiment 6
The weight fraction consumption of each component is as follows:
Polypropylene 100 grams
Methyl methacrylate 25 grams
Glycidyl methacrylate 25 grams
Dibenzoyl peroxide 0.5 gram
Water 300 grams
With the various raw materials in the above-mentioned prescription add successively the microwave special use, band stirs and the reaction flask of reflux in, under 650 watts microwave irradiation power, carry out the aqueous-phase suspending graft reaction 45 minutes, and made polypropylene grafted methyl methacrylate and glycidyl methacrylate copolymer.And under same recipe, when adopting traditional heating power heating method to carry out synthetic this graft copolymer of aqueous-phase suspending grafting, need 100 ℃ of reactions 3 hours down, product property is to such as table 5:
Table 5
| Index | The product of microwave-assisted synthesis method | The product of heating power heating method |
| Transformation efficiency | 73.3％ | 78.1％ |
| Percentage of grafting | 35.1％ | 24.5％ |
| Grafting efficiency | 95.8％ | 62.8％ |
As seen, adopt the polypropylene grafted methyl methacrylate and the glycidyl methacrylate copolymer of microwave-assisted synthetic technology preparation of the present invention, reaction times can reduce to 45 minutes from 3 hours of traditional heating power heating method, shorten more than two hour, production efficiency improves 4 times, energy consumption obviously reduces, and the percentage of grafting of product and grafting efficiency have all improved nearly 50%.
Claims (6)
1, the synthetic method of a kind of polyolefine and vinyl monomer graft copolymer is characterized in that comprising the steps:
(1) polyolefine, vinyl monomer, initiator, water are mixed;
(2) under the radiation power scope is 100～2000 watts microwave radiation, carry out the aqueous-phase suspending graft reaction 10～150 minutes, make the graft copolymer of polyolefine and vinyl monomer;
The weight fraction consumption of said components is as follows:
100 parts of polyolefine
10～100 parts of vinyl monomers
0.05～2.5 part of initiator
200～600 parts in water
Wherein:
Polyolefine is selected from polypropylene, high density polyethylene(HDPE), new LDPE (film grade), LLDPE, ultrahigh molecular weight polyethylene(UHMWPE), ethylene-vinyl acetate copolymer or chlorinatedpolyethylene;
Vinyl monomer be selected from polar functionalities vinyl monomer, contain in the vinyl monomer of non-polar group one or more;
Initiator is a radical polymerization initiator.
2, synthetic method according to claim 1 is characterized in that in the step (2), in radiation power is to carry out the aqueous-phase suspending graft reaction 20～120 minutes under 100～1500 watts the microwave radiation, makes polyolefine and vinyl monomer graft copolymer.
3, synthetic method according to claim 1 and 2 is characterized in that the weight fraction consumption of component in the step (1) is as follows:
100 parts of polyolefine
20～75 parts of vinyl monomers
0.1～1.5 part of initiator
250～500 parts in water.
4, synthetic method according to claim 3, the vinyl monomer that it is characterized in that described polar functionalities comprises one or more mixtures in vinylformic acid, methyl acrylate, butyl acrylate, glycidyl acrylate, propenoic acid beta-hydroxy propyl ester, methacrylic acid, methyl methacrylate, butyl methacrylate, glycidyl methacrylate, Jia Jibingxisuanβ-Qiang Yizhi, vinyl cyanide, acrylonitrile derivative, oleic acid, linolic acid, undecylenic acid, maleic anhydride, maleic acid ester, fumaric acid anhydride, the fumarate.
5, synthetic method according to claim 3 is characterized in that the described vinyl monomer that contains non-polar group comprises one or more mixtures in vinylbenzene, alpha-methyl styrene, the Vinylstyrene.
6,, it is characterized in that described radical polymerization initiator comprises dibenzoyl peroxide or Diisopropyl azodicarboxylate according to claim 4 or 5 described synthetic methods.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510033535XA CN1300201C (en) | 2005-03-15 | 2005-03-15 | Process for preparing polyolefin and vinyl monomer graft copolymer |
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|---|---|---|---|
| CNB200510033535XA CN1300201C (en) | 2005-03-15 | 2005-03-15 | Process for preparing polyolefin and vinyl monomer graft copolymer |
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| CN1670049A CN1670049A (en) | 2005-09-21 |
| CN1300201C true CN1300201C (en) | 2007-02-14 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100577701C (en) * | 2006-12-22 | 2010-01-06 | 中国石油化工股份有限公司 | Method for preparing polypropylene grafted copolymer |
| CN103483668B (en) * | 2013-10-08 | 2015-11-18 | 苏州市相城区明达复合材料厂 | There is the anti-plastic formula fractureed |
| CN103880989B (en) * | 2014-04-04 | 2016-03-23 | 中国科学院长春应用化学研究所 | A kind of modified chlorinated polyethylene, its preparation method, chlorinatedpolyethylene cross-linked rubber and preparation method thereof |
| CN106232646B (en) * | 2014-04-18 | 2018-11-20 | 日本A&L株式会社 | Graft copolymer and thermoplastic resin composition |
| EP3786202B1 (en) * | 2018-04-27 | 2024-03-13 | China Petroleum & Chemical Corporation | Polar monomer grafted polypropylene resin, preparation method therefor and application thereof |
| CN109053962A (en) * | 2018-08-11 | 2018-12-21 | 洛阳和梦科技有限公司 | The preparation method of cis-butenedioic anhydride grafted polyethylene |
| CN110698598A (en) * | 2019-09-17 | 2020-01-17 | 上海交通大学 | Polyolefin material with surface grafted with polymer, and preparation method and application thereof |
| CN112079962A (en) * | 2020-09-21 | 2020-12-15 | 哈尔滨理工大学 | Oil-resistant polyolefin elastomer graft and preparation method thereof |
| CN112694567A (en) * | 2020-12-31 | 2021-04-23 | 宁波能之光新材料科技股份有限公司 | Microwave-assisted polypropylene grafting method |
| CN115141317A (en) * | 2021-03-31 | 2022-10-04 | 中科先行(济宁)新材料研究院有限公司 | Tri-monomer grafted polyethylene initiated by dual initiators and preparation method thereof |
| CN113501911B (en) * | 2021-08-06 | 2022-08-09 | 中国科学院上海应用物理研究所 | Preparation method of chlorinated polyethylene grafted acrylic acid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100441A (en) * | 1993-06-10 | 1995-03-22 | 钟渊化学工业株式会社 | Modified polyolefin and composition containing the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100441A (en) * | 1993-06-10 | 1995-03-22 | 钟渊化学工业株式会社 | Modified polyolefin and composition containing the same |
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Assignee: Foshan Shunde Wheeling plastic Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2008.8.31 to 2014.8.31 contract change Contract record no.: 2009440001483 Denomination of invention: Process for preparing polyolefin and vinyl monomer graft copolymer Granted publication date: 20070214 License type: Exclusive license Record date: 2009.9.30 |
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