CN104558426A - Preparation method of polar polypropylene - Google Patents
Preparation method of polar polypropylene Download PDFInfo
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- CN104558426A CN104558426A CN201510004586.3A CN201510004586A CN104558426A CN 104558426 A CN104558426 A CN 104558426A CN 201510004586 A CN201510004586 A CN 201510004586A CN 104558426 A CN104558426 A CN 104558426A
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Abstract
The invention discloses a preparation method of polar polypropylene, and the preparation method can be used for solving the problems of high equipment requirement and defected products of an existing method for melting and performing solid phase grafting on modified polypropylene. The method comprises the following specific steps: totally adding all reaction raw materials into a reaction kettle and mixing; adding dimethyl ether serving as swelling agents into a mixture inside the reaction kettle and stirring; swelling reaction raw materials in the dimethyl ether and releasing the dimethyl ether; stirring and heating under nitrogen protection; performing solid-phase grafting reaction on the raw materials inside the reaction kettle; and purifying the product to obtain polar polypropylene products. According to the method, the mass transfer velocity of monomers and initiating agents in a polypropylene substrate can be improved while the process pressure can be effectively reduced, the uniform distribution of the monomers and the initiating agents in the polypropylene substrate can be realized, and products of which grafting chains are uniformly distributed, main chains are less in degradation and melting indexes are similar to that of polypropylene serving as the raw material can be prepared.
Description
Technical field
The present invention relates to polyolefine material modification field, particularly prepare the method for polar polypropylene.
Background technology
Polypropylene is one of common general-purpose plastics, there is due to it performances such as good mechanical property, thermal characteristics, chemical stability, electrical insulating property, weathering resistance, anti-multiple organic solvent and acid and alkali corrosion, still can keep good antioxidant property at a higher temperature, have that good insulativity and less dielectric constant, comprehensive physical mechanical property are excellent, the feature such as have wide range of applications.Because polypropylene surface is nonpolar, make its wetting ability, dyeability, static resistance and the poor compatibility with polar material, these deficiencies limit polypropylene application in a lot of fields.
In order to improve polyacrylic polarity, researchist both domestic and external has carried out a large amount of research work to polypropylene grafted modification, and object is not substantially affecting on the basis of the original premium properties of polypropylene, gives the performance that polypropylene is new.General graft modification is by after polypropylene, monomer, initiator mixing, makes monomer and polypropylene carry out graft polymerization reaction to realize modification through thermal initiation.Common grafting method has fusion-grafting, solid phase grafting.
Patent CN 101519477B reports and adopts auxiliary monomer 1,6-hexanediyl ester, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate etc. assist maleic anhydride modified polypropylene, and the grafted polypropylene resin of gained has higher percentage of grafting, molecular weight and viscosity.Patent CN 102924661 A reports and helps grafted monomer 2-propenyl-1-SULPHURYL CHLORIDE, five propenyl succinic acid, 1-phenyl-2-propenyl-1-ketone, triallyl cyanurate to assist the polyacrylic method of maleic anhydride melt grafting.The method significantly improves percentage of grafting, and the irritating smell of product is lower.But the temperature of reaction of fusion-grafting is generally 190 ~ 230 DEG C, monomer is volatile, and under the effect of initiator, the fracture of β position occurs polypropylene, causes auto-degradation still obviously, and in polypropylene matrix, residual monomer, initiator are difficult to remove, and have a strong impact on the purposes of modified polypropene.
Solid phase connection is a kind of energy-efficient method, especially many monomer copolymerizations technology, and Recent study is very active.This method temperature of reaction low (70 ~ 110 DEG C), reaction time is short, less degradation, expense are also lower, has good development prospect.But traditional solid phase grafting legal system is for modified polypropene, its graft reaction mainly occurs in polyacrylic surface or top layer, and not high (the Liu Tao of the percentage of grafting of monomer, Hu Guohua, Tong Gangsheng, et al. Industrial and Engineering Chemistry Research, 2005,44,4292-4299).Supercritical co is adopted to assist graft polypropylene to be a kind of novel method (the Wang Jian in recent years just grown up, Ran Yuxia, Zou Enguang, et al. Journal of Polymer Research, 2009,16,739-744) but the emergent pressure of supercritical co up to 7.38MPa, higher to the requirement of equipment.
Summary of the invention
The present invention be directed to that polypropylene fusion graft legal system is serious for modified polypropene degraded, solid phase grafting legal system for modified polypropene grafting uneven and supercritical co assist Solid-Phase Grafting of Methyl-Methacrylate swelling pressure to cross the problems such as high, a kind of preparation method of new polar polypropylene is provided, the method is on the basis of solid phase grafting method, introduce swelling agent, prepared polar polypropylene grafted chain is evenly distributed, main chain less degradation, and melting index is close with raw material polypropylene.
For achieving the above object; the technical solution used in the present invention is: a kind of preparation method of polar polypropylene; particularly: first by all reaction raw materials polypropylene, initiator, main monomer and help monomer all to join in reactor to mix; then add swelling agent dme in the mixture in reactor and stir; dme is released after swelling certain hour by reaction raw materials in swelling agent dme; stir under nitrogen protection afterwards and heat up simultaneously; in reactor, raw material carries out solid state shear pulrerizing, obtains polar polypropylene product after the purified process of product.
In described method, polypropylene is powder, initiator adopts the one in benzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate, main monomer adopts maleic anhydride, monomer is helped to adopt the one had in the vinylbenzene of electron donation, butyl acrylate, butyl methacrylate, methyl methacrylate, 1,6-hexylene glycol double methacrylate, Viscoat 295.
In described method, each component according to weight fraction ratio is: polypropylene 100 parts, and main monomer 1 ~ 6 part helps monomer 0 ~ 6 part, initiator 0.02 ~ 0.1 part, swelling agent 10 ~ 100 parts.
In described method, swelling temperature scope is 30 ~ 50 DEG C, and swelling time is 0.5 ~ 5h, and solid state shear pulrerizing temperature range is 70 ~ 100 DEG C, and the solid state shear pulrerizing time is 1 ~ 6h.
The beneficial effect of the inventive method: in inventive method, before polyreaction, employing dme is swelling agent, first carry out Low Temperature Solid-Phase swelling, monomer, initiator can be improved in polypropylene matrix inner transmission matter speed while effectively reducing pressure process, realize monomer, initiator being uniformly distributed in polypropylene matrix, finally prepare that grafted chain is evenly distributed, main chain less degradation, the polar polypropylene that melting index is close with raw material polypropylene.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.
The main monomer of maleic anhydride for a change polarity of polypropylene, the size of maleic anhydride grafting ratio weighs the leading indicator of polypropylene grafted product performance.In the application, polypropylene grafted product is after acetone extraction purification process, rejoin reflux in dimethylbenzene, to add again in excessive sodium hydroxide-ethanolic soln and maleic anhydride on polypropylene, then use the alkali of hydrochloric acid-aqueous isopropanol overtitration, thus calculate the maleic anhydride grafting ratio of grafted products.
The change of obtained polypropylene product surface water contact angle can illustrate the change of polypropylene surface polarity from an aspect.In the present invention, sample film be the polypropylene grafted product of purifying 190 DEG C, 10MPa hot pressing forms, the mensuration of water contact angle adopts sessile drop method.
In the present invention, in embodiment, the melting index testing standard of polypropylene grafted product is GB/ T3682-2000, and observe, record melting index test in extrude bar configuration of surface.
Embodiment 1
By polypropylene weight 100 parts, (Daqing petrochemical company is produced, trade mark T30S, melting index 3.2 ~ 4.5g/10min, following examples are identical therewith), maleic anhydride 2 parts, (monomer and initiator are Tianjin great Mao chemical reagent factory and produce benzoyl peroxide, analytical pure, following examples are identical therewith) 0.02 part add sealed reactor, (Shandong Jiutai Chemical Sci-Tech Co., Ltd. produces to add 20 parts of dme again, purity 99.9%, following examples are identical therewith), after 30 DEG C of mechanical stirring 1h, release dme, in nitrogen (Heilungkiang grand celebration Xue Long gas company limited, purity 99.9%, following examples are identical therewith) protection under, in 100 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Embodiment 2
By polypropylene weight 100 parts; maleic anhydride 3 parts; butyl methacrylate 4 parts; benzoyl peroxide 0.02 part adds sealed reactor, then adds 20 parts of dme, after 30 DEG C of mechanical stirring 1h; release dme; under nitrogen protection, in 100 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Comparative example 2
By polypropylene weight 100 parts, maleic anhydride 3 parts, butyl methacrylate 4 parts; benzoyl peroxide 0.02 part adds sealed reactor, after 30 DEG C of mechanical stirring 1h, under nitrogen protection; in 100 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Embodiment 3
By polypropylene weight 100 parts; maleic anhydride 3 parts; butyl acrylate 4 parts; dilauroyl peroxide 0.03 part adds sealed reactor, then adds 40 parts of dme, after 40 DEG C of mechanical stirring 1h; release dme; under nitrogen protection, in 90 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Embodiment 4
By polypropylene weight 100 parts; maleic anhydride 4 parts; butyl acrylate 5 parts; dilauroyl peroxide 0.03 part adds sealed reactor, then adds 40 parts of dme, after 40 DEG C of mechanical stirring 1h; release dme; under nitrogen protection, in 90 DEG C of mechanic whirl-nett reaction 3h, product is purified obtains polypropylene grafted product.
Embodiment 5
By polypropylene weight 100 parts; maleic anhydride 4 parts; Viscoat 295 6 parts; dilauroyl peroxide 0.03 part adds sealed reactor, then adds 50 parts of dme, after 40 DEG C of mechanical stirring 2h; release dme; under nitrogen protection, in 90 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Comparative example 5
By polypropylene weight 100 parts, maleic anhydride 4 parts, Viscoat 295 6 parts; dilauroyl peroxide 0.03 part adds sealed reactor, after 40 DEG C of mechanical stirring 2h, under nitrogen protection; in 90 DEG C of mechanic whirl-nett reaction 2h, product is purified obtains polypropylene grafted product.
Embodiment 6
By polypropylene weight 100 parts; maleic anhydride 4 parts; vinylbenzene 4 parts; Diisopropyl azodicarboxylate 0.02 part adds sealed reactor, then adds 70 parts of dme, after 40 DEG C of mechanical stirring 2h; release dme; under nitrogen protection, in 80 DEG C of mechanic whirl-nett reaction 3h, product is purified obtains polypropylene grafted product.
Embodiment 7
By polypropylene weight 100 parts; maleic anhydride 2 parts; vinylbenzene 3 parts; Diisopropyl azodicarboxylate 0.02 part adds sealed reactor, then adds 60 parts of dme, after 40 DEG C of mechanical stirring 2h; release dme; under nitrogen protection, in 90 DEG C of mechanic whirl-nett reaction 1h, product is purified obtains polypropylene grafted product.
Embodiment 8
By polypropylene 100 parts; maleic anhydride 4 parts; methyl methacrylate 3 parts; Diisopropyl azodicarboxylate 0.03 part adds sealed reactor, then adds 50 parts of dme, after 40 DEG C of mechanical stirring 1h; release dme; under nitrogen protection, in 80 DEG C of mechanic whirl-nett reaction 3h, product is purified obtains polypropylene grafted product.
In each embodiment and comparative example, the dependence test of obtained product the results are shown in Table 1:
The sign of each embodiment of table 1 and comparative example products obtained therefrom
In table 1, melting index is less shows that the molecular weight of gained grafted products is larger, less degradation, the polarity of water contact angle less explanation gained grafted products is higher, extrude bar surface uniform, smoothly show that the grafted chain of gained grafted products is evenly distributed, data from table 1 are more known, adopt dme in the inventive method, help monomer to assist maleic anhydride inoculated polypropylene, can obtain that melting index is close with raw material polypropylene, the uniform polar polypropylene of grafting, obviously be better than common solid phase grafting method.
Claims (4)
1. the preparation method of a polar polypropylene; particularly: first by all reaction raw materials polypropylene, initiator, main monomer and help monomer all to join in reactor to mix; then add swelling agent dme in the mixture in reactor and stir; dme is released after swelling certain hour by reaction raw materials in swelling agent dme; stir under nitrogen protection afterwards and heat up simultaneously; in reactor, raw material carries out solid state shear pulrerizing, obtains polar polypropylene product after the purified process of product.
2. the preparation method of polar polypropylene according to claim 1, it is characterized in that: described initiator adopts the one in benzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate, described main monomer adopts maleic anhydride, the described one helped in monomer employing vinylbenzene, butyl acrylate, butyl methacrylate, methyl methacrylate, 1,6-hexylene glycol double methacrylate, Viscoat 295.
3. the preparation method of polar polypropylene according to claim 1, is characterized in that: described each component according to weight fraction ratio is: polypropylene 100 parts, and main monomer 1 ~ 6 part helps monomer 0 ~ 6 part, initiator 0.02 ~ 0.1 part, swelling agent 10 ~ 100 parts.
4. the preparation method of polar polypropylene according to claim 1, it is characterized in that: described reaction raw materials swelling swelling temperature scope used in dme is 30 ~ 50 DEG C, swelling time is 0.5 ~ 5h, described solid state shear pulrerizing temperature range is 70 ~ 100 DEG C, and the solid state shear pulrerizing time is 1 ~ 6h.
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| CN201510004586.3A CN104558426A (en) | 2015-01-06 | 2015-01-06 | Preparation method of polar polypropylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317334A (en) * | 2016-08-19 | 2017-01-11 | 中国科学院化学研究所 | Graft modified ultra-high-molecular-weight ultra-fine propene polymer and solid-phase grafting method thereof |
| CN109467644A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | Maleic anhydride modified polypropylene and preparation method thereof |
| CN113563523A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Polypropylene graft containing anhydride group and preparation method and application thereof |
| CN113563520A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Application of polypropylene graft containing anhydride group as insulating material and insulating material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for carrying out solid-phase grafting modification on polypropylene by assistance of supercritical carbon dioxide |
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
| CN102993376A (en) * | 2012-12-17 | 2013-03-27 | 常州大学 | Polypropylene-hydrophilic monomer copolymer and preparation method thereof |
-
2015
- 2015-01-06 CN CN201510004586.3A patent/CN104558426A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863588A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for carrying out solid-phase grafting modification on polypropylene by assistance of supercritical carbon dioxide |
| CN102911316A (en) * | 2012-10-29 | 2013-02-06 | 哈尔滨工程大学 | Method for grafting polar monomer onto polypropylene through aqueous suspension solid-phase graft |
| CN102993376A (en) * | 2012-12-17 | 2013-03-27 | 常州大学 | Polypropylene-hydrophilic monomer copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵洪坤: "极性聚丙烯制备技术研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317334A (en) * | 2016-08-19 | 2017-01-11 | 中国科学院化学研究所 | Graft modified ultra-high-molecular-weight ultra-fine propene polymer and solid-phase grafting method thereof |
| CN106317334B (en) * | 2016-08-19 | 2019-01-22 | 中国科学院化学研究所 | The ultra-fine acrylic polymers of graft modification super high molecular weight and its solid phase grafting method |
| CN109467644A (en) * | 2017-09-07 | 2019-03-15 | 中国石油化工股份有限公司 | Maleic anhydride modified polypropylene and preparation method thereof |
| CN109467644B (en) * | 2017-09-07 | 2021-05-11 | 中国石油化工股份有限公司 | Maleic anhydride modified polypropylene and preparation method thereof |
| CN113563523A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Polypropylene graft containing anhydride group and preparation method and application thereof |
| CN113563520A (en) * | 2020-04-29 | 2021-10-29 | 中国石油化工股份有限公司 | Application of polypropylene graft containing anhydride group as insulating material and insulating material |
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