CN101016361A - Fusion preparation method for simultaneously reinforcing polarity and graft degree of polyolefin - Google Patents
Fusion preparation method for simultaneously reinforcing polarity and graft degree of polyolefin Download PDFInfo
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- CN101016361A CN101016361A CN 200710051283 CN200710051283A CN101016361A CN 101016361 A CN101016361 A CN 101016361A CN 200710051283 CN200710051283 CN 200710051283 CN 200710051283 A CN200710051283 A CN 200710051283A CN 101016361 A CN101016361 A CN 101016361A
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Abstract
The invention discloses a fusing method to increase polarity and graft degree of polyolefin, which comprises the following steps: blending polyolefin, long-chained monomer, polar monomer, initiator, crosslinking agent and interface agent with weight rate at 100;0-100:0-50:0.01-10:0-10 into reactor under 100-300 deg.c; stirring continuously to do copolymer reaction for 0.1-12h; obtaining the product.
Description
Technical field
The present invention relates to a kind of polyolefin modified method, particularly a kind of fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously.
Background technology
Polyolefinic premium properties makes them more and more be widely used, yet polyolefine also has many performance needs further to improve. strengthen by the polarity of correlation means non-polar polyolefinic, thereby improve they polarity and with the consistency of filler. therefore, improve polyolefinic polarity and have very significant meaning. domestic and international many scholars have also made number of research projects.
Yin Jinghua etc. utilize a small amount of pre-irradiation polypropylene to carry out the polyacrylic melting graft reaction of substrate as initiator to prepare functional poly propylene, the DeR in the time of can alleviating the polypropylene grafted reaction of complete pre-irradiation greatly; And by regulating the functional poly propylene that polyacrylic radiation dose of pre-irradiation and consumption can prepare different palliating degradation degrees; Moreover the production cost of functional poly propylene is reduced greatly along with the minimizing of polypropylene pre-irradiation processing cost.The functional poly propylene that obtains and the adhesiveproperties of metal are good, and can be used as expanding material or directly be used to prepare alloy materials such as polypropylene/polyester, polypropylene/polymeric amide as blend components.But this method need adopt the high-energy irradiation technology, and the polarity of product improvement degree is not high simultaneously, and only is confined to improve polyacrylic polarity.
Fu and green grass or young crops; Huang Hong; Zhang Xinya; Chen Huan adopts following steps by the emperor himself: 1. monomer, initiator and composite assistant are dissolved in the solvent, and then the adding polypropylene mixes; 2. at the twin screw extruder internal reaction; 3. the material that obtains is extruded postcooling, pelletizing and is promptly obtained modified polypropene.By the polypropylene product that the present invention prepares, monomer-grafted rate improves, and the PP palliating degradation degree reduces, and polarity, surfactivity, dyeability, binding property and static resistance all obtain bigger raising.The limitation of this method also is to be only to have improved polyolefinic polarity.
Wang Yazhen carries out melting graft reaction with oleic acid as second monomer and has solved in the polypropylene fusion graft maleic anhydride reaction process in twin screw extruder, percentage of grafting is low, the problem that degradation of polypropylene is serious.The percentage of grafting that improves maleic anhydride can reach 3-5%, and has reduced polyacrylic degraded, and polyacrylic melting index is constant before and after the reaction.This method has been improved the percentage of grafting of maleic anhydride on the polypropylene to a certain extent, has reduced melting index, but is not making contributions aspect the raising melt strength.
The P Robert is that main component is that grafted monomer passes through the melt blending extruding technology and prepared co-extruding adhesive with the unsaturated carboxylic acid with metallocene polyethylene and non-metallocene polyethylene mixture.This modification technology can not improve the melt strength of material or processing characteristics etc. except that the restriction that selected by type of polymer.
Summary of the invention
The objective of the invention is on the molecular polyolefin chain, to introduce polar group with the grafting of chemical bond form at sticking to merely of prior art existence, or the form that sticks to simple employing physical blending is distributed to certain polar polyolefin with another non-polar polyolefinic, and adopt the on-the-spot ipn technology that generates to make one or more long-chain monomers and one or more polar monomers in the target polyolefins melt, carry out crosslinking copolymerization, thereby a kind of fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously is provided, and the characteristics of this method are: 1. directly utilize modified monomer to carry out copolymerization in polyolefin melt and form crosslinked interpenetrating(polymer)networks; 2. do not use solvent; 3. do not need last handling process; 4. operation is simple, and effect is obvious, is suitable for improving all the polyolefinic degree of branching and polarity; 5. product polarity power and degree of branching may command.
The objective of the invention is to adopt following technical measures to realize:
With mass ratio is 100: 0～100: 0～50: 0.01～10: 0～10 blended polyolefine: long-chain monomer: polar monomer: initiator: linking agent joins in 100～300 ℃ of reactors, copolyreaction obtained the polyolefine that the polarity and the degree of branching are modified simultaneously after 0.1～12 hour under the stirring continuing.
Described polyolefine is polyethylene, polypropylene, ethylene-propylene rubber(EPR), polystyrene, polyvinyl chloride, polyisobutene, polyisoprene or polyhutadiene.
Described long-chain monomer is dodecenylsuccinic acid acid anhydride, dodecenylsuccinic acid and ester thereof, undecylenic acid and ester thereof, the different eyeball urea ester of tripropylene acid, dodecyl acrylate or octadecyl acrylate.
Described modified monomer is a maleic anhydride, oleic acid, vinylformic acid, α-Jia Jibingxisuan, acrylamide, N hydroxymethyl acrylamide, propylene cyanogen, methylene-succinic acid, itaconic anhydride, Phthalic acid, diallyl ester, Jia Jibingxisuanβ-Qiang Yizhi, glycidyl methacrylate, vinylformic acid stearyl alcohol ester, vinylbenzene, methyl methacrylate, the toxilic acid butyl ester, butyl acrylate, Octyl acrylate, butyl methacrylate, Octyl methacrylate, acrylic acid epoxy ester, tripropylene acid isonitrile urea acid esters, vinyl-acetic ester, along Ethylene Dichloride, zellon, dodecenylsuccinic acid acid anhydride or dodecenylsuccinic acid.
Described initiator is one or more mixtures of forming in dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, di-tert-butyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, the special butyl ester of peroxidation phenylformic acid, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the special penta special butyl ester of peroxidation.
Described linking agent is Vinylstyrene, N, N-methylene-bisacrylamide, vinylformic acid glycol ester, methacrylate glycol ester, 1,1,1-three (acryloyl-oxy methyl) propane, 2,2,2-three (acryloyl-oxy methyl) ethanol, 1,4-two (4 '-vinylphenoxyly) butane or vinyl tributanoximo silane.
The present invention has following advantage: 1. directly utilize one or more long-chain monomers and one or more polar monomers in the melt of target polyolefins, to carry out copolymerization and form crosslinked interpenetrating(polymer)networks, in this process copolymerization can betide on the polyolefine macromolecular chain also can ring or latticed form entangle the molecular polyolefin chain; 2. this method improvement polymer polarity and the degree of branching are applicable to that all strengthen the polarity of non-polar polyolefinic and improve the degree of branching; 3. do not use solvent in the modifying process, product does not need aftertreatment; 4. this method is carried out polyolefin modifiedly, and product polarity power is controlled.
Embodiment
Below the prepared modifier The performance test results of each specific embodiments list in the table 1.
Embodiment 1
With mass ratio is 100: 10: 5: 5: 0.5: 0.5 polypropylene (PP): dodecyl acrylate: maleic anhydride: vinylbenzene: dicumyl peroxide: it is that the twin screw extruder of 180-220 ℃ of rotating speed 180r/min gets modified polypropene (MPP) through extruding pelletization that linking agent joins temperature.Utilize the Rheotens instrument to measure melt strength down at 190 ℃ respectively, get the 5g product with xylene soluble backflow 15min spontaneous nucleation, filter and place the vacuum drying oven thorough drying, then dried powder is placed Soxhlet extractor with the abundant reflux extraction of acetone 72 hours, taking-up is placed on thorough drying in the vacuum drying oven, taking-up is placed on thorough drying in the vacuum drying oven, measures its acid content with the method for chemistry titration at last and sees Table 1.
Embodiment 2
With mass ratio is 100: 10: 5: 5: 0.5: 0.5 polypropylene (PP): undecylenic acid: maleic anhydride: vinylbenzene: dicumyl peroxide: it is that the twin screw extruder of 180-220 ℃ of rotating speed 180r/min gets modified polypropene (MPP) through extruding pelletization that linking agent joins temperature, utilize the Rheotens instrument to measure melt strength down at 190 ℃ respectively, get the 5g product with xylene soluble backflow 15min spontaneous nucleation, filter and place the vacuum drying oven thorough drying, then dried powder is placed Soxhlet extractor with the abundant reflux extraction of acetone 72 hours, taking-up is placed on thorough drying in the vacuum drying oven, taking-up is placed on thorough drying in the vacuum drying oven, measures its acid content with the method for chemistry titration at last and sees Table 1.
Embodiment 3
With mass ratio is 100: 10: 5: 5: 0.5: 0.5 polypropylene (PP): dodecenylsuccinic acid acid anhydride: maleic anhydride: vinylbenzene: dicumyl peroxide: it is that the twin screw extruder of 180-220 ℃ of rotating speed 180r/min gets modified polypropene (MPP) through extruding pelletization that linking agent joins temperature, utilize the Rheotens instrument to measure melt strength down at 190 ℃ respectively, get the 5g product with xylene soluble backflow 15min spontaneous nucleation, filter and place the vacuum drying oven thorough drying, then dried powder is placed Soxhlet extractor with the abundant reflux extraction of acetone 72 hours, taking-up is placed on thorough drying in the vacuum drying oven, taking-up is placed on thorough drying in the vacuum drying oven, measures its acid content with the method for chemistry titration at last and sees Table 1.
Embodiment 4
With mass ratio is 100: 10: 5: 5: 0.5: 0.5 linear low density polyethylenes (LLDPE): undecylenic acid: maleic anhydride: vinylbenzene: dicumyl peroxide: it is that the twin screw extruder of 180-220 ℃ of rotating speed 180r/min gets modification linear low density polyethylene (MLLDPE) through extruding pelletization that linking agent joins temperature, utilize the Rheotens instrument to measure melt strength down at 190 ℃ respectively, get the 5g product with xylene soluble backflow 15min spontaneous nucleation, filter and place the vacuum drying oven thorough drying, then dried powder is placed Soxhlet extractor with the abundant reflux extraction of acetone 72 hours, taking-up is placed on thorough drying in the vacuum drying oven, taking-up is placed on thorough drying in the vacuum drying oven, measures its acid content with the method for chemistry titration at last and sees Table 1.
Prepared modified polyolefin melt strength of each embodiment of table 1 and acid content
| Pure PP | Embodiment 1 | Embodiment 2 | Embodiment 3 | Pure LLDPE | Embodiment 4 | |
| Melt strength (CN) | 19.5 | 22.5 | 23.1 | 22.0 | 4.0 | 4.2 |
| Acid content (mmol KOH/g) | 0 | 0.12 | 0.13 | 0.25 | 0 | 0.29 |
Claims (6)
1, a kind of fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously, it is characterized in that: with mass ratio is 100: 0～100: 0～50: 0.01～10: 0～10 blended polyolefine: long-chain monomer: polar monomer: initiator: linking agent joins in 100～300 ℃ of reactors, copolyreaction obtained the polyolefine that the polarity and the degree of branching are modified simultaneously after 0.1～12 hour under the stirring continuing.
2, the fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously according to claim 1 is characterized in that: described polyolefine is polyethylene, polypropylene, ethylene-propylene rubber(EPR), polystyrene, polyvinyl chloride, polyisobutene, polyisoprene or polyhutadiene.
3, the fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously according to claim 1 is characterized in that: described long-chain monomer is dodecenylsuccinic acid acid anhydride, dodecenylsuccinic acid and ester thereof, undecylenic acid and ester thereof, the different eyeball urea ester of tripropylene acid, dodecyl acrylate or octadecyl acrylate.
4, the fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously according to claim 1 is characterized in that: described modified monomer is a maleic anhydride, oleic acid, vinylformic acid, α-Jia Jibingxisuan, acrylamide, N hydroxymethyl acrylamide, propylene cyanogen, methylene-succinic acid, itaconic anhydride, Phthalic acid, diallyl ester, Jia Jibingxisuanβ-Qiang Yizhi, glycidyl methacrylate, vinylformic acid stearyl alcohol ester, vinylbenzene, methyl methacrylate, the toxilic acid butyl ester, butyl acrylate, Octyl acrylate, butyl methacrylate, Octyl methacrylate, acrylic acid epoxy ester, tripropylene acid isonitrile urea acid esters, vinyl-acetic ester, along Ethylene Dichloride, zellon, dodecenylsuccinic acid acid anhydride or dodecenylsuccinic acid.
5, the fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously according to claim 1 is characterized in that: described initiator is one or more mixtures of forming in dibenzoyl peroxide, dicumyl peroxide, isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, di-tert-butyl peroxide, dilauroyl peroxide, peroxide tert pivalate ester, the special butyl ester of peroxidation phenylformic acid, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the special penta special butyl ester of peroxidation.
6, the fusion preparation method that strengthens the polyolefine polarity and the degree of branching simultaneously according to claim 1, it is characterized in that: linking agent is Vinylstyrene, N, N-methylene-bisacrylamide, vinylformic acid glycol ester, methacrylate glycol ester, 1,1,1-three (acryloyl-oxy methyl) propane, 2,2,2-three (acryloyl-oxy methyl) ethanol, 1,4-two (4 '-vinylphenoxyly) butane, Diethylene Glycol double methacrylate, polyoxyethylene glycol double methacrylate or tetramethylolmethane double methacrylate vinyl tributanoximo silane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450982B (en) * | 2007-11-29 | 2011-04-27 | 维龙(上海)新材料科技有限公司 | Couple method of polyolefin molecular chain |
| CN101591416B (en) * | 2008-05-28 | 2011-09-14 | 上海科领实业有限公司 | Environmental-friendly polypropylene compatilizer preparation method |
| WO2016037353A1 (en) * | 2014-09-12 | 2016-03-17 | Arkema (Changshu) Fluorochemical Co., Ltd. | Method for preparing a grafted unsaturated synthetic rubber |
| CN106459257A (en) * | 2014-03-31 | 2017-02-22 | 陶氏环球技术有限责任公司 | Crosslinkable polymeric compositions with diallylamide crosslinking coagents, methods for making the same, and articles made therefrom |
| CN109161120A (en) * | 2018-07-02 | 2019-01-08 | 广东威立瑞科技有限公司 | Anti-aging materials, preparation method and preparing the application in cable protection pipe |
| CN110804135A (en) * | 2019-11-22 | 2020-02-18 | 陕西煤业化工技术研究院有限责任公司 | High-melt-strength polypropylene and preparation method thereof |
| CN114592245A (en) * | 2021-11-02 | 2022-06-07 | 嘉兴逸鹏化纤有限公司 | Production method of circular-blowing direct-spinning polyester-nylon composite yarn |
-
2007
- 2007-01-18 CN CN 200710051283 patent/CN101016361A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450982B (en) * | 2007-11-29 | 2011-04-27 | 维龙(上海)新材料科技有限公司 | Couple method of polyolefin molecular chain |
| CN101591416B (en) * | 2008-05-28 | 2011-09-14 | 上海科领实业有限公司 | Environmental-friendly polypropylene compatilizer preparation method |
| CN106459257A (en) * | 2014-03-31 | 2017-02-22 | 陶氏环球技术有限责任公司 | Crosslinkable polymeric compositions with diallylamide crosslinking coagents, methods for making the same, and articles made therefrom |
| CN106459257B (en) * | 2014-03-31 | 2019-05-31 | 陶氏环球技术有限责任公司 | Crosslinkable polymeric composition with diene propionamide cross-linking aid, the article for manufacturing its method and being made from it |
| WO2016037353A1 (en) * | 2014-09-12 | 2016-03-17 | Arkema (Changshu) Fluorochemical Co., Ltd. | Method for preparing a grafted unsaturated synthetic rubber |
| CN109161120A (en) * | 2018-07-02 | 2019-01-08 | 广东威立瑞科技有限公司 | Anti-aging materials, preparation method and preparing the application in cable protection pipe |
| CN109161120B (en) * | 2018-07-02 | 2021-02-02 | 广东威立瑞科技有限公司 | Anti-aging material, preparation method and application in preparation of cable protection pipe |
| CN110804135A (en) * | 2019-11-22 | 2020-02-18 | 陕西煤业化工技术研究院有限责任公司 | High-melt-strength polypropylene and preparation method thereof |
| CN114592245A (en) * | 2021-11-02 | 2022-06-07 | 嘉兴逸鹏化纤有限公司 | Production method of circular-blowing direct-spinning polyester-nylon composite yarn |
| CN114592245B (en) * | 2021-11-02 | 2023-01-31 | 嘉兴逸鹏化纤有限公司 | Production method of circular-blowing direct-spinning polyester-nylon composite yarn |
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