CN106674431A - Preparation method of high-density polyethylene grafted maleic anhydride polymer - Google Patents
Preparation method of high-density polyethylene grafted maleic anhydride polymer Download PDFInfo
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- CN106674431A CN106674431A CN201611101822.4A CN201611101822A CN106674431A CN 106674431 A CN106674431 A CN 106674431A CN 201611101822 A CN201611101822 A CN 201611101822A CN 106674431 A CN106674431 A CN 106674431A
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- maleic anhydride
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- grafted maleic
- anhydride polymer
- polycthylene grafted
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a high-density polyethylene grafted maleic anhydride polymer, and belongs to the field of polymer grafted modification, and is intended to solve the problems of high crosslinking degree and low grafting ratio in maleic anhydride-grafted high-density polyethylene. The method comprises the following steps: step A: dissolving MAH, a crylic acid and an initiator into a disperse organic solvent; step B: mixing the HDPE with the mixture obtained in the step A; and step C: extruding and pelletizing by adopting a twin-screw extruder.
Description
Technical field
It is specifically that a kind of high-density polycthylene grafted maleic anhydride gathers the present invention relates to polymer graft modification field
The preparation method of compound.
Background technology
Maleic anhydride grafts are a kind of with maleic anhydride as monomer, are carried out with other materials under suitable temperature conditionss
Polymer obtained from grafting.Generally, grafting method mainly has solwution method, fusion method, radiation method and solid phase method etc..Wherein, melt
The method of melting be it is the most frequently used be also most important method.Due to having the polar group aldehyde radical and alkene apolar chain of maleic anhydride offer concurrently
Section, maleic anhydride grafts can be widely used in the modified of the materials such as PA, PP and PE.
High density polyethylene (HDPE) is a kind of widely used general-purpose plastics.Because its is cheap, crystallinity is high, comprehensive
Can it is good the advantages of and be widely used in making various life appliances and industrial devices.But the small HDPE of polarity and other materials
Cementability is bad, with the high molecular poor compatibility of polarity, is limited by very large its range of application.In order to improve HDPE
Performance and expand range of application, can be grafted with other polar monomers such as maleic anhydride.
But in existing graft reaction, side reaction is more, and residual monomer is difficult to away, the power of graft polymers is had a strong impact on
Performance is learned, particularly rigidity and toughness are difficult to have concurrently.
The content of the invention
It is an object of the invention to：For above-mentioned problem, there is provided a kind of high-density polycthylene grafted maleic anhydride
The preparation method of polymer, it is characterised in that comprise the following steps：
Step A：MAH, acrylic acid and initiator are dissolved in the middle of dispersion organic solvent；
Step B：Mixture after HDPE and step A is mixed；
Step C：Extruding pelletization is carried out using double screw extruder.
Wherein, described initiator is selected from benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, the tert-butyl group
Hydrogen peroxide, di-t-butyl peroxide, cumyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating trimethylacetic acid tert-butyl group
Ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.It is preferred that drawing
Hair agent is the mixture of di-t-butyl peroxide and lauroyl peroxide, and mol ratio is 1:（1-10）, described initiator is preferred
Weight is than the 0.1%-1% for HDPE.
Further, described dispersion organic solvent is selected from acetone, formamide, trifluoroacetic acid, DMSO, DMF, hempa
Sour acid amides, methyl alcohol, ethanol, acetic acid, trichloro ethylene, n-butanol, ether, n-butyl ether, carbon tetrachloride, hexamethylene, one kind of hexane,
The dispersion preferred acetone of organic solvent, weight is than the 5%-20% for MAH, acrylic acid weight.
Used as improvement, described MAH is the 2%-20% of HDPE weight.
Further, the mol ratio of described acrylic acid and MAH is preferably 1：（0.7-1.5）.
Double screw extruder can be using conventional technological parameter, preferably, the extrusion of described double screw extruder
Temperature is 140 DEG C -190 DEG C;The rotating speed of described double screw extruder is 20-50r/min.
Wherein in order to limit the generation of side reaction, in stepb to mixture list of the addition with Electron donor functionalities
Body, weight is than the 0.1-5% for mixture.
Preferably, Ismipur, propylthiouracil, Cys, 4- hydroxyl -2- sulfydryl -6- methyl are phonetic
Pyridine, 2,3- dimercapto -1- propyl alcohol, 2 mercapto ethanol, 2- sulfydryl -1- methylimidazoles, methimazole, 2-mercaptothiazoline, 4- mercaptos
Base toluene, sulfydryl benzene, 2- methylbenzene phenyl-sulfhydrates have preferable effect as the monomer with Electron donor functionalities.
The assay method of grafting rate：Graft is placed in 60mL dimethylbenzene after purification to take 0.5g, is heated to reflux, and is allowed to complete
Dissolving；Multiply heat to add the potassium hydroxide of 0.1mol/L is methanol solution 10mL, adds phenolphthalein indicator.0.1 mol/L is used again
Oxalic acid solution titration, calculate grafting rate and grafting efficiency.
The beneficial effects of the invention are as follows the obtained graft polymer product purity of the present invention is high, side reaction is less, while not
Reaction monomers content is few, while crosslinking side reaction does not have substantially.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Specific embodiment 1：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
2 parts and MAH 0.1 part of acrylic acid and initiator benzoyl peroxide with molal quantity of MAH is dissolved in point first
Dissipate in the middle of organic solvent-acetone；Secondly HDPE and said mixture are mixed, Ismipur monomer, weight is added to mixture
Than 0.1% for mixture；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 140 DEG C;Described double spiral shells
The rotating speed of bar extruder is 20r/min.
Specific embodiment 2：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
MAH20 parts and MAH 1 part of acrylic acid and initiator lauroyl peroxide with molal quantity is dissolved in dispersion first
In the middle of organic solvent-acetone；Secondly HDPE and said mixture are mixed, propylthiouracil monomer, weight is added to mixture
Than 5% for mixture；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 190 DEG C;Described twin-screw
The rotating speed of extruder is 50r/min.
Specific embodiment 3：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
Acrylic acid and initiator di-t-butyl peroxide first by 10 parts and MAH of MAH with molal quantity, 1 part be dissolved in
In the middle of dispersion organic solvent formamide；Secondly HDPE and said mixture are mixed, to mixture Cys monomer, weight
Than 3% for mixture；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 150 DEG C;Described twin-screw
The rotating speed of extruder is 30r/min.
Specific embodiment 4：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
First by 5 parts and MAH acrylic acid and initiator cumyl peroxide, the 0.5 part of dissolvings with molal quantity of MAH
In the middle of dispersion organic solvent-acetone；Secondly HDPE and said mixture are mixed, 2- sulfydryl -1- methyl miaows is added to mixture
Azoles, methimazole, 2-mercaptothiazoline, 4- sulfydryls toluene, sulfydryl benzene, 2- methylbenzene phenyl-sulfhydrate monomers, weight is than being mixture
5%；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 140 DEG C;The rotating speed of described double screw extruder
It is 50r/min.
Specific embodiment 5：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
First by the 10 parts and MAH acrylic acid and initiator di-cyclohexylperoxy di-carbonate 0.5 with molal quantity of MAH
Part is dissolved in the middle of dispersion organic solvent-acetone；Secondly HDPE and said mixture are mixed, to mixture 2 mercapto ethanol list
Body, weight is than 5% for mixture；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 140 DEG C;Described
The rotating speed of double screw extruder is 50r/min.
Specific embodiment 6：A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that
Comprise the following steps, wherein all raw materials are calculated in proportion with HDPE according to 100 weight portions.
First by 10 parts and MAH acrylic acid and initiator benzoyl peroxide, the 0.1 part excessively dissolvings with molal quantity of MAH
Disperseing in the middle of organic solvent, n-butanol；Secondly HDPE and said mixture are mixed, to mixture 4- sulfydryl toluene momomers, weight
Amount is than 0.3% for mixture；Extruding pelletization is finally carried out using double screw extruder, extrusion temperature is 190 DEG C;Described is double
The rotating speed of screw extruder is 20r/min.
Polymer and product properties to embodiment 1-6 are determined as follows, and wherein article fabrication methods are as follows：
Polymer after poly- grafting, is added to dimethylbenzene, is heated to reflux, and mixed liquor is poured into acetone stirring precipitation, by sediment
Washed with acetone, dried, product is obtained.
Claims (10)
1. a kind of preparation method of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that comprise the following steps：
Step A：MAH, acrylic acid and initiator are dissolved in the middle of dispersion organic solvent；
Step B：Mixture after HDPE and step A is mixed；
Step C：Extruding pelletization is carried out using double screw extruder.
2. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 1, it is characterised in that
Described initiator is selected from benzoyl peroxide, lauroyl peroxide, isopropyl benzene hydroperoxide, TBHP, peroxide
Change di-t-butyl, cumyl peroxide, peroxidized t-butyl perbenzoate, peroxidating trimethylacetic acid tertiary butyl ester, peroxidating first and second
Ketone, cyclohexanone peroxide, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.
3. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 2, it is characterised in that
Described initiator is the mixture of di-t-butyl peroxide and lauroyl peroxide, and mol ratio is 1:（1-10）, described draws
Hair agent weight is than the 0.1%-1% for HDPE.
4. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 1, it is characterised in that
Described dispersion organic solvent be selected from acetone, formamide, trifluoroacetic acid, DMSO, DMF, hexamethyl-phosphoramide, methyl alcohol, ethanol,
Acetic acid, trichloro ethylene, n-butanol, ether, n-butyl ether, carbon tetrachloride, hexamethylene, one kind of hexane.
5. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 1, it is characterised in that
Described MAH is the 2%-20% of HDPE weight.
6. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 5, it is characterised in that
Described acrylic acid and the mol ratio of MAH are 1：（0.7-1.5）.
7. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 6, it is characterised in that
The extrusion temperature of described double screw extruder is 140 DEG C -190 DEG C;The rotating speed of described double screw extruder is 20-50r/
min。
8. the preparation method of the high-density polycthylene grafted maleic anhydride polymer according to claim any one of 1-7, its
It is characterised by, in stepb to mixture monomer of the addition with Electron donor functionalities, weight is than the 0.1- for mixture
5%。
9. the preparation method of high-density polycthylene grafted maleic anhydride polymer according to claim 8, it is characterised in that
The described monomer with Electron donor functionalities is selected from：Ismipur, propylthiouracil, Cys, 4- hydroxyls-
2- sulfydryl -6- methylpyrimidines, 2,3- dimercapto -1- propyl alcohol, 2 mercapto ethanol, 2- sulfydryl -1- methylimidazoles, methimazole, 2-
Mercaptothiazoline, 4- sulfydryls toluene, sulfydryl benzene, 2- methylbenzene phenyl-sulfhydrates.
10. a kind of high-density polycthylene grafted maleic anhydride polymer, it is characterised in that formula includes：High density polyethylene (HDPE), horse
Come acid anhydrides, acrylic monomers, initiator.
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| CN201611101822.4A CN106674431B (en) | 2016-12-05 | 2016-12-05 | A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer |
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| CN201611101822.4A CN106674431B (en) | 2016-12-05 | 2016-12-05 | A kind of preparation method of high-density polycthylene grafted maleic anhydride polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109572118A (en) * | 2018-12-11 | 2019-04-05 | 厦门艾美森新材料科技股份有限公司 | A kind of ultralow thickness PE/PA laminated film and preparation method thereof |
Citations (7)
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| JPS56118411A (en) * | 1980-02-25 | 1981-09-17 | Mitsubishi Petrochem Co Ltd | Production of modified polyolefin having good adhesiveness |
| JPS5968319A (en) * | 1982-10-13 | 1984-04-18 | Mitsubishi Chem Ind Ltd | Modified polyethylene resin composition |
| JPH04248840A (en) * | 1991-01-25 | 1992-09-04 | Mitsui Petrochem Ind Ltd | Production of modified polyethylene particle |
| DE4123972A1 (en) * | 1991-07-19 | 1993-01-21 | Buna Ag | Carboxylated ethylene] useful as compatibiliser in glass-fibre reinforced compsns. - by grafting polyethylene@ with alpha, beta-unsatd. mono: and di:carboxylic acid in the solid phase, using peroxide initiator |
| CN103540074A (en) * | 2012-07-13 | 2014-01-29 | 上海日之升新技术发展有限公司 | Novel compatilizer masterbatch for high filled polyolefin material and preparation method thereof |
| US20150240017A1 (en) * | 2012-09-10 | 2015-08-27 | Reliance Industries Limited | Disentangled ultra high molecular weight polyethylene graft co-polymers and a process for preparation thereof |
| CN105859970A (en) * | 2016-03-28 | 2016-08-17 | 山东省科学院能源研究所 | Method for increasing polyolefin grafting efficiency |
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2016
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118411A (en) * | 1980-02-25 | 1981-09-17 | Mitsubishi Petrochem Co Ltd | Production of modified polyolefin having good adhesiveness |
| JPS5968319A (en) * | 1982-10-13 | 1984-04-18 | Mitsubishi Chem Ind Ltd | Modified polyethylene resin composition |
| JPH04248840A (en) * | 1991-01-25 | 1992-09-04 | Mitsui Petrochem Ind Ltd | Production of modified polyethylene particle |
| DE4123972A1 (en) * | 1991-07-19 | 1993-01-21 | Buna Ag | Carboxylated ethylene] useful as compatibiliser in glass-fibre reinforced compsns. - by grafting polyethylene@ with alpha, beta-unsatd. mono: and di:carboxylic acid in the solid phase, using peroxide initiator |
| CN103540074A (en) * | 2012-07-13 | 2014-01-29 | 上海日之升新技术发展有限公司 | Novel compatilizer masterbatch for high filled polyolefin material and preparation method thereof |
| US20150240017A1 (en) * | 2012-09-10 | 2015-08-27 | Reliance Industries Limited | Disentangled ultra high molecular weight polyethylene graft co-polymers and a process for preparation thereof |
| CN105859970A (en) * | 2016-03-28 | 2016-08-17 | 山东省科学院能源研究所 | Method for increasing polyolefin grafting efficiency |
Non-Patent Citations (1)
| Title |
|---|
| NORMAN G. GAYLORD等: "Peroxide‐catalyzed grafting of maleic anhydride onto molten polyethylene in the presence of polar organic compounds", 《JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109572118A (en) * | 2018-12-11 | 2019-04-05 | 厦门艾美森新材料科技股份有限公司 | A kind of ultralow thickness PE/PA laminated film and preparation method thereof |
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| CN106674431B (en) | 2019-01-01 |
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Effective date of registration: 20181116 Address after: Room 106, First Floor, No. 24 Factory Building, Huli Industrial Zone, Xiamen City, Fujian Province Applicant after: XIAMEN AMESON NEW MATERIAL INC. Address before: 611930 No. 50, Unity Street, Tianpeng Town, Pengzhou City, Chengdu City, Sichuan Province Applicant before: Pengzhou reaches the intellectual property rights service limited company |
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