CN103450403A - Preparation method of POE (polyolefin elastomer) chemically-grafted maleic anhydride - Google Patents
Preparation method of POE (polyolefin elastomer) chemically-grafted maleic anhydride Download PDFInfo
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- CN103450403A CN103450403A CN2013103825478A CN201310382547A CN103450403A CN 103450403 A CN103450403 A CN 103450403A CN 2013103825478 A CN2013103825478 A CN 2013103825478A CN 201310382547 A CN201310382547 A CN 201310382547A CN 103450403 A CN103450403 A CN 103450403A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92514—Pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Thermal Sciences (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a preparation method of POE (polyolefin elastomer) chemically-grafted maleic anhydride. The preparation method of the POE chemically-grafted maleic anhydride comprises the following steps: S1. compounding POE, maleic anhydride, peroxide initiators as well as heat stabilizers, adding an acetone solvent, and mixing evenly; S2, evenly stirring the materials in a high-speed stirrer so as to enable each component to be dispersed evenly and enable the solvent to be volatilized sufficiently, feeding the materials, setting the extrusion temperature of a single-screw extruder as 80-250 DEG C and the main engine frequency of the single-screw extruder as 25-50Hz, controlling the vacuum pressure of the single-screw extruder to be 0.06-0.1MPa, carrying out chemical grafting reaction for 2-4 minutes, staying, cooling, dicing grains, stirring and packaging. The preparation method of the POE chemically-grafted maleic anhydride, which is provided by the invention, can be used for solving defects in production of the POE chemically-grafted maleic anhydride and problems of a POE chemically-grafted maleic anhydride product in the prior art, and greatly improving the compatibility of POE and polar polymers.
Description
Technical field
The present invention relates to the maleic anhydride preparing technical field, more particularly, particularly a kind of preparation method of polyolefin elastomer chemical graft maleic anhydride.
Background technology
Polyolefin elastomer (POE) is to take the thermoplastic elastomer that relative molecular weight distributes and evenly short-chain branch distributes that has that metallocene is catalyzer, and its molecular structure and terpolymer EP rubber are similar.Therefore there are the excellent properties such as ageing-resistant, anti-ozone, resistant to chemical media, with terpolymer EP rubber, compare, polyolefin elastomer (POE) is granular, can save granulation and the premixing process of block EPDM complexity, and polyolefine can be realized the modification of high-speed extrusion molding.But polyolefin elastomer (POE) belongs to non-phasic property elastomerics, with polar polymer (as: PA6, PA66, PC) etc., be difficult to compatible.Therefore polyolefin elastomer is carried out to grafting modification, the consistency that improves itself and polar polymer is particularly important.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyolefin elastomer chemical graft maleic anhydride, to solve the above problems.
The invention provides a kind of preparation method of polyolefin elastomer chemical graft maleic anhydride, comprise step:
S1, spice: the polyolefin elastomer of 94.2%-98.5%, 0.8%～2.0% maleic anhydride, 0.05%～0.5% peroxide initiator and 0.15%～0.8% thermo-stabilizer are prepared burden by massfraction, and add 0.5%～2.5% acetone solvent, use high-speed mixer to mix;
S2, production: above-mentioned material is stirred in homogenizer, make each component evenly loose, and solvent is fully volatilized, and material is dropped into, setting the single screw extrusion machine extrusion temperature is 80～250 ℃, and the main frame frequency of single screw extrusion machine is: 25～50Hz, and the vacuum pressure of single screw extrusion machine is controlled at 0.06-0.1MPa, the chemical graft reaction times is 2～4 minutes, through check rod, cooling, pelletizing, stirring, packing.
Preferably, the hot hydrocarbon content of the a-of described bullet polyolefin elastomer is that between 28～40, density is less than 0.875g/cm
3, melting index is 0.5～2.0g/10min.
Preferably, described peroxide initiator is: any one or its arbitrarily multiple combination in di-t-butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene.
Preferably, described thermo-stabilizer is: any one or its arbitrarily multiple combination in 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, inorganic phosphate, five phosphate compounds.
Preferably, the requirement of the single screw extrusion machine adopted is: major diameter is between 25:1～40:1, the disconnected length of shearing of single screw rod is that 25～50cm is long, shear section and adopt the right-angled intersection design, the main frame frequency control is between 25～50Hz, the 7th section of single screw extrusion machine, vacuum port is set, vacuum pressure will reach 0.06-0.1MPa, guarantees the sucking-off of residual monomer.
The preparation method of polyolefin elastomer chemical graft maleic anhydride provided by the invention, its characteristics are: in the reaction of polyolefin elastomer (POE) grafted maleic anhydride (MAH), owing to using thermo-stabilizer, effectively prevent because of maleic anhydride monomer residual too much and screw rod shearing cross strong prevent gel and xanthochromia, utilize vacuum unit can extract remaining MAH monomer simultaneously, can effectively reduce smell and the xanthochromia of product.Carry out the manufacture of maleic anhydride by production method provided by the invention, its gel content is extremely low, and percentage of grafting is high, can reach 0.9～1%, with the toughening effect of similar products at home and abroad, compares, and surpasses the over-all properties of these products.
The preparation method of polyolefin elastomer chemical graft maleic anhydride provided by the invention, can solve current polyolefin elastomer chemical graft maleic anhydride and produce the problem of Shortcomings and product existence, improve dramatically the consistency of polyolefin elastomer and polar polymer.
The accompanying drawing explanation
The schema that Fig. 1 is polyolefin elastomer chemical graft maleic anhydride preparation method in an embodiment of the present invention.
Embodiment
Below by specific embodiment, also by reference to the accompanying drawings the present invention is described in further detail.
Please refer to Fig. 1, the schema that Fig. 1 is polyolefin elastomer chemical graft maleic anhydride preparation method in an embodiment of the present invention.
Embodiment 1
A kind of method of polyolefin elastomer grafted maleic anhydride, after mixing with acetone solution maleic anhydride, initiator, thermo-stabilizer and polyolefin elastomer, mixture is dropped into to single screw extrusion machine melt blending extruding pelletization, make the grafts POE-g-MAH that polyolefin elastomer and toxilic acid are joined; During granulation, the screw slenderness ratio of single screw extrusion machine is 30:1, and the shearing length of thread is 35cm, and the forcing machine rotating speed is 45HZ, and extruder temperature is 80-250 ℃, and vacuum pressure is controlled at 0.08MPa.
In this programme is implemented, initiator is dicumyl peroxide, and thermo-stabilizer is 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, and grafted monomer is maleic anhydride; By massfraction: polyolefin elastomer is 97.4 parts, and maleic anhydride is 0.4 part of 0.9 part, 0.3 part of initiator, 1 part, acetone and thermo-stabilizer.
Embodiment 2
A kind of method of polyolefin elastomer grafted maleic anhydride, after mixing with acetone solution maleic anhydride, initiator, thermo-stabilizer and polyolefin elastomer, mixture is dropped into to single screw extrusion machine melt blending extruding pelletization, make the grafts POE-g-MAH that polyolefin elastomer and toxilic acid are joined; During granulation, the screw slenderness ratio of single screw extrusion machine is 35:1, and the shearing length of thread is 35cm, and the forcing machine rotating speed is 45HZ, and extruder temperature is 80-250 ℃, and vacuum pressure is controlled at 0.08MPa.
In this programme is implemented, initiator is dicumyl peroxide, and thermo-stabilizer is 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, and grafted monomer is maleic anhydride; By massfraction: polyolefin elastomer is 97.4 parts, and maleic anhydride is 0.4 part of 0.9 part, 0.3 part of initiator, 1 part, acetone and thermo-stabilizer.
Embodiment 3
A kind of method of polyolefin elastomer grafted maleic anhydride, after mixing with acetone solution maleic anhydride, initiator, thermo-stabilizer and polyolefin elastomer, mixture is dropped into to single screw extrusion machine melt blending extruding pelletization, make the grafts POE-g-MAH that polyolefin elastomer and toxilic acid are joined; During granulation, the screw slenderness ratio of single screw extrusion machine is 40:1, and the shearing length of thread is 35cm, and the forcing machine rotating speed is 45HZ, and extruder temperature is that 80-250 ℃ of vacuum pressure is controlled at 0.08MPa.
In this programme is implemented, initiator is dicumyl peroxide, and thermo-stabilizer is 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, and grafted monomer is maleic anhydride; By massfraction: polyolefin elastomer is 97.4 parts, and maleic anhydride is 0.4 part of 0.9 part, 0.3 part of initiator, 1 part, acetone and thermo-stabilizer.
Embodiment 4
A kind of method of polyolefin elastomer grafted maleic anhydride, after mixing with acetone solution maleic anhydride, initiator, thermo-stabilizer and polyolefin elastomer, mixture is dropped into to single screw extrusion machine melt blending extruding pelletization, make the grafts POE-g-MAH that polyolefin elastomer and toxilic acid are joined; During granulation, the screw slenderness ratio of single screw extrusion machine is 35:1, and the shearing length of thread is 35cm, and the forcing machine rotating speed is 45HZ, and extruder temperature is 80-250 ℃, and vacuum pressure is controlled at 0.08MPa.
In this programme is implemented, initiator is dicumyl peroxide dicumyl peroxide and t-butylperoxy isopropyl benzene, the ratio 2:1 of employing, and thermo-stabilizer is 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, grafted monomer is maleic anhydride; By massfraction: polyolefin elastomer is 97.1 parts, and maleic anhydride is 0.4 part of 1.2 parts, 0.3 part of initiator, 1 part, acetone and thermo-stabilizer.
MAH percentage of grafting performance characterization:
Take the POE-g-MAH of certainweight, use xylene soluble, the cooling rear acetone that slowly adds shook up, and is settled out grafts, vacuum filtration, uses washing with acetone 3 times again, 80 degree oven drying 2 hours.
Accurately take the 1g sample, put into the xylene solution of 100ml, reflux, after grafts all dissolves, cooling 30min, add the KOH-ethanolic soln 20ml that concentration is 0.05mol/L, reflux 10min, use the hydrochloric acid of concentration 0.05mol/L-aqueous isopropanol titration while hot, usings phenolphthalein as indicating liquid, repeat to average for 3 times, by following formula, calculate percentage of grafting:
Percentage of grafting=(N1V1-N2V2) * 100% * 98/ (1000 * 2)
In formula: the concentration of N1-KOH-ethanolic soln, mol/L; The volume of V1-KOH-ethanolic soln, m1; The concentration of N2-KOH-ethanolic soln, mol/L; The volume of V2-KOH-ethanolic soln, ml.
The mensuration of gel content:
Accurately take 1gPOE-g-MAH, in the 120 order stainless (steel) wire bags of packing into, take dimethylbenzene as solvent adds 1% oxidation inhibitor, take out the stainless (steel) wire bag after backflow 12h, in 80 ℃ of loft drier, dry 2h, repeat 3 times and average, by following formula calculated for gel content:
Gel content=(W1-W2+W3) * 100%/W1
In formula: W1-grafts quality; Pack into the quality of net bag after sample of W2-; The quality of net bag after W3-refluxes.
| The embodiment sequence number | Percentage of grafting % | Gel content % |
| Embodiment 1 | 0.92 | 0.43 |
| Embodiment 2 | 0.94 | 0.45 |
| Embodiment 3 | 0.94 | 0.51 |
| Embodiment 4 | 0.95 | 0.42 |
Claims (5)
1. the preparation method of a polyolefin elastomer chemical graft maleic anhydride, is characterized in that, comprising:
Step 1, spice: the polyolefin elastomer of 94.2%-98.5%, 0.8%～2.0% maleic anhydride, 0.05%～0.5% peroxide initiator and 0.15%～0.8% thermo-stabilizer are prepared burden by massfraction, and add 0.5%～2.5% acetone solvent, use high-speed mixer to mix;
Step 2, production: above-mentioned material is stirred in homogenizer, make each component evenly loose, and solvent is fully volatilized, and material is dropped into, setting the single screw extrusion machine extrusion temperature is 80～250 ℃, and the main frame frequency of single screw extrusion machine is: 25～50Hz, and the vacuum pressure of single screw extrusion machine is controlled at 0.06-0.1MPa, the chemical graft reaction times is 2～4 minutes, through check rod, cooling, pelletizing, stirring, packing.
2. the preparation method of polyolefin elastomer chemical graft maleic anhydride according to claim 1, is characterized in that,
The hot hydrocarbon content of the a-of described bullet polyolefin elastomer is that between 28～40, density is less than 0.875g/cm3, and melting index is 0.5～2.0g/10min.
3. the preparation method of polyolefin elastomer chemical graft maleic anhydride according to claim 1, is characterized in that,
Described peroxide initiator is: any one or its arbitrarily multiple combination in di-t-butyl peroxide, dicumyl peroxide, t-butylperoxy isopropyl benzene.
4. the preparation method of polyolefin elastomer chemical graft maleic anhydride according to claim 1, is characterized in that,
Described thermo-stabilizer is: any one or its arbitrarily multiple combination in 3.5-di-tert-butyl-hydroxy phenyl propionic acid ten caprylates, inorganic phosphate, five phosphate compounds.
5. the preparation method of polyolefin elastomer chemical graft maleic anhydride according to claim 1, is characterized in that,
The requirement of the single screw extrusion machine adopted is: major diameter is between 25:1～40:1, the disconnected length of shearing of single screw rod is that 25～50cm is long, shear section and adopt the right-angled intersection design, the main frame frequency control is between 25～50Hz, the 7th section of single screw extrusion machine, vacuum port is set, vacuum pressure will reach 0.06-0.1MPa, guarantees the sucking-off of residual monomer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755876A (en) * | 2013-12-31 | 2014-04-30 | 广州鹿山新材料股份有限公司 | Polar monomer graft-modified amorphous poly-alpha-olefin and preparation method thereof |
| CN105778000A (en) * | 2014-12-16 | 2016-07-20 | 中国石油天然气股份有限公司 | Isoprene rubber grafted maleic anhydride and preparation method thereof |
| CN111635483A (en) * | 2020-07-07 | 2020-09-08 | 江苏中煤电缆有限公司 | POE (polyolefin elastomer) graft polymer for enhancing PP (polypropylene) printing performance and preparation process thereof |
| CN113651917A (en) * | 2021-10-19 | 2021-11-16 | 北京能之光科技有限公司 | Method for improving grafting rate of low-odor maleic anhydride grafted polyolefin for automobile |
| CN114261162A (en) * | 2020-09-16 | 2022-04-01 | 三芳化学工业股份有限公司 | Film, process for producing the same and use thereof |
| US11912837B2 (en) | 2020-08-07 | 2024-02-27 | San Fang Chemical Industry Co., Ltd. | Thin film, manufacturing method and uses thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263897A (en) * | 2000-03-16 | 2000-08-23 | 上海交通大学 | Process for preparing thermoplastic elastomer modified by maleic acid anhydride graft |
-
2013
- 2013-08-28 CN CN2013103825478A patent/CN103450403A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263897A (en) * | 2000-03-16 | 2000-08-23 | 上海交通大学 | Process for preparing thermoplastic elastomer modified by maleic acid anhydride graft |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755876A (en) * | 2013-12-31 | 2014-04-30 | 广州鹿山新材料股份有限公司 | Polar monomer graft-modified amorphous poly-alpha-olefin and preparation method thereof |
| CN103755876B (en) * | 2013-12-31 | 2016-01-20 | 广州鹿山新材料股份有限公司 | Unformed poly-alpha olefins of a kind of polar monomer graft modification and preparation method thereof |
| CN105778000A (en) * | 2014-12-16 | 2016-07-20 | 中国石油天然气股份有限公司 | Isoprene rubber grafted maleic anhydride and preparation method thereof |
| CN111635483A (en) * | 2020-07-07 | 2020-09-08 | 江苏中煤电缆有限公司 | POE (polyolefin elastomer) graft polymer for enhancing PP (polypropylene) printing performance and preparation process thereof |
| US11912837B2 (en) | 2020-08-07 | 2024-02-27 | San Fang Chemical Industry Co., Ltd. | Thin film, manufacturing method and uses thereof |
| CN114261162A (en) * | 2020-09-16 | 2022-04-01 | 三芳化学工业股份有限公司 | Film, process for producing the same and use thereof |
| CN113651917A (en) * | 2021-10-19 | 2021-11-16 | 北京能之光科技有限公司 | Method for improving grafting rate of low-odor maleic anhydride grafted polyolefin for automobile |
| CN113651917B (en) * | 2021-10-19 | 2022-01-25 | 北京能之光科技有限公司 | Method for improving grafting rate of low-odor maleic anhydride grafted polyolefin for automobile |
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Application publication date: 20131218 |