CN105131203A - Preparation method for polypropylene grafted maleic anhydride with high graft ratio and low odor - Google Patents
Preparation method for polypropylene grafted maleic anhydride with high graft ratio and low odor Download PDFInfo
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- CN105131203A CN105131203A CN201510448574.XA CN201510448574A CN105131203A CN 105131203 A CN105131203 A CN 105131203A CN 201510448574 A CN201510448574 A CN 201510448574A CN 105131203 A CN105131203 A CN 105131203A
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Abstract
The invention discloses a preparation method for polypropylene grafted maleic anhydride with a high graft ratio and low odor. The method comprises the following steps: adding double-bond-containing petroleum resin with a concentration of 1% to 50% into a system, then adding an auxiliary monomer styrene and modifying a composite material of polypropylene and the petroleum resin with maleic anhydride under the action of an initiator with temperature controlled to be 170 to 230 DEG C; and removing unreacted impurities in the system through vacuumization. A compatibilizing agent with a high graft ratio and low odor can be prepared by utilizing the method in the invention. The prepared polypropylene grafted maleic anhydride compatibilizing agent can improve bonding strength between polypropylene and inorganic fillers like calcium carbonate, glass fiber and mica, thereby enhancing tensile strength, thermal deformation temperature and the like of polypropylene.
Description
Technical field:
The present invention relates to processing of high molecular material technical field, be specifically related to the preparation method of polypropylene grafted maleic anhydride of a kind of high percentage of grafting, low smell.
Background technology:
Polypropylene as general-purpose plastics, wide application large with output and inexpensive and famous.But polypropylene has nonpolar and crystallinity, make the poor compatibility such as itself and polar polymer, inorganic fill and strongthener, need to add compatilizer to reduce interfacial tension during blended and compound use.Grafting is carried out to polypropylene, molecular chain is introduced suitable polarity side chain, utilize polarity and the reactivity of side chain, improve the deficiency in its performance, increase again new character simultaneously.Therefore graft modification is the simple and effective method of one expanding polypropylene application.
Be a kind of common and effective compatilizer with the grafts that maleic anhydride modified polypropylene is obtained, can use it for modified plastics, the method for grafting has solution graft copolymerization, fusion-grafting, solid phase grafting and Suspension Graft method.In these methods, fusion-grafting method is a kind of simple to operate, and cost less investment, is applicable to the preparation method of suitability for industrialized production.
The percentage of grafting of the grafts that maleic anhydride modified polypropylene obtains is relevant with the add-on of maleic anhydride, and percentage of grafting increases along with the increase of maleic anhydride add-on.But the increase of maleic anhydride add-on can cause the smell of final grafted material comparatively large, the PP higher to odor requirements can not be used for and strengthen in automotive material, greatly limit its application.
The size of percentage of grafting and smell is the important indicator judging maleic anhydride modified polypropylene quality quality.Merely with a kind of raw material of maleic anhydride modified polypropylene, the grafts percentage of grafting of obtained low smell is general lower.Introduce obtained grafts percentage of grafting in disclosed patent CN101519477B and CN101885806B embodiment now and can reach more than 2.6%, on actual market, good PP-g-MAH product percentage of grafting only has about 1%, and there is the larger problem of smell.The present invention adds the percentage of grafting that intermingling material petroleum resin can improve grafted material, makes grafted material with more polar group, thus improves the consistency of grafted material and polar material, solves the problem that smell is large simultaneously.
In the system of maleic anhydride melt grafting PP, due to maleic anhydride symmetrical configuration, reactive behavior is lower.The monomer styrene with electron supplying capacity is added in system, the electric charge in maleic anhydride double bond can be made to produce asymmetric, and make its key have the feature of radical anion, thus improve maleic anhydride reactive behavior, improve percentage of grafting.On the other hand, cinnamic adding can suppress PP molecular radical generation chain-scission degradation, thus keeps the mechanical property of grafts.
Petroleum resin have excellent alkali resistance, water tolerance, corrosion-resistant and have the advantages such as good intermiscibility with organic substance, and cheap, apply more and more extensive.On the molecular chain of petroleum resin, double bond is under the existence of initiator, with the monomer generation Raolical polymerizable such as double bond containing maleic anhydride, makes polar monomer graft on petroleum resin molecular chain, becomes the polymer molecule monomer of a band polar group.
Summary of the invention:
The object of this invention is to provide the preparation method of a kind of high percentage of grafting, low odor polypropylene grafted maleic anhydride, this polypropylene grafted maleic anhydride has the advantages such as higher percentage of grafting and low smell, effectively can improve the bonding force of the mineral filler such as polypropylene and calcium carbonate, glass fibre, mica, thus can polyacrylic tensile strength, heat-drawn wire etc. be improved.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for the polypropylene grafted maleic anhydride of high percentage of grafting, low smell, comprises the following steps:
(1) polypropylene and petroleum resin are added in reactor, be evacuated to-0.1MPa, be warming up to material and all melt, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, under nitrogen protection, add maleic anhydride, be stirred to PP and mix with maleic anhydride;
(3) when temperature-stable is at 170 ~ 230 DEG C, add catalyzer and cinnamic mixed solution, time for adding controls 10 ~ 30min;
(4) after being added dropwise to complete, isothermal reaction 30 ~ 60min;
(5), after question response completes, vacuum pump is utilized to remove unreacted impurity, vacuum degree control-0.1MPa, except miscellaneous time 1 ~ 4h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain the polypropylene grafted maleic anhydride of high percentage of grafting, low smell.
Preferred as technique scheme, described polypropylene is homo-polypropylene or Co-polypropylene, and described polyacrylic form is powdery or granular.
Preferred as technique scheme, described petroleum resin are selected from one or more mixing in group aliphatic resin (C5), alicyclic resin (DCPD), aromatic resin (C9), aliphatic/aromatic copolymer resins (C5/C9) and hydrogenated petroleum resin, C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin.
Preferred as technique scheme, described petroleum resin add-on is 1% ~ 50% of polypropylene weight, is preferably 10% ~ 50%.
Preferred as technique scheme, described maleic anhydride add-on is 1% ~ 5% of polypropylene weight, is preferably 1% ~ 3%.
Preferred as technique scheme, described catalyzer is selected from dialkyl peroxide class initiator, be preferably two (t-butylperoxyisopropyl) benzene, 2, at least one in 5-dimethyl-2,5-di-t-butyl hexane peroxide, dicumyl peroxide, t-tutyl cumyl peroxide and ditertiary butyl peroxide.
Preferred as technique scheme, described peroxide catalyst consumption is 0.3% ~ 1.65% of polypropylene weight, is preferably 0.3% ~ 1%.
Preferred as technique scheme, described vinylbenzene consumption is polypropylene weight 2% ~ 10%, is preferably 2% ~ 6%.
Preferred as technique scheme, in step (4), described temperature of reaction controls at 170 ~ 230 DEG C, is preferably 170 ~ 190 DEG C.
In method of the present invention, melt process equipment can be various melt blending equipment of the prior art, if Banbury mixer, intermittence mixing machine, continuously extrusion equipment are as single screw extrusion machine, twin screw extruder etc., and preferred reaction type reactor.
The present invention has following beneficial effect:
Maleic anhydride monomer is grafted on the molecular chain of acrylic resin by the reaction of melting free radical grafting by the present invention, except adding grafted monomer maleic anhydride, auxiliary monomer vinylbenzene is also added in described melting graft reaction, and by peroxide initiator initiation reaction;
In addition, in reaction system, add a small amount of petroleum resin, effectively improve percentage of grafting, and increase the polar group number of grafts, improve its compatibilization, the maleic anhydride remained in system also can reduce thereupon, and the polypropylene grafted maleic anhydride grafts smell prepared is also lighter.
Embodiment:
For a better understanding of the present invention, below by embodiment, the present invention is further described, and embodiment, only for explaining the present invention, can not form any restriction to the present invention.
In comparative example of the present invention and embodiment, PP used is homopolymer, and melting means (230 DEG C, 2.16kg) is 10 ~ 15g/10min, and all the other raw materials are commercially available industrial raw material.
Comparative example 1
(1) 1000 grams of PP are added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 14.3 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 6 grams of t-tutyl cumyl peroxides, time controling 10 ~ 30min, after being added dropwise to complete, continue logical nitrogen reaction 30 ~ 60min;
(4), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(5), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Comparative example 2
(1) PP of 1000 grams is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 14 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 4 gram of 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and 20 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Embodiment 1
(1) PP of a 500 grams and 500 gram C 5 petroleum resin is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 20 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 4 gram of 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and 20 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Embodiment 2
(1) PP of a 750 grams and 250 gram C 9 petroleum resin is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 15 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 4 gram of 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and 20 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Embodiment 3
(1) PP of a 900 grams and 100 gram C 5 petroleum resin is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 15 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 4 gram of 2,5-dimethyl-2,5-di-t-butyl hexane peroxide and 25 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Embodiment 4
(1) PP of 900 grams and 100 gram C 5/C nine copolymerized petroleum resin is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 25 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 5 grams of t-tutyl cumyl peroxides and 25 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
Embodiment 5
(1) PP of a 800 grams and 200 gram C 5 petroleum resin is added in reactor, vacuumize, be warming up to 190 ~ 230 degree, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, pass into nitrogen, add 20 grams of maleic anhydrides, be stirred to PP and maleic anhydride mixes;
(3) until temperature-stable after 170 ~ 190 degree, start to drip 3 grams of t-tutyl cumyl peroxides and 30 grams of vinylbenzene mixed solutions, time controling 10 ~ 30min;
(4), after being added dropwise to complete, logical nitrogen reaction 30 ~ 60min is continued;
(5), after having reacted, keep temperature of reaction, slowly vacuumize and remove unreacted impurity, time controling is at 1 ~ 2h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain product.
The testing method of above comparative example and embodiment percentage of grafting and smell is as follows:
1, the percentage of grafting test procedure of polypropylene grafted maleic anhydride product:
(1) refining sample: take 2g grafts (PP-g-MAH) and be placed in 500ml Florence flask, add 100ml dimethylbenzene, 135 DEG C of reflux are all dissolved to grafting samples, add 80ml acetone while hot, leave standstill cooling 30min, filter, clean three times with acetone, then sample is placed in 80 DEG C of vacuum drying ovens, dry more than 12h until constant weight.
(2) take the sample that about 0.5g is refining, be dissolved in 100ml dimethylbenzene, 135 DEG C of reflux are until sample all dissolves, and cooling 5min, pipettes 0.2mol/L (C with transfer pipet
1) KOH-ethanol standardized solution 2ml, 135 DEG C of reflux 1h, cool 30min, add 0.1mol hydrochloric acid aqueous isopropanol 10ml, 135 DEG C of reflux 30min, cool 30min, drips 2 phenolphthalein, and then with the hydrochloric acid of 0.2mol/LKOH-ethanolic soln overtitration, record the volume consumed and be designated as V
1.
(3) take the PP that about 0.5g does not connect skill, repeat (2) experimental procedure, record the volume consumed and be designated as V
2.With following formulae discovery percentage of grafting: MAH (%)=9.806* [C
1(V
1-V
2)]/2m.
2, the smell testing method step of polypropylene grafted maleic anhydride product is as follows:
(1) take 20 ± 2g and treat that test sample puts into odor bottle, and odor bottle is covered tightly put into 80 ± 2 DEG C of force ventilated baking ovens of constant temperature, 80 ± 2 DEG C of constant temperature 2h, when oven temperature is cooled to 60 ± 5 DEG C, open odor bottle lid rapidly and carry out smell assessment.
(2) more objective in order to assess, assessment number is at least 3 people (that is assessment panel is at least made up of 3 people).Gap between the mark that everyone gives can not be greater than 2 points.If scoring gap is greater than 2 points, then 30min placed by the baking oven continuing to put into 80 ± 2 DEG C, assessed by other 2 people again.
(3) detected result evaluation grade divides
The evaluation of smell can be marked according to mark 1 to 6 according to opinion rating (referring to form below) to all possible variable, also can be divided into 0.5 point between mark and carry out.
| Grade | Standard |
| 1 | Can not experience |
| 2 | Can experience, unobstructive |
| 3 | Can obviously experience, but not too large obstruction |
| 4 | There is obstruction |
| 5 | There is larger obstruction |
| 6 | Insufferable |
According to above-mentioned detection method, comparative example 1,2, the result of the percentage of grafting that embodiment 1,2,3,4,5 is tested and smell is as table 1.
Table 1
| Title | Percentage of grafting % | Smell |
| Comparative example 1 | 0.568 | 4 |
| Comparative example 2 | 0.953 | 5 |
| Embodiment 1 | 1.465 | 3 |
| Embodiment 2 | 1.365 | 3 |
| Embodiment 3 | 1.340 | 3 |
| Embodiment 4 | 1.280 | 3 |
| Embodiment 5 | 1.450 | 3 |
Found by contrast, comparative example 1, owing to not adding vinylbenzene, causes percentage of grafting lower, and comparative example 2 adds vinylbenzene, and percentage of grafting is higher, but smell is larger.And after adding petroleum resin in embodiment, percentage of grafting is significantly improved, smell obviously declines.Therefore, effectively improve the bonding force of the mineral filler such as PP and calcium carbonate, glass fibre, mica, reduce the disadvantageous effect of smell to environment.
Claims (9)
1. a preparation method for the polypropylene grafted maleic anhydride of high percentage of grafting, low smell, is characterized in that, comprise the following steps:
(1) polypropylene and petroleum resin are added in reactor, be evacuated to-0.1MPa, be warming up to material and all melt, vacuum removal of impurities 1 ~ 2h;
(2) stop vacuumizing, under nitrogen protection, add maleic anhydride, be stirred to PP and mix with maleic anhydride;
(3) when temperature-stable is at 170 ~ 230 DEG C, add catalyzer and cinnamic mixed solution, time for adding controls 10 ~ 30min;
(4) after being added dropwise to complete, reaction 30 ~ 60min;
(5), after question response completes, vacuum pump is utilized to remove unreacted impurity, vacuum degree control-0.1MPa, except miscellaneous time 1 ~ 4h;
(6), after removal of impurities, utilize nitrogen to be pressed into by material in single screw extrusion machine and carry out extruding pelletizing, obtain the polypropylene grafted maleic anhydride of high percentage of grafting, low smell.
2. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, described polypropylene is homo-polypropylene or Co-polypropylene, and described polyacrylic form is powdery or granular.
3. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, it is characterized in that, described petroleum resin are selected from one or more mixing in group aliphatic resin (C5), alicyclic resin (DCPD), aromatic resin (C9), aliphatic/aromatic copolymer resins (C5/C9) and hydrogenated petroleum resin, C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin.
4. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, described petroleum resin add-on is 1% ~ 50% of polypropylene weight, is preferably 10% ~ 50%.
5. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, described maleic anhydride add-on is 1% ~ 5% of polypropylene weight, is preferably 1% ~ 3%.
6. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, it is characterized in that, described catalyzer is selected from dialkyl peroxide class initiator, be preferably two (t-butylperoxyisopropyl) benzene, 2, at least one in 5-dimethyl-2,5-di-t-butyl hexane peroxide, dicumyl peroxide, t-tutyl cumyl peroxide and ditertiary butyl peroxide.
7. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, described peroxide catalyst consumption is 0.3% ~ 1.65% of polypropylene weight, is preferably 0.3 ~ 1%.
8. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, described vinylbenzene consumption is polypropylene weight 2% ~ 10%, is preferably 2% ~ 6%.
9. the preparation method of the polypropylene grafted maleic anhydride of a kind of high percentage of grafting as claimed in claim 1, low smell, is characterized in that, in described step (4), described temperature of reaction controls at 170 ~ 230 DEG C, is preferably 170 ~ 190 DEG C.
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Cited By (8)
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| CN106117445A (en) * | 2016-07-27 | 2016-11-16 | 浙江佳华精化股份有限公司 | A kind of preparation method of low odor polypropylene grafted maleic anhydride |
| CN106496423A (en) * | 2016-11-03 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of high percent grafting Graft Polyolefin and the application of the high percent grafting Graft Polyolefin |
| CN107903167A (en) * | 2017-11-21 | 2018-04-13 | 江西宏远化工有限公司 | A kind of low smell zinc stearate preparation method |
| CN108892752A (en) * | 2018-07-20 | 2018-11-27 | 厦门科艾斯塑胶科技有限公司 | A kind of low smell grafting compatilizer and preparation method thereof |
| CN108976348A (en) * | 2018-07-05 | 2018-12-11 | 上海理工大学 | A kind of method that rotary evaporation assists the maleic anhydride for preparing high grafting rate to be grafted ethylene propylene diene rubber |
| 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 |
| CN114085324A (en) * | 2021-12-31 | 2022-02-25 | 山东天风新材料有限公司 | Low-odor polypropylene grafted maleic anhydride and preparation method thereof |
| CN116355139A (en) * | 2023-02-28 | 2023-06-30 | 杭州师范大学 | Modified polypropylene with adjustable grafting, crosslinking and degradation, preparation method and application thereof |
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| CN106117445A (en) * | 2016-07-27 | 2016-11-16 | 浙江佳华精化股份有限公司 | A kind of preparation method of low odor polypropylene grafted maleic anhydride |
| CN106496423A (en) * | 2016-11-03 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of high percent grafting Graft Polyolefin and the application of the high percent grafting Graft Polyolefin |
| CN107903167A (en) * | 2017-11-21 | 2018-04-13 | 江西宏远化工有限公司 | A kind of low smell zinc stearate preparation method |
| CN108976348A (en) * | 2018-07-05 | 2018-12-11 | 上海理工大学 | A kind of method that rotary evaporation assists the maleic anhydride for preparing high grafting rate to be grafted ethylene propylene diene rubber |
| CN108976348B (en) * | 2018-07-05 | 2020-10-09 | 上海理工大学 | Method for preparing maleic anhydride grafted ethylene propylene diene monomer with high grafting rate in auxiliary manner by rotary evaporation method |
| CN108892752A (en) * | 2018-07-20 | 2018-11-27 | 厦门科艾斯塑胶科技有限公司 | A kind of low smell grafting compatilizer and preparation method thereof |
| CN108892752B (en) * | 2018-07-20 | 2020-08-04 | 厦门科艾斯塑胶科技有限公司 | Low-odor grafting compatilizer and preparation method 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 |
| CN114085324A (en) * | 2021-12-31 | 2022-02-25 | 山东天风新材料有限公司 | Low-odor polypropylene grafted maleic anhydride and preparation method thereof |
| CN114085324B (en) * | 2021-12-31 | 2024-03-26 | 山东天风新材料有限公司 | Low-odor polypropylene grafted maleic anhydride and preparation method thereof |
| CN116355139A (en) * | 2023-02-28 | 2023-06-30 | 杭州师范大学 | Modified polypropylene with adjustable grafting, crosslinking and degradation, preparation method and application thereof |
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Application publication date: 20151209 |
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