CN1171936C - Prepn of high-toughness and high-flowability modified polypropylene - Google Patents
Prepn of high-toughness and high-flowability modified polypropylene Download PDFInfo
- Publication number
- CN1171936C CN1171936C CNB011129808A CN01112980A CN1171936C CN 1171936 C CN1171936 C CN 1171936C CN B011129808 A CNB011129808 A CN B011129808A CN 01112980 A CN01112980 A CN 01112980A CN 1171936 C CN1171936 C CN 1171936C
- Authority
- CN
- China
- Prior art keywords
- rubber
- terpolymer
- polypropylene
- linking agent
- toughness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention relates to a preparation method of high-toughness and high-fluidity modified polypropylene. Granular polypropylene, granular ethylene propylene terpolymer rubber, an organic peroxide crosslinking agent and an allyl ester auxiliary crosslinking agent are proportionally and thoroughly mixed, the weight ratio of the polypropylene to the ethylene propylene terpolymer rubber is equal to 100:5 to 35, the weight ratio of the ethylene propylene terpolymer rubber to the organic peroxide crosslinking agent is equal to 100:0.05 to 0.45, and the weight ratio of the ethylene propylene terpolymer rubber to the auxiliary crosslinking agent is equal to 100:0.5 to 3.5. The mixture is added into a double-screw extruding machine, melted, blended, extruded and granulated. The modified polypropylene material finally obtained, which has the advantages of high impact toughness and high processing fluidity, can embody favorable combination performance.
Description
The present invention relates to the preparation of high-toughness and high-flowability modified polypropylene, particularly the material modified of increasing tougheness is the preparation of the high-toughness and high-flowability modified polypropylene of terpolymer EP rubber.
Polypropylene is since industrialization, because its raw material sources are abundant, synthesis technique is simple, and is cheap, the resin over-all properties is good and of many uses, development in recent years is rapid, has become output at present and has only occupied polyethylene and polyvinyl chloride the third-largest general-purpose plastics kind afterwards.But therefore the fatal shortcoming of polypropylene flexible (especially low-temperature flexibility) difference is paid attention to all the time to polyacrylic toughening modifying very much.Polypropylene toughness-increasing modified method commonly used mainly contains chemical modification such as copolymerization, crosslinked, grafting etc., and physically modified is as two big classes such as filling, blend.With respect to chemical modification, the modification handiness is big, the performance designability is strong, product easily forms advantages such as series, so the research of physically modified is more paid close attention to owing to having for physically modified.In the prior art, mostly be to add rubber or other elastomerics in polypropylene to polyacrylic blending toughening modification, wherein adopting maximum is to add terpolymer EP rubber.The comparatively sophisticated processing method of the blending toughening modification of polypropylene/terpolymer EP rubber is simple and mechanical blend, it drops into melt blending equipment simultaneously with polypropylene and terpolymer EP rubber, in single screw extrusion machine, twin screw extruder, open mill or closed plasticator, by the mechanical shearing effect, two kinds of polymkeric substance of polypropylene and terpolymer EP rubber are mutually disperseed under molten state and mixes, finally the terpolymer EP rubber dispersed phase distribution is in polypropylene external phase.The impelling strength of polypropylene/ethylene propylene diene monomer (EPDM) material that simple blend obtains increases, but because the terpolymer EP rubber molecular flexibility is very big and molecular chain is very long, in the blend process and in the blended product that is obtaining, molecule is usually curls the winding aggregating state, the blend shear-stress often can only make its lengthening deformation, diminishes and be difficult to it is broken.This just makes that terpolymer EP rubber phase particle size is relatively large in polypropylene/ethylene propylene diene monomer (EPDM) material, size distribution is inhomogeneous, thereby toughening effect performance is not obvious, even agglomerating particles can become a focal point of stress, damage that so on the contrary can accelerated material; Another important defective is because the long flexible chain molecule of terpolymer EP rubber easily twines mutually, causes the mobile variation of melt-processed of material.
We know that terpolymer EP rubber can make molecule be crosslinked state with some linking agent reaction, twines thereby avoid molecule to produce.Plastics with blend rubber the time by the acting in conjunction of chemical assistants such as linking agent and intensive mechanical shearing stress, make plastics and rubber in blend, be uniformly distributed in the rubber components concurrent biochemical crosslinking reaction (in Rubber processing be called " sulfuration ") of plastics in mutually, mechanical shearing stress makes the refinement of rubber grain particle diameter again, the rubber that finally makes crosslinked is distributed in the plastics external phase with the uniform particles of appropriate particle size, thisly melts physical blending and chemical crosslink reaction is commonly called " dynamic vulcanization " in the complicated modifying process of one.
" dynamic vulcanization " technology is applied to the preparation of blending thermoplastic elastomer already.In thermoplastic elastomer, the weight ratio of rubber and plastics is generally 100: (5～40)." dynamic vulcanization " technology is applied to the toughness reinforcing of plastics, particularly terpolymer EP rubber is to polyacrylic toughness reinforcing, still make slow progress up to now, this mainly is because cross-linking system can act on terpolymer EP rubber and the polypropylene in the individual system that exists together simultaneously, and polyacrylic amount is greatly more than terpolymer EP rubber, this just is difficult to guarantee that polypropylene is not crosslinked system and acts on, in case the external phase polypropylene is crosslinked or degrades, all with the mechanical property and the processing flowability of grievous injury tenacity-increased profax.Once having in the prior art " dynamic vulcanization " is applied to the trial of rubber to polypropylene toughening, is that 95117929 Chinese patent application has proposed a kind of modified poly propylene composition with high tenacity and high workability as application number.In this technical scheme, used a small amount of superoxide dicumyl peroxide etc., the existence of these superoxide has crosslinked action in blend, but because the amount that adds seldom, so this technical scheme is to polyacrylic toughening modifying and give that good mobility mainly still realizes by adding high tenacity copolymerization polypropylene and high workability Co-polypropylene in composition.
The preparation method who the purpose of this invention is to provide a kind of high-toughness and high-flowability modified polypropylene, it has solved " dynamic vulcanization " technology and has been applied in the preparation of polypropylene/elastomeric material, linking agent can act on rubber and this problem of polypropylene simultaneously, the product that obtains has very high impelling strength and higher processing fluidity, can embody good comprehensive performances.
The preparation method of high-toughness and high-flowability modified polypropylene provided by the invention comprises following process:
1) with particulate state polypropylene, particulate state terpolymer EP rubber, organo-peroxide linking agent and allyl ester class additional crosslinker thorough mixing in proportion, four weight ratio is:
Polypropylene: terpolymer EP rubber=100: (5～35);
Terpolymer EP rubber: organo-peroxide linking agent=100: (0.05～0.45);
Terpolymer EP rubber: allyl ester class additional crosslinker=100: (0.5～3.5);
Above-mentioned organo-peroxide linking agent is dicumyl peroxide or diisopropylbenzenehydroperoxide;
Above-mentioned allyl ester class additional crosslinker is Phthalic acid, diallyl ester or p-benzoqui(o)none dioxime.
The blended step is that the organo-peroxide linking agent is dissolved in earlier in the organic solvent, then solution and particulate state terpolymer EP rubber is mixed, treat organic solvent evaporation after, the particulate state terpolymer EP rubber mixes with polypropylene again.
2) mixture that obtains of step 1) adds twin screw extruder melt blending and extruding pelletization, the temperature of twin screw extruder and mouthful mould is controlled at 180 ℃～210 ℃, screw speed is 50～200 rev/mins, and the residence time of mixture in twin screw extruder was controlled at 30～240 seconds.
Above-mentioned organo-peroxide linking agent is dicumyl peroxide preferably; Additional crosslinker is Phthalic acid, diallyl ester preferably.
And the weight ratio of particulate state polypropylene, particulate state terpolymer EP rubber, organo-peroxide linking agent and allyl ester class additional crosslinker is preferably:
Polypropylene: terpolymer EP rubber=100: (10～30);
Terpolymer EP rubber: organo-peroxide linking agent=100: (0.10～0.25);
Terpolymer EP rubber: allyl ester class additional crosslinker=100: (0.1～2.5).
The organic solvent that is used to dissolve organic peroxide cross-linking agent can be toluene or dimethylbenzene.
In the present invention, the existence of additional crosslinker is very crucial, and it can reconnect the polypropylene chains free radical that has been initiated, degrades thereby suppress polypropylene.
The present invention comparatively successfully is applied to " dynamic vulcanization " technology in the preparation of polypropylene/elastomeric material, the product that makes not only has very significantly toughening effect, and has a good processing flowability, the plastic shaping working method that applicable injection molding, extrusion moulding etc. are commonly used.
To describe details of the present invention by embodiment below, in an embodiment, the product performance testing method that obtains is:
The socle girder notched Izod impact strength:
With polypropylene/terpolymer EP rubber pellet, be molded as the standard testing batten by screw-type injection machine, press the GB1843-80 regulation, the room temperature of test bars and low temperature (20 ℃) socle girder notched Izod impact strength.
Melt flow rate (MFR):
With polypropylene/terpolymer EP rubber pellet, press GB3682-83 regulation and measure melt flow rate (MFR) (MFR), W=2160g wherein, T=230 ℃.
Tensile strength:
With polypropylene/terpolymer EP rubber pellet, be molded as the standard testing batten by screw-type injection machine, press the GB1840-79 regulation, the tensile strength of test bars and elongation at break.
Embodiment 1～10:
Particulate state polypropylene, particulate state terpolymer EP rubber, organo-peroxide linking agent and the proportioning weighing in accordance with regulations of allyl ester class additional crosslinker.Earlier the organo-peroxide linking agent is dissolved in toluene or dimethylbenzene organic solvent (concentration is controlled at 5%～30%), pours above-mentioned solution into the particulate state terpolymer EP rubber again and stir, in ventilation plant, leave standstill to solvent and all volatilize.Polypropylene GRANULES, the terpolymer EP rubber particle that is mixed with the organo-peroxide linking agent and allyl ester class additional crosslinker are placed same container, mix, reach basic homodisperse degree.
Above-mentioned compound is put into the twin screw extruder hopper of running, along with compound progresses into extruder barrel, physical process and chemical process that i.e. generation is carried out simultaneously, the temperature controlling range of twin screw extruder and mouthful mould is 180 ℃～210 ℃, screw speed is 50～200 rev/mins, and is keeping under the screw rod rotating state constant temperature more than 30 minutes.Mix melt under the squeezing action of forcing machine, by being loaded on forcing machine forward mouth model hole, be shaped to the identical bar of shape of cross section by force, after air-cooled solidifying, be cut into particle, promptly get the modified polypropene product.
Raw material and consumption that each embodiment is detailed see Table 1, and the performance test data that obtains product sees Table 2.
Table 1.
| PP charging capacity (gram) | EPDM charging capacity (gram) | Linking agent | Dosage of crosslinking agent (gram) | Additional crosslinker | Additional crosslinker consumption (gram) | |
| Embodiment 1 | 2000 | 100 | DCP | 0.05 | DAP | 2.7 |
| Embodiment 2 | 2000 | 200 | DCP | 0.60 | GM | 1.0 |
| Embodiment 3 | 2000 | 300 | DCP | 1.05 | GM | 3.6 |
| Embodiment 4 | 2000 | 300 | Diisopropylbenzenehydroperoxide | 0.36 | DAP | 9.3 |
| Embodiment 5 | 2000 | 400 | DCP | 0.80 | DAP | 6.0 |
| Embodiment 6 | 2000 | 400 | Diisopropylbenzenehydroperoxide | 0.60 | GM | 8.0 |
| Embodiment 7 | 2000 | 500 | DCP | 0.20 | DAP | 14.0 |
| Embodiment 8 | 2000 | 500 | Diisopropylbenzenehydroperoxide | 1.35 | GM | 17.5 |
| Embodiment 9 | 2000 | 600 | DCP | 1.08 | DAP | 13.2 |
| Embodiment 10 | 2000 | 700 | DCP | 3.15 | GM | 17.5 |
Annotate: the PP=polypropylene; The EPDM=terpolymer EP rubber;
The DCP=dicumyl peroxide; The DAP=Phthalic acid, diallyl ester;
The GM=p-benzoqui(o)none dioxime.
Table 2.
| Socle girder notched Izod impact strength (J/m) | Melt flow rate (MFR) (g/10min) | Tensile strength (MPa) | Elongation at break (%) | ||
| Room temperature | -20℃ | ||||
| Embodiment 1 | 129 | 53.6 | 3.90 | 35.9 | 110 |
| Embodiment 2 | 202 | 44.8 | 4.32 | 34.1 | 330 |
| Embodiment 3 | 275 | 59.4 | 4.78 | 31.8 | 425 |
| Embodiment 4 | 270 | 60.0 | 4.77 | 32.0 | 405 |
| Embodiment 5 | 370 | 82.1 | 4.92 | 26.1 | ＞580 |
| Embodiment 6 | 363 | 81.3 | 4.90 | 26.0 | ＞580 |
| Embodiment 7 | 520 | 114.2 | 4.97 | 23.0 | ＞580 |
| Embodiment 8 | 531 | 118.9 | 4.99 | 23.2 | ＞580 |
| Embodiment 9 | ＞600 | 169.0 | 4.41 | 20.5 | ＞580 |
| Embodiment 10 | ＞600 | 245.0 | 3.97 | 18.9 | ＞580 |
Claims (5)
1, a kind of preparation method of high-toughness and high-flowability modified polypropylene comprises following process:
1) with particulate state polypropylene, particulate state terpolymer EP rubber, organo-peroxide linking agent and allyl ester class additional crosslinker thorough mixing in proportion, four weight ratio is:
Polypropylene: terpolymer EP rubber=100: (5～35);
Terpolymer EP rubber: organo-peroxide linking agent=100: (0.05～0.45);
Terpolymer EP rubber: additional crosslinker=100: (0.5～3.5);
Above-mentioned organo-peroxide linking agent is dicumyl peroxide or diisopropylbenzenehydroperoxide, and allyl ester class additional crosslinker is Phthalic acid, diallyl ester or p-benzoqui(o)none dioxime,
The blended step is that the organo-peroxide linking agent is dissolved in earlier in the organic solvent, then solution and particulate state terpolymer EP rubber is mixed, treat organic solvent volatilization after, the particulate state terpolymer EP rubber mixes with polypropylene again,
2) mixture that obtains of step 1) adds twin screw extruder melt blending and extruding pelletization, the temperature of twin screw extruder and mouthful mould is controlled at 180 ℃～210 ℃, screw speed is 50～200 rev/mins, and the residence time of mixture in twin screw extruder was controlled at 30～240 seconds.
2, the preparation method of high-toughness and high-flowability modified polypropylene according to claim 1 is characterized in that described organo-peroxide linking agent is a dicumyl peroxide.
3, the preparation method of high-toughness and high-flowability modified polypropylene according to claim 1 is characterized in that described allyl ester class additional crosslinker is a Phthalic acid, diallyl ester.
4, the preparation method of high-toughness and high-flowability modified polypropylene according to claim 1, it is characterized in that in the described step 1) that the weight ratio of particulate state polypropylene, particulate state terpolymer EP rubber, organo-peroxide linking agent and allyl ester class additional crosslinker is:
Polypropylene: terpolymer EP rubber=100: (10～30);
Terpolymer EP rubber: organo-peroxide linking agent=100: (0.10～0.25);
Terpolymer EP rubber: allyl ester class additional crosslinker=100: (0.1～2.5).
5, the preparation method of high-toughness and high-flowability modified polypropylene according to claim 1 is characterized in that the described organic solvent that is used to dissolve organic peroxide cross-linking agent is toluene or dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011129808A CN1171936C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011129808A CN1171936C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388166A CN1388166A (en) | 2003-01-01 |
| CN1171936C true CN1171936C (en) | 2004-10-20 |
Family
ID=4659725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011129808A Expired - Fee Related CN1171936C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1171936C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603523A (en) * | 2012-03-23 | 2012-07-25 | 苏州大学 | Preparation method of allyl esters |
| CN107383583B (en) * | 2017-09-15 | 2020-10-13 | 广州市合诚化学有限公司 | Outer cover material with high rigidity and low opening force, and preparation method and application thereof |
| CN109608754B (en) * | 2018-12-25 | 2022-05-17 | 山东东宏管业股份有限公司 | Special material for high-wear-resistance polyolefin pipeline and preparation method thereof |
-
2001
- 2001-05-24 CN CNB011129808A patent/CN1171936C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1388166A (en) | 2003-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2467418B1 (en) | Process of producing thermoplastic starch/polymer blends | |
| US20080206503A1 (en) | Solid concentrate composition for polymeric chain extension | |
| CN1155652C (en) | Toughened plastics and its preparing process | |
| CN1159372C (en) | Prepn of high-toughness and high-flowability modified polypropylene agglomerate | |
| CN1171936C (en) | Prepn of high-toughness and high-flowability modified polypropylene | |
| CN109679332A (en) | Flexible PA6 of a kind of low temperature resistant HI high impact height and preparation method thereof | |
| CN1227285C (en) | Method for preparing thermoplastic cross-linked rubber | |
| CN114276641A (en) | In-situ compatibilization and chain extension based regenerated HIPS/PP alloy material and preparation method thereof | |
| CN113024737A (en) | Method for compatibilization of polypropylene/polyethylene blend | |
| CN1218998C (en) | Polyethanediol terephthalate composition and its preparation method | |
| CN1137933C (en) | High-rigidity high-toughness plastics and its preparing process | |
| CN101067014A (en) | Process of grafting maleic anhydride with vinyl methacrylate | |
| US6921792B2 (en) | Chemically modified polyolefin elastomer composition and method for preparing the same | |
| EP0841149A2 (en) | Method for manufacturing articles from a polymer blend | |
| CN1180012C (en) | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method | |
| DE69706866T2 (en) | MASTERBATCHES CONTAINING VOLCANIZING AGENTS | |
| CN1229437C (en) | Polybutanediol terephthalate composition and its preparation method | |
| CN1927904A (en) | Fusion graft process for modified polypropylene/acrylic acid polyester ether | |
| CN1253507C (en) | Method of preparing poly thylene terephthalate polyamide-6 blend | |
| CN1480489A (en) | Toughening polyamide combination and prepn method | |
| CN1381520A (en) | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process | |
| CN1412229A (en) | Composite powder rubber, its preparation method and application | |
| CN1254504C (en) | Nano-particle modified small bulk polypropylene material and its preparation method | |
| CN1112406C (en) | High-toughness polyamide and its preparing process | |
| Pesneau et al. | PP/EMA TPV: Dynamic cross‐linking through an alcoholysis reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20041020 Termination date: 20180524 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |