CN1159372C - Prepn of high-toughness and high-flowability modified polypropylene agglomerate - Google Patents
Prepn of high-toughness and high-flowability modified polypropylene agglomerate Download PDFInfo
- Publication number
- CN1159372C CN1159372C CNB011129794A CN01112979A CN1159372C CN 1159372 C CN1159372 C CN 1159372C CN B011129794 A CNB011129794 A CN B011129794A CN 01112979 A CN01112979 A CN 01112979A CN 1159372 C CN1159372 C CN 1159372C
- 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 mother granules. 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 100:70 to 130, 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 allyl ester auxiliary crosslinking agent is equal to 100:0.5 to 3.5; the mixture is added into a double-screw extruding machine, melted, extruded and granulated. The obtained mother granules can be conveniently mixed with a common polypropylene material, melted 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 agglomerate, 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 master batch that obtains can carry out the mixed melting granulation with the plain polypropylene material easily, the modified polypropene material that finally 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 agglomerate 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: (70～130);
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 and melt extrudes granulation, 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; Allyl ester class 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: (85～115);
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 allyl ester class additional crosslinker is very crucial, and it can reconnect the polypropylene chains free radical that has been initiated, produces crosslinked or degraded thereby suppress polypropylene.The present invention comparatively successfully is applied to " dynamic vulcanization " technology in the preparation of polypropylene/elastomeric material, finally the modified polypropene material that is made by master batch 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.
A kind of method for preparing high-toughness and high-flowability modified polypropylene by the master batch two-step approach that provides is provided in the present invention, the master batch that obtains should carry out the melt blending granulation by a certain percentage again with the plain polypropylene material, and its weight ratio is plain polypropylene/master batch=100/10～60.Had the plain polypropylene resource for itself, but do not wanted to increase the plastics production firm of modified polypropene feedstock production operation, this master batch two-step approach is a very attractive.
To describe details of the present invention by embodiment below, in an embodiment, the modified polypropene product performance testing method that finally 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 solvent is all volatilized.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, the physical process and the chemical process of carrying out simultaneously takes place promptly.The temperature controlling range of twin screw extruder and mouthful mould is 180 ℃～210 ℃, and 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 modified polypropene masterbatch product.
Raw material and consumption that each embodiment is detailed see Table 1, master batch that obtains and plain polypropylene be by weight: the melt blending granulation is carried out in plain polypropylene/master batch=100/10～60 in twin screw extruder, the temperature of twin screw extruder and mouthful mould is controlled at 180 ℃～210 ℃, screw speed is 50～150 rev/mins, and the performance test data that finally obtains the modified polypropene 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) | The PP/ masterbatch | |
| Embodiment 1 | 1000 | 700 | Diisopropylbenzenehydroperoxide | 2.45 | DAP | 7.7 | 100/55 |
| Embodiment 2 | 1000 | 800 | DCP | 0.40 | GM | 4.0 | 100/42 |
| Embodiment 3 | 1000 | 900 | Diisopropylbenzenehydroperoxide | 1.17 | GM | 28.8 | 100/32 |
| Embodiment 4 | 1000 | 900 | DCP | 2.61 | DAP | 23.4 | 100/10 |
| Embodiment 5 | 1000 | 1000 | DCP | 2.20 | DAP | 21.0 | 100/41 |
| Embodiment 6 | 1000 | 1000 | Diisopropylbenzenehydroperoxide | 2.70 | GM | 28.0 | 100/56 |
| Embodiment 7 | 1000 | 1100 | DCP | 4.40 | DAP | 26.4 | 100/17 |
| Embodiment 8 | 1000 | 1100 | Diisopropylbenzenehydroperoxide | 1.10 | GM | 16.5 | 100/60 |
| Embodiment 9 | 1000 | 1200 | Diisopropylbenzenehydroperoxide | 2.16 | DAP | 42.0 | 100/44 |
| Embodiment 10 | 1000 | 1300 | DCP | 5.85 | GM | 23.4 | 100/50 |
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.
| The socle girder notched Izod impact strength | Melt flow rate (MFR) (g/10min) | Tensile strength (MPa) | Elongation at break (%) | ||
| (J/m) room temperature | Low temperature | ||||
| Embodiment 1 | 340 | 73.6 | 4.18 | 30.2 | ＞580 |
| Embodiment 2 | 313 | 68.0 | 4.32 | 30.7 | ＞580 |
| Embodiment 3 | 295 | 62.4 | 4.38 | 31.8 | 425 |
| Embodiment 4 | 170 | 45.0 | 4.36 | 34.0 | 355 |
| Embodiment 5 | 330 | 75.3 | 4.22 | 29.2 | ＞580 |
| Embodiment 6 | ＞600 | 189.0 | 4.17 | 25.5 | ＞580 |
| Embodiment 7 | 220 | 54.2 | 4.47 | 33.0 | ＞390 |
| Embodiment 8 | ＞600 | 222.0 | 4.02 | 22.2 | ＞580 |
| Embodiment 9 | ＞520 | 202.0 | 4.10 | 24.0 | ＞580 |
| Embodiment 10 | ＞600 | 213.0 | 4.08 | 23.3 | ＞580 |
Claims (5)
1, a kind of preparation method of high-toughness and high-flowability modified polypropylene agglomerate 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: (70～130);
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 volatilization after, the particulate state terpolymer EP rubber mixes with polypropylene again,
2) mixture that obtains of step 1) adds twin screw extruder and melt extrudes granulation, 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 agglomerate 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 agglomerate 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 agglomerate 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: (85～115);
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 agglomerate 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 |
|---|---|---|---|
| CNB011129794A CN1159372C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene agglomerate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011129794A CN1159372C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene agglomerate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1388165A CN1388165A (en) | 2003-01-01 |
| CN1159372C true CN1159372C (en) | 2004-07-28 |
Family
ID=4659724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011129794A Expired - Fee Related CN1159372C (en) | 2001-05-24 | 2001-05-24 | Prepn of high-toughness and high-flowability modified polypropylene agglomerate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1159372C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671144B (en) * | 2008-09-09 | 2011-11-16 | 河南现代交通道路科技有限责任公司 | Rubber powder modified asphalt and preparation method thereof |
| CN102391577B (en) * | 2011-09-23 | 2013-08-28 | 余大双 | High-haze low-gloss extinction master batch for BOPP (biaxially-oriented polypropylene) film and production process thereof |
| CN103834110A (en) * | 2014-03-12 | 2014-06-04 | 南通加隆塑胶有限公司 | Toughening-type polypropylene master batch formula |
| CN106584700B (en) * | 2015-10-20 | 2020-01-07 | 中国石油化工集团公司 | Preparation method of solid organic peroxide master batch and application of roll-type granulator in preparation of solid organic peroxide master batch |
| CN105968581A (en) * | 2016-07-01 | 2016-09-28 | 湖北洋田塑料制品有限公司 | Thermoplastic elastomer for children's vehicles and preparation method of thermoplastic elastomer |
| CN113402872B (en) * | 2021-07-29 | 2022-07-15 | 公牛集团股份有限公司 | Spraying-free material with terrazzo effect and preparation method thereof |
-
2001
- 2001-05-24 CN CNB011129794A patent/CN1159372C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1388165A (en) | 2003-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2467418B1 (en) | Process of producing thermoplastic starch/polymer blends | |
| CN1522269A (en) | Modified postcondensed polyester | |
| US20080206503A1 (en) | Solid concentrate composition for polymeric chain extension | |
| CN107814996B (en) | Preparation method of crosslinkable polyethylene modified material | |
| CN1944497A (en) | Method for preparing thermoplastic vulcanized rubber by peroxide vulcanizing system | |
| CN112159564A (en) | Low-density and low-emission polypropylene material and preparation method thereof | |
| CN1159372C (en) | Prepn of high-toughness and high-flowability modified polypropylene agglomerate | |
| CN102504504A (en) | High-impact-resistance heat-resistant polylactic acid alloy material and preparation method thereof | |
| CN110358097B (en) | PLA-based compatibilizer with excellent performance and preparation method and application thereof | |
| 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 | |
| CN111138754A (en) | High-fluidity and high-rigidity alloy composite material and preparation method thereof | |
| CN111875952A (en) | TPU (thermoplastic polyurethane) grafted-OBC (on-board carbon) modified thermoplastic polyurethane elastomer foam material and preparation method thereof | |
| CN1137933C (en) | High-rigidity high-toughness plastics and its preparing process | |
| CN1513912A (en) | Polyethanediol terephthalate composition and its preparation method | |
| CN112724501B (en) | Toughened composite, PBT composite material and preparation method thereof | |
| EP0841149A2 (en) | Method for manufacturing articles from a polymer blend | |
| CN1261498C (en) | Method of preparing polystyrenel polyamide-6 nano blend | |
| CN1188469C (en) | Toughening polyamide combination and prepn method | |
| CN1164663C (en) | Thermoplastic full-sulfurized nitrile rubber/polypropylene elastomer and its preparing process | |
| CN1180012C (en) | Oil-resisting fully-vulcanized thermoplastic elastic body and its preparation method | |
| CN1009105B (en) | Polypropylene with high fluidity and toughness and the prodn. thereof | |
| CN1229437C (en) | Polybutanediol terephthalate composition and its preparation method | |
| CN1253507C (en) | Method of preparing poly thylene terephthalate polyamide-6 blend |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040728 Termination date: 20180524 |