CN101812165A - Polypropylene with high melt strength and preparation method thereof - Google Patents
Polypropylene with high melt strength and preparation method thereof Download PDFInfo
- Publication number
- CN101812165A CN101812165A CN201010147765A CN201010147765A CN101812165A CN 101812165 A CN101812165 A CN 101812165A CN 201010147765 A CN201010147765 A CN 201010147765A CN 201010147765 A CN201010147765 A CN 201010147765A CN 101812165 A CN101812165 A CN 101812165A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- melt strength
- peroxide
- propylene
- high melt
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a polypropylene with high melt strength, which contains a long branched chain structure, and a preparation method thereof. In the method, Ziegler-Natta catalyst is firstly used for synthesizing a reactive polypropylene intermediate the side chain of which contains styrene groups, then the intermediate is added into a free base reaction system, the polypropylene with high melt strength, which has clear structure and adjustable branching content, is prepared by the reactivity of double bond of styrene via reactive extrusion, and the polypropylene with high melt strength, which has different performance, can be prepared by adjusting the dosage of the reactive polypropylene intermediate. The polypropylene has unique tensile property and excellent heat resistance, thereby having wide application prospects and practical value, can be widely used in the fields of extrusion foaming, thermoforming, extrusion coating, film blowing and the like, especially shows large market and application prospects in the aspect of producing foam materials, and has broad development and utilization prospects.
Description
Technical field:
The present invention relates to a kind of method of extruding with reaction by the polypropylene preparation of linear structure contain high melt strength polypropylene material of long branched chain structure and preparation method thereof, belong to the plastics technology field.
Background technology:
Though polypropylene is fastest-rising a kind of in the thermoplastic resin, but after entering 21 century, the phenomenon of whole world polypropylene overcapacity will appear gradually, cruel market competition will be inevitable, this changes a lot with regard to the product structure that forces global polypropylene manufacturing enterprise, and to variation, functionalization development.Unique tensile property and excellent heat resisting that high melt strength, propylene had, it is had broad application prospects and practical value, can be widely used in fields such as extrusion foaming, thermoforming, extrusion coated and blown film, especially demonstrating huge market and application prospect aspect the production polypropylene foam, have and progressively replace traditional PS, ABS, to the trend of engineering plastics development, exploitation prospect is wide
Polyacrylic in the prior art foaming is compared very difficulty with polystyrene with polyethylene, its major cause is that the molecular chain of general purpose polypropylene is a linear structure, after temperature rises to its melt temperature, its melt elasticity sharply descends, and under molten state, the polypropylene of linear structure does not have strain hardening effect, lower melt strength can't guarantee the effect of the tensile stress that cell wall is born in the bubble propagation process, cause bubble generation to subside and break, this makes that the process window of polypropylene extrusion foaming is very narrow, the temperature that is suitable for the general purpose polypropylene foaming to such an extent as to the percentage of open area of polypropylene foam is very high, can't satisfy service requirements only for 4-6 ℃.Therefore the polypropylene that will produce extrusion foaming at first needs high melt strength polypropylene material.
In theory, improving polyacrylic melt strength can be by increasing molecular weight, broadening molecular weight distribution or introducing long branched chain structure and realize.The technology of preparation high melt strength, propylene mainly contains radiation (superoxide) grafting, chemically crosslinked and blending and modifying etc.
Cover your company of Mount Tai in Chinese invention patent ZL94116148, introduced activity keto concentration less than 15% environment in, with energetic ray homopolymerization and Co-polypropylene or its composition are carried out 1 hour radiation, thereby and then make radiating free radical inactivation obtain the method for the high melt strength, propylene of branching.The special company of amaurosis in Chinese invention patent CN86100791, CN1105033, CN1045107 and Basel company similar method is disclosed respectively in Chinese invention patent CN1313879.It is said that the high melt strength, propylene that in this way obtains does not contain gel, melt elasticity is high also a tangible strain hardening effect, thereby in foaming and extrude occasion such as coating and have wide practical use.Thereby the main drawback of method for radio-grafting is to produce the required very big high melt strength, propylene that causes preparing of facility investment of energetic ray to cost an arm and a leg, and this has limited its widespread use; Moreover because the unreactiveness of polypropylene itself, ray radiation method is lower to MODIFICATION OF POLYPROPYLENE efficient, the structure of products therefrom is more complicated also, free radical on the polypropylene chains is very easy to take place β-division and crosslinking reaction each other under x ray irradiation x simultaneously, and these factors are all unfavorable to improving polyacrylic melt strength.
Chinese invention patent CN1693330 has introduced thereby double bond containing long chain molecules such as unsaturated polyester have been grafted to the method that forms branched structure on the polypropylene molecular chain by initiator, the amount that the weakness of this method is the long chain molecule that needs is big (content is more than 5%), has influenced the mechanical property of material.
Chinese invention patent CN1869119 provides a kind of preparation method of partial cross-linked high melt strength, propylene, it is that hydrolysis by silane links together different polypropylene molecular chain, polyacrylic melt strength after crosslinked is significantly improved, the major defect of this method is gel content up to more than 20%, and this is for the continuous extrusion foaming of material and reclaim to reuse and to have brought very big difficulty.Chinese invention patent CN1775851 provides and maleic anhydride (ester) or acrylic ester grafted polypropylene are cross-linked into reticulated structure by the small molecules organic amine improve polyacrylic melt strength, used the graft polypropylene of high molten finger in this method in a large number, this makes the melt strength by the formed material of this method be subjected to significant limitation.
Chinese invention patent CN1594412 provides by polypropylene, compatilizer and clay blend being improved the method for melt strength, in this method, the existence of compatilizer is absolutely necessary to the homodisperse of clay, but the melt strength of compatilizer itself is generally very low, and this has had a strong impact on the melt strength of formed material.
Different with radiation grafting, the superoxide initiation grafting generally is to extrude in twin screw extruder by reaction to carry out, and facility investment is lower, and is easy to continuous production, thereby is more paid close attention to.How the difficult point of this method is control degradation and side reaction such as crosslinked.
Wang Xiaochun (Journal of Applied PolymerScience, 1996, Vol.61,1395-1404) and D.Graebling (Journal ofApplied Polymer Science, 1996, Vol.66 809-819) has reported that respectively polypropylene and more function group monomer acrylate under superoxide causes, carry out the method that fusion-grafting prepares high melt strength, propylene by twin screw extruder.D.Graebling (Macromolecules, 2002, Vol.35 4602-4610) has further reported by introducing thiuram and can control the grafting process better, is not contained the high melt strength, propylene of gel.
In Chinese invention patent CN101434681 and CN101376683, disclose improvement, replaced the concentration of thiuram control free radical with dithiocar-bamate the D.Graebling method.Then the macromonomer with the band peroxy-radical replaces thiuram in Chinese invention patent CN101338010, has then introduced styrene monomer in Chinese invention patent CN101418064.
As described in Chinese invention patent CN1594412 and CN1869119, the introducing of nanoclay is useful for the raising of polypropylene system melt strength, but only just has this effect with the homodisperse clay of nanoscale in system.Simultaneously, the homodisperse of clay has important meaning for the bubble nucleating stage in the foaming process, it can be used as the nucleation that nucleator causes bubble, and have only homodisperse clay could make a large amount of bubbles grow up simultaneously, improve cell density and expansion ratio, homodisperse clay nano lamella can also play certain iris action to the escape of foamed gas in the air bubble growth process.In addition, well-known, nanoclay can improve the rigidity and the thermotolerance of polypropylene matrix, and this application to foaming product is very valuable.But as previously mentioned, the simple interpolation of clay can not form the homodisperse structure of nanoscale, is very disadvantageous and use compatilizer for the melt strength of system.The method of extruding with reaction is disclosed in Chinese invention patent ZL200710062451, when forming branched structure, make the clay homodisperse, obtained not containing substantially high melt strength polypropylene material gel, that have excellent physical mechanical property and foam performance.
A kind of method that obtains high bath strength acrylic resin with Ziegler-Natta catalyst catalysis non-conjugated dienes hydrocarbon is disclosed in Chinese invention patent CN101456927, the high melt strength, propylene of gained has the structure of long chain branching, and the shortcoming of this method is that the price of long-chain non-conjugated dienes hydrocarbon is higher.
China's disclosure of the Invention number discloses a kind of high melt strength, propylene and preparation method thereof in the patent of CN1955199, obtains the multipolymer of propylene and Vinylstyrene earlier, and pair keys are reacted, and obtains high melt strength, propylene.The shortcoming of this method is that this multipolymer costs an arm and a leg and generates crosslinking structure easily.
Summary of the invention:
Thereby goal of the invention is can prepare the expanded polypropylene material that high melt strength polypropylene material obtains containing tiny even abscess according to preparation method provided by the invention.
It is method in CN1955199 and the CN101456927 patent that the present invention has used for reference publication number, synthesized the reactive polypropylene intermediate that side chain contains styrene group earlier, it is joined in the free radical reaction system again, utilize the reactive behavior of the two keys of vinylbenzene, it is clear and definite to prepare structure by free radical reaction, the high melt strength, propylene of the long chain branched that branching content is adjustable.
The preparating mechanism of the inventive method is characterized as: the elementary free radical that decomposition of initiator produces reacts with styrene group earlier, generate comparatively stable vinylbenzene free radical (I), remaining elementary free radical can generate PP macromolecular radical (II) with PP molecule generation hydrogen abstraction reaction, and part PP macromolecular radical β-fracture can take place produces PP chain rupture free radical.Side chain contain the vinylbenzene free radical polypropylene molecule can with PP macromolecular radical and PP chain rupture free radical generation coupling reaction, generate the high melt strength, propylene contain long branched chain structure (III, IV).
A kind of high melt strength, propylene of the present invention and preparation method thereof, proportion of raw materials consists of: (A) polypropylene 100 weight parts, (B) reactive polypropylene intermediate 0.2-40 weight part, (C) initiator 0.004-0.4 weight part.
(A) polypropylene is melt flow index (230 ℃, the homopolymer of propylene 2.16kg) or ethylene content are not more than 40% propylene and the multipolymer of ethene or their mixture less than 10.
(B) the reactive polypropylene intermediate is that the copolymerization of Ziegler-Natta catalyst system catalyzing propone and Vinylstyrene is made.Ziegler-Natta catalyst system Primary Catalysts is titanium tetrachloride/diisobutyl phthalate/magnesium chloride or titanium tetrachloride/dibutyl phthalate/magnesium chloride, promotor is triethyl aluminum, trimethyl aluminium or triisobutyl aluminium, and external electron donor is a silicane.The polyreaction for preparing this reactive polypropylene intermediate is carried out in solvent, and used solvent is toluene, heptane, hexane or pentane.Styryl mass contg in the reactive polypropylene intermediate is 0.05～5%, when the styryl mass contg is lower than 0.05%, terminal free-radical contents by its generation is not enough to produce abundant long branched chain structure, and the content of wishing to get styrene group is higher than 5% reactive polypropylene intermediate, and then the Vinylstyrene that is added in polymerization process can make catalyst deactivation so that polymerization process stop.
Vinylstyrene is 1,4-Vinylstyrene or 1, the mixture of 3-Vinylstyrene or their arbitrary proportions.
(C) initiator comprises tertbutyl peroxide, 1,1,3,3 one tetramethyl-monobutyl hydrogen peroxide, cumyl hydroperoxide, p-Methylisopropylbenzene base hydrogen peroxide, di-isopropylbenzene hydroperoxide, 2,5 one dimethyl 1,5 one two hydroperoxy hexanes, the cyclic group ketone peroxide, methyl cyclic group ketone peroxide, 3,3,5 one trimethylammonium cyclic group ketone peroxides, ditertiary butyl peroxide, dicumyl peroxide, tert butyl isopropyl benzene peroxide, the peroxidation oxalic acid, peroxy dicarbonate, dipropyonyl peroxide, peroxidation two butyryl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, two (3,5,5 one trimethyl acetyls) superoxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, 2,5-dimethyl-2,5-di-t-butyl peroxy-3-is alkynes.
When the consumption of reactive polypropylene intermediate and initiator is lower than above-mentioned lower value, be not enough to produce abundant long branched chain structure, also just be not enough to improve the melt strength of material; When the consumption of initiator surpasses above-mentioned higher limit, can cause polyacrylic remarkable degraded, when the consumption of reactive polypropylene surpasses above-mentioned higher limit, then can produce tangible gel.Gel content is by hot gel-filtration test determination, and this polymer dissolution in 135 ℃ 1% xylene solution, and is filtered by 325 purpose copper mesh, and the ratio that calculate not by the polymkeric substance of copper mesh the oven dry back is gel content.
A kind of high melt strength, propylene of the present invention and preparation method thereof, prepare according to following step: polypropylene, reactive polypropylene intermediate and initiator are pre-mixed evenly, feed in the twin screw extruder then, under temperature, rotating speed and the feed rate condition of control, melt extrude and granulation, be prepared into high melt strength, propylene.
The length-to-diameter ratio of twin screw extruder is in the scope of 20-80, rotating speed is 30-500 rev/min, and controllable temperature is between 50-500 ℃, and the length-to-diameter ratio of forcing machine is preferably in the scope of 28-48, each section temperature preferably is controlled at 150-250 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
The present invention relates to advantage and positively effect that a kind of high melt strength, propylene and preparation method thereof is compared with prior art had, its advantage and positively effect are that the porous plastics that preparation in accordance with the present invention obtains has advantages such as density is little, specific tenacity is high, energy absorption capability is strong, sound isolating and heat insulating performance is good.In thermoplastic foamed polyolefine plastic, compare with polyethylene foamed with polystyrene foamed, expanded polypropylene has the advantage of a lot of uniquenesses: (1) polyacrylic modulus in flexure approximately is 1.52GPa, be higher than poly about 200MPa far away, so the static load ability of polypropylene foam is better than polyethylene; (2) polyacrylic second-order transition temperature is lower than room temperature, and its pars amorpha at room temperature is in elastomeric state, and unbodied polystyrene (second-order transition temperature is 105 ℃) at room temperature is in vitreous state, so the impact property of polypropylene foam is better than polystyrene foam; (3) polystyrene foam takes place softening and distortion when using more than 105 ℃; Polyethylene is also seldom using more than 100 ℃, and the fusing point of polypropylene foam is than higher (165 ℃), and resistance to elevated temperatures is good.Can in hot environment, use; (4) polypropylene has very good chemical resistance energy, can match in excellence or beauty with polyethylene; (5) because the existence of pending methyl group, polypropylene is easy to degrade, and polypropylene foam is convenient to recycling, and its environment friendly is better than other foam materials.Just be based on above-mentioned advantage, expanded polypropylene material not only can substitute existing polystyrene and polyethylene, and especially has competitive power in the application of automotive industry and food packaging industry in the application of many industrial circles.
Figure of description:
Description of drawings:
I is the vinylbenzene free radical;
II is the PP macromolecular radical;
III is the polypropylene molecule that side chain contains the vinylbenzene free radical;
IV is a PP chain rupture free radical
The polypropylene T30S that the PP representative is used.
Fig. 1 is the preparating mechanism figure of high melt strength, propylene;
Fig. 2 is the nuclear magnetic spectrogram of reactive polypropylene intermediate;
Fig. 3 is the viscosity-shearing rate figure of product among the different embodiment;
Fig. 4 is the storage modulus-dynamic shearing frequency plot of product among the different embodiment;
In Fig. 3, Fig. 4, the viscosity under the low shear rate and the storage modulus under the low frequency all are the signs of melt strength, and the more big then melt strength of their value is more high. By Fig. 3 and Fig. 4 as seen, in polypropylene, only add initator (L0) or only add the decline that reactive polypropylene intermediate (L5) all causes melt strength, and three's blend melt strength after reaction is extruded is improved, and along with the increase melt strength of reactive polypropylene intermediate consumption improves, this is owing to formed long-chain branch in the reaction extrusion, its mechanism as shown in Figure 1, the consumption of reactive polypropylene intermediate is more many, then the quantity of branch point is more many, the long-chain branch amount that forms increases, and melt strength improves.
Specific embodiment:
Embodiment 1:
250 milliliters of there-necked flasks of exsiccant are vacuumized, lead to argon replaces three times, propylene displacement secondary.Oil bath is warming up to temperature of reaction, adds an amount of heptane, dimethoxy diphenyl silane, and 1, the promotor triethyl aluminum of 4-Vinylstyrene and aequum starts stirring, with the propylene pressure maintenance 1.03 * 10 of the magnetic valve hierarchy of control
5Pa adds the catalyzer of aequum subsequently, begins to carry out propylene polymerization.Close the propylene valve behind the 30min, ethanol solution hydrochloride termination reaction with 10%.With washing with alcohol, filtration, 60 ℃ of vacuum-dryings are to constant weight.
The starting material component: component (A) is 100 parts of homo-polypropylene, Daqing petrochemical company production, and the trade mark is T30S; Component (B) is the reactive polypropylene intermediate PP-co-DVB that 5 parts of above-mentioned reactions obtain; Component (C) is for being scattered in 0.1 part of 0.08 part of dicumyl peroxide in the acetone (commercially available).
Twin screw extruder structure and function: the forcing machine that is adopted is for rotating cord wood engagement type twin screw extruder in the same way, and screw diameter is 30mm, and length-to-diameter ratio is 40, and seven sections heating temperature controls are adopted in speed control by frequency variation.
The preparation of high melt strength, propylene: with high-speed mixer above-mentioned all components is mixed, in twin screw extruder, react extruding pelletization then and promptly make product of the present invention, be designated as L1.200 rev/mins of control forcing machine rotating speeds, each section temperature is controlled to be from the spout to the head: 160 ℃, 180 ℃, 190 ℃, 200 ℃, 205 ℃, 200 ℃, 185 ℃.
Comparative example 1 is not except that containing the B component, and other composition is identical with embodiment 1 with preparation process, and products obtained therefrom is designated as L0.
Embodiment 2:
Remove the umber of B component and change into 10 especially, other composition is identical with embodiment 1 with preparation process, and products obtained therefrom is designated as L2.
Comparative example 2 is not except that containing component C, and other composition is identical with embodiment 2 with preparation process, and products obtained therefrom is designated as L5.
Embodiment 3
Remove the umber of B component and change into 15 especially, other composition is identical with embodiment 1 with preparation process, and products obtained therefrom is designated as L3.
Embodiment 4
Remove the umber of B component and change into 20 especially, other composition is identical with embodiment 1 with preparation process, and products obtained therefrom is designated as L4.
Claims (14)
1. high melt strength, propylene and preparation method thereof, make by polypropylene, reactive polypropylene intermediate and initiator, it is characterized in that: the proportioning of raw material polypropylene and reactive polypropylene intermediate and initiator is 100: 0.2-40: 0.004-0.4, its preparation method is: polypropylene, reactive polypropylene intermediate and initiator are pre-mixed evenly, feed in the twin screw extruder then, under controlled temperature, rotating speed and feed rate condition, melt extrude and granulation, be prepared into high melt strength, propylene.
2. a kind of high melt strength, propylene according to claim 1 and preparation method thereof is characterized in that initiator is a tertbutyl peroxide, 1,1,3,3 one tetramethyl-monobutyl hydrogen peroxide, cumyl hydroperoxide, p-Methylisopropylbenzene base hydrogen peroxide, di-isopropylbenzene hydroperoxide, 2,5 one dimethyl 1,5 one two hydroperoxy hexanes, the cyclic group ketone peroxide, methyl cyclic group ketone peroxide, 3,3,5 one trimethylammonium cyclic group ketone peroxides, ditertiary butyl peroxide, dicumyl peroxide, tert butyl isopropyl benzene peroxide, the peroxidation oxalic acid, peroxy dicarbonate, dipropyonyl peroxide, peroxidation two butyryl, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, two (3,5,5 one trimethyl acetyls) superoxide, dibenzoyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, 2,5-dimethyl-2,5-di-t-butyl peroxy-3-hexin.
3. a kind of high melt strength, propylene according to claim 1 and preparation method thereof is characterized in that the reactive polypropylene intermediate is the multipolymer of propylene and Vinylstyrene.
4. a kind of high melt strength, propylene according to claim 1 and preparation method thereof is characterized in that polypropylene being melt flow index (230 ℃, the homopolymer of propylene 2.16kg) or ethylene content is not more than 40% propylene and the multipolymer of ethene or their mixture less than 10.
5. reactive polypropylene intermediate according to claim 3, the mass fraction that it is characterized in that described reactive polypropylene intermediate is 0.5-20, preferred 5-20.
6. initiator according to claim 2 is characterized in that described initiator mass fraction is 0.01-0.2, preferred 0.04-0.1.
7. reactive polypropylene intermediate according to claim 3 is characterized in that the copolymerization that described reactive polypropylene intermediate is Ziegler-Natta catalyst system catalyzing propone and Vinylstyrene makes.
8. a kind of high melt strength, propylene according to claim 1 and preparation method thereof, the length-to-diameter ratio that it is characterized in that described twin screw extruder is in the scope of 20-80, and rotating speed is 30-500 rev/min, and controllable temperature is between 50-500 ℃.
9. twin screw extruder according to claim 8 is characterized in that each section temperature of described twin screw extruder is controlled at 150-250 ℃, and wherein the temperature of feed zone is lower than the temperature of other each section.
10. reactive polypropylene intermediate according to claim 3 is characterized in that the styryl mass contg in the described reactive polypropylene intermediate is 0.05～5%.
11. according to claim 3 or 7 described reactive polypropylene intermediates, it is characterized in that: described Vinylstyrene is 1,4-Vinylstyrene or 1, the mixture of 3-Vinylstyrene or their arbitrary proportions.
12. Ziegler-Natta catalyst system according to claim 7, the Primary Catalysts that it is characterized in that described catalyzer is titanium tetrachloride/diisobutyl phthalate/magnesium chloride or titanium tetrachloride/dibutyl phthalate/magnesium chloride, promotor is triethyl aluminum, trimethyl aluminium or triisobutyl aluminium, and external electron donor is a silicane.
13. according to claim 3 or 5 or 7 or 10 described reactive polypropylene intermediates, it is characterized in that: the polyreaction for preparing this reactive polypropylene intermediate is carried out in solvent, used solvent is toluene, heptane, hexane or pentane.
14. twin screw extruder according to claim 8, the length-to-diameter ratio that it is characterized in that described twin screw extruder is in the scope of 28-48.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010147765A CN101812165A (en) | 2010-04-16 | 2010-04-16 | Polypropylene with high melt strength and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010147765A CN101812165A (en) | 2010-04-16 | 2010-04-16 | Polypropylene with high melt strength and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101812165A true CN101812165A (en) | 2010-08-25 |
Family
ID=42619540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010147765A Pending CN101812165A (en) | 2010-04-16 | 2010-04-16 | Polypropylene with high melt strength and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101812165A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317608A (en) * | 2015-06-25 | 2017-01-11 | 中国石油化工股份有限公司 | Composition used for preparing polypropylene foaming material and prepared foaming formed body |
| WO2017027101A1 (en) | 2015-08-13 | 2017-02-16 | Exxonmobil Chemical Patents Inc. | Multi-layered sheets comprising a high melt strength polypropylene |
| CN114292364A (en) * | 2021-12-21 | 2022-04-08 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
| CN115232401A (en) * | 2022-08-23 | 2022-10-25 | 江苏中科聚合新材料产业技术研究院有限公司 | High-temperature-resistant flame-retardant foaming polypropylene master batch and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0570533A (en) * | 1991-09-11 | 1993-03-23 | Kao Corp | Propylene/styrene block copolymer and its production |
| US20040215404A1 (en) * | 2001-06-15 | 2004-10-28 | Arriola Daniel J | Alpha-olefin based branched polymer |
| CN1693330A (en) * | 2004-05-08 | 2005-11-09 | 华东理工大学 | Branched polypropylene suitable for foaming and it preparation process |
| CN1955199A (en) * | 2005-10-24 | 2007-05-02 | 中国科学院化学研究所 | High melt strength polypropylene and its preparation method |
-
2010
- 2010-04-16 CN CN201010147765A patent/CN101812165A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0570533A (en) * | 1991-09-11 | 1993-03-23 | Kao Corp | Propylene/styrene block copolymer and its production |
| US20040215404A1 (en) * | 2001-06-15 | 2004-10-28 | Arriola Daniel J | Alpha-olefin based branched polymer |
| CN1693330A (en) * | 2004-05-08 | 2005-11-09 | 华东理工大学 | Branched polypropylene suitable for foaming and it preparation process |
| CN1955199A (en) * | 2005-10-24 | 2007-05-02 | 中国科学院化学研究所 | High melt strength polypropylene and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 《高分子材料科学与工程》 20070130 石金永等 高熔体强度聚丙烯的制备与应用进展 第28-31，36页 1-14 第23卷, 第1期 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317608A (en) * | 2015-06-25 | 2017-01-11 | 中国石油化工股份有限公司 | Composition used for preparing polypropylene foaming material and prepared foaming formed body |
| WO2017027101A1 (en) | 2015-08-13 | 2017-02-16 | Exxonmobil Chemical Patents Inc. | Multi-layered sheets comprising a high melt strength polypropylene |
| CN114292364A (en) * | 2021-12-21 | 2022-04-08 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
| CN114292364B (en) * | 2021-12-21 | 2022-12-02 | 日丰企业集团有限公司 | Silane grafted polypropylene, crosslinked polypropylene material and preparation method thereof |
| CN115232401A (en) * | 2022-08-23 | 2022-10-25 | 江苏中科聚合新材料产业技术研究院有限公司 | High-temperature-resistant flame-retardant foaming polypropylene master batch and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100535047C (en) | Polypropylene material with high bath strength and preparation method | |
| KR101559638B1 (en) | A process for preparing high melt strength propylene polymers | |
| CN102264828B (en) | Polypropylene resin compositions having high melt strength and method for preparing same | |
| CN101376683B (en) | Preparation of high melt strength polypropylene | |
| US8921466B2 (en) | Concurrent solid and melt state grafting of coagents for making long chain branched polypropylene via direct reactive extrusion process | |
| CN1537875A (en) | Polyolefins and process for production thereof | |
| CN108948522A (en) | A kind of preparation method of high fluidity punching proof acrylic material | |
| CN1045107A (en) | Preparation method and application thereof with propene polymer of free-end long chain branching | |
| CN105504170B (en) | A kind of preparation method of high melt strength, propylene | |
| CN103756124A (en) | Polypropylene foaming material, production and preparation method of product | |
| CN109749235B (en) | Reversible micro-crosslinked high-melt-strength polypropylene and preparation method thereof | |
| CN101812165A (en) | Polypropylene with high melt strength and preparation method thereof | |
| CN105399902A (en) | High-melt-strength polypropylene and preparation method thereof | |
| CN110229372A (en) | Low molding energy consumption polypropylene foamed particles of one kind and preparation method thereof | |
| CN102408521A (en) | High melt strength polypropylene and preparation process | |
| CN104072880B (en) | The preparation method of a kind of TPO foam microspheres and application | |
| CN113402678B (en) | Method for preparing high-melt-strength polylactic resin through two-step reaction | |
| CN103497423A (en) | High melt strength polypropylene (PP) composition and preparation method thereof | |
| CN102504113B (en) | Long-branched polyethylene resin and preparation method thereof | |
| CN101418064B (en) | Method for preparing long-chain branch high fused mass strength polypropylene resin | |
| CN105440216B (en) | A kind of high melt strength, propylene and preparation method thereof | |
| CN114806068B (en) | High-strength high-rigidity environment-friendly weather-resistant ABS resin and preparation method thereof | |
| CN101696254B (en) | Method for improving melt strength of polypropylene by using fullerene | |
| CN100448902C (en) | Acrylic resin with high bath strength, and preparation method | |
| CA3187879A1 (en) | Linear polar - nonpolar diblock copolymers and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100825 |