CN102329405B - Preparation method of continuous high-melt-strength polypropylene based on grafting reaction - Google Patents
Preparation method of continuous high-melt-strength polypropylene based on grafting reaction Download PDFInfo
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- CN102329405B CN102329405B CN201110170503.XA CN201110170503A CN102329405B CN 102329405 B CN102329405 B CN 102329405B CN 201110170503 A CN201110170503 A CN 201110170503A CN 102329405 B CN102329405 B CN 102329405B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/922—Viscosity; Melt flow index [MFI]; Molecular weight
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92266—Mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92695—Viscosity; Melt flow index [MFI]; Molecular weight
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92761—Mechanical properties
Abstract
The invention relates to a preparation method of a continuous high-melt-strength polypropylene based on a grafting reaction. The continuous high-melt-strength polypropylene comprises the following components: 100 parts by weight of polypropylene, 0.01-1 part by weight of initiator, 0.1-5 parts by weight of a first grafting monomer and 0.1-5 parts by weight of a second grafting monomer. The first grafting monomer is a vinyl silicone oil compound, and the second grafting monomer is a C5-C10 monoolefin or polyene compound. The preparation method comprises the following steps: weighing the polypropylene, the initiator, the first grafting monomer and the second grafting monomer, adequately mixing the mixture, and then, adding the mixture to a twin-screw extruder, milling, extruding and granulating the mixture at 140-250 DEG C. The invention provides a method for preparing the high-melt-strength polypropylene which has no gelatin, has favorable color and luster and contains a long branch chain through a one-step silane method which has a simple process, flexibility in operation and an industrial implementation foreground, and a high-melt-strength polypropylene material obtained by the preparation method is applicable to the application fields of foaming, thermal forming, film blow molding, extrusion coating and the like.
Description
[technical field]
The present invention relates to polypropylene technology field, specifically, is a kind of preparation method of the continuous high-melt-strength polypropylene based on graft reaction.
[background technology]
Polypropylene (PP) is most widely used general in the world at present, one of resin that increase of production is the fastest.But by the general goods PP of Ziegler-Natta and metallocene catalyst catalytic production, be linear structure, cause the shortcomings such as the low and Sag Resistance of its molecular weight distribution relative narrower, melt strength is poor, thereby greatly limited the application at aspects such as foaming, thermoforming, blowing, Extrusion Coatings.Therefore, improving PP melt strength is the important topic in PP new product development.
Improve at present PP melt strength and mainly contain three kinds of methods: (1) reactor modification method improves the relative molecular mass of PP, in resin polymerization process or the polymerization later stage carry out graft reaction, the directly synthetic polypropylene that contains long-chain branch, it is large that the method is prepared difficulty, and the countries such as investment is large, current Belgium have such technology; (2) carry out the relative molecular weight that non-reacted blending and modifying increases PP and distribute, as with the blend such as polyethylene and elastomerics, though this method has improved the melt strength of PP, its thermotolerance and readily degradable also significantly reduce; (3) post-reactor modification method is introduced long-chain branch, directly existing PP is carried out to controlled grafting or partial cross-linked by different methods, and this class methods less investment, production technique are relatively simple, can keep again the various performances of polypropylene itself simultaneously.
Existing many by PP grafting and the partial cross-linked method of preparing high melt strength, propylene at present, the method for mainly extruding by x ray irradiation x and reaction realizes.
Montell company x ray irradiation x legal system for aspect HMSPP in first place in the world, the up to the present HMSPP commodity of existing multiple Profax trades mark.Patent US5414027 and patent EU190889 have adopted high-energy ray irradiation method to make common high molecular weight linear polypropylene produce long chain branching, produce the high melt strength, propylene of higher weight average molecular mass and higher branch degree.
Although in industrial production, the method for electron radiation is commonplace at present, complex process and safeguard protection require higher, so people hanker after the method exploitation that adopts reaction to extrude.
Chinese patent (publication number CNl01125947A) has been announced by Graft Polypropylene (as polypropylene grafted maleic anhydride) and in screw extrusion press, has been reacted with the molecule of amino-contained or hydroxy functional group the method for preparing HMSPP, though this technique gel-free produces, but product color is poor, and cost is high.M.Kster (M.Kster and G. Hellmann.Macromolecular Materials and Engineering, 2001, 286 (12), 769-773) and Li, S (Li, S., et al.Polymer, 2009, 50 (25), 6121-6128) etc. also adopt reaction extrusion molding first to prepare PP-g-MAn and PP-g-GMA taking maleic anhydride (MAn) and glycidyl methacrylate (GMA) as grafted monomer respectively, afterwards by its with again prepare by extrusion reaction the HMSPP that contains long branched chain structure with amino polyfunctional group chainextender, though this method does not contain gel, but this method not only needs secondary high-temperature reaction extrusion to affect product performance, can make its colour changed into yellow of product due to amino existence simultaneously.
Nachtigall, S (Nachtigall, S., et al.Journal of Applied Polymer Science, 1999, 72 (10), 1313-1319) etc. and Wang, Z (Wang, Z., et al.Polymer International, 2005, 54 (2), 442-447) etc. employing vinylsiloxane is that grafted monomer is first prepared vinyl silanes graft polypropylene (PP-g-VTES) by reaction extrusion molding, afterwards PP-g-VTES poach is cross-linked to form to the high melt strength, propylene that contains long-chain branch and crosslinking structure, though this method only needs single step reaction to extrude, but need to pass through follow-up poach process, program complexity, very high to the thickness requirement of moulded products.Chinese patent (publication number is 1869119A) has disclosed the technology that a step silane thermal decomposition process is prepared partly cross-linked dystectic strength polypropylene, be pre-mixed by polypropylene, unsaturated silane and alcoholysis agent, organic modified sheet silicate, silicon alcohol condensation catalyst, organic peroxide evocating agent, grafting auxiliary agent, feed in screw extrusion press and melt extrude together again, thereby a step reaches the grafting of polypropylene and silane with crosslinked, although this method has been simplified the complicated technology of conventional silanes method, for polyacrylic degraded and the more difficult control of crosslinking degree.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of the continuous high-melt-strength polypropylene based on graft reaction is provided.
The object of the invention is to be achieved through the following technical solutions:
Based on a continuous high-melt-strength polypropylene for graft reaction, the parts by weight of its raw material composition are, polypropylene 100 weight parts, initiator 0.01～1 weight part, the first grafted monomer 0.1～5 weight part, and the second grafted monomer 0.1～5 weight part.
Described initiator is selected from peroxide, azo radical initiator or its combination; Be specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination;
The first described grafted monomer is selected from vinyl silicone oil, and vinyl silicone oil compounds is the linear polysiloxanes product that keeps liquid state under room temperature, and structural formula is as follows: in formula, R1～R5 is alkyl, aryl; R is alkyl, aryl, hydrogen, carbon functional group and polyether chain etc.; X is alkyl, aryl, alkenyl, amino, hydrogen, hydroxyl, alkoxyl group, acetoxyl group, chlorine, carbon functional group and polyether chain etc.; N, m=0,1,2,3 ..., wherein n value size is selected according to the contents of ethylene of requirement of experiment, and the vinyl mass percent of all types vinyl silicone oil is all 0.01～15wt%;
The second described grafted monomer is C5～C10 class monoolefine or Polyene Hydrocarbons compound, as vinylbenzene, norbornylene acid anhydrides, m-pentadiene, isoprene, cyclopentadiene, dicyclopentadiene, divinyl, 1,3-hexadiene, 2,4-hexadiene, 4-methyl isophthalic acid, 3 pentadienes, 1, one or more in 4-pentadiene, Isosorbide-5-Nitrae-hexadiene and Isosorbide-5-Nitrae-heptadiene, pungent ethene, the ninth of the ten Heavenly Stems ethene, last of the ten Heavenly stems ethene etc.
A kind of preparation method of the continuous high-melt-strength polypropylene based on graft reaction, polypropylene, initiator, the first grafted monomer, the second grafted monomer are dry mixed or evenly rear feeding twin screw extruder of solvent, controlling under the condition of temperature, screw speed and feed rate, carry out frit reaction and extrude also granulation, be prepared into high melt strength, propylene; Or polypropylene, initiator are dry mixed or solvent after add from spout, and the first grafted monomer and the second grafted monomer distribute from other opening for feed continuously feedings of forcing machine, carry out that frit reaction is extruded and granulation, prepare high melt strength, propylene;
Wherein, in the scope that the length-to-diameter ratio of described twin screw extruder is 15～100, rotating speed is 60～600rpm, and controllable temperature is between 50～400 DEG C.Forcing machine the second heating zone and the 4th heating zone are furnished with side direction liquid drawing-in device, and its liquid feeding can be as accurate as 1%.In addition, lean on the vacuum evacuating system of outlet position with condensate recycling device in forcing machine heating tail end section, can collect the small-molecule substance discharging in reaction extrusion, be convenient to material component analysis in reaction process.
The length-to-diameter ratio scope of described twin screw extruder is 32～50.
Each section of temperature of described forcing machine is controlled between 140～250 DEG C, and wherein the temperature of feed zone is lower than other temperature of each section.
Compared with prior art, positively effect of the present invention is:
The present invention is by controlling ratio, the residence time and the temperature of reaction of polypropylene, initiator, grafted monomer, and utilize polyacrylic degraded in the second grafted monomer control graft modification process, thereby obtain the well behaved high melt strength, propylene that contains long-chain branch gel-free.This product has all embodied its superiority in all many-sides such as color and luster, mechanical property and processing characteristicies, be applicable to the Application Areass such as foaming, thermoforming, film blowing and Extrusion Coating, and preparation method is simple, processing ease, be convenient to control, there is the prospect of industrializing implementation, be easy to apply.
[embodiment]
The preparation method's of a kind of continuous high-melt-strength polypropylene based on graft reaction of the present invention embodiment is below provided.
Embodiment 1
Starting material component (by weight): 100 parts of homo-polypropylene, Jiujiang petro-chemical corporation produces, trade mark T30S; Initiator is 0.8 part of benzoyl peroxide; The first grafted monomer is 2 parts of substituted hydroxy vinyl silicone oils; The second grafted monomer is 2 parts of cyclopentadiene;
Twin screw extruder structure and function: the forcing machine adopting is extruding machine with two screw rods engaging in the same way, and screw diameter is 30mm, and length-to-diameter ratio is 40, adopts seven sections of heated for controlling temperatures, carry out vacuum exhaust the 6th section of forcing machine.
The preparation of high melt strength, propylene: above-mentioned all components is mixed with high-speed mixer, then add and react extruding pelletization in twin screw extruder and make product of the present invention.Control screw speed is 150rpm, and each section of Heating temperature of forcing machine is: 165 DEG C, and 170 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 200 DEG C, 200 DEG C.
Embodiment 2
Starting material component (by weight): 100 parts of homo-polypropylene, Jiujiang petro-chemical corporation produces, trade mark T30S; Initiator is 0.5 part of dicumyl peroxide; The first grafted monomer is 0.5 part of substituted-phenyl vinyl silicone oil; The second grafted monomer is 0.5 part of norbornene dicarboxylic anhydride;
Its operation steps and implementation method are all with embodiment 1.
Embodiment 3
Starting material component (by weight): 100 parts of homo-polypropylene, Jiujiang petro-chemical corporation produces, trade mark T30S; Initiator is 0.5 part of 0.5 part of di-t-butyl peroxide and azo isobutyronitrile; 1 part of the first 1 part of grafted monomer substituted-phenyl vinyl silicone oil and substituted hydroxy vinyl silicone oil; The second grafted monomer is 0.1 part of 0.5 part of oleic acid and vinylbenzene;
Its operation steps and implementation method are all with embodiment 1.
Comparative example 1
Feed composition only contains 100 parts of homo-polypropylene, and preparation process is identical with embodiment 1.
Comparative example 2
Except not containing component the first grafted monomer, other component is identical with embodiment 1 with preparation process.
Comparative example 3
Except not containing component the second grafted monomer, other component is identical with embodiment 1 with preparation process.
Comparative example 4
Except not containing component initiator, other component is identical with embodiment 1 with preparation process.
The material property being obtained by each embodiment is in table 1.
The performance of high melt strength, propylene prepared by table 1 embodiment
In the data of table 1, melt strength is measured with Rhedtens71.97 (Germany, Gottfert) melt strength tester, and roller rotation acceleration is 6mm/s
2; While measuring Tc, adopt the temperature rate of 20 DEG C/min; MFI and individual character mechanical property are measured according to the respective standard of ASTM.Profax-814 sample in table 1 is the high melt strength, propylene product of Basell company.No matter visible, to obtain with the inventive method high melt strength, propylene, be melt strength or mechanical property, all suitable with the performance of the like product of Basell company.
The present invention overcomes the shortcoming existing in prior art, provide that a kind of technique is simple, flexible operation, the step silane thermal decomposition process with industrializing implementation prospect are prepared gel-free, good colour, containing the method for the high melt strength, propylene of long-chain branch.The high melt strength polypropylene material that the present invention obtains is applicable to the Application Areass such as foaming, thermoforming, film blowing and Extrusion Coating.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (7)
1. the continuous high-melt-strength polypropylene based on graft reaction, is characterized in that, the parts by weight of raw material composition are, polypropylene 100 weight parts, initiator 0.01～1 weight part, the first grafted monomer 0.1～5 weight part, and the second grafted monomer 0.1～5 weight part;
The first grafted monomer is selected from vinyl silicone oil;
The second grafted monomer is cyclopentadiene, norbornene dicarboxylic anhydride, oleic acid and vinylbenzene.
2. a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 1, is characterized in that, described initiator is specially BP, dicumyl peroxide, di-t-butyl peroxide, Diisopropyl azodicarboxylate or its combination.
3. a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 1, it is characterized in that, described vinyl silicone oil compound is the linear polysiloxanes product that keeps liquid state under room temperature, and structural formula is as follows: in formula, R1～R5 is alkyl, aryl; R is alkyl, aryl, hydrogen and polyether chain; X is alkyl, aryl, alkenyl, amino, hydrogen, hydroxyl, alkoxyl group, acetoxyl group, chlorine, carbon functional group and polyether chain; N=0,1,2,3..., wherein n value size is selected according to the contents of ethylene of requirement of experiment, and the vinyl mass content of all types vinyl silicone oil is all 0.01～15wt%;
4. the preparation method of a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 1, it is characterized in that, polypropylene, initiator, the first grafted monomer, the second grafted monomer are dry mixed or evenly rear feeding twin screw extruder of solvent, controlling under the condition of temperature, screw speed and feed rate, carry out frit reaction and extrude also granulation, be prepared into high melt strength, propylene; Or polypropylene, initiator are dry mixed or solvent after add from spout, and the first grafted monomer and the second grafted monomer be respectively from other opening for feed continuously feedings of forcing machine, carries out that frit reaction is extruded and granulation, prepares high melt strength, propylene.
5. the preparation method of a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 4, it is characterized in that, the length-to-diameter ratio of described twin screw extruder is that in 15～100 scope, rotating speed is 60～600rpm, and controllable temperature is between 50～400 DEG C.
6. the preparation method of a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 4, is characterized in that, the length-to-diameter ratio scope of described twin screw extruder is 32～50.
7. the preparation method of a kind of continuous high-melt-strength polypropylene based on graft reaction as claimed in claim 4, it is characterized in that, each section of temperature of described forcing machine is controlled between 140～250 DEG C, and wherein the temperature of feed zone is lower than other temperature of each section.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110170503.XA CN102329405B (en) | 2011-06-22 | 2011-06-22 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
| PCT/CN2012/075794 WO2012174965A1 (en) | 2011-06-22 | 2012-05-21 | Method for preparing long chain branched polypropylene based on multi-copolymerization grafting reaction |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110170503.XA CN102329405B (en) | 2011-06-22 | 2011-06-22 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
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| CN102329405B true CN102329405B (en) | 2014-07-09 |
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| WO (1) | WO2012174965A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021262777A1 (en) * | 2020-06-24 | 2021-12-30 | Dow Global Technologies Llc | Compositions made from crosslinkable olefin/silane interpolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329405B (en) * | 2011-06-22 | 2014-07-09 | 华东理工大学 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
| CN102408521A (en) * | 2011-09-15 | 2012-04-11 | 中国石油化工股份有限公司 | High melt strength polypropylene and preparation process |
| CN102603983B (en) * | 2012-03-23 | 2013-09-18 | 陕西省轻工业研究设计院 | Method for preparing polypropylene with high-melt-strength by modifying T30s through acetone solvent method |
| CN103483687A (en) * | 2013-10-12 | 2014-01-01 | 大庆工大用军科技开发有限公司 | High-strength polypropylene resin and preparation method thereof |
| US10059037B2 (en) * | 2014-09-23 | 2018-08-28 | Dart Container Corporation | Insulated container and methods of making and assembling |
| CN105801757A (en) * | 2016-03-24 | 2016-07-27 | 中国石油化工股份有限公司 | Long-chain-branch high-melt-strength polypropylene resin and preparation method thereof |
| CN107118719A (en) * | 2017-06-01 | 2017-09-01 | 安徽国登管业科技有限公司 | A kind of line plastic-steel tube special bonding resin and preparation method thereof |
| CN108329440B (en) * | 2018-01-24 | 2020-08-25 | 中国科学院长春应用化学研究所 | Low drug adsorption TPS and preparation method and application thereof |
| CN108822468B (en) * | 2018-05-24 | 2020-11-24 | 万华化学集团股份有限公司 | High melt strength grafted polypropylene prepared step by step and preparation method and application thereof |
| CN109535325B (en) * | 2018-10-15 | 2021-07-20 | 宁波工程学院 | Method for preparing norbornene grafted polypropylene by solution method |
| CN110804135B (en) * | 2019-11-22 | 2022-03-08 | 陕西煤业化工技术研究院有限责任公司 | High-melt-strength polypropylene and preparation method thereof |
| CN111978472A (en) * | 2020-08-27 | 2020-11-24 | 哈尔滨理工大学 | Preparation method of silane grafted modified polypropylene by melting method |
| CN114316146A (en) * | 2020-10-12 | 2022-04-12 | 杨建强 | Organosilicon modified polypropylene compound, preparation method and application in melt-blown material |
| CN112321981A (en) * | 2020-10-28 | 2021-02-05 | 施仕全 | Preparation process of polypropylene material |
| CN113024737A (en) * | 2021-04-07 | 2021-06-25 | 贵州大学 | Method for compatibilization of polypropylene/polyethylene blend |
| CN113136147A (en) * | 2021-05-07 | 2021-07-20 | 浙江祥邦科技股份有限公司 | Cut-off thermoplastic POE (polyolefin elastomer) packaging adhesive film for flexible component and preparation method thereof |
| CN114181454B (en) * | 2021-11-26 | 2023-06-02 | 中科检测技术服务(重庆)有限公司 | High-strength polypropylene material and preparation method thereof |
| CN115232393A (en) * | 2022-07-09 | 2022-10-25 | 苏州净涵新材料科技有限公司 | Gamma ray irradiation resistant polypropylene material and preparation method thereof |
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| CN1456430A (en) * | 2002-05-10 | 2003-11-19 | 王雅珍 | Promoting agent for graft copolymerization of polypropylene with maleic anhydride |
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| CN101418064B (en) * | 2008-12-02 | 2010-09-15 | 华东理工大学 | Method for preparing long-chain branch high fused mass strength polypropylene resin |
| CN101768242B (en) * | 2010-02-10 | 2011-08-31 | 中国科学院长春应用化学研究所 | Method for preparing polypropylene melt with high melt strength |
| CN102329405B (en) * | 2011-06-22 | 2014-07-09 | 华东理工大学 | Preparation method of continuous high-melt-strength polypropylene based on grafting reaction |
| CN102408521A (en) * | 2011-09-15 | 2012-04-11 | 中国石油化工股份有限公司 | High melt strength polypropylene and preparation process |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021262777A1 (en) * | 2020-06-24 | 2021-12-30 | Dow Global Technologies Llc | Compositions made from crosslinkable olefin/silane interpolymer |
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| WO2012174965A1 (en) | 2012-12-27 |
| CN102329405A (en) | 2012-01-25 |
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