CN107337801A - The method that electron irradiation crosslinking prepares high melt strength, propylene - Google Patents
The method that electron irradiation crosslinking prepares high melt strength, propylene Download PDFInfo
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- CN107337801A CN107337801A CN201710665015.3A CN201710665015A CN107337801A CN 107337801 A CN107337801 A CN 107337801A CN 201710665015 A CN201710665015 A CN 201710665015A CN 107337801 A CN107337801 A CN 107337801A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention provides a kind of method that electron irradiation crosslinking prepares high melt strength, propylene, it includes step：By proportioning polypropylene, crosslinking sensitizer and antioxidant, premix is obtained；Premix extruding pelletization, turn into polypropylene pellet to be irradiated；Simultaneously polypropylene pellet to be irradiated and polypropylene wax are heated, obtains the polypropylene pellet to be irradiated of polypropylene wax parcel；The polypropylene pellet to be irradiated of polypropylene wax parcel is cooled down, obtains the pretreated polypropylene pellet to be irradiated of core shell structure；Electron ray irradiates pretreated polypropylene pellet to be irradiated, obtains high melt strength, propylene pellet.The present invention can reduce polyacrylic degradation rate in irradiation process, improve polyacrylic melt strength and mechanical performance, improve machinability.
Description
Technical field
The present invention relates to polymer modification and manufacture field, and it is strong to prepare high melt more particularly to a kind of crosslinking of electron irradiation
Spend polyacrylic method.
Background technology
Polypropylene (PP) is because density is small, nontoxic odorless, high temperature resistant, corrosion-resistant, obtained foamed plastics, it may have good
Heat endurance, dimensional stability, higher mechanical strength, suitable and submissive surface, excellent microwave adaptability and can
Recycle property and by attention.But the industrial plain polypropylene largely produced is typically that the coordination polymerization that Z-N is catalyzed is anti-
Should be obtained, it is a kind of linear polymer, no long-chain branch, crystallinity is high, and narrow molecular weight distribution, fusing point connects very much with softening point
Closely, melting range is short, so that in process, it is before solid state not reach fusing point, hardly flows, reaches melt after fusing point
Intensity and viscosity decline to a great extent rapidly, so plain polypropylene is difficult to pin gas in foaming, gas escape, abscess easily occurs
Cave in, merge the phenomenon of even melt fracture, so, the melt strength for improving polypropylene material is production performance excellent PP foaming
The key technology of material.
High melt strength, propylene mainly has direct synthesis technique and cross-linking modified method at present.The core technology of direct synthesis technique
Also grasp in the hand of major company abroad, valuable product.Cross-linking modified method has chemical crosslinking, blending and cross-linking radiation, its
Middle chemical crosslinking, effect is undesirable, chemical contamination in production process be present, and the feature of environmental protection is poor；PP foams with LDPE mechanical blendings, effect
Fruit is obvious, but mechanical strength is not so good as virgin pp；Irradiation crosslinking, technique is simple, easily manipulation, but be crosslinked in irradiation process
Occur simultaneously with degraded, the infiltration of especially extraneous oxygen, the occurrence probability for the solution that more falls sharply, easily material is caused in itself to damage
Wound, reduce the usability and mechanical property of material.
The content of the invention
In view of problem present in background technology, is crosslinked it is an object of the invention to provide a kind of electron irradiation and prepares Gao Rong
The polyacrylic method of body, polypropylene wax parcel polypropylene granules, reduces oxygen infiltration capacity during irradiation, reduces polypropylene irradiation and hands over
Degradation rate during connection, melt strength is improved, while ensure polyacrylic machinability.
To reach above-mentioned purpose, the invention provides a kind of crosslinking of electron irradiation to prepare the polyacrylic method of high melt, wraps
Include following steps：
(1) by proportioning polypropylene, crosslinking sensitizer and antioxidant, premix is obtained；
(2) by the premix extruding pelletization in step (1), polypropylene pellet to be irradiated is turned into；
(3) polypropylene pellet to be irradiated and polypropylene wax in simultaneously blend step (2) are heated, obtains the poly- of polypropylene wax parcel
Propylene pellet to be irradiated；
(4) the polypropylene pellet to be irradiated of the polypropylene wax parcel in cooling step (3), obtains the pretreatment of core shell structure
The polypropylene pellet to be irradiated crossed；
(5) polypropylene pellet to be irradiated pretreated in electron ray irradiation steps (4) is used, obtains high fondant-strength
Polypropylene granules.
Optionally, the crosslinking sensitizer in step (1) is pentaerythritol triacrylate, 1,6- hexanediyls
Ester, trimethylolpropane trimethacrylate, neopentylglycol dimethacrylate, triallyl isocyanurate, acrylic acid are different pungent
Any one in ester, either any two kinds or two or more any combinations, preferably trimethylolpropane trimethacrylate.
Optionally, the antioxidant in step (1) is antioxidant 1010.
Optionally, the mass ratio of polypropylene, trimethylolpropane trimethacrylate and antioxidant 1010 is 100：1~5：
0.3~0.9.
Optionally, double screw extruder extruding pelletization is used in step (2).
Optionally, double screw extruder is engagement type, operating temperature in the same direction：One 150 ± 5 DEG C of area, two 155 ± 5 DEG C of areas, three
185 ± 5 DEG C of area, four 200 ± 5 DEG C of areas, five 210 ± 5 DEG C of areas, six 175 ± 5 DEG C of areas.
Optionally, the electron ray energy exposure dose in step (4) is 0.4~1.5KGy.
Optionally, mixed in step (1) using high-speed mixer, running parameter：20-60 DEG C of temperature, rotating speed 60-
300 revs/min.
Optionally, mixed in step (3) using high-speed mixer, running parameter：120-180 DEG C of temperature, rotating speed 500
~1000 revs/min.
It was found by the inventors of the present invention that, it is high to be implicitly present in synthesis in manufacture high melt strength, propylene in the prior art
The cost of Melt strength polypropylene is high, and technology controlling and process is difficult, and existing electron irradiation cross-linking method, and irradiation dose is big, and due to oxygen
The problem of air infiltration enters material internal and causes irradiation-induced degradation rate high.Therefore, the technical assignment or want that the present invention to be realized
The technical problem of solution be it is that those skilled in the art never expect or it is not expected that, therefore the present invention is a kind of new skill
Art scheme.
One of the present invention has technical effect that, polypropylene wax outer wrap polypropylene pellet to be irradiated, obstructs or reduces
Oxygen penetrates into inside, reduces the irradiation-induced degradation caused by oxygen content is too high, so as to improve the polyacrylic degree of cross linking, prepares
High melt strength, propylene, opposite outer do not wrap up the polypropylene of polypropylene wax, and gel content is high, and melt index improves, be molten
Body outlet diameter is big, high mechanical strength.
Another of the present invention has technical effect that polypropylene wax uniformly wraps up each PP GRANULES, is not influenceing to melt
In the case of body intensity, ensure the machinability of high melt strength, propylene.
High melt strength, propylene prepared by the present invention is applied to the neck such as extrusion foaming, thermoforming, inflation film and coating
Domain, the ceiling for preparing automobile that is particularly suitable for use in, door-plate, vehicle body outer bottom backplate and seat backup board etc..
By the way that to the detailed description of exemplary embodiment of the invention, further feature of the invention and its advantage will below
It is made apparent from.
Embodiment
To enable the above-mentioned purpose of invention, feature and advantage more obvious understandable, below to the specific implementation of the present invention
Mode is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
It is different from other manner described here using other to implement, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
The electron irradiation crosslinking of the present invention prepares the polyacrylic method of high melt, and its step includes：(1) it is poly- by proportioning mixing
Propylene, crosslinking sensitizer and antioxidant, obtain premix；(2) by the premix extruding pelletization in step (1), polypropylene is turned into
Pellet to be irradiated；(3) polypropylene pellet to be irradiated and polypropylene wax in simultaneously blend step (2) are heated, obtains polypropylene wax parcel
Polypropylene pellet to be irradiated；(4) the polypropylene pellet to be irradiated of the polypropylene wax parcel in cooling step (3), obtains nucleocapsid
The pretreated polypropylene pellet to be irradiated of structure；(5) polypropylene pretreated in electron ray irradiation steps (4) is used
Pellet to be irradiated, obtain high melt strength, propylene pellet.
Polypropylene wax outer wrap polypropylene pellet to be irradiated, barrier or reduction oxygen penetrate into inside, avoid because oxygen contains
Measure it is too high caused by irradiation-induced degradation rate, so as to improve the polyacrylic degree of cross linking, the high melt strength, propylene prepared, relatively
Outside does not wrap up the polypropylene of polypropylene wax, and gel content is high, and melt index improves, melt outlet diameter is big, high mechanical strength.
Polypropylene wax uniformly wraps up each PP GRANULES, in the case where not influenceing melt strength, ensures that high melt is strong
Spend polyacrylic machinability.
The crosslinking sensitizer is pentaerythritol triacrylate, 1,6 hexanediol diacrylate, trimethylolpropane
Any one in triacrylate, neopentylglycol dimethacrylate, triallyl isocyanurate, Isooctyl acrylate monomer,
Either any two kinds or two or more any combinations, preferably trimethylolpropane trimethacrylate.
The antioxidant is antioxidant 1010.
The mass ratio of the polypropylene, trimethylolpropane trimethacrylate and antioxidant 1010 is 100：1~5：2~
10：0.3~0.9.
The double screw extruder extruding pelletization.
The double screw extruder is engagement type, operating temperature in the same direction：One 150 ± 5 DEG C of area, two 155 ± 5 DEG C of areas, 3rd area
185 ± 5 DEG C, four 200 ± 5 DEG C of areas, five 210 ± 5 DEG C of areas, six 175 ± 5 DEG C of areas.
The electron ray energy exposure dose is 0.4~1.5KGy.
High-speed mixer, running parameter are used in the step (1)：20-60 DEG C of temperature, 60-300 revs/min of rotating speed.
Mixed in the step (3) using high-speed mixer, running parameter：120-180 DEG C of temperature, rotating speed 500~
1000 revs/min.
The electron irradiation crosslinking of the present invention prepares the polyacrylic method of high melt, can reduce oxygen in irradiation process and penetrate into
Amount, the degradation rate during polypropylene cross-linking radiation is reduced, shorten the electron irradiation time, while poly- third prepared through this method
Alkene, melt strength is high, and machinability is good.
Hereinafter, a kind of electron irradiation crosslinking in conjunction with specific embodiments to the present invention prepares the polyacrylic method of high melt and done
Illustrate.
Main raw material(s) explanation used：
Acrylic resin：T30S, technical grade, Beijing yanshan petrochemical Co., Ltd
Polypropylene wax：Licocene 1302, particle, German Clariant
Trimethylolpropane trimethacrylate (TMPTA)：Sensitizer, technical grade, Yixing City Hong Hui Chemical Co., Ltd.s
Neopentylglycol dimethacrylate：Sensitizer, technical grade, Zhengzhou Ai Kemu Chemical Co., Ltd.s
1,6 hexanediol diacrylate：AgiSyn 2816, DSM-Xin Limei
Antioxidant：Model 1010, White crystal, Ningbo Aksu
Embodiment 1
Step includes：(1) in mass ratio 100：3：0.6, weigh polypropylene, trimethylolpropane trimethacrylate and antioxygen
Agent 1010, high-speed mixer mixed at high speed 20 minutes at 40 DEG C of temperature, the Parameter Conditions that 180 revs/min of rotating speed, is premixed
Material；(2) premix in step (1) is turned into polypropylene grain to be irradiated with engaging double-screw rod extruder extruding pelletization in the same direction
Material, operating temperature：One 150 DEG C of area, two 155 DEG C of areas, three 185 DEG C of areas, four 200 DEG C of areas, five 210 DEG C of areas, six 175 DEG C of areas；(3) add
Polypropylene pellet to be irradiated and polypropylene wax in heat and blend step (2), are mixed with high-speed mixer, obtain polypropylene wax
The polypropylene pellet to be irradiated of parcel, running parameter：160 DEG C of temperature, 800 revs/min of rotating speed, 30 minutes time；(4) it is naturally cold
But the polypropylene pellet to be irradiated of the polypropylene wax parcel in step (3), the pretreated polypropylene for obtaining core shell structure are treated
Irradiate pellet；(5) polypropylene pellet to be irradiated pretreated in electron ray irradiation steps (4) is used, it is strong to obtain high melt
Spend polypropylene granules, irradiation dose 1KGy.
Certainly, those skilled in the art also can neatly selective cross-linking polypropylene according to the actual requirements, sensitizer and antioxygen
Agent, obtain high melt strength, propylene.
Embodiment 2
With embodiment 1, the difference is that：
(1) in mass ratio 100：5：0.3, polypropylene, neopentylglycol dimethacrylate and antioxidant 1010 are weighed, it is high
Fast mixer mixed at high speed 20 minutes at 40 DEG C of temperature, the Parameter Conditions that 180 revs/min of rotating speed, obtain premix；
(5) polypropylene pellet to be irradiated pretreated in electron ray irradiation steps (4) is used, obtains high fondant-strength
Polypropylene granules, irradiation dose 0.4KGy.
Embodiment 3
With embodiment 1, the difference is that：
(1) in mass ratio 100：1：0.9, polypropylene, 1,6- hexanediyl esters and antioxidant 1010 are weighed, at a high speed
Mixer mixed at high speed 20 minutes at 40 DEG C of temperature, the Parameter Conditions that 180 revs/min of rotating speed, obtain premix；
(5) polypropylene pellet to be irradiated pretreated in electron ray irradiation steps (4) is used, obtains high fondant-strength
Polypropylene granules, irradiation dose 1.5KGy.
Embodiment 4
With embodiment 1, the difference is that：
(1) in mass ratio 100：3：0.6, polypropylene, 1,6- hexanediyl esters and antioxidant 1010 are weighed, at a high speed
Mixer mixed at high speed 20 minutes at 20 DEG C of temperature, the Parameter Conditions that 300 revs/min of rotating speed, obtain premix；
(3) polypropylene pellet to be irradiated and polypropylene wax in simultaneously blend step (2) are heated, is mixed with high-speed mixer
Close, obtain the polypropylene pellet to be irradiated of polypropylene wax parcel, running parameter：120 DEG C of temperature, 1000 revs/min of rotating speed, time
30 minutes.
Embodiment 5
With embodiment 1, the difference is that：
(1) in mass ratio 100：3：0.6, polypropylene, 1,6- hexanediyl esters and antioxidant 1010 are weighed, at a high speed
Mixer mixed at high speed 20 minutes under temperature 60 C, the Parameter Conditions that 60 revs/min of rotating speed, obtain premix；
(3) polypropylene pellet to be irradiated and polypropylene wax in simultaneously blend step (2) are heated, is mixed with high-speed mixer
Close, obtain the polypropylene pellet to be irradiated of polypropylene wax parcel, running parameter：180 DEG C of temperature, 500 revs/min of rotating speed, time
30 minutes.
Comparative example 1
As different from Example 1：
Unused polypropylene wax wraps up polypropylene pellet to be irradiated.
To examine high melt strength, propylene made from embodiment and comparative example, with the country for characterizing melt strength of polypropylene
It is as shown in table 1 that standard method of test obtains result.
Gel content method of testing：120 mesh steel wires wrap up sample, boil 20 in the xylene solvent of 120 DEG C of constant temperature
Hour, the gel extracted is dried in 150 degrees Celsius of vacuum and journey amount.Gel content is the gel dried out and radiated
P corpse weight ratio.
Melt index：Tested according to standard GB/T 3682-2000, temperature setting is 230 DEG C, load 2.16Kg.
Melt outlet diameter：Laser diameter measuring instrument is placed in fixed position below fusion index instrument capillary outlet, will
PP particles after irradiation take to be put into barrel in right amount, and temperature setting is 230 DEG C, makes its melting, is put into compressing rod, places 5Kg weights
Counterweight, PP is slowly flowed out capillary, measure PP melts at the same pressure and temperature, when flowing out capillary fixed position
Melt diameter.
Tensile strength and elongation at break：Tensile property test is carried out to PP sheet materials by standard GB/T 1040.1-2006,
Rate of extension 5mm/min, use I pattern bar.
The electron irradiation crosslinking of table 1 prepares the performance comparison table of high melt strength, propylene
By above example it can be seen that wrapping up polypropylene pellet to be irradiated, the high melt prepared by polypropylene wax
Gel content, melt outlet diameter, tensile strength and the elongation at break of strength polypropylene greatly improve, and melt index improves,
Illustrate that polypropylene wax parcel polypropylene pellet to be irradiated can improve polyacrylic melt strength after irradiation, and ensure machinability.
High melt strength, propylene prepared by the present invention is applied to the neck such as extrusion foaming, thermoforming, inflation film and coating
Domain, the ceiling for preparing automobile that is particularly suitable for use in, door-plate, vehicle body outer bottom backplate and seat backup board etc..
Although some specific embodiments of the present invention are described in detail by example, the skill of this area
Art personnel it should be understood that above example merely to illustrating, the scope being not intended to be limiting of the invention.The skill of this area
Art personnel to above example it should be understood that can modify without departing from the scope and spirit of the present invention.This hair
Bright scope is defined by the following claims.
Claims (9)
1. a kind of electron irradiation crosslinking prepares the polyacrylic method of high melt, including step：
(1) by proportioning polypropylene, crosslinking sensitizer and antioxidant, premix is obtained；
(2) by the premix extruding pelletization in step (1), polypropylene pellet to be irradiated is turned into；
(3) polypropylene pellet to be irradiated and polypropylene wax in simultaneously blend step (2) are heated, obtains the polypropylene of polypropylene wax parcel
Pellet to be irradiated；
(4) the polypropylene pellet to be irradiated of the polypropylene wax parcel in cooling step (3), obtains the pretreated of core shell structure
Polypropylene pellet to be irradiated；
(5) polypropylene pellet to be irradiated pretreated in electron ray irradiation steps (4) is used, obtains high fondant-strength poly- third
Alkene pellet.
2. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that step (1)
In crosslinking sensitizer for pentaerythritol triacrylate, 1,6 hexanediol diacrylate, trimethylolpropane tris acrylic acid
Any one in ester, neopentylglycol dimethacrylate, triallyl isocyanurate, Isooctyl acrylate monomer, or arbitrarily
Two kinds or two or more any combinations, preferably trimethylolpropane trimethacrylate.
3. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that the step
(1) antioxidant in is antioxidant 1010.
4. the electron irradiation crosslinking as described in any one in claim 1-4 prepares the polyacrylic method of high melt, its feature
It is, the mass ratio of polypropylene, trimethylolpropane trimethacrylate and antioxidant 1010 is 100:1~5:0.3~0.9.
5. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that step (2)
It is middle to use double screw extruder extruding pelletization.
6. electron irradiation crosslinking as claimed in claim 5 prepares the polyacrylic method of high melt, it is characterised in that twin-screw squeezes
It is engagement type, operating temperature in the same direction to go out machine：One 150 ± 5 DEG C of area, two 155 ± 5 DEG C of areas, three 185 ± 5 DEG C of areas, four areas 200 ± 5
DEG C, five 210 ± 5 DEG C of areas, six 175 ± 5 DEG C of areas.
7. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that step (4)
In electron ray energy exposure dose be 0.4~1.5KGy.
8. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that step (1)
It is middle to be mixed using high-speed mixer, running parameter：20-60 DEG C of temperature, 60-300 revs/min of rotating speed.
9. electron irradiation crosslinking as claimed in claim 1 prepares the polyacrylic method of high melt, it is characterised in that step (3)
It is middle to be mixed using high-speed mixer, running parameter：120-180 DEG C of temperature, 500~1000 revs/min of rotating speed.
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| CN108822314A (en) * | 2018-04-18 | 2018-11-16 | 大庆海跃达科技有限公司 | A kind of polypropylene cooling masterbatch and its production method and the production die orifice for implementing this method |
| CN111621093A (en) * | 2020-06-11 | 2020-09-04 | 哈尔滨理工大学 | High-melt-strength polypropylene and preparation method thereof |
| CN112500643A (en) * | 2020-11-27 | 2021-03-16 | 中广核俊尔（上海）新材料有限公司 | High-temperature-resistant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| WO2023090767A1 (en) * | 2021-11-22 | 2023-05-25 | 롯데케미칼 주식회사 | Polypropylene resin composition having long chain branches |
| WO2024117647A1 (en) * | 2022-11-30 | 2024-06-06 | 롯데케미칼 주식회사 | Polypropylene resin composition having excellent melt strength and method for preparing same |
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| CN112500643A (en) * | 2020-11-27 | 2021-03-16 | 中广核俊尔（上海）新材料有限公司 | High-temperature-resistant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| WO2023090767A1 (en) * | 2021-11-22 | 2023-05-25 | 롯데케미칼 주식회사 | Polypropylene resin composition having long chain branches |
| WO2024117647A1 (en) * | 2022-11-30 | 2024-06-06 | 롯데케미칼 주식회사 | Polypropylene resin composition having excellent melt strength and method for preparing same |
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