CN101469092A - High melt strength polypropylene blend and method of preparing same - Google Patents
High melt strength polypropylene blend and method of preparing same Download PDFInfo
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- CN101469092A CN101469092A CNA2007101728730A CN200710172873A CN101469092A CN 101469092 A CN101469092 A CN 101469092A CN A2007101728730 A CNA2007101728730 A CN A2007101728730A CN 200710172873 A CN200710172873 A CN 200710172873A CN 101469092 A CN101469092 A CN 101469092A
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Abstract
The invention relates to a product. The product is prepared by the following steps: mixing 18 to 99.979 weight portions of polypropylene, 0.01 to 80 weight portions of filler, 0.01 to 1 weight portion of initiator, and 0.001 to 1 weight portion of branching promoter; and carrying out the reaction of the mixed raw materials in a Banbury mixer or a screw extruder at the reaction temperature of between 140 and 250 DEG C. Compared with the prior art, the obtained branched high bath strength polypropylene co-mixture has a simple process and good product processing rheological performance.
Description
Technical field
The present invention relates to polypropylene blend, relate in particular to a kind of high melt strength polypropylene blend and preparation method thereof.
Background technology
Polypropylene has the fusing point height as one of five big general-purpose plastics, and good heat resistance, characteristics such as density is little, weather-proof, mechanical property is excellent and chemical stability is good are widely used in fields such as wrapping material, component of machine, household electrical appliance, synthon.But conventional polypropylene is because the linear structure of molecular chain, cause its melt strength after temperature is higher than fusing point, sharply to descend, directly cause polypropylene some defectives in melt-processed, edge curl occurs, be difficult to blown film and prepare foaming product during, extrusion coated calendering even, greatly limited its range of application as inhomogeneity of wall thickness when the thermoforming.
High melt strength, propylene is a kind of polypropylene that contains long-chain branch, be a kind of contain one or more its chain lengths and critical entangled chain appearance when or the side chain branch polypropylene longer than critical entanglement chain length.Compare with the linear polypropylene with same molecular amount, the polypropylene of long-chain branch shows the high sensitivity, zero of cutting and cuts viscosity, melt elasticity and high impact.The long-chain branch polypropylene shows higher viscosity under low shear rate, and shows lower viscosity under high shear rate.Its melt strength is high more a lot of than the plain polypropylene with similar flow characteristics.Its most important characteristics are under constant strain speed, and the stress of its melt flow is the trend of exponential increase, shows tangible strain hardening behavior, thereby polymkeric substance has the capacity of self-regulation of homogeneous deformation when guaranteeing that thermoforming stretches.Therefore, high melt strength, propylene can be used for plastic uptake, blown film, foaming, section bar is extruded and aspects such as thermoforming.
The preparation method of the high melt strength, propylene of existing at present report and use mainly contains two kinds: polypropylene modification method and in-situ copolymerization method.The first kind also is to use maximum class methods, by free radical reaction linear polypropylene being carried out modification exactly handles, comprise the resinous blending method, irradiation crosslinking, chemical crosslink technique in the presence of organo-peroxide and linking agent and reaction extruding graft method etc.Because the complicacy of free radical reaction, the product that these methods obtain is generally various mixture of products, and complete processing is difficult to control.Up to the present, the successful method of the domestic and international preparation high melt strength, propylene of developing is the high-energy ray irradiation method.But first kind method all needs the adding of polyfunctional monomer intermolecular grafting could take place, form long chain branched, obtain high melt strength, propylene.Another kind of method is to utilize metallocene catalyst to produce long chain branched in the copolymerization of propylene reaction.The end group that adds special preparation in the propylene polymerization system has vinyl double bond, and (polypropylene macromers CH=CH2) makes it and the propylene monomer copolymerization, obtains long-chain branching polypropylene.But owing to the sterically hindered reason, macromonomer with lower molecular weight is easier to be inserted in the polypropylene molecular chain, form branched structure, and the macromonomer with higher molecular weight is difficult for inserting, thereby cause branched chain length not reach the critical molecular weight that forms chain entanglement, can not effectively improve polyacrylic melt strength.Lal, J.; Senyek, M.L. (US Patent 4551503,1985) etc. allow propylene and non-conjugated α under the metallocene catalyst effect, ω-diolefin is as 1,7 octadiene etc.But this method is difficult to control only to be formed long chain branching and not to form cross-linked structure.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of high melt strength polypropylene blend that obtains branching for the defective that overcomes above-mentioned prior art existence, and technology is simple, high melt strength polypropylene blend that the product processing rheological property is good and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of high melt strength polypropylene blend is characterized in that, this blend comprises following composition and content (weight part):
Polypropylene 18～99.979;
Filler 0.01～80;
Initiator 0.01～1;
Branching promotor 0.001～1.
Described polypropylene comprises one or both in Co-polypropylene or the homo-polypropylene, and its molten how is 0.1～100g/10min.
Described Co-polypropylene is the binary or the multiple copolymer of propylene, ethene or other C atomicity olefinic monomer that is 4-12.
Described filler comprises inorganics or organic molecule material, and described initiator is the radical initiator of peroxide or azo class.
Described filler comprises talcum powder, lime carbonate, carbon black, calcium stearate, halogen containing flame-retardant, pigment; Described initiator comprises benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-t-butyl peroxide (DBP), Diisopropyl azodicarboxylate (AIBN).
Described branching promotor comprises thiurams, thiazoles (2-thiol benzothiazole, curing Dibenzo thiazole, 2-thiol benzothiazole zinc salt, N, N-diethyl-dithio aminobenzothiazole, 2-(4-morpholinodithio) benzothiazole etc.), sulfenamide (N-cyclohexyl-2-benzothiazole sulfonamide, the N-tertiary butyl-2-benzothiazole sulfonamide, N-oxygen diethylene base-2-benzothiazole sulfonamide, N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N-oxygen diethylidene thiocarbamyl-N '-oxygen diethylidene sulphenamide etc.), guanidine class (vulkacit D, di-o-tolylguanidine etc.), dithiocarbamate(s) (ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, zinc-ethylphenyl dithiocarbamate, zinc dibenzyldithiocarbamate, cupric dimethyldithiocarbamate, ferric dimethyl dithiocarbamate, diethyl thiocarbamate tellurium etc.), Thiourea (1, the 2-ethylene thiourea, diethyl thiourea, N-N '-diphenyl thiourea, N, N '-di-n-butyl thiocarbamide etc.), dialkyl dithiophosphate class (zinc dialkyl dithiophosphate etc.), and other single functionality, in two sulfur esters of difunctionality and polyfunctionality one or more.
The branching promotor of described thiurams has with the following formula I structure:
Formula I
Wherein, x is 1 or 2; R
1, R
2, R
3, R
4, be the alkyl or aryl of C atomicity 1-10.
A kind of preparation method of high melt strength polypropylene blend, it is characterized in that, with raw material polypropylene 18～99.979 weight parts, filler 0.01～80 weight part, initiator 0.01～1 weight part, branching promotor 0.001～1 weight part mixes, and reaction promptly gets product in Banbury mixer or screw extrusion press, and temperature of reaction is 140～250 ℃.
The screw speed of described screw extrusion press is 30～600rpm.
The adding order of described raw material can once add also can substep and/or subregion adding.
Compared with prior art, the present invention carries out chain transfer and grafting by the free radical that produces in the control degradation of polypropylene process, can obtain the high melt strength polypropylene blend of branching, in the degradation of polypropylene process, introduce branching promotor, cause with superoxide, the employing reaction is extruded or banburying gets the polypropylene that the method preparation has long-chain branch.Because the introducing of branching promotor can obviously suppress the β cleavage reaction and must carry out, synthetic no crosslinked branched p 0 lypropylene.The inventive method does not need to add the monomer or the auxiliary agent of the two keys of other band C=C, and it is simple to have technology, the characteristics that the product processing rheological property is good.The melt strength of the high melt strength polypropylene blend that finally obtains is 0.2～2N.
Embodiment
Below in conjunction with specific embodiment method involved in the present invention and technology are described.
The polyacrylic testing method of the present invention:
1. the mensuration of melt strength
Melt strength adopts the GeottfertRheotens melt strength instrument of German Geottfert Werkstoff Pruefmaschinen company to measure.This method is utilized Brabender forcing machine feed, and screw diameter is 19mm, input speed 8g/min; Head adds a kapillary, long 30mm, diameter 2mm.Melt temperature is 200～230 ℃ during test, and melt polypropylene goes out behind the die orifice to clamp with two rotor wheels and draws, and the traction acceleration is 20mm/s
2Up to fracture.The power value of correspondence when measuring fracture, i.e. drawing force value, this power value has reflected the absolute value of the intensity of melt polypropylene under this test condition.
2. the mensuration of melting index is according to ASTM D1238, and 230 ℃, 2.16kg.
Embodiment 1
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 98.99,
Lime carbonate 0.01,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 305.8mN, the molten 2.10g/10min that refers to.
Embodiment 2
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 69,
Talcum powder 30,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 328.7mN, the molten 2.08g/10min that refers to.
Embodiment 3
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 39,
Talcum powder 60
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 344.9mN, the molten 2.01g/10min that refers to.
Embodiment 4
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 39,
Lime carbonate 60,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 340.3mN, the molten 2.03g/10min that refers to.
Embodiment 5
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 79,
EPDM 20，
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 358.4mN, the molten 1.98g/10min that refers to.
Embodiment 6
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 49,
EPDM (trade mark J-4045) 20
Talcum powder 30
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 377.6mN, the molten 1.93g/10min that refers to.
Embodiment 7
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 29,
EPDM (trade mark J-4045) 40,
Talcum powder 30,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 391.3.mN, the molten 1.86g/10min that refers to.
Embodiment 8
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 68.9,
Talcum powder 30,
Dicumyl peroxide 1,
Thiuram dithioesters 0.1,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 285.2mN, the molten 2.35g/10min that refers to.
Embodiment 9
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 69.49,
Talcum powder 30,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.01,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 248.3mN, the molten 3.06g/10min that refers to.
Embodiment 10
Each composition weight umber is:
Polypropylene (MFR=4.50g/10min) 99.85,
Talcum powder 30,
Dicumyl peroxide 0.05,
Thiuram dithioesters 0.1,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 220.7mN, the molten 3.80g/10min that refers to.
Embodiment 11
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 69,
Talcum powder 30,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 474.9mN, the molten 1.23g/10min that refers to.
Embodiment 12
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Dicumyl peroxide 0.5,
Thiuram dithioesters 0.5,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 564.3mN, the molten 1.04g/10min that refers to.
Embodiment 13
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Diisopropyl azodicarboxylate 0.5,
2-(4-morpholinodithio) benzothiazole 0.1,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 517.6mN, the molten 1.12g/10min that refers to.
Embodiment 14
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Benzoyl peroxide 0.5,
Zinc diethyldithiocarbamate 0.1.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 492.7mN, the molten 1.19g/10min that refers to.
Embodiment 15
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Dicumyl peroxide 0.5,
Tetra methylthiuram dithioesters 0.1,
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 230 ℃ of conversion zones, 200 ℃ of extruding zones.The polyacrylic melt strength of gained is 575.3mN, the molten 0.98g/10min that refers to.
Embodiment 16
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Dicumyl peroxide 0.5,
Tetra methylthiuram dithioesters 0.1.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 10kg/h speed, the setting of rotating speed 400rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 590.5mN, the molten 0.92g/10min that refers to.
Embodiment 17
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Dicumyl peroxide 0.5,
Tetra methylthiuram dithioesters 0.1.
At L/D=60, in the twin screw extruder of D=35mm, with the charging of 5kg/h speed, the setting of rotating speed 100rpm. temperature is divided into three sections, transmits 160 ℃ of sections, 200 ℃ of conversion zones, 190 ℃ of extruding zones.The polyacrylic melt strength of gained is 604.7mN, the molten 0.89g/10min that refers to.
Embodiment 18
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 49.4,
EPDM (trade mark J-4045) 20,
Talcum powder 30,
Dicumyl peroxide 0.5,
Tetra methylthiuram dithioesters 0.1.
In 200 ℃ Banbury mixer, rotating speed 100rpm. banburying 5min.The polyacrylic melt strength of gained is 508.3mN, the molten 1.13g/10min that refers to.
Embodiment 19
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 18, its molten how is 0.1～100g/10min;
Calcium stearate 80,
Diisopropyl azodicarboxylate (AIBN) 0.01,
Tetra methylthiuram dithioesters 0.01.
In 140 ℃ Banbury mixer, rotating speed 30rpm. banburying 5min.The polyacrylic melt strength of gained is 508.3mN, the molten 1.13g/10min that refers to.
Embodiment 20
Each composition weight umber is:
Polypropylene (MFR=2.51g/10min) 99.979, its molten how is 0.1～100g/10min;
Carbon black 0.01,
Dicumyl peroxide (DCP) 1,
Zinc diethyldithiocarbamate 1.
In 250 ℃ Banbury mixer, rotating speed 600rpm. banburying 15min.The polyacrylic melt strength of gained is 508.3mN, the molten 1.13g/10min that refers to.
Claims (10)
1. a high melt strength polypropylene blend is characterized in that, this blend comprises following composition and content (weight part):
Polypropylene 18～99.979;
Filler 0.01～80;
Initiator 0.01～1;
Branching promotor 0.001～1.
2. high melt strength polypropylene blend according to claim 1 is characterized in that described polypropylene comprises one or both in Co-polypropylene or the homo-polypropylene, and its molten how is 0.1～100g/10min.
3. high melt strength polypropylene blend according to claim 2 is characterized in that, described Co-polypropylene is the binary or the multiple copolymer of propylene, ethene or other C atomicity olefinic monomer that is 4-12.
4. high melt strength polypropylene blend according to claim 1 is characterized in that, described filler comprises inorganics or organic molecule material, and described initiator is the radical initiator of peroxide or azo class.
5. according to claim 1 or 4 described high melt strength polypropylene blends, it is characterized in that described filler comprises talcum powder, lime carbonate, carbon black, calcium stearate, halogen containing flame-retardant, pigment; Described initiator comprises benzoyl peroxide (BPO), dicumyl peroxide (DCP), di-t-butyl peroxide (DBP), Diisopropyl azodicarboxylate (AIBN).
6. high melt strength polypropylene blend according to claim 1, it is characterized in that, described branching promotor comprises thiurams, thiazoles (2-thiol benzothiazole, curing Dibenzo thiazole, 2-thiol benzothiazole zinc salt, N, N-diethyl-dithio aminobenzothiazole, 2-(4-morpholinodithio) benzothiazole etc.), sulfenamide (N-cyclohexyl-2-benzothiazole sulfonamide, the N-tertiary butyl-2-benzothiazole sulfonamide, N-oxygen diethylene base-2-benzothiazole sulfonamide, N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N-oxygen diethylidene thiocarbamyl-N '-oxygen diethylidene sulphenamide etc.), guanidine class (vulkacit D, di-o-tolylguanidine etc.), dithiocarbamate(s) (ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, zinc-ethylphenyl dithiocarbamate, zinc dibenzyldithiocarbamate, cupric dimethyldithiocarbamate, ferric dimethyl dithiocarbamate, diethyl thiocarbamate tellurium etc.), Thiourea (1, the 2-ethylene thiourea, diethyl thiourea, N-N '-diphenyl thiourea, N, N '-di-n-butyl thiocarbamide etc.), dialkyl dithiophosphate class (zinc dialkyl dithiophosphate etc.), and other single functionality, in two sulfur esters of difunctionality and polyfunctionality one or more.
7. high melt strength polypropylene blend according to claim 6 is characterized in that, the branching promotor of described thiurams has with the following formula I structure:
Formula I
Wherein, x is 1 or 2; R
1, R
2, R
3, R
4, be the alkyl or aryl of C atomicity 1-10.
8. the preparation method of a high melt strength polypropylene blend as claimed in claim 1, it is characterized in that, with raw material polypropylene 18～99.979 weight parts, filler 0.01～80 weight part, initiator 0.01～1 weight part, branching promotor 0.001～1 weight part mixes, and reaction promptly gets product in Banbury mixer or screw extrusion press, and temperature of reaction is 140～250 ℃.
9. the preparation method of high melt strength polypropylene blend according to claim 8 is characterized in that, the screw speed of described screw extrusion press is 30～600rpm.
10. the preparation method of high melt strength polypropylene blend according to claim 8 is characterized in that, the adding order of described raw material can once add also can substep and/or subregion adding.
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| CN102477202A (en) * | 2010-11-23 | 2012-05-30 | 黎明 | Waste polypropylene modified thin-walled corrugated tube and manufacture method thereof |
| CN105968564A (en) * | 2016-05-31 | 2016-09-28 | 江苏金发科技新材料有限公司 | Inflaming retarding polypropylene composition with excellent stress absorption property and high rigidity and heat resistance and preparing method thereof |
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| CN102477202A (en) * | 2010-11-23 | 2012-05-30 | 黎明 | Waste polypropylene modified thin-walled corrugated tube and manufacture method thereof |
| CN102477202B (en) * | 2010-11-23 | 2016-01-20 | 黎明 | Waste polypropylene modified thin-walled corrugated tube and manufacture method thereof |
| CN105968564A (en) * | 2016-05-31 | 2016-09-28 | 江苏金发科技新材料有限公司 | Inflaming retarding polypropylene composition with excellent stress absorption property and high rigidity and heat resistance and preparing method thereof |
| CN106496770A (en) * | 2016-09-27 | 2017-03-15 | 柳州市瑞和塑料科技有限责任公司 | A kind of granule modified method for making plastic formwork of waste and old polypropylene |
| CN106496771A (en) * | 2016-09-27 | 2017-03-15 | 柳州市瑞和塑料科技有限责任公司 | A kind of method for improving waste and old polypropylene melt strength |
| CN107190347A (en) * | 2017-06-07 | 2017-09-22 | 巢湖市鼎盛渔具有限公司 | A kind of fishing net waste material polymerization of nylon 6 |
| CN110527187A (en) * | 2019-08-15 | 2019-12-03 | 合肥市和裕达塑业有限公司 | Low odor scratch-resistant physical blowing squeezes out PP composite material and preparation method |
| CN113105831A (en) * | 2021-03-30 | 2021-07-13 | 江苏大易材料科技有限公司 | High-bonding-strength high-molecular bonding resin |
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