CN111423541A - High-melt-strength polypropylene and preparation method thereof - Google Patents
High-melt-strength polypropylene and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 87
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 83
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 64
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000002978 peroxides Chemical class 0.000 claims abstract description 37
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001125 extrusion Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5e)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 5
- 125000002252 acyl group Chemical group 0.000 abstract description 4
- 238000005660 chlorination reaction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005482 strain hardening Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses high melt strength polypropylene and a preparation method thereof, and relates to the technical field of high polymer materials. The high melt strength polypropylene is prepared by crosslinking long chain branching in extrusion processing by taking graphene grafted peroxide as an initiator; the graphene grafted peroxide is prepared by reacting and grafting acyl chloride graphene and tert-butyl hydroperoxide; the acyl chlorination graphene is prepared by reacting graphene oxide with thionyl chloride to perform acyl chlorination on carboxyl on the surface of the graphene oxide. According to the high-melt-strength polypropylene disclosed by the invention, the dispersion of peroxide can be improved through the grafting of the graphene, and meanwhile, the decomposition speed of the peroxide can be controlled through the good thermal conductivity of the graphene, so that the conditions of overhigh local concentration, severe local decomposition and the like of the peroxide in the extrusion processing process are avoided, and the generation of gel is effectively avoided.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to high melt strength polypropylene and a preparation method thereof.
Background
The polypropylene is one of the most popular resins consumed at present, has the advantages of excellent performance, low price, low density, no toxicity, good processing performance, good mechanical property, good electrical insulation property and the like, and is widely applied to the fields of automobile interior and exterior decoration, household appliances, packaging, building materials and the like. However, polypropylene has low melt strength and lacks strain hardening, which limits its application in foaming, extrusion molding, blow molding, and other fields. The low melt strength of polypropylene is mainly due to the fact that polypropylene is a semi-crystalline material, the softening point of which is very close to the melting point, and the high melt strength temperature window between the softening point and the melting point is narrow; whereas the melt strength of polypropylene decreases rapidly with increasing temperature after the temperature exceeds the melting point. In addition, the polypropylene melt is substantially free of strain hardening phenomena due to the linear structure and narrow molecular weight distribution of the general purpose polypropylene. Therefore, general purpose polypropylene has limited applications in areas with melt strength requirements.
High melt strength polypropylene (HMSPP) is a new polypropylene material developed for the above deficiencies, i.e. a polypropylene whose melt strength is less sensitive to temperature; the product prepared from the HMSPP has the characteristics of good thermal stability, high dimensional stability at high temperature, high toughness and tensile strength, excellent microwave adaptability, good environmental effect, easiness in recycling and the like.
Methods for improving the melt strength and strain hardening of polypropylene include increasing molecular weight, broadening the molecular weight distribution, and introducing long chain branching; wherein, increasing molecular weight has larger influence on the processing performance of polypropylene, and broadening molecular weight distribution has obvious influence on the mechanical influence of polypropylene, so that introducing long chain branching is more ideal, and is also the method for improving the melt strength and strain hardening of polypropylene which is most widely applied at present. At present, methods for introducing long-chain branching into polypropylene include direct polymerization, radiation crosslinking, chemical crosslinking, and the like. The direct polymerization method utilizes a special catalyst to realize long chain branching through chain transfer in the polymerization process, and the main products at present comprise WB260HMSPP, WF420HMS and the like of northern Europe chemical engineering company. The high melt strength polypropylene produced by the direct polymerization method has the advantages of low TVOC and low gel index, but the high melt strength polypropylene produced by the method has higher price and limited application range due to higher cost of the catalyst. The radiation crosslinking method is to generate free radicals through radiation, introduce a long-chain branched structure on a linear polypropylene main chain, and represents a product of Bassell company PF 814. The PF814 is already stopped because of high equipment investment, complex operation, dark color of the polypropylene product and the like. The chemical crosslinking method realizes the crosslinking of linear polypropylene in the extrusion processing process through a chemical initiator, and has the advantages of simple process, controllable cost, easy large-scale production and the like.
The initiator used in the chemical crosslinking method is mainly organic peroxide; during the processing of polypropylene, the melting point of polypropylene is higher, and the decomposition temperature of peroxide is lower, which can lead to nonuniform dispersion, higher local concentration and violent decomposition of peroxide in polypropylene, thereby leading to the occurrence of local gel of polypropylene. Therefore, the skilled person in the art needs to solve the above-mentioned drawbacks of the chemical crosslinking method.
Disclosure of Invention
In view of this, the embodiment of the present invention provides a high melt strength polypropylene and a preparation method thereof, and mainly aims to solve the problem that the high melt strength polypropylene is easy to generate a gel phenomenon in the preparation process.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a high melt strength polypropylene, which is a long-chain branched high melt strength polypropylene formed by crosslinking polypropylene initiated by graphene grafted peroxide.
Preferably, the high melt strength polypropylene has a melt index of 0.1 to 10g/10min and a melt strength of 15 to 60 cN. The melt index and melt strength of the high melt strength polypropylene are slightly different according to the difference of the mixture ratio of the reaction raw materials and the like. The melt index of the high melt strength polypropylene is preferably 1-10g/10min, and the melt strength is 20-60cN, more preferably, the melt index of the high melt strength polypropylene is 2-10 g/10min, for example, 3-10 g/10min, and the melt strength is 25-60 cN.
Preferably, the graphene grafted peroxide is obtained by reacting acyl chloride graphene with organic peroxide in alkali liquor.
Preferably, the organic peroxide is tert-butyl hydroperoxide; the alkali solution is sodium hydroxide solution.
Preferably, the preparation method of the graphene grafted peroxide comprises the following steps: cooling the tert-butyl hydroperoxide to below 20 ℃. The reaction temperature affects the stability of the tert-butyl hydroperoxide, and when the temperature is higher than 20 ℃, the decomposition speed of the tert-butyl hydroperoxide is too high, thus affecting the reaction yield.
Preferably, the sodium hydroxide solution is 10% by mass.
Preferably, the mixing and stirring time of the tert-butyl hydroperoxide and the sodium hydroxide solution is 10-20 min; and stirring and reacting the acyl chloride graphene and the mixed solution for 60-120 min. The stirring time affects the reaction progress, and when the stirring time is too short, the reaction is incomplete and the reaction yield is low.
Preferably, the molar ratio of the tert-butyl hydroperoxide to the sodium hydroxide is 1: 1-1.5; the mass ratio of the acyl chloride graphene to the tert-butyl hydroperoxide is 1: 1-5. The molar ratio of tert-butyl hydroperoxide to sodium hydroxide mainly affects the solubility of tert-butyl hydroperoxide, and when the ratio is too low, the concentration of tert-butyl hydroperoxide is too low, and when the ratio is too high, the tert-butyl hydroperoxide cannot be completely dissolved. The mole ratio of the acylchlorinated graphene to the tert-butyl hydroperoxide mainly influences the grafting ratio, when the ratio is too low, the grafting ratio is too low, and when the ratio is too high, insufficient acyl chloride groups do not react with the tert-butyl hydroperoxide, so that the waste of the tert-butyl hydroperoxide is caused.
Preferably, the preparation method of the acylchlorinated graphene comprises the following steps: mixing graphene oxide, thionyl chloride and a catalyst (adding the mixture into a reactor with a reflux device), carrying out reflux reaction in a 250W power ultrasonic bath at a constant temperature of 80 ℃, and reducing pressure to evaporate redundant thionyl chloride after the reaction is finished so as to obtain the acyl chlorinated graphene.
Preferably, the oxygen content of the graphene oxide is 1 to 20 wt%. When the oxygen content is too low, the number of effective groups on the graphene oxide is too small, and the number of generated grafts is too small. When the oxygen content is too high, the graphene oxide is not stable enough and is easily oxidized and degraded by tert-butyl hydroperoxide in the subsequent reaction.
Preferably, the mass ratio of the graphene oxide to the thionyl chloride is 1: 1-5. The proportion is determined by the oxygen content of graphene, and when the proportion is too low, too few acyl chloride groups are generated to influence grafting, and when the proportion is too high, thionyl chloride waste is caused.
Preferably, the catalyst is pyridine, N-dimethylformamide or tetramethylethylenediamine, and the addition amount of the catalyst is 0.05-0.5% of the total mass of the graphene oxide and the thionyl chloride. When the proportion of the catalyst is too low, the catalytic efficiency is affected, and when the proportion is too high, too many impurities are introduced, so that the product performance is affected.
Preferably, the reflux reaction time is 3 to 8 hours. The reaction time is inversely proportional to the amount of catalyst added, the higher the catalyst addition rate, the shorter the reaction time. Too short a reaction time may result in incomplete reaction and too long a reaction time is meaningless.
In another aspect, an embodiment of the present invention provides a graphene grafted peroxide, where the graphene grafted peroxide is obtained by reacting acylchlorinated graphene with tert-butyl hydroperoxide in an alkali solution.
In still another aspect, the present invention provides a method for preparing the above high melt strength polypropylene, comprising the steps of: mixing 100 parts of polypropylene, 0.01-1 part of graphene grafted peroxide, 0.5-5 parts of asymmetric diene monomer and 0.01-0.5 part of antioxidant in parts by weight, setting the extrusion temperature of a screw to be 200 ℃, the rotation speed of the screw to be 500rpm, and carrying out melt extrusion reaction by using double screws to form the long-chain branched chain type high-melt-strength polypropylene.
Preferably, the asymmetric diene monomer is at least one of isoprene, 1, 5-heptadiene, ethylidene norbornene, dicyclopentadiene and methylcyclopentadiene, and the antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite and bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
Aiming at the problem that the high melt strength polypropylene is easy to gel in the preparation process, the initiator is modified, and particularly, the method is realized by taking graphene grafted peroxide as the initiator and crosslinking long chain branching in extrusion processing; the graphene grafted peroxide is prepared by reacting and grafting acyl chloride graphene and tert-butyl hydroperoxide; the acyl chlorination of graphene is realized by reacting graphene oxide with thionyl chloride to acyl chloridize carboxyl on the surface of the graphene oxide.
The high melt strength polypropylene can improve the dispersion of peroxide through the grafting of the graphene, and can control the decomposition speed of the peroxide through the good thermal conductivity of the graphene, so that the conditions of overhigh local concentration, violent local decomposition and the like of the peroxide in the extrusion processing process are avoided, and the generation of gel is effectively avoided.
Compared with the prior art, the beneficial effects of the invention comprise the following aspects:
(1) according to the method, the graphene is grafted, so that the dispersity of the peroxide is improved, and the local over-high concentration of the peroxide in the polypropylene extrusion processing process is avoided;
(2) according to the method, through the good heat-conducting property of the graphene, a chain reaction caused by decomposition and heat release of the peroxide is avoided, and the condition that the peroxide is decomposed locally and violently is avoided;
(3) through the two points, the invention avoids the polypropylene from generating polypropylene gel in the extrusion processing reaction and improves the quality stability of the high melt strength polypropylene product.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, technical solutions, features and effects according to the present invention will be given with preferred embodiments. The particular features, structures, or characteristics may be combined in any suitable manner in the embodiments or embodiments described below.
The present invention prepares graphene grafted peroxide by the following examples 1-3.
Example 1
Mixing 100g of graphene oxide with oxygen content of 1%, 100g of thionyl chloride and 1g of pyridine, adding the mixture into a reactor with a reflux device, carrying out reflux reaction for 3 hours in a 250W power ultrasonic bath at constant temperature of 80 ℃, and reducing pressure to evaporate redundant thionyl chloride after the reaction is finished to obtain acylchlorinated graphene;
cooling 10g of tert-butyl hydroperoxide to 20 ℃, dropwise adding 100ml of 10% sodium hydroxide solution, continuously stirring for 20min, adding 50g of graphene chloride acylate into the mixed solution, and continuously stirring for 60 min. And filtering the reaction product, and drying under reduced pressure to obtain the graphene grafted peroxide.
Example 2
Mixing 100g of graphene oxide with the oxygen content of 20%, 500g of thionyl chloride, 0.3g N and N-dimethylformamide, adding the mixture into a reactor with a reflux device, carrying out reflux reaction in a 250W power ultrasonic bath at the constant temperature of 80 ℃ for 8 hours, and reducing pressure to evaporate redundant thionyl chloride after the reaction is finished so as to obtain acyl chlorinated graphene;
and (2) cooling 40g of tert-butyl hydroperoxide to 20 ℃, dropwise adding 600ml of 10% sodium hydroxide solution, continuously stirring for 10min, adding 50g of graphene chloride acylate into the mixed solution, and continuously stirring for 120 min. And filtering the reaction product, and drying under reduced pressure to obtain the graphene grafted peroxide.
Example 3
Mixing 100g of graphene oxide with the oxygen content of 10%, 300g of thionyl chloride and 1g of tetramethylethylenediamine, adding the mixture into a reactor with a reflux device, carrying out reflux reaction for 5 hours in a 250W power ultrasonic bath at the constant temperature of 80 ℃, and reducing pressure to evaporate redundant thionyl chloride after the reaction is finished to obtain acylchlorinated graphene;
cooling 25g of tert-butyl hydroperoxide to 20 ℃, dropwise adding 400ml of 10% sodium hydroxide solution, continuously stirring for 15min, adding 50g of graphene chloride acylate into the mixed solution, and continuously stirring for 90 min. And filtering the reaction product, and drying under reduced pressure to obtain the graphene grafted peroxide.
The invention high melt strength polypropylene is prepared by the following examples 4-8.
Example 4
Mixing 100 parts of polypropylene, 0.01 part of graphene grafted peroxide prepared in example 1, 0.5 part of isoprene and 0.01 part of antioxidant 1076, and carrying out melt extrusion reaction by using a double screw at the extrusion temperature of 200 ℃ and the screw rotation speed of 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
Example 5
Mixing 100 parts of polypropylene, 1 part of graphene grafted peroxide prepared in example 2, 5 parts of 1, 5-heptadiene, 0.4 part of antioxidant 1010 and 0.1 part of antioxidant 168, and performing melt extrusion reaction by using a double screw, wherein the extrusion temperature is 200 ℃ and the screw rotation speed is 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
Example 6
Mixing 100 parts of polypropylene, 0.5 part of graphene grafted peroxide prepared in example 3, 3 parts of ethylidene norbornene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 626, and performing melt extrusion reaction by using a double screw, wherein the extrusion temperature is 200 ℃ and the screw rotation speed is 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
Example 7
Mixing 100 parts of polypropylene, 1 part of graphene grafted peroxide prepared in example 3,5 parts of dicyclopentadiene, 0.4 part of antioxidant 1010 and 0.1 part of antioxidant 626, and performing double-screw melt extrusion reaction at the extrusion temperature of 200 ℃ and the screw rotation speed of 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
Example 8
Mixing 100 parts of polypropylene, 0.01 part of graphene grafted peroxide prepared in example 3, 0.5 part of methylcyclopentadiene, 0.05 part of antioxidant 1010 and 0.01 part of antioxidant 626, and performing melt extrusion reaction by using a double screw, wherein the extrusion temperature is 200 ℃ and the screw rotation speed is 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
Comparative example
This comparative example differs from example 6 in that the graphene grafted peroxide in example 6 was replaced with t-butyl hydroperoxide; mixing 100 parts of polypropylene, 0.5 part of tert-butyl hydroperoxide, 3 parts of ethylidene norbornene, 0.1 part of antioxidant 1010 and 0.05 part of antioxidant 626, and performing double-screw melt extrusion reaction at the extrusion temperature of 200 ℃ and the screw rotation speed of 500 rpm; and performing water cooling granulation after extrusion to obtain the high melt strength polypropylene granules.
The high melt strength polypropylene pellets prepared in the raw polypropylene, examples 4 to 8 and comparative example were respectively tested for melt strength, melt index, gel content, tensile strength, flexural modulus, notched impact strength, and the results are shown in Table 1.
TABLE 1 raw polypropylene, examples 4-8 and comparative test data
As can be seen from the comparative data, the melt strength of the polypropylene prepared by the invention is obviously improved, and simultaneously, the tensile strength, the flexural modulus and the notch impact strength are obviously improved. Compared with the method that peroxide which is not grafted by graphene is used for initiating crosslinking (comparative example), the high melt strength polypropylene prepared by the method has low gel content and more uniform distribution of crosslinking points, so that the high melt strength polypropylene prepared by the method has higher melt strength and better mechanical property. For example, the content of the high melt strength polypropylene gel produced by the method of the present invention is 5% or less, preferably 4% or less, 3%Below, even 2% or less, 1% or less, or O. And has good mechanical property, the flexural modulus is more than 1100MPa, such as between 1100MPa and 1200MPa or between 1150-1200 MPa; the notch impact strength is 8-10kJ/m2E.g. in the range of 9-10kJ/m2。
The embodiments of the present invention are not exhaustive, and those skilled in the art can select them from the prior art.
The above disclosure is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and shall be covered by the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the above claims.
Claims (10)
1. The high melt strength polypropylene is characterized in that the high melt strength polypropylene is long-chain branched chain type high melt strength polypropylene formed by polypropylene crosslinking initiated by graphene grafted peroxide.
2. A high melt strength polypropylene according to claim 1 having a melt index of from 0.1 to 10g/10min and a melt strength of from 15 to 30 cN.
3. The high melt strength polypropylene according to claim 1, wherein the graphene grafted peroxide is obtained by reacting an acylchlorinated graphene with an organic peroxide in an alkaline solution.
4. A high melt strength polypropylene according to claim 3 wherein said organic peroxide is t-butyl hydroperoxide; the alkali solution is sodium hydroxide solution.
5. The high melt strength polypropylene according to claim 4, wherein the graphene grafted peroxide is prepared by the following steps:
cooling the tert-butyl hydroperoxide to below 20 ℃, and then mixing and stirring the tert-butyl hydroperoxide and the sodium hydroxide solution to obtain a mixed solution; wherein the mass percent of the sodium hydroxide solution is 10%, and the mixing and stirring time of the tert-butyl hydroperoxide and the sodium hydroxide solution is 10-20 min;
and mixing and stirring the graphene chloride acylate and the mixed solution, wherein the stirring reaction time of the graphene chloride acylate and the mixed solution is 60-120 min.
6. A high melt strength polypropylene according to claim 4 wherein the molar ratio of t-butyl hydroperoxide to sodium hydroxide is from 1: 1-1.5; the mass ratio of the acyl chloride graphene to the tert-butyl hydroperoxide is 1: 1-5.
7. The high melt strength polypropylene according to claim 3, wherein the preparation method of the graphene oxychloride comprises the following steps: mixing graphene oxide, thionyl chloride and a catalyst, carrying out reflux reaction in a 250W power ultrasonic bath at a constant temperature of 80 ℃, and reducing pressure to evaporate redundant thionyl chloride after the reaction is finished, thereby obtaining the graphene oxychloride.
8. A high melt strength polypropylene according to claim 7 wherein the graphene oxide has an oxygen content of 1 to 20 wt%; the mass ratio of the graphene oxide to the thionyl chloride is 1: 1-5; the catalyst is pyridine, N-dimethylformamide or tetramethylethylenediamine, and the addition amount of the catalyst is 0.05-0.5% of the total mass of the graphene oxide and the thionyl chloride; the time of the reflux reaction is 3 to 8 hours.
9. The process for producing a high melt strength polypropylene according to any one of claims 1 to 8, wherein the process comprises the steps of: mixing 100 parts of polypropylene, 0.01-1 part of graphene grafted peroxide, 0.5-5 parts of asymmetric diene monomer and 0.01-0.5 part of antioxidant in parts by weight, setting the extrusion temperature of a screw to be 200 ℃, the rotation speed of the screw to be 500rpm, and carrying out melt extrusion reaction by using double screws to form the long-chain branched chain type high-melt-strength polypropylene.
10. The method of claim 9, wherein the asymmetric diene monomer is at least one of isoprene, 1, 5-heptadiene, ethylidene norbornene, dicyclopentadiene, and methylcyclopentadiene, and the antioxidant is at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite, and bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
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| CN111826054A (en) * | 2020-07-22 | 2020-10-27 | 浙江工业大学 | Preparation method of low-fineness graphene oil-based resin slurry |
| CN114085501A (en) * | 2021-12-01 | 2022-02-25 | 苏明生 | High-performance wear-resistant packaging material and processing technology thereof |
| CN117843874A (en) * | 2024-01-09 | 2024-04-09 | 江门职业技术学院 | Light-weight reinforced flame-retardant polypropylene composite material and preparation method thereof |
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| CN110305401A (en) * | 2019-05-13 | 2019-10-08 | 山东寿光鲁清石化有限公司 | A kind of high fondant-strength PP resin and its preparation process |
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