CN113429521B - High-melt-strength polypropylene and preparation method thereof - Google Patents
High-melt-strength polypropylene and preparation method thereof Download PDFInfo
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- CN113429521B CN113429521B CN202110829397.5A CN202110829397A CN113429521B CN 113429521 B CN113429521 B CN 113429521B CN 202110829397 A CN202110829397 A CN 202110829397A CN 113429521 B CN113429521 B CN 113429521B
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- -1 polypropylene Polymers 0.000 title claims abstract description 143
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 135
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 11
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 6
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 6
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 4
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 3
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 claims description 3
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 claims description 2
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 claims description 2
- SYXTYIFRUXOUQP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy butaneperoxoate Chemical compound CCCC(=O)OOOC(C)(C)C SYXTYIFRUXOUQP-UHFFFAOYSA-N 0.000 claims 1
- FIYMNUNPPYABMU-UHFFFAOYSA-N 2-benzyl-5-chloro-1h-indole Chemical compound C=1C2=CC(Cl)=CC=C2NC=1CC1=CC=CC=C1 FIYMNUNPPYABMU-UHFFFAOYSA-N 0.000 claims 1
- HTCRKQHJUYBQTK-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-yloxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)CC HTCRKQHJUYBQTK-UHFFFAOYSA-N 0.000 claims 1
- CARSMBZECAABMO-UHFFFAOYSA-N 3-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC=C(Cl)C(C)=C1C(O)=O CARSMBZECAABMO-UHFFFAOYSA-N 0.000 claims 1
- 238000012661 block copolymerization Methods 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims 1
- 238000013508 migration Methods 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- 238000012545 processing Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000005187 foaming Methods 0.000 abstract description 7
- 238000010096 film blowing Methods 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 4
- 238000000071 blow moulding Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical group CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- SKVOYPCECYQZAI-UHFFFAOYSA-N 2-ethylhexyl 2-methylbutan-2-ylperoxy carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)CC SKVOYPCECYQZAI-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- HARQWLDROVMFJE-UHFFFAOYSA-N ethyl 3,3-bis(tert-butylperoxy)butanoate Chemical compound CCOC(=O)CC(C)(OOC(C)(C)C)OOC(C)(C)C HARQWLDROVMFJE-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The high melt strength polypropylene is prepared from the following raw materials in parts by weight: 92.70-99.79% of polypropylene, 0.01-0.30% of organic peroxide, 0.10-4.00% of o-diallyl bisphenol A diglycidyl ether and 0.10-3.00% of polycarboxylic compound; the ratio of the mole number of carboxyl groups of the polycarboxyl compound to the mole number of epoxy groups of the o-diallyl bisphenol A diglycidyl ether is 0.5:1.0-3.0: 1.0. The invention also provides a preparation method of the high melt strength polypropylene. The high melt strength polypropylene prepared by the invention not only has the advantage of high melt strength, but also has extremely low total migration volume and VOC value, thereby ensuring that the high melt strength polypropylene completely conforms to food safety certification and ensuring the safety and health of consumers. The invention has the advantages of continuous production, high production efficiency and low processing cost, and can meet the requirement of large-scale production. The high melt strength polypropylene is suitable for processing and forming processes based on a stretching flow field, such as kettle pressure foaming, mould pressing foaming, extrusion foaming, thermal forming, film blowing, blow molding and the like.
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
Polypropylene has the advantages of low density, excellent toughness balance, chemical corrosion resistance, processing formability and the like, so that polypropylene is widely applied to the fields of automobile industry, household appliances, electronic products, packaging products, furniture and the like.
However, polypropylene has the inherent disadvantage of low melt strength, and exhibits significant strain softening behavior during melt drawing. As a result, the problems of uneven wall thickness and the like of polypropylene products are easily caused in the molding modes such as film blowing, bottle blowing, thermal molding and the like; in the foam molding method, polypropylene is difficult to enclose gas, so that cells are easy to break and collapse, and qualified foamed products are difficult to obtain. Therefore, the common polypropylene is difficult to meet the high-precision requirement of the processing and forming process based on the stretching flow field, such as film blowing, bottle blowing, thermal forming, foaming and the like. Therefore, the low melt strength of polypropylene greatly limits the processing and molding modes and application fields of polypropylene. The melt strength of the polypropylene is improved, and the polypropylene has important significance for improving the processing performance and the application value of the polypropylene. At present, the high melt strength polypropylene technology is mainly mastered in a few foreign enterprises such as northern Europe chemical industry, Saudi foundation, Korea Samsung and Liandersaer, and the high melt strength polypropylene provided by domestic enterprises is not seen in the market. Further, the high melt strength polypropylene still has problems of high price and small supply amount.
It is reported that the melt strength of the polymer can be remarkably improved by introducing a long-chain branched structure into the molecular chain of the polymer. The reported preparation method of long-chain branched polypropylene mainly includes radiation or organic peroxide induced free radical grafting reaction of polypropylene and compound containing multiple carbon-carbon double bonds (for example, Chinese patent application publication Nos. CN107075013A, CN106459432A, CN110248995A and CN 102264828A), and chemical reaction of maleic anhydride grafted functional polypropylene and polyfunctional compound (for example, Chinese patent application publication Nos. CN101450982A and CN 101125947A). However, the free radical grafting technology has the problems of easily causing polypropylene degradation, and the use amount of peroxide is often high, so that the content of volatile components in a polypropylene product is easily high; the graft ratio of functional polypropylene grafted with maleic anhydride and the like is low, a radical stabilizer such as styrene and the like with extremely high volatility needs to be added to improve the graft ratio, and the functional polypropylene contains more volatile substances due to the addition of a large amount of unreacted grafting monomers and radical stabilizers. Thus, high melt strength polypropylenes produced by the prior art often fail to meet the safety certification for food contact products and the safety certification for low VOC.
Disclosure of Invention
The invention aims to solve the technical problem of providing the high melt strength polypropylene and the preparation method thereof, the high melt strength polypropylene not only has excellent melt strength and can completely meet the requirements of processing and forming modes related to melt stretching, but also has extremely low total migration volume and VOC value, and the safety and health of consumers are effectively ensured. The technical scheme is as follows:
the high melt strength polypropylene is characterized by being prepared from the following raw materials in parts by weight: 92.70-99.79% of polypropylene, 0.01-0.30% of organic peroxide, 0.10-4.00% of o-diallyl bisphenol A diglycidyl ether and 0.10-3.00% of polycarboxylic compound; the ratio of the mole number of carboxyl groups of the polycarboxyl compound to the mole number of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 0.5:1.0-3.0: 1.0.
Preferably, the high melt strength polypropylene is prepared from the following raw materials in parts by weight: 94.80-99.47% of polypropylene, 0.03-0.20% of organic peroxide, 0.30-3.00% of o-diallyl bisphenol A diglycidyl ether and 0.20-2.00% of polycarboxylic compound.
Preferably, the polypropylene is one or a combination of more of homo-polypropylene, random co-polypropylene and block co-polypropylene. More preferably, the polypropylene is a powdery or granular polypropylene. Most preferably, the polypropylene is a powdered polypropylene.
Preferably, the organic peroxide is one or more of alkyl peroxide, aryl peroxide, diaryl acyl peroxide, peroxyketal, peroxyester, peroxycarbonate and cyclic peroxide. More preferably, the organic peroxide is one or a combination of a peroxyester and a peroxycarbonate. Still more preferably, the organic peroxide is a peroxycarbonate.
Still more preferably, the organic peroxide is t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (t-butylperoxy) valerate, ethyl-3, 3-di (t-butylperoxy) butyrate, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, t-amylperoxy-2-ethylhexyl carbonate, di (2-ethylhexyl) peroxydicarbonate, di- (tetradecyl) peroxydicarbonate, di- (hexadecyl) peroxydicarbonate, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane or the combination of a plurality of the same.
The polycarboxy compound contains two or more carboxy functional groups. Preferably, the polycarboxyl compound is one or a combination of more of 1, 4-succinic acid, 1, 6-adipic acid, malic acid, itaconic acid, citric acid and 1,2,3, 4-butanetetracarboxylic acid. More preferably, the polycarboxyl compound is one or a combination of malic acid, itaconic acid and citric acid; it is still further preferred that the above-mentioned polycarboxyl compound is one or a combination of both of itaconic acid and citric acid; most preferably, the polycarboxyl compound is itaconic acid.
Preferably, the ratio of the number of moles of carboxyl groups of the above-mentioned polycarboxyl compound to the number of moles of epoxy groups of the o-diallylbisphenol A diglycidyl ether is 0.8:1.0 to 2.0:1.0, more preferably 1.0:1.0 to 1.5: 1.0.
The invention also provides a preparation method of the high-melt-strength polypropylene, which is characterized by comprising the following steps of:
(1) the following raw materials are prepared by weight: 92.70-99.79% of polypropylene, 0.01-0.30% of organic peroxide, 0.10-4.00% of o-diallyl bisphenol A diglycidyl ether and 0.10-3.00% of polycarboxylic compound;
(2) uniformly mixing polypropylene, organic peroxide, o-diallyl bisphenol A diglycidyl ether and a polycarboxylic compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
In a preferable scheme, in the step (2), the organic peroxide, the o-diallyl bisphenol A diglycidyl ether and the polycarboxyl compound are uniformly mixed, and then the mixture is uniformly mixed with the polypropylene to obtain a mixed material.
In another preferred scheme, in the step (2), the organic peroxide compound and the o-diallyl bisphenol A diglycidyl ether are uniformly mixed, then the mixture is uniformly mixed with the polypropylene, and then the mixture is uniformly mixed with the polycarboxyl compound to obtain a mixed material.
Preferably, the screw length-diameter ratio of the twin-screw extruder in the above step (3) is 36:1 to 56:1, more preferably 44:1 to 52: 1.
Preferably, the temperature in the barrel of the twin-screw extruder in the step (3) is 170- o C, more preferably 180 ℃ to 230 ℃.
The o-diallyl bisphenol A diglycidyl ether has two C = C bonds in the molecule which can carry out free radical grafting reaction with polypropylene, and has the advantages that: the o-diallyl bisphenol A diglycidyl ether has higher grafting efficiency, and the o-diallyl bisphenol A diglycidyl ether with high grafting rate is favorable for reducing the total migration volume and pungent smell of novel environment-friendly functional polypropylene, so that the safety and health of consumers are ensured; one o-diallyl bisphenol A diglycidyl ether molecule can be subjected to free radical grafting with two polypropylene molecular chains, so that the problem that the molecular weight of polypropylene is greatly reduced due to polypropylene degradation induced by organic peroxide can be effectively solved.
The high melt strength polypropylene of the invention has the following advantages:
(1) according to the invention, organic peroxide with extremely low content is adopted to induce o-diallyl bisphenol A diglycidyl ether to perform free radical grafting reaction with polypropylene, and carboxyl of a polycarboxyl compound and epoxy of o-diallyl bisphenol A diglycidyl ether are subjected to chemical reaction, so that polypropylene is promoted to form a long branched chain structure, and the polypropylene is endowed with the characteristic of high melt strength. The organic peroxide is extremely low in dosage, and auxiliaries with extremely high volatility such as maleic anhydride and styrene are not adopted, so that the high-melt-strength polypropylene prepared by the method has the advantage of high melt strength, and has extremely low total migration volume and VOC value, so that the high-melt-strength polypropylene is ensured to completely accord with food safety certification, and the safety and health of consumers are ensured;
(2) the invention adopts the double-screw reactive extrusion technology to prepare the high-melt-strength polypropylene, has the advantages of continuous production, high production efficiency and low processing cost, and can meet the requirement of large-scale production;
(3) the high melt strength polypropylene in the invention can be suitable for processing and forming processes based on a stretching flow field, such as kettle pressure foaming, mould pressing foaming, extrusion foaming, thermal forming, film blowing, blow molding and the like, and has important significance for expanding the application field of polypropylene and improving the application value of polypropylene.
Detailed Description
Example 1
In this embodiment, the preparation method of the high melt strength polypropylene sequentially includes the following steps:
(1) the following raw materials are prepared by weight: 97.00% of polypropylene (both granular homo-polypropylene), 0.10% of organic peroxide (both tert-butyl peroxy-2-ethylhexanoate), 2.00% of o-diallyl bisphenol A diglycidyl ether, and 0.90% of polycarboxylic compound (both malic acid);
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 1.41: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with a polycarboxyl compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
The length-diameter ratio of the screw of the double-screw extruder in the step (3) is 48: 1.
The temperature in the cylinder of the twin-screw extruder in the above step (3) was 175 ℃ and 205 ℃.
Example 2
In this embodiment, the preparation method of the high melt strength polypropylene sequentially includes the following steps:
(1) the following raw materials are prepared by weight: 97.85% of polypropylene (both granular random copolymer polypropylene), 0.15% of organic peroxide (both tert-butyl peroxy-2-ethylhexanoate), 1.50% of o-diallyl bisphenol A diglycidyl ether, and 0.50% of polycarboxylic compound (both citric acid);
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 1.09: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with a polycarboxyl compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 44:1.
The temperature in the cylinder of the double-screw extruder in the step (3) is 180-210 ℃.
Example 3
In this embodiment, the preparation method of the high melt strength polypropylene sequentially includes the following steps:
(1) the following raw materials are prepared by weight: 98.20% of polypropylene (both granular homo-polypropylene), 0.20% of organic peroxide (both tert-butyl peroxy-2-ethylhexanoate), 1.00% of o-diallyl bisphenol A diglycidyl ether, and 0.60% of polycarboxylic compound (both itaconic acid);
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 1.90: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with a polycarboxyl compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 52: 1.
The temperature in the cylinder of the double-screw extruder in the step (3) is 170-200 ℃.
Example 4
In this embodiment, the preparation method of the high melt strength polypropylene sequentially includes the following steps:
(1) the following raw materials are prepared by weight: 96.90% of polypropylene (both granular random copolymer polypropylenes), 0.30% of organic peroxide (both di (2-ethylhexyl) peroxydicarbonate), 1.80% of o-diallylbisphenol A diglycidyl ether, and 1.00% of polycarboxyl compound (both 1,2,3, 4-butanetetracarboxylic acid);
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 1.99: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with a polycarboxyl compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 52: 1.
The temperature in the cylinder of the twin-screw extruder in the step (3) is 170-200 ℃.
Example 5
In this embodiment, the preparation method of the high melt strength polypropylene sequentially includes the following steps:
(1) the following raw materials are prepared by weight: 96.80% of polypropylene (both granular block copolymer polypropylene), 0.20% of organic peroxide (both 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane), 2.00% of o-diallyl bisphenol A diglycidyl ether and 1.00% of polycarboxylic compound (both 1, 4-succinic acid);
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 1.78: 1.00;
(2) uniformly mixing organic peroxide, o-diallyl bisphenol A diglycidyl ether and a polycarboxyl compound to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating the extruded material strips after cooling to obtain the granular polypropylene with high melt strength.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 56: 1.
The temperature in the cylinder of the twin-screw extruder in the step (3) is 200-230 ℃.
Comparative example 1
The comparative example is pure polypropylene.
Comparative example 2
The preparation method of the modified polypropylene in this comparative example comprises the following steps:
(1) the following raw materials are prepared by weight: 95.90% of polypropylene (all particle homopolymerized polypropylene), 0.20% of organic peroxide (all dicumyl peroxide), 1.50% of maleic anhydride, 1.00% of styrene and 1.40% of 1, 4-butanediamine;
(2) firstly, uniformly mixing organic peroxide and maleic anhydride to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with styrene and 1, 4-butanediamine to obtain a mixture C;
(3) and (3) performing melt extrusion on the mixture C through a double-screw extruder, and cutting the extruded material strips into particles after cooling to obtain granular modified polypropylene.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 52: 1.
The temperature in the cylinder of the double-screw extruder in the step (3) is 180-210 ℃.
Comparative example 3
The preparation method of the modified polypropylene in this comparative example comprises the following steps:
(1) the following raw materials are prepared by weight: 97.90% of polypropylene (both granular random copolymer polypropylene), 0.60% of organic peroxide (both 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane), 1.50% of trimethylolpropane triacrylate;
(2) firstly, uniformly mixing organic peroxide and trimethylolpropane triacrylate to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B;
(3) and performing melt extrusion on the mixture B through a double-screw extruder, and granulating after cooling extruded material strips to obtain granular modified polypropylene.
The length-diameter ratio of the screw of the double-screw extruder in the step (3) is 48: 1.
The temperature in the cylinder of the double-screw extruder in the step (3) is 170-200 ℃.
Comparative example 4
The preparation method of the modified polypropylene in this comparative example comprises the following steps:
(1) the following raw materials are prepared by weight: 98.15% of polypropylene (both granular homo-polypropylene), 0.15% of organic peroxide (tert-butyl peroxy-2-ethyl hexanoate), 1.50% of o-diallyl bisphenol A diglycidyl ether and 0.20% of citric acid;
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 0.44: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with citric acid to obtain a mixture C;
(3) and (3) performing melt extrusion on the mixture C through a double-screw extruder, and cutting the extruded material strips into particles after cooling to obtain granular modified polypropylene.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 44:1.
The temperature in the cylinder of the twin-screw extruder in the step (3) is 180-210 ℃.
Comparative example 5
The preparation method of the modified polypropylene in this comparative example comprises the following steps:
(1) the following raw materials are prepared by weight: 96.85% of polypropylene (both of which are granular block copolymer polypropylene), 0.15% of organic peroxide (tert-butyl peroxy-2-ethylhexanoate), 1.50% of o-diallyl bisphenol A diglycidyl ether, and 1.50% of citric acid;
the ratio of the number of moles of carboxyl groups of the polycarboxyl compound to the number of moles of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 3.28: 1.00;
(2) firstly, uniformly mixing organic peroxide and o-diallyl bisphenol A diglycidyl ether to obtain a mixture A; then uniformly mixing the mixture A with polypropylene to obtain a mixture B, and finally uniformly mixing the mixture B with citric acid to obtain a mixture C;
(3) and (3) performing melt extrusion on the mixture C through a double-screw extruder, and cutting the extruded material strips into particles after cooling to obtain granular modified polypropylene.
The length-diameter ratio of the screw of the twin-screw extruder in the step (3) is 44:1.
The temperature in the cylinder of the twin-screw extruder in the step (3) is 180-210 ℃.
The polypropylene pellets obtained in examples 1 to 5 and comparative examples 1 to 5 were mixed at 80 o C drying in a vacuum oven for 12h, then testing all samples at 210 o Melt Strength (MS) and Total transfer volume (4 vol% acetic acid solution, temperature 40) at C o C, time 10 days). The test results are shown in tables 1 and 2 below, where table 1 is the melt strength and total migration for each example and table 2 is the melt strength and total migration for the comparative example.
Table 1: melt Strength (MS) and Total migration of the products of examples 1 to 5 according to the invention
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| MS（cN） | 35.1 | 38.3 | 42.9 | 39.2 | 36.6 |
| Total migration volume (mg/kg) | 8.2 | 5.7 | 6.3 | 5.6 | 7.2 |
Table 2: melt Strength (MS) and Total migration of comparative product
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| MS（cN） | 7.5 | 26.8 | 21.3 | 17.7 | 21.4 |
| Total migration volume (mg/kg) | 3.6 | 26.5 | 18.3 | 5.6 | 8.7 |
It can clearly be seen that examples 1-5 have higher melt strength relative to comparative examples 1-5. Among them, the modified polypropylene prepared in example 2 (the amount of citric acid added is moderate) has higher melt strength than the modified polypropylenes in comparative examples 4 to 5 (the amount of citric acid added is too low in comparative example 4 and the amount of citric acid added is too high in comparative example 5), because the carboxyl group in citric acid can sufficiently react with the epoxy group in the ortho-diallyl bisphenol a diglycidyl ether, and thus a long-chain structure can be more efficiently introduced into the polypropylene.
The technology disclosed by the invention is not only limited to the preparation of high-melt-strength polypropylene, but also is suitable for preparing other long-chain branched polyolefin and long-chain branched polyester biodegradable materials. The embodiments described above are presented to facilitate an understanding and appreciation of the invention by those skilled in the art. Those skilled in the art can modify the above embodiments and apply them to other fields without inventive effort, so that the present invention is not limited to the above embodiments, and those skilled in the art can make modifications and variations within the scope of the present invention.
Claims (10)
1. The high melt strength polypropylene is characterized by being prepared from the following raw materials in parts by weight: 92.70-99.79% of polypropylene, 0.01-0.30% of organic peroxide, 0.10-4.00% of o-diallyl bisphenol A diglycidyl ether and 0.10-3.00% of polycarboxylic compound; the ratio of the mole number of carboxyl groups of the polycarboxyl compound to the mole number of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 0.5:1.0-3.0: 1.0.
2. The high melt strength polypropylene according to claim 1, wherein the high melt strength polypropylene is prepared from the following raw materials in parts by weight: 94.80-99.47% of polypropylene, 0.03-0.20% of organic peroxide, 0.30-3.00% of o-diallyl bisphenol A diglycidyl ether and 0.20-2.00% of polycarboxylic compound.
3. The high melt strength polypropylene according to claim 1 or 2, wherein: the polypropylene is one or the combination of more of homopolymerized polypropylene, random copolymerization polypropylene and block copolymerization polypropylene.
4. The high melt strength polypropylene according to claim 1 or 2, wherein: the organic peroxide is one or the combination of more of alkyl peroxide, aryl peroxide, diaryl acyl peroxide, peroxyketal, peroxyester, peroxycarbonate and cyclic peroxide.
5. The high melt strength polypropylene according to claim 4, wherein: the organic peroxide is tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, n-butyl-4, 4-di (tert-butylperoxy) valerate, ethyl-3, 3-di (tert-butylperoxy) butyrate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, di (2-ethylhexyl) peroxydicarbonate, di- (tetradecyl) peroxydicarbonate, di- (hexadecyl) peroxydicarbonate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane or the combination of a plurality of the 6, 9-trimethyl-1, 4, 7-triperoxonane.
6. The high melt strength polypropylene according to claim 1 or 2, wherein: the polycarboxyl compound is one or a combination of more of 1, 4-succinic acid, 1, 6-adipic acid, malic acid, itaconic acid, citric acid and 1,2,3, 4-butanetetracarboxylic acid;
the ratio of the mole number of carboxyl groups of the polycarboxyl compound to the mole number of epoxy groups of the ortho-diallyl bisphenol A diglycidyl ether is 0.8:1.0-2.0: 1.0.
7. The process for producing a high melt strength polypropylene according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) the following raw materials are prepared by weight: 92.70-99.79% of polypropylene, 0.01-0.30% of organic peroxide, 0.10-4.00% of o-diallyl bisphenol A diglycidyl ether and 0.10-3.00% of polycarboxylic compound;
(2) uniformly mixing polypropylene, organic peroxide, o-diallyl bisphenol A diglycidyl ether and a polycarboxyl compound to obtain a mixed material;
(3) and (3) performing melt extrusion on the mixed material through a double-screw extruder, and granulating after cooling extruded material strips to obtain the granular polypropylene with high melt strength.
8. The process for producing high melt strength polypropylene according to claim 7, wherein: in the step (2), the organic peroxide, the o-diallyl bisphenol A diglycidyl ether and the polycarboxyl compound are uniformly mixed, and then the mixture is uniformly mixed with the polypropylene to obtain a mixed material.
9. The process for producing high melt strength polypropylene according to claim 7, wherein: in the step (2), the organic peroxide compound and the o-diallyl bisphenol A diglycidyl ether are uniformly mixed, then the mixture is uniformly mixed with the polypropylene, and then the mixture is uniformly mixed with the polycarboxyl compound to obtain a mixed material.
10. The process for producing high melt strength polypropylene according to claim 7, wherein: the length-diameter ratio of the screw of the double-screw extruder in the step (3) is 36:1-56: 1;
the temperature in the cylinder of the double-screw extruder in the step (3) is 170- o C。
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