CN115141317A - Tri-monomer grafted polyethylene initiated by dual initiators and preparation method thereof - Google Patents
Tri-monomer grafted polyethylene initiated by dual initiators and preparation method thereof Download PDFInfo
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- CN115141317A CN115141317A CN202110346715.2A CN202110346715A CN115141317A CN 115141317 A CN115141317 A CN 115141317A CN 202110346715 A CN202110346715 A CN 202110346715A CN 115141317 A CN115141317 A CN 115141317A
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- 239000003999 initiator Substances 0.000 title claims abstract description 70
- -1 polyethylene Polymers 0.000 title claims abstract description 65
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 64
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000009977 dual effect Effects 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 title abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 44
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 42
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 20
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 20
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 20
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- 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 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 230000002522 swelling effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 13
- 230000004913 activation Effects 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 3
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010819 recyclable waste Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting 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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
Landscapes
- 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)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a dual-initiator initiated tri-monomer grafted polyethylene and a preparation method thereof, wherein the raw materials of the product comprise polyethylene, an interfacial agent, maleic anhydride, glycidyl methacrylate, butyl acrylate, an initiator A and an initiator B; the preparation method comprises the following steps: putting polyethylene and an interfacial agent into a reaction kettle, heating under the protection of vacuum and nitrogen, and uniformly stirring; dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in an interfacial agent to obtain a mixed solution B, spraying the mixed solution B into a reaction kettle, and uniformly stirring; dissolving an initiator A and an initiator B in an interfacial agent C to obtain a mixed solution C, spraying the mixed solution C into a reaction kettle, uniformly stirring, and heating for reaction to obtain a crude graft; the crude graft is washed, filtered and dried to obtain a final product PE-g-MAH/GMA/BA, which has low odor and high grafting rate and can reduce the pollution to the environment in the preparation process.
Description
Technical Field
The invention mainly relates to the technical field of modified polyolefin, in particular to a tri-monomer grafted polyethylene initiated by a double initiator and a preparation method thereof.
Background
Low-density polyethylene (LDPE) and polypropylene are one of the most promising thermoplastic polymer materials in development nowadays due to their advantages of low price, light weight, excellent physical and chemical properties, simple processing technology, etc. However, due to the nonpolar structure of polyethylene, the surface dyeing property, hydrophilicity, adhesiveness with other materials, antistatic property and compatibility with inorganic materials are poor, which limits the further development of the application field. The solid phase grafting modification of polyethylene can raise its hydrophilicity, adhesion, biocompatibility, conductivity, lubricating property, polarity and other performance and expand its application field.
In recent years, maleic Anhydride (MAH) has been highly toxic and is easily volatilized and is gradually replaced by maleic ester monomers, and basic functional group monomers include dimethylamino (meth) acrylate, glycidyl Methacrylate (GMA), and oxazoline. In the grafting process, because the polyolefin is easy to generate side reactions such as degradation crosslinking and the like to influence the grafting rate, under the condition of a main monomer GMA, a second monomer with an electron donating effect is selected as a comonomer to improve the grafting rate and the grafting efficiency of the main monomer, and the commonly used comonomer is styrene (St), acrylate, acrylamide and maleate. MAH (Q =0.86, e = 3.69) and GMA (Q =1.03, e = 0.57) have Q values relatively close to each other, and e values are much different, so that MAH and GMA are easily subjected to alternate copolymerization. It generally refers to a grafting reaction carried out with 2 or more than 2 monomers. In the multi-component monomer grafting system, firstly, PE generates hydrogen elimination reaction under the action of peroxide free radicals to form PP macromolecular free radicals which can generate grafting or chain scission reaction; for example, because the reactivity of the MAH to PE macromolecular radicals is higher than that of GMA, the MAH is preferentially grafted to the PE to form more stable MAH radical macromolecular radicals, and then the MAH reacts with the GMA, and the reaction rate of the MAH is far greater than that of the GMA and PP macromolecular radicals, so that the grafting rate can be improved. The Butyl Acrylate (BA) can be used as a soft monomer and added into a reaction system at the glass transition temperature (Tg = -56 ℃), has a synergistic effect with MAH and GMA, improves the grafting rate, can endow the polypropylene resin with ductility, cold resistance and the like, and expands the application of the polypropylene resin.
Solid phase grafting an initiator with appropriate activation energy and half-life is selected according to the polymerization temperature, for example, an initiator with activation energy of 138-183 kJ/mol, such as cumene hydroperoxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate, at high temperature (> 100 ℃); the initiator with the activation energy of 110-138 kJ/mol at the medium temperature (30-100 ℃) comprises benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and persulfate; the initiator with the activation energy of 63-110 kJ/mol at the low temperature of (-10-30 ℃) comprises cumene hydroperoxide/ferrous chloride and benzoyl peroxide/N, N-dimethylaniline. Generally, initiators having a half-life on the order of or comparable to the polymerization time should be selected. The initiator is proper in dosage, too much initiator is not needed, and too much initiator is needed, so that the reaction speed is too high and the control is difficult; if the amount of the catalyst is small, the catalyst is not easy to initiate, the reaction can not be normally carried out, and the performance of the polymer is influenced. Therefore, by compounding more than two initiators, the half-life period can be adjusted, and under the condition, the grafting rate is better.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of initiating a tri-monomer grafted polyethylene by using a dual initiator, and the process can be used for preparing the polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate (PE-g-MAH/GMA/BA for short) with low odor and high grafting rate; the method avoids using the acetone which is a national control solvent, avoids using high boiling point water to cause a large amount of energy consumed by separating water and maleic anhydride at the later stage, and generates a large amount of acidic water to pollute the environment.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention provides a dual-initiator initiated three-monomer grafted polyethylene, which comprises the following raw materials: polyethylene, an interfacial agent, maleic anhydride, glycidyl methacrylate, butyl acrylate, an initiator A and an initiator B.
The invention provides a dual-initiator initiated tri-monomer grafted polyethylene, which comprises the following raw materials in parts by weight: 100 parts of polyethylene, 0.1-30 parts of interfacial agent, 1-10 parts of maleic anhydride, 1-5 parts of glycidyl methacrylate, 0.5-5 parts of butyl acrylate, 1-5 parts of initiator A and 0.1-5 parts of initiator B.
Preferably, the interfacial agent is 10-25 parts, and may be, for example, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, or 30 parts. The addition amount of the maleic anhydride can be 2 parts, 4 parts, 5 parts, 6 parts, 8 parts and 10 parts.
Selecting an initiator with appropriate activation energy and half-life according to the polymerization reaction temperature, for example, an initiator with activation energy of 138-183 kJ/mol, such as cumene hydroperoxide, tert-butyl hydroperoxide and tert-butyl peroxybenzoate, at high temperature (> 100 ℃); the initiator with the activation energy of 110-138 kJ/mol at the medium temperature (30-100 ℃) comprises benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile and persulfate; the initiator with the activation energy of 63-110 kJ/mol at the low temperature (-10-30 ℃) comprises cumene hydroperoxide/ferrous chloride and benzoyl peroxide/N, N-dimethylaniline. Generally, initiators having a half-life on the order of or comparable to the polymerization time should be selected. According to the technical scheme of the invention, the initiator A and the initiator B are peroxides or azo initiators; preferably, the initiator A and the initiator B are respectively one of lauroyl peroxide, benzoyl peroxide, cumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and azobisisobutyronitrile, and two of the initiators are compounded; further preferably, the 2 initiating agents with the half-life of 4-40min within the range of 80-140 ℃ are compounded to control the half-life of the initiating agent; more preferably, the initiator A is benzoyl peroxide, and the initiator B is tert-butyl peroxybenzoate.
Preferably, the dual-initiator initiated trimonomer grafted polyethylene provided by the invention comprises the following raw materials in parts by weight: 100 parts of polyethylene, 10-25 parts of an interfacial agent, 5 parts of maleic anhydride, 2 parts of glycidyl methacrylate, 1 part of butyl acrylate, 3 parts of benzoyl peroxide and 1 part of tert-butyl peroxybenzoate.
The interfacial agent is an organic solvent having a dissolving or swelling effect on polyethylene.
The interfacial agent is one or more of benzene, alkyl substituted benzene and decahydronaphthalene.
The alkyl substituted benzene can be C1-8 alkyl substituted benzene, and the substitution can be mono-substitution or multi-substitution, for example, the alkyl substituted benzene is at least one of toluene, xylene and the like; the organic solvent is preferably one or more of benzene, toluene and xylene; more preferably xylene.
The viscosity average molecular weight of the polyethylene is (1 x 10) 3 )-(1×10 7 ). Preferably (1X 10) 4 )-(6×10 6 ) (ii) a Illustratively, it has a viscosity average molecular weight of 5X 10 3 、1×10 5 、5×10 5 、1×10 6 、5×10 6 . The inert gas may be selected from nitrogen and/or argon, preferably nitrogen.
The invention relates to a preparation method of initiating trimonomer grafted polyethylene by using a dual initiator, which comprises the following steps:
(1) Putting polyethylene and an interfacial agent into a reaction kettle, heating and uniformly stirring under the vacuum condition and under the protection of inert gas;
(2) Dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in an interfacial agent to obtain a mixed solution B, spraying the mixed solution B into a reaction kettle, and uniformly stirring;
(3) Dissolving an initiator A and an initiator B in an interfacial agent to obtain a mixed solution C, spraying the mixed solution C into a reaction kettle, uniformly stirring, and heating for reaction to obtain a crude graft;
(4) And washing, filtering and drying the crude graft to obtain a final product of polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate.
Preferably, the preparation method of the dual-initiator initiated three-monomer grafted polyethylene comprises the following steps:
(1) Putting polyethylene and an interfacial agent A into a reaction kettle, vacuumizing until the pressure in the reaction kettle is 0-minus 0.02MPa, supplementing inert gas to 0.00MPa, heating and uniformly stirring under the protection of the inert gas, and heating by adopting a heat-conducting oil medium to 50-70 ℃;
(2) Dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in an interfacial agent to obtain a mixed solution B, spraying the mixed solution B into a reaction kettle, uniformly stirring, and heating a heat transfer oil medium to 70-90 ℃;
(3) Dissolving benzoyl peroxide and tert-butyl peroxybenzoate in an interfacial agent to obtain a mixed solution C, spraying the mixed solution C into a reaction kettle, uniformly stirring, heating until the temperature of materials in the reaction kettle is 110-120 ℃, reacting for a time to obtain a crude graft, and introducing inert gas for protection in the reaction process;
(4) And after the crude graft is cooled, cooling to 70-90 ℃, adding ethyl acetate into the reaction kettle to wash and filter the crude graft, repeating for 2-3 times, and carrying out vacuum drying on the washed product at the drying temperature of 50-70 ℃ for 8-12 hours to obtain the final product of polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate.
The invention adopts a three-in-one (reaction, washing and filtration) reaction kettle, and the process does not need to be transferred from the beginning of the reaction to the obtaining of the grafting product, thereby reducing the material loss, having simple and convenient operation and avoiding the loss of solvent transfer in the process.
Compared with the prior art, the invention has the beneficial effects that:
1. the process can prepare the polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate (PE-g-MAH/GMA/BA for short) with low odor and high grafting rate.
2. The method avoids using a national control solvent acetone, avoids using high boiling point water to cause a large amount of energy consumed by later separation of water and maleic anhydride, and generates a large amount of acidic water to pollute the environment.
3. The sample is prepared by the solid phase grafting method, the reaction temperature is low, the main chain is basically not damaged, the grafting reaction is facilitated, and compared with the traditional melt grafting, the smell of the product is smaller.
4. The three-in-one (reaction, washing and filtration) reaction kettle is adopted, the operation is simple, the loss of solvent transfer in the process is avoided, and the utilization rate is high. Simple post-treatment, recyclable waste liquid, convenience, economy, high efficiency and energy conservation.
5. The solid phase grafting process can not avoid the condition of polyethylene degradation and influence the mechanical property of the material, the three monomers are initiated by a dual initiator, a low-dose interfacial agent is adopted, the dose range is preferably 15-20%, the process has a remarkable effect on the wetting and swelling of the polyethylene, and the grafting rate is obviously improved.
Detailed Description
The present invention will be further described with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope defined by the present application.
Example 1
The initiating trimonomer grafted polyethylene of a kind of dual initiator, by weight, the raw materials include the following components: 1000 g of polyethylene, 250 g of interfacial agent, 50 g of maleic anhydride (MAH for short), 20 g of glycidyl methacrylate (GMA for short), 10 g of butyl acrylate (MA for short), 30 g of benzoyl peroxide and 10 g of tert-butyl peroxybenzoate.
The interfacial agent is xylene.
The preparation method comprises the following steps:
(1) Putting polyethylene and part of an interface agent (marked as an interface agent A, and accounting for 25 g) into a reaction kettle, vacuumizing until the pressure in the reaction kettle is 0-0.02 MPa, supplementing nitrogen to 0.00MPa, heating and uniformly stirring under the protection of nitrogen, and heating by adopting a circulating heat-conducting oil medium which is heated to 60 ℃;
(2) Dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in part of an interfacial agent (marked as an interfacial agent B, and the amount of the interfacial agent B is 150 g) to obtain a mixed solution B, spraying the mixed solution B into a reaction kettle, uniformly stirring, and heating a heat-conducting oil medium to 80 ℃;
(3) Dissolving benzoyl peroxide and tert-butyl peroxybenzoate in the remaining interface agent (marked as interface agent C, 75 g) to obtain a mixed solution C, spraying the mixed solution C into a reaction kettle, uniformly stirring, heating until the temperature of materials in the reaction kettle is 120 ℃ and the reaction time is 3 hours, so as to obtain a crude graft, and introducing nitrogen for protection in the reaction process;
(4) After the crude graft is cooled, the cooling temperature is 60 ℃, ethyl acetate is added into the reaction kettle, the crude graft is washed and filtered under the conditions that the temperature of a heat transfer oil medium is 60 ℃ and the stirring speed is 100r/min, the operation is repeated for 2 to 3 times, the washed product is dried in vacuum, the drying temperature is 60, and the drying time is 10 hours, so that the final product, namely polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate (PE-g-MAH/GMA/BA) is obtained. The waste liquid containing the ethyl acetate is rectified by a rectifying device and then recycled.
Finally, 1 gram of the dried sample is randomly weighed and placed in a 250mL flask, 80mL of xylene is added, and the mixture is heated and refluxed until dissolved. After cooling, an excess of 0.1mol/L KOH-ethanol solution was added, the mixture was heated under reflux for 2 hours, and after cooling, phenolphthalein was used as an indicator and titration was carried out with 0.1mol/L HCl-isopropanol solution. The amount of base added and the amount of acid consumed for neutralization were recorded and the grafting ratio of the solid phase graft reaction product was calculated to be 5.26% according to the following formula.
MAH(%)=9.806*[C 1 V 1 -C 2 V 2 )]/2m,
In the formula: c. C 1 The concentration of KOH-ethanol solution is mol/L; v 1 The volume of the excess KOH-ethanol solution, mL; c. C 2 The concentration is HCl-isopropanol solution, mol/L; v 2 The volume of HCl-isopropanol solution consumed for titration of neutralizing base, mL; m is the mass of polypropylene grafted maleic anhydride, g.
Example 2
A kind of three-monomer grafted polyethylene initiated by double initiator, the raw materials comprise the following components in parts by weight: 1000 g of polyethylene, 200 g of interfacial agent, 40 g of maleic anhydride (MAH for short), 10 g of glycidyl methacrylate (GMA for short), 5 g of butyl acrylate (MA for short), 30 g of benzoyl peroxide and 10 g of tert-butyl peroxybenzoate.
The interfacial agent is dimethylbenzene, the interfacial agent A is 25 g, the interfacial agent B is 150 g, and the interfacial agent C is 25 g. The other preparation was carried out in the same manner as in example 1, and the graft ratio was found to be 4.48%.
Example 3
The initiating trimonomer grafted polyethylene of a kind of dual initiator, by weight, the raw materials include the following components: 1000 g of polyethylene, 250 g of dimethylbenzene, 60 g of maleic anhydride (MAH for short), 25 g of glycidyl methacrylate (GMA for short), 5 g of butyl acrylate (MA for short), 30 g of benzoyl peroxide and 10 g of tert-butyl peroxybenzoate.
Example 3 was prepared in the same manner as example 1 and the graft ratio was found to be 4.24%.
Example 4
The initiating trimonomer grafted polyethylene of a kind of dual initiator, by weight, the raw materials include the following components: 1000 g of polyethylene, 250 g of dimethylbenzene, 50 g of maleic anhydride (MAH for short), 20 g of glycidyl methacrylate (GMA for short), 10 g of butyl acrylate (MA for short), 40 g of benzoyl peroxide and 15 g of tert-butyl peroxybenzoate.
Example 4 was prepared in the same manner as example 1 and the graft ratio was found to be 3.21%.
Example 5
The initiating trimonomer grafted polyethylene of a kind of dual initiator, by weight, the raw materials include the following components: 1000 g of polyethylene, 250 g of dimethylbenzene, 50 g of maleic anhydride (MAH for short), 20 g of glycidyl methacrylate (GMA for short), 10 g of butyl acrylate (MA for short), 25 g of benzoyl peroxide and 15 g of tert-butyl peroxybenzoate.
The preparation of example 5 was carried out in the same manner as in example 1, and the graft ratio was found to be 3.36%.
The grafting rate of the existing market-sold optical polyethylene grafting product is about 1.0, the grafting rate of the beno polyethylene grafting product is about 1.0, and the grafting rate of the prepared dual-initiator initiated trimonomer grafted polyethylene is far higher than that of the polyethylene grafting product in the existing market.
Claims (10)
1. The dual-initiator initiated trimonomer grafted polyethylene is characterized by comprising the following raw materials: polyethylene, an interfacial agent, maleic anhydride, glycidyl methacrylate, butyl acrylate, an initiator A and an initiator B.
2. The dual-initiator initiated trimonomer grafted polyethylene according to claim 1, characterized in that the raw materials comprise the following components in parts by weight: 100 parts of polyethylene, 0.1-30 parts of interfacial agent, 1-10 parts of maleic anhydride, 1-5 parts of glycidyl methacrylate, 0.5-5 parts of butyl acrylate, 1-5 parts of initiator A and 0.1-5 parts of initiator B.
3. The dual initiator initiated trimonomer grafted polyethylene of claim 1, wherein the initiator A and the initiator B are peroxide or azo initiators; the initiator A and the initiator B are respectively one of lauroyl peroxide, benzoyl peroxide, cumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, di-tert-butyl peroxide and azobisisobutyronitrile.
4. The dual initiator initiated trimonomer grafted polyethylene of claim 3, wherein the initiator A is benzoyl peroxide and the initiator B is tert-butyl peroxybenzoate.
5. The dual-initiator initiated trimonomer grafted polyethylene according to claim 4, characterized in that the raw materials comprise the following components in parts by weight: 100 parts of polyethylene, 10-25 parts of an interface agent, 5 parts of maleic anhydride, 2 parts of glycidyl methacrylate, 1 part of butyl acrylate, 3 parts of benzoyl peroxide and 1 part of tert-butyl peroxybenzoate.
6. The diinitiator initiated trimonomer grafted polyethylene of claim 1, wherein the interfacial agent is an organic solvent having a dissolving or swelling effect on polyethylene, and the interfacial agent is one or more of benzene, alkyl substituted benzene and decalin.
7. The dual initiator initiated trimonomer graft polyethylene of claim 6, wherein the alkyl substituted benzene can be C1-8 alkyl substituted benzene, and the substitution can be mono-or poly-substitution.
8. The dual initiator initiated trimonomer grafted polyethylene of claim 1, wherein said polyethylene has a viscosity average molecular weight of (1 x 10) 3 )-(1×10 7 )。
9. The process of any one of claims 1 to 8 for the preparation of a dual initiator initiated trimonomer grafted polyethylene comprising the steps of:
(1) Putting polyethylene and an interfacial agent into a reaction kettle, heating and uniformly stirring under the vacuum condition and under the protection of inert gas;
(2) Dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in an interfacial agent to obtain a mixed solution B, spraying the mixed solution B into a reaction kettle, and uniformly stirring;
(3) Dissolving an initiator A and an initiator B in an interfacial agent to obtain a mixed solution, spraying the mixed solution C into a reaction kettle, uniformly stirring, and heating for reaction to obtain a crude graft;
(4) And washing, filtering and drying the crude graft to obtain a final product of polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate.
10. The method of claim 9, comprising the steps of:
(1) Putting polyethylene and an interfacial agent into a reaction kettle, vacuumizing until the pressure in the reaction kettle is 0-0.02 MPa, supplementing inert gas to 0.00MPa, heating and uniformly stirring under the protection of the inert gas, and heating by adopting a heat-conducting oil medium to 50-70 ℃;
(2) Dissolving maleic anhydride, glycidyl methacrylate and butyl acrylate in an interfacial agent to obtain a mixed solution, spraying the mixed solution into a reaction kettle, uniformly stirring, and heating a heat transfer oil medium to 70-90 ℃;
(3) Dissolving benzoyl peroxide and tert-butyl peroxybenzoate in an interfacial agent to obtain a mixed solution C, spraying the mixed solution C into a reaction kettle, uniformly stirring, heating until the temperature of materials in the reaction kettle is 80-120 ℃, and reacting for 2-6 hours to obtain a crude graft, and introducing inert gas for protection in the reaction process;
(4) And after the crude graft is cooled, cooling to 70-90 ℃, adding ethyl acetate into the reaction kettle to wash and filter the crude graft, repeating for 2-3 times, and carrying out vacuum drying on the washed product at the drying temperature of 50-70 ℃ for 8-12 hours to obtain the final product of polyethylene grafted maleic anhydride/glycidyl methacrylate/butyl acrylate.
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CN1283642A (en) * | 2000-08-30 | 2001-02-14 | 华南理工大学 | Process for preparing soild-phase graft copolymer of polyolefine and three monomers and its application |
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