CN103509192B - A kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing and preparation method thereof - Google Patents
A kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing and preparation method thereof Download PDFInfo
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- CN103509192B CN103509192B CN201310419485.3A CN201310419485A CN103509192B CN 103509192 B CN103509192 B CN 103509192B CN 201310419485 A CN201310419485 A CN 201310419485A CN 103509192 B CN103509192 B CN 103509192B
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- polyoxyethylene glycol
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229920003171 Poly (ethylene oxide) Polymers 0.000 title claims abstract description 38
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 16
- -1 polypropylene Polymers 0.000 claims abstract description 75
- 239000004743 Polypropylene Substances 0.000 claims abstract description 58
- 229920001427 mPEG Polymers 0.000 claims abstract description 57
- 229920001155 polypropylene Polymers 0.000 claims abstract description 56
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 32
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
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- 238000009826 distribution Methods 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
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- 125000003944 tolyl group Chemical group 0.000 claims 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
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- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
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- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to polypropylene modification, aim to provide a kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing and preparation method thereof.The present invention adopts isocyanic ester coupling method, first isocyanic ester is introduced methoxy poly (ethylene glycol) end, then by terminal isocyanate group polyoxyethylene glycol and the coupling of terminal hydroxy group isotatic polypropylene, has prepared iPP-b-mPEG.Compared with prior art, step of the present invention is simple, easily realizes; The raw material used is common industrial raw material, cheap, is easy to suitability for industrialized production; By regulating the length of two kinds of segments, the performance (number-average molecular weight of iPP is the number-average molecular weight of 1000 ~ 15000 g/mol, mPEG is 300 ~ 5300 g/mol) of regulation and control segmented copolymer; In the iPP-b-mPEG of preparation, iPP segment maintains very high degree of isotacticity.
Description
Technical field
The present invention relates to polypropylene modification technology, particularly a kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing and preparation method thereof.
Background technology
Polypropylene because its mechanical property is good, the good and cost performance advantages of higher of thermal characteristics and stable chemical performance, electrical insulation capability makes it have a wide range of applications in fields such as packaging, automobile, building and even military affairs.Within 2010, Pp In The World demand reaches 53,570kt, and aggregated capacity reaches 60,980kt/a, and the demand in the PP whole world and production capacity all kept sane growth in recent years.But because polypropylene itself is in unreactiveness, the nonpolar and crystalline feature of its molecular chain makes it have low surface energy and hydrophobic characteristic.Extremely low surface energy causes polypropylene interface compatibility when preparing matrix material with other organic and inorganic material is blended very poor, and the mechanical property of matrix material is greatly affected; Polyacrylic hydrophobicity also limit its application in dyeing, bonding, printing etc.Polypropylene is divided into isotatic polypropylene, syndiotactic polypropylene and Atactic Polypropelene, and wherein the consumption of isotatic polypropylene is maximum, and therefore the functionalization of isotatic polypropylene is the focus of scientific research always.
Polyacrylic functionalization mainly contains four kinds of methods: 1) surface treatment: be put into by isotatic polypropylene in the atmosphere of air, ozone, ammonia, with energetic ray, electron beam or plasma radiation, polyacrylic surface is processed, make its Surface Creation hydroxyl, carboxyl isopolarity group.This method needs expensive equipment, and modified effect can disappear with the prolongation of duration of service; 2) free radical grafting modification: mixed with maleic anhydride, vinylformic acid or acrylamide isopolarity monomer by polypropylene, causes polar monomer with radical initiator and carries out graft copolymerization, thus generates side base or the side chain of polarity.But easily there is degraded or crosslinked in polypropylene, greatly destroy the intrinsic mechanical property of polypropylene and processing characteristics in reaction process; 3) directly copolymerization: by propylene monomer and the monomer direct copolymerization under the effect of catalyzer with functional group, the multipolymer of preparation containing specific functional groups.Although direct copolymerization method introduces specific functional groups method the most fast in polypropylene, but the functional poly propylene that degree of isotacticity is very high can not be obtained, and very easily form stable complex compound and inactivation with N, O atom on polar monomer due to conventional Ziegler-Natta catalyst and metallocene catalyst, greatly limit its suitability for industrialized production; 4) physical blending or surface-coated: these two kinds of methods are widely used in polypropylene modification because of advantages such as production cost are low, simple to operate, flexible and changeable.But isotatic polypropylene has high regularity and crystallizing power, this makes it and other polymkeric substance, or even the consistency of its homologue (as syndiotactic polypropylene, Atactic Polypropelene) is all very poor.When therefore modification being carried out to isotatic polypropylene by the method for physical blending or surface-coated, often need to use segmented copolymer containing isotatic polypropylene segment as compatilizer, obviously could improve the consistency of polypropylene and polar polymer.
The main thought that current synthesis contains the segmented copolymer of isotatic polypropylene segment is: the isotatic polypropylene first being prepared end group functional by polycoordination, then adopts radical polymerization, the method for activity/controllable polymerization mode or coupling prepares one section of segmented copolymer containing isotatic polypropylene.(Macromolecules, 1998,31 (17): 5943 such as Chung; Macromolecules, 1999,32 (8): 2525.) with the isotatic polypropylene of boron end-blocking for raw material, prepared polypropylene-b-(maleic anhydride-alt-vinylbenzene) segmented copolymer by radical polymerization.Kashiwa (Journal of Polymer Science Part A:Polymer Chemistry.2009,47 (3): 812) directly by the polypropylene bromination of band edge ethyl, form the initiator of controllable free-radical polymerisation, then cause the monomer polymerizations such as vinylbenzene, methyl methacrylate and n-butyl acrylate, prepare polypropylene block copolymer.Dong (J. Am. Chem. Soc., 2001.123 (21): 4871) polypropylene of p-methylstyrene end-blocking etc. has been prepared, then pass through benzyl methyl lithiation, active anionic polymerization initiator is introduced at polypropylene end, cause styrenic anion living polymerization, prepare polypropylene/styrene block copolymer.(Macromolecules, 2000,43 (20): 8331 such as Dong; Appl Organomet Chem., 2011,25 (8): 632)) etc. rac-Me is used
2si [2-Me-4-Ph-Ind]
2zrCl
2(SiPh)/AlOct
2/ CPh
3b (C
6f
5)
4/ ZnOct
2catalyst system has prepared end iodo isotatic polypropylene, then is translated into end azido-isotatic polypropylene; By the isotatic polypropylene of the terminal hydroxy group of preparation, at two-(trichloromethyl) carbonate and NMe
4under the effect of Cl, and the reaction of propargyl amine, prepare end alkynyl radical isotatic polypropylene; Finally by the isotatic polypropylene segmented copolymer of click chemistry reaction preparation functionalization.Although above method all can prepare one section of di-block copolymer for isotatic polypropylene, also there is various problem: 1) radical polymerization can not realize the controlled of molecular weight and structure, is difficult to regulate and control the performance of block polymer; 2) in controllable free-radical polymerisation, need to remove transition metal complex after ATRP method reaction terminates, in RAFT method, the preparation process complicated difficult of two thioesters is with industrial applications, and NMRP rule exists the shortcomings such as suitable monomers scope is little; 3) anionic polymerisation condition is harsh, cannot realize large-scale industrial production; 4) click chemistry preparation process is complicated, there is the problem of postorder industrialization difficulty equally.For above problem, the invention provides a kind of simple isotatic polypropylene-b-polyoxyethylene glycol two block thing (iPP-b-mPEG) and preparation method thereof.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, provides a kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing and preparation method thereof.The present invention adopts isocyanic ester coupling method, first isocyanic ester is introduced methoxy poly (ethylene glycol) end, then by terminal isocyanate group polyoxyethylene glycol and the coupling of terminal hydroxy group isotatic polypropylene, has prepared iPP-b-mPEG.
For technical solution problem, solution of the present invention is:
There is provided a kind of isotatic polypropylene-b-polyoxyethylene glycol two block thing, its structural formula is as shown in any one in formula I ~ (IV):
In formula I ~ (IV), the arbitrary integer between m=7 ~ 120, the arbitrary integer between n=100 ~ 400.
Invention further provides the method preparing aforementioned isotatic polypropylene-b-polyoxyethylene glycol two block thing, comprise the following steps:
(1) be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add reactant methoxy poly (ethylene glycol), vulcabond, catalyst dibutyltin dilaurylate and solvent chloroform successively; There is nucleophilic substitution reaction in methoxy poly (ethylene glycol) and vulcabond, obtain terminal isocyanate group polyoxyethylene glycol under the effect of catalyst dibutyltin dilaurylate; The mol ratio of described methoxy poly (ethylene glycol) and vulcabond is 1:5 ~ 1:100, and the add-on of dibutyl tin laurate is 1% of reactant total mass, and the concentration of methoxy poly (ethylene glycol) in reaction system is 0.03 mol/L ~ 0.1 mol/L; Temperature of reaction is 25 DEG C ~ 60 DEG C, and the reaction times is 4 ~ 24 h;
(2) be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add terminal hydroxy group functionalization isotatic polypropylene, the terminal isocyanate group polyoxyethylene glycol prepared, organic solvent and catalyst dibutyltin dilaurylate successively; There is nucleophilic addition in terminal isocyanate group polyoxyethylene glycol and terminal hydroxy group functionalization isotatic polypropylene, obtain isotatic polypropylene-b-polyoxyethylene glycol two block thing under the effect of catalyst dibutyltin dilaurylate; The terminal hydroxyl of terminal hydroxy group isotatic polypropylene and the mol ratio of terminal isocyanate group polyoxyethylene glycol are 1:1 ~ 1:10, the add-on of dibutyl tin laurate is 1% ~ 5% of reactant total mass, and the concentration of terminal hydroxy group isotatic polypropylene in reaction system is 0.03 mol/L ~ 0.1 mol/L; Temperature of reaction is 90 DEG C ~ 130 DEG C, and the reaction times is 4 ~ 24 h.
In the present invention, the organic solvent in described step (2) is toluene, dimethylbenzene, heptane, octane or its any mixture.
In the present invention, described methoxy poly (ethylene glycol) is thread-like molecule, and its molecular weight is 350 ~ 5300 g/mol, and molecular weight distribution is 1.1 ~ 1.9.
In the present invention, described terminal hydroxy group functionalization isotatic polypropylene number-average molecular weight is 3000 ~ 15000 g/mol, and molecular weight distribution is 3 ~ 10.
In the present invention, described vulcabond is hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate.
Compared with prior art, beneficial effect of the present invention is:
1) connect PEG by hydroxyl and vulcabond linked reaction at the iPP end of terminal hydroxy group functionalization, prepare the iPP-b-mPEG of compound with regular structure, the method step is simple, easily realizes;
2) raw material (as vulcabond, methoxy poly (ethylene glycol), dibutyl tin laurate etc.) used is common industrial raw material, cheap, is easy to suitability for industrialized production;
3) by regulating the length of two kinds of segments, the performance (number-average molecular weight of iPP is the number-average molecular weight of 1000 ~ 15000 g/mol, mPEG is 300 ~ 5300 g/mol) of regulation and control segmented copolymer;
4) in the iPP-b-mPEG prepared, iPP segment maintains very high degree of isotacticity.
Accompanying drawing explanation
Fig. 1 is the typical case of iPP-b-mPEG two block thing in the embodiment of the present invention 17
1h NMR schemes.
Embodiment
Isotatic polypropylene-b-polyoxyethylene glycol two block thing of the present invention, its structural formula is following any one: as the isophorone type isotatic polypropylene-b-polyoxyethylene glycol two block thing (the present invention is called for short iPP-IPDI-mPEG) of formula I, or the ditan type polypropylene-b-polyoxyethylene glycol two block thing (the present invention is called for short iPP-MDI-mPEG) of formula II, or the hexa-methylene type isotatic polypropylene-b-polyoxyethylene glycol two block thing (the present invention is called for short iPP-HDI-mPEG) of formula III, or the toluene type isotatic polypropylene-b-polyoxyethylene glycol two block thing (the present invention is called for short iPP-TDI-mPEG) of formula IV.
The invention provides the preparation method of this kind of isotatic polypropylene-b-polyoxyethylene glycol bi-block copolymer:
One, the preparation of terminal isocyanate group polyoxyethylene glycol
By methoxy poly (ethylene glycol) (Methoxy Polyethylene Glycol, be called for short mPEG) and vulcabond at dibutyl tin laurate (dibutyltin dilaurate, be called for short DBTDL) catalysis under carry out nucleophilic addition, preparation terminal isocyanate group polyoxyethylene glycol (the present invention is called for short mPEG-t-NCO), described methoxy poly (ethylene glycol) chemical formula is:
In this formula, the arbitrary integer between n=7 ~ 120.
Vulcabond chemical formula used is for shown in formula (I ') or formula (II ') or formula (III ') or formula (IV '):
Dibutyl tin laurate chemical formula used is:
Be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add methoxy poly (ethylene glycol), vulcabond, catalyst dibutyltin dilaurylate and solvent (chloroform, tetrachloroethane or toluene) successively.The temperature of reaction of this reaction is 25 DEG C ~ 60 DEG C, and the reaction times is 4 ~ 24 h; The mol ratio of methoxy poly (ethylene glycol) and vulcabond is 1:5 ~ 1:100; The add-on of dibutyl tin laurate is 1% of reactant quality; The concentration of methoxy poly (ethylene glycol) in reaction system is 0.03 mol/L ~ 0.1 mol/L; Methoxy poly (ethylene glycol) used is line style, and its molecular weight is 350 ~ 5300 g/mol; Vulcabond used is one or more in hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI) or diphenylmethanediisocyanate (MDI).
Intermediate product molecular formula is formula (V ') isophorone type terminal isocyanate group polyoxyethylene glycol, (the present invention is called for short mPEG-IPDI-NCO) or formula (VI ') hexa-methylene type terminal isocyanate group polyoxyethylene glycol, (the present invention is called for short mPEG-HDI-NCO) or formula (VII ') toluene type terminal isocyanate group polyoxyethylene glycol, (the present invention is called for short mPEG-TDI-NCO) or formula (VIII ') ditan type terminal isocyanate group polyoxyethylene glycol, shown in (the present invention is called for short mPEG-MDI-NCO):
Formula (V ') ~ formula (VIII ') in, the arbitrary integer between n=7 ~ 120.
Two, the preparation of isotatic polypropylene-b-polyoxyethylene glycol two block thing
Be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add terminal isocyanate group polyoxyethylene glycol (the present invention is called for short mPEG-t-NCO) and solvent prepared by terminal hydroxy group functionalization isotatic polypropylene (hydroxy-terminated polypropylene is called for short iPP-t-OH) and upper step successively, catalyst dibutyltin dilaurylate (dibutyltin dilaurate is added after stirring, be called for short DBTDL), temperature of reaction is 90 DEG C ~ 130 DEG C; Reaction times is 4 ~ 24 h; The mol ratio of terminal isocyanate group polyoxyethylene glycol and terminal hydroxy group isotatic polypropylene is 1:1 ~ 1:1.6, the add-on of dibutyl tin laurate is 1 ~ 5% of reactant quality, and the concentration of terminal hydroxy group functionalization isotatic polypropylene in reaction system is 0.03 mol/L ~ 0.1 mol/L; Terminal hydroxy group functionalization isotatic polypropylene used is line style, tacticity>=95%, and number-average molecular weight is 3000 ~ 15000
g/mol, molecular weight distribution is 3 ~ 10, terminal hydroxy group ending ratio>=70%.Prepare isotatic polypropylene-b-polyoxyethylene glycol two block thing (the present invention is called for short iPP-b-mPEG), described terminal hydroxy group functionalization isotatic polypropylene chemical formula is:
Arbitrary integer between m=100 ~ 400
Embodiment 1
Be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add 3.5 g (0.01mol) mPEG(M successively
n=350), 2.5 g (0.1 mol) MDI, 0.06 g dibutyl tin laurate (1wt.%) and 200 mL chloroforms, be warmed up to 25 DEG C of reaction 8 h, product precipitates in a large amount of ether, after chloroform/ether dissolution/circulation precipitation three times, at 40 DEG C, vacuum drying is to constant weight, prepares intermediate product mPEG-t-NCO white powder 5.5g.
Embodiment 2
Other experiment condition, with embodiment 1, adds 10 g (0.1 mol) (M
n=1000), 12.5g (0.5 mol) MDI, 0.225g dibutyl tin laurate, prepare intermediate product mPEG-t-NCO white powder 8.3g.
Embodiment 3
Other experiment condition, with embodiment 1, adds 10 g (0.005 mol) mPEG(M
n=2000), 0.125g dibutyl tin laurate, prepares intermediate product mPEG-t-NCO white powder 12.1g.
Embodiment 4
Other experiment condition, with embodiment 1, adds 5.3g (0.001 mol) mPEG(M
n=5300), 0.078g dibutyl tin laurate, prepares intermediate product mPEG-t-NCO white powder 5.02g.
Embodiment 5
Other experiment condition is with embodiment 1, and temperature of reaction is 40 DEG C, prepares intermediate product mPEG-t-NCO white powder 5.8 g.
Embodiment 6
Other experiment condition is with embodiment 1, and temperature of reaction is 60 DEG C, prepares intermediate product mPEG-t-NCO white powder 5.2 g.
Embodiment 7
Other experiment condition is with embodiment 1, and solvent chloroform 333 mL(controls methoxy poly (ethylene glycol) concentration 0.03 mol/L), prepare intermediate product mPEG-t-NCO white powder 5.8 g.
Embodiment 8
Other experiment condition is with embodiment 1, and solvent chloroform 200 mL(controls methoxy poly (ethylene glycol) concentration 0.05 mol/L), prepare intermediate product mPEG-t-NCO white powder 5.3 g.
Embodiment 9
Other experiment condition is with embodiment 1, and solvent chloroform 125 mL(controls methoxy poly (ethylene glycol) concentration 0.08 mol/L), prepare intermediate product mPEG-t-NCO white powder 5.5 g.
Embodiment 10
Other experiment condition is with embodiment 1, and solvent chloroform 100 mL(controls methoxy poly (ethylene glycol) concentration 0.1 mol/L), prepare intermediate product mPEG-t-NCO white powder 5.0 g.
Embodiment 11
Other experiment condition adds 1.68 gHDI with embodiment 1,0.052 g dibutyl tin laurate, prepares intermediate product mPEG-t-NCO white powder 4.8 g.
Embodiment 12
Other experiment condition, with embodiment 1, adds 1.74 g TDI, 0.052 g dibutyl tin laurate, prepares intermediate product mPEG-t-NCO white powder 4.3 g.
Embodiment 13
Other experiment condition, with embodiment 1, adds 2.2 g IPDI, 0.057 g dibutyl tin laurate, prepares intermediate product mPEG-t-NCO white powder 5.2 g.
Embodiment 14
Other experiment condition is with embodiment 1, and the reaction times is 4 h, prepares intermediate product mPEG-t-NCO white powder 5.3 g.
Embodiment 15
Other experiment condition is with embodiment 1, and the reaction times is 12 h, prepares intermediate product mPEG-t-NCO white powder 5.7 g.
Embodiment 16
Other experiment condition is with embodiment 1, and the reaction times is 24 h, prepares intermediate product mPEG-t-NCO white powder 5.7 g.
Embodiment 17
Be equipped with reflux condensing tube, strict dry and in the Schlenk bottle of nitrogen pump drainage 3 times, by 2.25g (1 mmol) mPEG-t-NCO(Mn=2250 g/mol), 4.43g iPP-t-OH(M
n=3100, terminal hydroxy group ratio>=70%, controlling hydroxy radical content is 1 mmol) and solvent toluene 200 mL join successively and be equipped with in the Schlenk bottle of reflux condensing tube, 0.0668g dibutyl tin laurate (1wt.%) is added after stirring, be warmed up to 100 DEG C of reaction 8h, revolve and steam except after desolventizing, remove unreacted mPEG-t-NCO with acetone repetitive scrubbing, at 40 DEG C, vacuum drying is to constant weight, prepares bi-block copolymer iPP-MDI-mPEG white powder 4.9 g.
Embodiment 18
Other experiment condition adds 6.86g iPP-t-OH(M with embodiment 17
n=4800, terminal hydroxy group ratio>=70%, controlling hydroxy radical content is 1 mmol), 0.0911g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-MDI-mPEG white powder 5.58 g.
Embodiment 19
Other experiment condition, with embodiment 17, adds 0.225g (1 mmol) mPEG-t-NCO, 0.842 g iPP-t-OH(M
n=5900, terminal hydroxy group ratio>=70%, controlling hydroxy radical content is 0.1 mmol), 0.0107g catalyst dibutyltin dilaurylate, (1wt.%) prepares bi-block copolymer iPP-MDI-mPEG white powder 0.98g.
Embodiment 20
Other experiment condition adds 1.143g iPP-t-OH(M with embodiment 19
n=8000, terminal hydroxy group ratio>=70%, controlling hydroxy radical content is 0.1 mmol), 0.0136g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-MDI-mPEG white powder 1.28g
Embodiment 21
Other experiment condition adds 2.142g iPP-t-OH(M with embodiment 19
n=15000, terminal hydroxy group ratio>=70%, controlling hydroxy radical content is 0.1 mmol), 0.0237g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-MDI-mPEG white powder 2.15g.
Embodiment 22
Other experiment condition, with embodiment 17, adds solvent toluene 333 mL(control end hydroxyl isotatic polypropylene concentration 0.03 mol/L), prepare bi-block copolymer iPP-MDI-mPEG white powder 4.08g.
Embodiment 23
Other experiment condition, with embodiment 17, adds solvent toluene 200 mL(control end hydroxyl isotatic polypropylene concentration 0.05 mol/L), prepare bi-block copolymer iPP-MDI-mPEG white powder 4.1g.
Embodiment 24
Other experiment condition, with embodiment 17, adds solvent toluene 100 mL(control end hydroxyl isotatic polypropylene concentration 0.1 mol/L), prepare bi-block copolymer iPP-MDI-mPEG white powder 3.5g.
Embodiment 25
Other experiment condition adds solvent n-heptane with embodiment 17, temperature of reaction 90 DEG C, reaction times 24 h, prepares bi-block copolymer iPP-MDI-mPEG white powder 3.1g.
Embodiment 26
Other experiment condition adds solvent octane with embodiment 17, temperature of reaction 110 DEG C, reaction times 6 h, prepares bi-block copolymer iPP-MDI-mPEG white powder 3.4g.
Embodiment 27
Other experiment condition adds solvent xylene with embodiment 17, temperature of reaction 130 DEG C, reaction times 4 h, prepares bi-block copolymer iPP-MDI-mPEG white powder 5.2g.
Embodiment 28
Other experiment condition adds 2.17g mPEG-HDI-NCO(M with embodiment 17
n=2168,1 mmol), 0.0465g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-HDI-mPEG white powder 3.9 g.
Embodiment 29
Other experiment condition adds 2.17g mPEG-TDI-NCO(M with embodiment 17
n=2174,1 mmol), 0.0465g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-TDI-mPEG white powder 3.6g.
Embodiment 30
Other experiment condition adds 2.22g mPEG-IPDI-NCO(M with embodiment 17
n=2222,1 mmol), 0.0470g catalyst dibutyltin dilaurylate (1wt.%), prepares bi-block copolymer iPP-IPDI-mPEG white powder 3.9g.
Embodiment 31
Other experiment condition, with embodiment 17, adds 0.20g catalyst dibutyltin dilaurylate (3wt.%), prepares bi-block copolymer iPP-MDI-mPEG white powder 4.8g.
Embodiment 32
Other experiment condition, with embodiment 17, adds 0.334g catalyst dibutyltin dilaurylate (5wt.%), prepare bi-block copolymer iPP-MDI-mPEG white powder 4.8g.
Claims (5)
1. an isotatic polypropylene-b-polyoxyethylene glycol two block thing, is characterized in that, its structural formula is as shown in any one in formula I ~ (IV):
In formula I ~ (IV), the arbitrary integer between m=7 ~ 120, the arbitrary integer between n=100 ~ 400.
2. prepare a method for isotatic polypropylene-b-polyoxyethylene glycol two block thing described in claim 1, it is characterized in that, comprise the following steps:
(1) be equipped with reflux condensing tube, dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add reactant methoxy poly (ethylene glycol), vulcabond, catalyst dibutyltin dilaurylate and solvent chloroform successively; There is nucleophilic substitution reaction in methoxy poly (ethylene glycol) and vulcabond, obtain terminal isocyanate group polyoxyethylene glycol under the effect of catalyst dibutyltin dilaurylate; The mol ratio of described methoxy poly (ethylene glycol) and vulcabond is 1:5 ~ 1:100, and the add-on of dibutyl tin laurate is 1% of reactant total mass, and the concentration of methoxy poly (ethylene glycol) in reaction system is 0.03mol/L ~ 0.1mol/L; Temperature of reaction is 25 DEG C ~ 60 DEG C, and the reaction times is 4 ~ 24h;
(2) be equipped with reflux condensing tube, dry and in the Schlenk bottle of nitrogen pump drainage 3 times, add terminal hydroxy group functionalization isotatic polypropylene, terminal isocyanate group polyoxyethylene glycol, organic solvent and catalyst dibutyltin dilaurylate successively; There is nucleophilic addition in terminal isocyanate group polyoxyethylene glycol and terminal hydroxy group functionalization isotatic polypropylene, obtain isotatic polypropylene-b-polyoxyethylene glycol two block thing under the effect of catalyst dibutyltin dilaurylate; The terminal hydroxyl of terminal hydroxy group isotatic polypropylene and the mol ratio of terminal isocyanate group polyoxyethylene glycol are 1:1 ~ 1:10, the add-on of dibutyl tin laurate is 1% ~ 5% of reactant total mass, and the concentration of terminal hydroxy group isotatic polypropylene in reaction system is 0.03mol/L ~ 0.1mol/L; Temperature of reaction is 90 DEG C ~ 130 DEG C, and the reaction times is 4 ~ 24h; Described organic solvent is toluene, dimethylbenzene, heptane, octane or its any mixture.
3. method according to claim 2, is characterized in that, described methoxy poly (ethylene glycol) is thread-like molecule, and its molecular weight is 350 ~ 5300g/mol, and molecular weight distribution is 1.1 ~ 1.9.
4. method according to claim 2, is characterized in that, described terminal hydroxy group functionalization isotatic polypropylene number-average molecular weight is 3 ~ 15 × 10
3g/mol, molecular weight distribution is 3 ~ 10.
5. method according to claim 2, is characterized in that, described vulcabond is hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate or diphenylmethanediisocyanate.
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| CN105694055A (en) * | 2016-02-23 | 2016-06-22 | 浙江大学 | Isotactic polypropylene-b-polytetrafluoroethylene double-segment polymer and method for preparing same |
| CN105778114A (en) * | 2016-04-15 | 2016-07-20 | 浙江大学 | Hyperbranched polyethylene-b-polyethylene glycol diblock copolymer and preparation method thereof |
| CN105860120B (en) * | 2016-05-11 | 2018-12-14 | 浙江大学 | A kind of super-hydrophobic polypropylene film and preparation method thereof |
| US20200017658A1 (en) * | 2018-07-10 | 2020-01-16 | Nano And Advanced Materials Institute Limited | Germ-repellent elastomer |
| CN109306120B (en) * | 2018-09-25 | 2021-06-25 | 宁波瑞成包装材料有限公司 | Production method of blending-method high-barrier-property polypropylene packaging film |
| CN109233106B (en) * | 2018-09-25 | 2021-06-29 | 宁波瑞成包装材料有限公司 | Production method of low-cost high-barrier polypropylene film |
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| CN110229343B (en) * | 2019-06-28 | 2021-07-30 | 郑州轻工业学院 | Polylactic acid-metal organic framework composite material and preparation method thereof |
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