CN102391443B - Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof - Google Patents

Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof Download PDF

Info

Publication number
CN102391443B
CN102391443B CN 201110247529 CN201110247529A CN102391443B CN 102391443 B CN102391443 B CN 102391443B CN 201110247529 CN201110247529 CN 201110247529 CN 201110247529 A CN201110247529 A CN 201110247529A CN 102391443 B CN102391443 B CN 102391443B
Authority
CN
China
Prior art keywords
polyisobutene
pib
block
diblock
isoprene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN 201110247529
Other languages
Chinese (zh)
Other versions
CN102391443A (en
Inventor
倪沛红
王怀超
张明祖
周明星
朱秀林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN 201110247529 priority Critical patent/CN102391443B/en
Publication of CN102391443A publication Critical patent/CN102391443A/en
Application granted granted Critical
Publication of CN102391443B publication Critical patent/CN102391443B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The invention belongs to field of organic polymer compound, disclose a kind of amphipathic nature block polymer and preparation method thereof containing polyisobutene and polyanion, the chemical structural formula of the polyisobutylene block copolymer are as follows:
Figure DDA0000086313550000011
In formula,X=18~60,Y=10~120,M+ represents K+ or Na+ ion; The present invention provides a kind of amphipathic copolymer for containing hydrophobic polyisobutene segment and hydrophilic polyanion segment simultaneously,The application range of the block copolymer containing polyisobutene has been expanded,It makes it possible to be applied in heterogeneous system; Synthesis step of the present invention is simple,Overcome conventional anion polymerization reaction need extremely low temperature,The shortcomings that being carried out under the harsh conditions such as high vacuum,It is easily controllable,It can carry out at room temperature,Reactivity is high,Reaction speed is fast,Conversion ratio approach 100%,Molecular weight is controllable,And products pure,Almost it is not necessarily to last handling process.

Description

A kind of amphipathic nature block polymer and preparation thereof that contains polyisobutene and polyanion
Technical field
The invention belongs to the organic high molecular compound field, relate to a kind of amphipathic nature block polymer and preparation thereof that contains polyisobutene and polyanion.
Background technology
Polyolefine material comprises polyethylene (PE), polypropylene (PP), poly 1-butene, polyisobutene, poly(4-methyl-1-pentene), ethylene-propylene rubber(EPR) (EPR), EPDR (EPDM) etc., have P/C than high, mechanical property is good and thermal characteristics is stablized and the characteristics such as crystallinity modulation scope is large, processing characteristics is good, security and stability good, recycling capable of circulation.But the intrinsic nonpolar and inertia of polyolefine makes its printing and dyeing property, agglutinating value(of coal) and all relatively poor with the consistency of other materials.Dow chemical company has developed a kind of new olefin block copolymers (OBCs) by the breakthrough of catalysis technique, i.e. ethylene-octene segmented copolymer (Olefin Block Copolymers, OBCs).Because " hard (high rigidity) " and " soft (snappiness) " segment alternative arrangement in the molecular chain, and variable-length, thereby has the overall equilbrium performance of flexibility, thermotolerance, wear resistance, compression set performance and the processing characteristics etc. of uniqueness.Yet this class olefin block copolymers still is hydrophobic, can't be applied in the diphasic system of polar/non-polar.
In recent years, increasing to the demand of high-activity polyisobutene in the world.Polyisobutene (PIB) be iso-butylene through the product of cationoid polymerisation, roughly can be three grades of high, medium and low molecular weight by molecular size range.Colourless polyisobutene is tasteless, nontoxic, nonflammable, good, acidproof, alkaline-resisting, water-fast, cold-resistant, heat-resisting, ageing-resistant, the anti-ozone of chemical stability, oxytolerant, UV resistant, and its purposes is very extensive.And high-activity polyisobutene (HRPIB; Highly Reactive-Polyisobutylene) be polyisobutene α-terminal double link content greater than 85% low-molecular-weight polyisobutylene, its principal feature is to go out by the explained hereafter of environmental protection polyisobutene ashless dispersant (internal combustion engine lubrication oil additive), the all good and not halogen-containing products of this dispersing property and low-temperature performance just enjoy user's favor once coming out, almost be penetrated into low-molecular-weight polyisobutylene (LPIB) all Application Areass, especially lubricating oil additive and fuel oil additive industry.In addition, also be widely used in fields such as emulsion explosive, tensio-active agent, sanitising agent and rust-preventive agent, market outlook are wide.
High-activity polyisobutene can also prepare various grafting and segmented copolymer, many new purposes also develop gradually, such as multi-functional wetting agent polyisobutene acid glyceride, macromolecular material internal plasticizer etc., but these segmented copolymer overwhelming majority are hydrophobic, still can't be generalized in the nonhomogeneous system and use.Therefore, synthetic to have amphipathic polyisobutylene block copolymer imperative, and application potential is huge, has very large market outlook in the future.
In the prior art, mainly contain based on the research of synthesizing polyisobutylene segmented copolymer:
(1) the Matyjaszewski K. of U.S. Carnegie Mellon University seminar atom transfer radical polymerization (ATRP) method, take polyisobutene as precursor synthesis the ATRP macromole evocating agent, cause vinylbenzene (St) and methyl methacrylate (MMA) polymerization, form segmented copolymer PIB-b-PS and PIB-b-PMMA.(referring to: Jakubowski, W.; Tsarevsky, N.V.; Higashihara, T.; Faust, R.; Matyjaszewski, K.Macromolecules 2008,41,2318-2323);
(2) rubber performance of the uniqueness of polyisobutene and polyethylene ferrocene (PVFc) segmented copolymer (PIB-b-PVFc) has been studied by Faust R. seminar in Massachusetts, USA university Lu Weier branch school.(referring to: Higashihara, T.; Faust, R.Macromolecules 2007,40,7453-7463);
(3) the Storey seminar of American South University of Mississippi has synthesized the segmented copolymer (PAA of polyacrylic acid and polyisobutene and polystyrene with the method for cationoid polymerisation and atom transfer radical polymerization (ATRP) associating 2-PIB-b-PS).(referring to: Breland, L.K.; Storey, R.F.Polymer 2008,49,1154-1163);
(4) the Puskas J.E. of U.S.'s Akron university seminar adopts cationic polymerization process, prepare the organic/inorganic composite material (PIB-POSS) based on polyisobutene and multiaspect oligomeric silsesquioxanes (POSS), strengthened the mechanical property of material.(referring to: Soytas, S.H.; Lim, G.T.; Puskas, J.E.Macromol.Rapid Commun.2009,30,2112-2115);
(5) patent No. is invented for 200310116817.7 China and is provided a kind of for filling-modified coupling agent of organic polymer and preparation method thereof, this coupling agent is to utilize maleic anhydride and polyisobutene, under the effect of initiator or no initiator, carry out graft reaction and prepare maleic anhydride graft polyisobutene polymkeric substance, its percentage of grafting controlled range is 1～80%.Wherein polyisobutene is that molecular weight is common polyisobutene or the high-activity polyisobutene of 800～10000g/mol, 120～250 ℃ of graft reaction temperature, 30～240 minutes reaction times.The coupling agent of preparation can improve consistency and the bounding force of organic polymer and inorganic filler effectively, have pollution-free, percentage of grafting control accurately, applied range etc.;
(6) patent No. provides a kind of solvothermal preparation method of maleic anhydride graft polyisobutene co-polymer for China's invention of 200810038559.8: in autoclave, put into liquid polyisobutene, maleic anhydride, initiator and oxidation inhibitor, and put into when needed coordinative solvent, the control temperature of reaction makes system be in the postcritical state of class and carries out graft reaction and prepare the maleic anhydride graft polyisobutene.The maleic anhydride graft polyisobutene of preparation can be directly used in the toughner of polycarbonate, polyester, nylon, urethane, polyvinyl chloride isopolarity resin, can obtain preferably matrix material of over-all properties;
(7) patent No. provides a kind of preparation method of glycidyl methacrylate graft polyisobutene copolymer for China's invention of 200910048737.X, in autoclave, put into polyisobutene, glycidyl methacrylate, comonomer, initiator and stablizer, and put into when needed corresponding solvent, in control temperature of reaction and the reaction times, make system be in the postcritical state of class and carry out graft reaction and prepare glycidyl methacrylate graft polyisobutene copolymer.The glycidyl methacrylate graft polyisobutene copolymer of preparation can be directly used in the toughner of unsaturated polyester, Resins, epoxy, polycarbonate, saturated polyester, nylon, urethane polar materials, can obtain preferably matrix material of over-all properties.
Yet, according to our investigation, research report for the amphipathic nature block polymer that contains polyisobutene and polyanion and preparation thereof in the above-mentioned technology is very few, the polyisobutylene block copolymer overwhelming majority that contains of having reported is hydrophobic, do not have the amphipathic of hydrophilic-oleophylic, still can't be generalized in the nonhomogeneous system and use, thereby have certain limitation.
Amphipathic nature block polymer (amphiphilic block copolymer), in broad terms, two blocks that form the copolymer molecule chain are respectively wetting ability and hydrophobic chain segment.This analog copolymer when concentration reaches micelle-forming concentration (critical micelle concentration, cmc), can form the self-assembly aggregate in solvent.Amphipathic nature polyalcohol had both contained hydrophilic segment in same macromolecular chain, also contain the lipophilicity segment, thereby have unique surface property, can be used as antithrombotics, tensio-active agent and polymer blending material in emulsifying agent, dispersion agent, stablizer, the aqueous solution and the compatilizer of matrix material.
Usually the method for preparing amphipathic nature block polymer mainly contains: active anionic polymerization, group transfer polymerization (GTP), nitroxyl free radical polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition-fracture chain transfer polymerization (RAFT) and oxygen anion initiated polymerization (OIP).These controlled/living polymerisation process are the strong technique means of preparation segmented copolymer.Wherein, the oxygen anion initiated polymerization has many advantages: reactive behavior is high, and speed is fast; By the change of initiator system structure, can design synthetic various novel, end with amphipathic multipolymer and the diversified Model Polymers of specific function group.Compare with active anionic polymerization, the method for oxygen anion initiated polymerization is easy, is easy to control, can at room temperature carry out.
Therefore, need a kind of get everything ready method of amphipathic polyisobutylene block copolymer of oxygen anion initiated polymerization legal system of utilizing of research and development, expand the range of application of polyisobutylene block copolymer.
Summary of the invention
Goal of the invention of the present invention provides a kind of amphipathic polyisobutylene block copolymer and preparation method thereof.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of polyisobutylene block copolymer, and the chemical structural formula of described polyisobutylene block copolymer is:
Figure BDA0000086313530000041
In the formula, x=18～60, y=10～120, M +Represent K +Or Na +Ion.
In the technique scheme, the number-average molecular weight of described polyisobutylene block copolymer is 2000～14000g/mol.
Above-mentioned polyisobutylene block copolymer since simultaneously contain hydrophobic polyisobutene segment and hydrophilic polyanion segment (contain carboxyl-COOH or-COO -Negatively charged ion), therefore, one section is hydrophilic chain, and another section is hydrophobic chain, belongs to typical amphipathic nature block polymer.
The preparation method of above-mentioned polyisobutylene block copolymer may further comprise the steps: at first utilize high-activity polyisobutene, by the hydroboration method for oxidation, prepare terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH); Then in the presence of potassium hydride KH (KH), the polyisobutene terminal hydroxyl is converted into oxygen anion PIB-O -K +, as macromole evocating agent, cause the Tert-butyl Methacrylate polymerization, obtain polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA; Then under trifluoroacetic acid catalysis, the side group hydrolysis with the polymethyl tert-butyl acrylate segment obtains to contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA; Further, described segmented copolymer PIB-b-PMAA in alkaline medium, carboxyl formation-COO -Negatively charged ion namely obtains containing the amphipathic nature block polymer of polyisobutene and polyanion;
Wherein, the structural formula of high-activity polyisobutene is:
Figure BDA0000086313530000042
Terminal hydroxyl (structural formula of polyisobutene PIB-OH OH) is:
Figure BDA0000086313530000043
The structural formula of polyisobutene oxygen anion macromole evocating agent is:
Figure BDA0000086313530000044
The structural formula of polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA is:
Figure BDA0000086313530000051
The structural formula that contains polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA is:
Figure BDA0000086313530000052
The structural formula that contains the amphipathic nature block polymer of polyisobutene and polyanion is:
Say that strictly PIB-b-PMAA should be amphipathic multipolymer, only becomes at carboxyl-COOH-COO -After, just can be called " segmented copolymer that contains polyanion ".Can form polyanion because it has been generally acknowledged that polymethyl acrylic acid, so two kinds of structures of general designation are polyanion in the application's book.
Particularly, the preparation method of above-mentioned polyisobutylene block copolymer may further comprise the steps:
(1) (polyisobutene PIB-OH (HTPIB) OH) :-5～0 ℃ under the ice-water bath condition, take anhydrous tetrahydro furan as solvent, with sodium borohydride (NaBH to prepare terminal hydroxyl 4) adding solvent, slowly the Eorontrifluoride etherate [(C of the amounts such as dropping and sodium borohydride 2H 5O) 2BF 3] solution, reacted 1～3 hour; Drip again high-activity polyisobutene (HRPIB) solution that is dissolved in anhydrous tetrahydro furan, reacted 15～20 hours; Then use sodium hydroxide solution regulation system pH to 10～about 12, slowly drip hydrogen peroxide (H 2O 2) solution, reacted 5～8 hours; Extraction, dry organic layer, desolventizing obtains terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH);
Above-mentioned reaction process is as follows:
Figure BDA0000086313530000054
Wherein, described high-activity polyisobutene (HRPIB) is commercial compound, and its number-average molecular weight is 1000～4000g/mol, and described high-activity polyisobutene (HRPIB) contains terminal double link, and its end alkene content is more than 85%; Preferably, described high-activity polyisobutene is selected from a kind of in the following commercialization high-activity polyisobutene: trade(brand)name and number-average molecular weight thereof
Figure BDA0000086313530000061
Be respectively JH-1000
Figure BDA0000086313530000062
Figure BDA0000086313530000063
JH-1300
Figure BDA0000086313530000064
JH-2300 Or JH-3300
Figure BDA0000086313530000066
(2) the terminal oxygen anion (PIB-O of polyisobutene -K +) preparation of macromole evocating agent: under the anhydrous and oxygen-free condition, under the atmosphere of inert gases, under 35～45 ℃, take anhydrous tetrahydro furan as solvent, make potassium hydride KH with etc. the hydroxyl reaction of polyisobutene PIB-OH end of amount, form the terminal oxygen anion (PIB-O of polyisobutene -K +), as the macromole evocating agent of oxygen anion initiated polymerization;
Above-mentioned reaction process is as follows:
Figure BDA0000086313530000067
(3) preparation of polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock: with the terminal oxygen anion (PIB-O of polyisobutene -K +) macromole evocating agent and monomer Tert-butyl Methacrylate (tBMA) polymerization, consist of polymerization system with mol ratio 1: 1～120, adopt oxygen anion polymerization polymerization 1～2 hour; Termination reaction is purified, and namely obtains polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA;
Above-mentioned reaction process is as follows:
Figure BDA0000086313530000068
The structural formula of above-mentioned Tert-butyl Methacrylate is:
Figure BDA0000086313530000069
(4) preparation contains the amphipathic nature block polymer of polyisobutene and polyanion: take methylene dichloride as solvent, under the condition that trifluoroacetic acid exists, the tertiary butyl of polyisobutene-b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is hydrolyzed; React complete rear rotary evaporation desolventizing, carry out deposition and purification with cold acetone, be dried to constant weight, namely obtain required polyisobutene and the polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA of containing;
Above-mentioned reaction process is as follows:
Figure BDA0000086313530000071
In the formula, x is 18～60; Y is 10～120.
In the further technical scheme, above-mentioned polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PMAA, in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO -Negatively charged ion obtains the amphipathic nature block polymer that contains polyisobutene and polyanion shown in the following structural formula:
Figure BDA0000086313530000072
In the formula, x is 18～60; Y is 10～120; M +Represent K +Or Na +Ion.
The present invention is polyisobutene PIB-OH (HTPIB) and the application in preparation dependency structure macromolecular material thereof of claimed above-mentioned end hydroxyl simultaneously.
The present invention is the polyisobutene (PIB-O of claimed above-mentioned end oxo-anions simultaneously -K +) and as the application of macromole evocating agent in preparation dependency structure macromolecular material.
The present invention is claimed above-mentioned polyisobutene and polymethyl tert-butyl acrylate segmented copolymer (PIB-b-PtBMA) and the application in preparation dependency structure macromolecular material thereof simultaneously.
The present invention is claimed above-mentioned polyisobutene and polymethyl acrylic acid segmented copolymer (PIB-b-PMAA) and the application in preparation dependency structure macromolecular material thereof simultaneously.
The present invention is the claimed above-mentioned amphipathic nature block polymer that contains polyisobutene and polyanion also
Figure BDA0000086313530000073
And the application in other Polymer materialspreparations.
When reality prepares, for guaranteeing the purity of product, can make with extra care raw material first, its method is to use the alkaline Al of activation before Tert-butyl Methacrylate (tBMA) uses 2O 3Post is processed, and then uses CaH 2More than the dry 12h, at high-purity N 2Carry out underpressure distillation under the protection; KH seals up for safekeeping in mineral oil for subsequent use; Solvents tetrahydrofurane (THF) was used potassium hydroxide dry three days, added benzophenone as indicator, carried out anaerobic with the sodium silk and refluxed, until be intense violet color, steamed before the use.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1. the invention provides a kind of contain simultaneously hydrophobic polyisobutene segment and hydrophilic polyanion segment (contain carboxyl-COOH or-COO -Negatively charged ion) amphipathic copolymer has overcome the deficiency that only has the segmented copolymer of Non-amphiphilic polyisobutene in the prior art, has expanded the range of application of the segmented copolymer that contains polyisobutene, makes it to be applied in the nonhomogeneous system; Owing to there is the polymethyl acrylic acid segment in final product, it has preferably wetting ability, thereby can obtain a kind of amphipathic nature block polymer that contains polyisobutene and polyanion; Can be applied to the fields such as the emulsifying agent of rubber modifier, blending additive, letex polymerization and fabric-treating agent.
The present invention utilize potassium hydride KH with etc. the terminal hydroxyl of amount (behind polyisobutene PIB-OH (HTPIB) stirring reaction OH), form the terminal oxygen anion (PIB-O of polyisobutene -K +), the polymerization process that utilizes oxygen anion to cause by the change of initiator system structure and the change of [monomer]/[primosome] proportioning, prepares the polymkeric substance of different chain length degree, different hydrophilic and hydrophobic, different blocks as required.
3. synthesis step of the present invention is simple, overcome the shortcoming that traditional anionic polymerisation need to carry out under the severe condition such as extremely low temperature, high vacuum, be easy to control, can at room temperature carry out, reactive behavior is high, and speed of response is fast, transformation efficiency convergence 100%, molecular weight is controlled, and product is pure, almost need not the aftertreatment sepn process.
4. gained amphipathic copolymer of the present invention can be applicable to rubber accelerator, papermaking and fabric auxiliary agent, emulsifier for emulsion polymerization and field of medical materials.
Description of drawings
Fig. 1 be (JH-3300) gel permeation chromatography (GPC) elution curve of the highly active polyisobutene of commercialization (HRPIB) among embodiment one and the embodiment two (standard specimen: polystyrene), actual test value:
Figure BDA0000086313530000081
Figure BDA0000086313530000082
Fig. 2 be the highly active polyisobutene of commercialization (HRPIB) among embodiment one and the embodiment two proton nmr spectra ( 1H NMR) spectrogram, solvent are deuterochloroform (CDCl 3);
Fig. 3 be terminal hydroxyl among embodiment one and the embodiment two (proton nmr spectra of polyisobutene PIB-OH (HTPIB) OH) ( 1H NMR) spectrogram, solvent are deuterochloroform (CDCl 3);
Fig. 4 is polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PIB-b-PtBMA among the embodiment one 53) proton nmr spectra ( 1H NMR) spectrogram, solvent are deuterochloroform (CDCl 3);
Fig. 5 is HTPIB, PIB-b-PtBMA among the embodiment one 53And PIB-b-PtBMA among the embodiment two 36Gel permeation chromatography (GPC) elution curve figure (standard specimen: methyl methacrylate);
Fig. 6 is PIB-b-PtBMA among the embodiment one 53And PIB-b-PtBMA among the embodiment two 36Thermogravimetric analysis (TGA) curve;
Fig. 7 is polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock (PIB-b-PMAA among the embodiment one 53) proton nmr spectra ( 1H NMR) spectrogram, solvent are deuterated dimethyl sulfoxide (DMSO-d 6).
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment one: PIB-b-PtBMA 53The preparation method
(1) the terminal hydroxyl (preparation of polyisobutene PIB-OH (HTPIB) OH): under-5～0 ℃ of ice-water bath condition, take anhydrous tetrahydro furan as solvent, add the sodium borohydride (NaBH of certain amount of substance in the three-necked flask 4).Slowly drip the Eorontrifluoride etherate [(C of Isoequivalent weight 2H 5O) 2BF 3] solution reaction 1.5 hours; Drip again highly active polyisobutene (HRPIB) solution that is dissolved in anhydrous tetrahydro furan, reacted 20 hours.Drip NaOH solution, about regulation system pH to 12, slowly drip 30% H 2O 2Solution reacted 7 hours.Obtain organic layer with extracted with diethyl ether, with anhydrous magnesium sulfate (MgSO 4) dry rear rotary evaporation, desolventizing, products therefrom drying under the vacuum drying oven room temperature namely obtained terminal hydroxyl (polyisobutene PIB-OH (HTPIB) OH) in 24 hours.
The molecular weight of the highly active polyisobutene of employed commercialization (HRPIB) and molecular weight distribution thereof are measured by gel permeation chromatography (GPC) in the present embodiment, as shown in Figure 1.The structure of HRPIB proton nmr spectra ( 1H NMR) proves, as shown in Figure 2.
Reaction product in the present embodiment, namely the molecular structure of the polyisobutene PIB-OH (HTPIB) of terminal hydroxyl through proton nmr spectra ( 1H NMR) checking, as shown in Figure 3, the chemical shift of terminal hydroxyl proton is at δ 2.18ppm.
(2) preparation of KH: the magnetic agitation rotor is put into the dry reaction flask with arm in advance, with turned welt soft rubber ball jam-pack.Then link to each other with vacuum pump with syringe needle, emulsion tube, be filled with high-purity argon gas while vacuumizing, remove oxygen and aqueous vapor in the bottle, so repeatable operation is three times.After moving into a certain amount of KH in the reaction flask, inject the anhydrous tetrahydrofuran (THF) of 5ml (THF) with the dry injection device, agitator treating staticly contains the THF of mineral oil with the syringe sucking-off afterwards, three times so repeatedly, dries up at last the THF solution of remnants with high-purity argon gas.(0.2～0.3g about 5.0～7.5mmol) to utilize the amount of KH in the decrement method accurate weighing reaction flask.
(3) preparation of macromole evocating agent: a certain amount of anhydrous THF is expelled in the polymerization bottle that KH is housed.Reaction flask is inserted (about 35～45 ℃) in the oil bath; magnetic agitation; ((HTPIB is dissolved in anhydrous THF to polyisobutene PIB-OH (HTPIB) OH) to the terminal hydroxyl of the amounts such as injection and KH in advance simultaneously; argon shield); reaction 10～12h fully reacts HTPIB and KH and generates polyisobutene oxygen anion (PIB-O -K +).
(4) polyreaction: then reaction flask is moved in 25 ℃ of constant temperature oil baths, syringe with drying adds monomer Tert-butyl Methacrylate (tBMA), with the mol ratio of macromole evocating agent be 55: 1, reaction 1～1.5h uses dry methyl alcohol termination reaction at last.Reacted polymkeric substance under 60～70 ℃ of conditions, revolves the steaming desolventizing, continues to carry out deposition and purification with cold methyl alcohol, and triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Obtain required product, record productive rate greater than 98%.
The structure of the polyisobutene that obtains and polymethyl tert-butyl acrylate (PIB-b-PtBMA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock proton nmr spectra ( 1H NMR) detects, as shown in Figure 4.Figure 5 shows that the elution curve of gel permeation chromatography (GPC) of the polyisobutene (HTPIB) of PIB-b-PtBMA Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and terminal hydroxyl, by relatively finding out, the elution time of PIB-b-PtBMA Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock shortens, illustrate that molecular weight of copolymer increases, and can prove to successfully synthesize PIB-b-PtBMA thus 53
By the thermogravimetric analysis curve, as shown in Figure 6, two heat decomposition temperatures are arranged in the curve, this be because: segmented copolymer is because the weight-loss curve in obvious two stages appears in formation polyisobutene and polymethyl tert-butyl acrylate microcell separately, thus, can prove equally and successfully synthesize Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-b-PtBMA.
(5) hydrolysis reaction: with gained PIB-b-PtBMA polymer dissolution in methylene dichloride, reaction flask is as in the ice-water bath, drip the trifluoroacetic acid of a certain amount of methylene dichloride dilution by constant pressure funnel, dropwised in 1～2 hour, the Water Under solution of room temperature two days, under 30～40 ℃ of conditions, the rotary evaporation desolventizing, carry out deposition and purification with cold acetone, triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Namely obtain required product P IB-b-PMAA, record productive rate greater than 90%.
The structure of the polyisobutene that obtains and polymethyl acrylic acid (PIB-b-PMAA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock proton nmr spectra ( 1H NMR) detect, as shown in Figure 7, the chemical shift of carboxyl proton has obtained target product in δ 12.25ppm proof.
Embodiment two: PIB-b-PtBMA 36The preparation method
(1) the terminal hydroxyl (preparation of polyisobutene PIB-OH (HTPIB) OH): with embodiment one.
(2) preparation of KH: with embodiment one.
(3) preparation of macromole evocating agent: with embodiment one.
(4) polyreaction: then in the constant temperature oil bath with 25 ℃ of reaction flask immigrations, syringe with drying adds monomer Tert-butyl Methacrylate (tBMA), with the mol ratio of macromole evocating agent be 40: 1, reaction 1.0～1.5h uses dry methyl alcohol termination reaction at last.Reacted polymkeric substance, under 30～40 ℃ of conditions, the rotary evaporation desolventizing continues to carry out deposition and purification with cold methyl alcohol, and triplicate is dried to constant weight 40～50 ℃ of vacuum drying ovens at last.Obtain required product, record productive rate greater than 98%.
The molecular weight of the polyisobutene that obtains and polymethyl tert-butyl acrylate (PIB-b-PtBMA) Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock and molecular weight distribution are measured with gel permeation chromatography (GPC), and its GPC elution curve as shown in Figure 5.By with polyisobutene (HTPIB) and the PIB-b-PtBMA of terminal hydroxyl 53The GPC elution curve of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock relatively can be found out the PIB-b-PtBMA that present embodiment synthesized 36The elution curve of Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is between the said two devices curve.Proof adopts the oxygen anion initiated polymerization thus, by regulating the proportioning of [monomer]/[initiator], can control well structure and the molecular weight of multipolymer, obtains target product.
(5) hydrolysis reaction: with embodiment one.

Claims (5)

1. a polyisobutylene block copolymer is characterized in that, the chemical structural formula of described polyisobutylene block copolymer is:
Or
Figure 923140DEST_PATH_IMAGE002
In the formula, x=18～60, y=10～120, M +Represent K +Or Na +Ion; The number-average molecular weight of described polyisobutylene block copolymer is 2000～14000 g/mol.
2. the preparation method of the described polyisobutylene block copolymer of claim 1 is characterized in that, may further comprise the steps: at first utilize high-activity polyisobutene, by the hydroboration method for oxidation, prepare the polyisobutene PIB-OH of terminal hydroxyl; Then in the presence of potassium hydride KH, the polyisobutene terminal hydroxyl is converted into oxygen anion PIB-O -K +, as macromole evocating agent, cause the Tert-butyl Methacrylate polymerization, obtain polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-P tBMA; Then under trifluoroacetic acid catalysis, the side group hydrolysis with the polymethyl tert-butyl acrylate segment obtains to contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-PMAA; Further, described Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-PMAA in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO -Negatively charged ion namely obtains containing the amphipathic nature block polymer of polyisobutene and polyanion
Figure 114167DEST_PATH_IMAGE002
In the formula, x=18～60, y=10～120, M +Represent K +Or Na +Ion;
Wherein, the structural formula of high-activity polyisobutene is:
Figure DEST_PATH_IMAGE003
；
The structural formula of the polyisobutene PIB-OH of terminal hydroxyl is:
；
The structural formula of polyisobutene oxygen anion macromole evocating agent is:
；
Polyisobutene and polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-P tThe structural formula of BMA is:
Figure 534227DEST_PATH_IMAGE006
；
Contain polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- bThe structural formula of-PMAA is:
Figure 682442DEST_PATH_IMAGE001
；
In the formula, x=18～60, y=10～120.
3. the preparation method of the described polyisobutylene block copolymer of claim 2 is characterized in that, specifically may further comprise the steps:
(1) the polyisobutene PIB-OH of the terminal hydroxyl of preparation: under-5 ~ 0 ℃ of ice-water bath condition, take anhydrous tetrahydro furan as solvent, sodium borohydride is added solvent, slowly the Eorontrifluoride etherate solution of the amounts such as dropping and sodium borohydride reacted 1 ~ 3 hour; Drip again the high-activity polyisobutene solution that is dissolved in anhydrous tetrahydro furan, reacted 15 ~ 20 hours; Then use sodium hydroxide solution regulation system pH to 10 ~ about 12, slowly drip hydrogen peroxide H 2O 2Solution reacted 5 ~ 8 hours; Extraction, dry organic layer, desolventizing obtains the polyisobutene PIB-OH of terminal hydroxyl;
(2) the terminal oxygen anion PIB-O of polyisobutene -K +The preparation of macromole evocating agent: under the anhydrous and oxygen-free condition, under the atmosphere of inert gases, under 35 ~ 45 ℃, take anhydrous tetrahydro furan as solvent, make potassium hydride KH with etc. the hydroxyl reaction of PIB-OH end of amount, form the terminal oxygen anion PIB-O of polyisobutene -K +, as the macromole evocating agent of oxygen anion initiated polymerization;
(3) polyisobutene- bThe preparation of-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock: with the terminal oxygen anion macromole evocating agent of polyisobutene and the polymerization of monomer Tert-butyl Methacrylate, consist of polymerization system with mol ratio 1: 1～120, adopt oxygen anion initiated polymerization method reaction 1～2 hour; Termination reaction is purified, namely obtain polyisobutene- b-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-P tBMA;
(4) preparation contains the amphipathic nature block polymer of polyisobutene and polyanion: take methylene dichloride as solvent, in the presence of trifluoroacetic acid, to polyisobutene- bThe tertiary butyl of-polymethyl tert-butyl acrylate Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is hydrolyzed; React complete rear rotary evaporation desolventizing, carry out deposition and purification with cold acetone, be dried to constant weight, namely obtain required polyisobutene and the polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB-of containing b-PMAA;
(5) above-mentioned polyisobutene and polymethyl acrylic acid Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock PIB- b-PMAA, in alkaline medium, the carboxyl in the polymethyl acrylic acid segment-COOH formation-COO -Negatively charged ion obtains the amphipathic nature block polymer that contains polyisobutene and polyanion shown in the following structural formula:
Figure 286730DEST_PATH_IMAGE002
；
In the formula, x=18～60, y=10～120, M +Represent K +Or Na +Ion.
4. the preparation method of the described polyisobutylene block copolymer of claim 3 is characterized in that, in the step (1), the end alkene content of described high-activity polyisobutene is more than 85%; The number-average molecular weight of described highly active polyisobutene is 1000～4000 g/mol.
5. a polyisobutene and polymethyl tert-butyl acrylate segmented copolymer is characterized in that the structural formula of described polyisobutene and polymethyl tert-butyl acrylate segmented copolymer is:
In the formula, x=18～60, y=10～120.
CN 201110247529 2011-08-24 2011-08-24 Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof Expired - Fee Related CN102391443B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110247529 CN102391443B (en) 2011-08-24 2011-08-24 Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110247529 CN102391443B (en) 2011-08-24 2011-08-24 Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof

Publications (2)

Publication Number Publication Date
CN102391443A CN102391443A (en) 2012-03-28
CN102391443B true CN102391443B (en) 2013-04-17

Family

ID=45858840

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110247529 Expired - Fee Related CN102391443B (en) 2011-08-24 2011-08-24 Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof

Country Status (1)

Country Link
CN (1) CN102391443B (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7196142B2 (en) * 2002-04-04 2007-03-27 The University Of Akron Polyisobutylene-based block anionomers and cationomers and synthesis thereof
DE10303275A1 (en) * 2003-01-28 2004-07-29 Basf Ag Functionalization of isobutene polymers, useful for the production of polyurethanes, comprises reaction of at least one isobutene polymer having terminal unsaturation with a hydroboration agent
CN1271102C (en) * 2003-06-12 2006-08-23 中国科学院化学研究所 Method for preparation of functional polyolefin block copolymer
DE10338245A1 (en) * 2003-08-20 2005-03-24 Basf Ag molding compound
US7135529B2 (en) * 2004-08-09 2006-11-14 Acushnet Company Golf ball comprising saturated rubber/ionomer block copolymers

Also Published As

Publication number Publication date
CN102391443A (en) 2012-03-28

Similar Documents

Publication Publication Date Title
CN104672403B (en) A kind of environmentally friendly silicone acrylic emulsion and preparation method thereof
CN102585123B (en) Poly-((methyl) crylic acid-b-styrene-b-butadiene-b-styrene) segmented copolymer latex and preparation method thereof
CN104177528B (en) A kind of ethylene/longer chain α-olefin copolymer and preparation method thereof
CN100554291C (en) The preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit
CN102391444B (en) Amphipathic block copolymer containing polyisobutylene and polycation and preparation thereof
Lu et al. Well‐defined amphiphilic polymethylene‐b‐poly (acrylic acid) diblock copolymers: New synthetic strategy and their self‐assembly
CN102633961A (en) Preparation method of segmented copolymer from vinylidene chloride copolymer and polyethylene glycol
CN110475795A (en) Polyolefm-polystyrene segmented copolymer, is used to prepare its organic zinc compound and preparation method thereof
CN102361096A (en) Lithium ion gel electrolyte based on polymethyl methacrylate-polystyrene diblock copolymer, and preparation method thereof
WO2007105898A1 (en) Method for preparation of 1-alkene-acrylate based copolymer
CN107418125A (en) A kind of method that multiphase polymer material is prepared using segmented copolymer latex
CN100412101C (en) Amphipathic fluoride block copolymer and production thereof
CN102391443B (en) Amphipathic block copolymer containing polyisobutylene and polyanion and preparation thereof
CN107098997A (en) A kind of isotactic polypropylene containing ammonium ion is from aggressiveness and preparation method
CN107163203B (en) A kind of multiform looks organic nano particle and its preparation method and application
CN100376614C (en) Fluorine-contg. block copolymers of pH-responsed and its prepn. method
CN100422228C (en) Fluorine-containing superbranching-grafting block polymer and its preparation
CN105367777A (en) Two-block polyvinyl hyperbranched polymer and preparation method and application thereof
CN102453303A (en) Monovinylarene-conjugated diene block copolymer composition and preparation method thereof
CN109575327A (en) Polyacrylate soft component/metal coordination polyacrylic polymer hard component coordination supramolecule elastomer and preparation method thereof
CN111499857B (en) Conjugated diene and epoxy compound block copolymer and preparation method thereof
CN103819700A (en) Method for improving flexibility of polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol
CN103044697A (en) Method for preparing microphase structural latex film
CN107793542B (en) Method for synthesizing hydrogenated styrene/isoprene block copolymer
CN106117410A (en) Can the preparation method of end-vinyl liquid fluoroelastomer of room temperature fast-curing

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee
CP02 Change in the address of a patent holder

Address after: Suzhou City, Jiangsu province 215137 Xiangcheng District Ji Road No. 8

Patentee after: Soochow University

Address before: 215123 Suzhou City, Suzhou Province Industrial Park, No. love road, No. 199

Patentee before: Soochow University

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130417

Termination date: 20160824

CF01 Termination of patent right due to non-payment of annual fee