CN100554291C - The preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit - Google Patents
The preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit Download PDFInfo
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- CN100554291C CN100554291C CNB2006100120742A CN200610012074A CN100554291C CN 100554291 C CN100554291 C CN 100554291C CN B2006100120742 A CNB2006100120742 A CN B2006100120742A CN 200610012074 A CN200610012074 A CN 200610012074A CN 100554291 C CN100554291 C CN 100554291C
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Abstract
The invention belongs to polymeric material field, be specifically related to a kind of preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit.Step of the present invention: multipolymer (seeing the bottom right formula) is dissolved in organic solvent with the unsaturated monomer that can carry out radical polymerization is mixed with solution, wherein the proportioning of multipolymer and unsaturated monomer is 0.001～0.1g/mL, and the mass concentration of polymeric reaction solution is 10～100wt%.With above-mentioned solution polymerization 5min～50h under 60 ℃～140 ℃ temperature, reaction is poured reaction soln in the precipitation agent into after finishing, and obtains throw out under the nitrogen protection; Throw out is separated drying, obtain containing the segmented copolymer of alpha-methyl styrol structural unit.Do not use any other initiator in present method, use range is wide, and is little to the susceptibility of impurity, and the controllability of reaction increases; Products therefrom better performances and the effect of environmental protection is arranged.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of multipolymer that contains alpha-methyl styrol structural unit and its production and application.
Background technology
Macromole evocating agent is meant and has the macromolecular compound that can decompose the group that produces free radical on molecular chain.Compare with the small molecules initiator, have the following advantages: 1. nearly all monomer can carry out radical polymerization; 2. the susceptibility to impurity is little; 3. the segmented copolymer relative molecular mass that causes gained distributes narrow usually.Because the diffusion of macromole evocating agent and reactivity are all lower, the radical termination reaction is reduced, the controllability of reaction increases, so use its synthetic segmented copolymer, becomes at present the focus of research both at home and abroad.The kind of the macromole evocating agent of developing at present is a lot, as azo class, peroxide, carboxylic acid halides class, carbon oxygen class, carbon sulphur class etc., still, because the general relative complex of building-up process of these macromole evocating agents, and cost is higher, has hindered its suitability for industrialized production and has applied.
Alpha-methyl styrene (AMS) is the by product of cumene method coproduction phenol and acetone, the equilibrium temperature of its homopolymer depolymerization lower (under a normal atmosphere, being 61 ℃), so AMS is difficult to autohemagglutination under normal pressure.But many monomeric reactivity ratios such as AMS and glycidyl methacrylate, maleic anhydride, vinylbenzene are all less than 1, so be easy to form multipolymer with other monomer.The continuous elimination reaction (opening zippering reaction) of monomer chain link under heating condition, easily takes place owing to contain quaternary carbon atom in the chain link in the multipolymer of these α vinyl toluenes, i.e. depolymerization reaction, thus can form free radical.Based on this, can cause the generation of a series of polyreactions with the multipolymer that contains alpha-methyl styrol structural unit as macromole evocating agent.But up to now, we do not find the report about the applied research of alpha-methyl styrene polymer depolymerization characteristic as yet at home and abroad on the document.
For a period of time, people are used as fuel to AMS as refuse and have burnt.In recent years, both at home and abroad the scientific worker had carried out number of research projects to the comprehensive utilization of AMS, had obtained a series of scientific payoffss: be raw material with AMS, can synthesize have the banksia rose, fruital, amber and Moschus type spices; With AMS and phenol is that raw material can synthesize cumylphenol, can be used for making nonionic surface active agent, sterilant, anti-enzyme agent etc.; The dimer of AMS has good flowability, ageing resistance, is the good properties-correcting agent that processing of high molecular material is used, and especially the processing to PVC has good plastification.But generally speaking, the AMS using value is still not high.
At present, the producer that China produces phenol is a lot, as Beijing Yanshan Petrochemical, and Jilin Chemical Industry Company, the Shanghai Gaoqiao petrochemical industry, east wind chemical plant, Fushun, Lanzhou chemical industrial company etc. adopts cumene method, but does not all carry out rational exploitation and utilization for AMS.Some producer (as Yanshan Petrochemical, Jiization) carries out hydrogenating reduction with AMS and becomes isopropyl benzene, sends reaction again in the system back to, and this is inappropriate from considering economically.Adopt the phenol-acetone by-product AMS500 ton of 10,000 tons of the every productions of cumene method, it is a considerable number of.Therefore, no matter still consider that from economic benefit the development and utilization of alpha-methyl styrene all has broad prospects from the utilization of by-product reasonable resources.Abroad research and the application facet at alpha-methyl styrene maintains the leading position, and domesticly then is in the starting stage.Therefore, can infer that this patent will play great pushing effect in the application in bigger field to this monomer for the comprehensive utilization that contains the alpha-methyl styrol structural unit multipolymer.
Segmented copolymer is the very important polymer of a class, and the segmented copolymer that is formed by different monomers has particular performances, has a wide range of applications aspect many in the modification of polymkeric substance, blend etc.It is the most frequently used method of present synthetic segmented copolymer that the living anion polymerization system adds different monomers successively.Because macromole evocating agent can make traditional radical polymerization also have the ability of preparation similar " reactive polymer ", it also can be used to the segmented copolymer of synthetic predetermined structure as anionoid polymerization.Along with development of technology, people also day by day improve the interest of free radical block copolymerization.The radical polymerization mild condition is easy to control, and mechanism research is thorough, and the advantage of uniqueness is also arranged by the block copolymerization of free radical: it is more that (1) can carry out the monomer of radical polymerization, promptly monomeric range of choice broad; (2) radical polymerization does not resemble the ionic polymerization the impurity sensitivity.What is more important, it can obtain the unavailable copolymerization product of other polymerization processs, and gives its excellent performance.The multipolymer that employing contains alpha-methyl styrol structural unit can prepare various segmented copolymers equally as macromole evocating agent, for the development and Design of novel material is opened up a new prospect.
Polypropylene (PP) is because its abundant raw material, synthesis technique is fairly simple, compare with other interchangeable heat thermoplastic plastics, PP has that relative density is little, price is low, and outstanding proof stress, cracking behavior and wear resistance arranged, development in recent years is rapid, becomes fastest-rising kind in the interchangeable heat thermoplastic plastic, but polypropylene also exists that low temperature brittleness, physical strength and hardness are lower, molding shrinkage big, easy shortcoming such as aging, temperature tolerance difference.Yet, because the nonpolar and crystallinity of its molecular structure, make its dyeability, cementability, static resistance, wetting ability and and polar polymer, consistency, affinity as nylon (PA), polybutylene terephthalate, polyethylene terephthalate, polycarbonate, urethane and mineral filler are relatively poor, have limited further and have applied.In order to overcome above-mentioned shortcoming, people have done number of research projects to the modification of PP.Studying more is by the grafted method, introduces polar group or rigid radical on nonpolar PP chain, thereby overcomes above-mentioned defective effectively.At present, the common method about the PP graft modification has: solution grafting, fusion-grafting method, radiation graft process, light-initiated grafting method, solid phase grafting method etc.Wherein, the fusion-grafting method easy and simple to handle, economical owing to it, be fit to characteristics such as suitability for industrialized production and become one of present topmost method of modifying.
Along with the fast development of modern society, PP institute inherent performance can not meet the demands far away, and is increasing to the demand of PP high performance.Adopt copolymerization, blending modification method can improve the polymer properties defective, wherein the copolymerization process technical difficulty is bigger, and the resin trade mark of being produced is less, does not satisfy the demand in the PP practical application.Blending modification method can effectively improve the performance deficiency of PP, and less investment, instant effect, therefore is subjected to paying close attention to widely both at home and abroad.For the co-mixing system of being made up of two or more polymkeric substance, if thermodynamics is compatible fully, blend might form the homogeneous morphological structure, and its final performance is generally the adduction of original polymer performance.If two kinds of polymkeric substance are incompatible fully on thermodynamics, blend forms heterogeneous structure so, shows macroscopic and is separated, bonding force is low between polymer interface, and under stress, not only the power transmission is obstructed, phase can not stablized yet simultaneously, so there is not practical value.The blending and modifying polymkeric substance that actual application value is big has limited compatibility between its component polymer, even consistency is very poor, forms heterogeneous morphological structure.If this class blending and modifying polymkeric substance takes measures to make its interface that more intense interaction is arranged, often have the performance when substantially exceeding each component Individual existence, also can possess the novel performance that each component does not have.Increase-volume is the technology of the interfacial property of incompatible blend being carried out modification, by morphology Control and interface modification, increases the cohesive force of phase interface, the performance of incompatible blend is improved greatly, thereby prepare the industrial novel material that using value is arranged.
As expanding material, reducing surface energy and surface tension with polypropylene grafted thing, promote two alternate molecular diffusion, reach the effect that strengthens interface bonding, refinement and stable phase dispersing morphology, is a kind of efficient ways.At present, both at home and abroad take with superoxide (as dicumyl peroxide DCP or dibenzoyl peroxide BPO) for the preparation of this polypropylene grafted thing is initiator more, and the method by fusion-grafting is with monomer-grafted approach to the polymer macromolecule chain.This method is simple, but also there is many-sided defective: at first, the graft reaction mechanism complexity that superoxide causes, cause product complexity, various, give the research of reaction mechanism and the control of reacting is brought difficulty, superoxide causes polyacrylic excessive degradation, its mechanical property of grievous injury easily under the high temperature simultaneously; Secondly, autohemagglutination can take place in monomer when carrying out graft polymerization, cause percentage of grafting lower; In addition, the residual unstable properties that makes graft product of superoxide finally has influence on the performance of blend; At last, in the process of grafting, monomeric toxicity and high-temperature volatile also can work the mischief to human body and environment.The present invention is based on above consideration, utilization contains the depolymerization characteristic of alpha-methyl styrol structural unit multipolymer, prepare functional poly propylene not needing to add under the situation of peroxide initiator and small molecule monomer, this product can improve polyacrylic performance deficiency, or be applied to polyacrylic blending and modifying field, have wide applicating and exploitation prospect.
Summary of the invention
The at first synthetic a kind of multipolymer that contains alpha-methyl styrol structural unit of the present invention, utilize this multipolymer when being heated to more than 60 ℃, the characteristic that can depolymerization forms free radical, can be used as macromole evocating agent, cause the chemical reaction of following several respects: first, cause other monomeric polyreaction, thus synthetic segmented copolymer; Second, the covalent linkage fracture takes place under the effect of shear extrusion repeatedly of high temperature and processing units easily in conjunction with polypropylene, thereby form the characteristic of macromolecular chain free radical, in polypropylene fusion graft process, realize this multipolymer and polyacrylic graft copolymerization, the gained graft copolymer can be used as functional poly propylene and uses separately, also can be used as the expanding material of polypropylene co-mixing system; The 3rd, utilize second described this multipolymer can with the characteristic of polypropylene generation melting graft reaction, this multipolymer directly is added in the polyacrylic blending modification system, can play the original position compatibilization.
A kind of multipolymer that contains alpha-methyl styrol structural unit provided by the invention, its structural formula is as follows
R is and the structural unit of alpha-methyl styrene reactivity ratio less than 1 unsaturated monomer in the formula, and these monomers comprise one of methacrylic acid, glycidyl methacrylate, hydroxyethyl methylacrylate, methyl methacrylate, maleic anhydride, vinyl cyanide, vinyl acetate, vinylchlorid, vinylbenzene and derivative thereof.
The copolymer method that this contains alpha-methyl styrol structural unit is characterized in that, may further comprise the steps:
1) with α-Jia Jibenyixidanti with at least aly can be dissolved in solvent with the mixture that alpha-methyl styrene carries out free-radical polymerized unsaturated monomer and initiator and be mixed with solution polymerization system, wherein the mass ratio of monomer summation is 0.001: 1～0.1: 1 in initiator and the polymerization system, and the mol ratio of the unsaturated monomer of alpha-methyl styrene and copolymerization is 1: 1～1: 20; Or with α-Jia Jibenyixidanti with at least aly can carry out free-radical polymerized unsaturated monomer, initiator, emulsifying agent with alpha-methyl styrene and be dissolved in deionized water and be mixed with emulsion polymerization systems, wherein the mol ratio of the unsaturated monomer of alpha-methyl styrene and copolymerization is 1: 1～1: 20, the mass ratio of monomer summation is 0.001: 1～0.1: 1 in initiator and the polymerization system, and the mass ratio of monomer summation is 0.001: 1～0.1: 1 in emulsifying agent and the polymerization system; Or with α-Jia Jibenyixidanti with at least aly can carry out free-radical polymerized unsaturated monomer, initiator, dispersion agent with alpha-methyl styrene and be dissolved in deionized water and be mixed with suspension polymerization system, wherein the mol ratio of the unsaturated monomer of alpha-methyl styrene and copolymerization is 1: 1～1: 20, the mass ratio of monomer summation is 0.001: 1～0.1: 1 in initiator and the polymerization system, and the mass ratio of deionized water is 0.001: 1～0.04: 1 in dispersion agent and the polymerization system.
2) under the nitrogen protection with one of above-mentioned polymerization system behind polymerase 10 .1h～50h under 30 ℃～140 ℃ the temperature, pour in the precipitation agent, obtain throw out;
3) throw out is separated drying, obtain containing the multipolymer of alpha-methyl styrol structural unit.
Wherein, initiator is peroxide initiator, azo initiator or redox initiation system.
Wherein, described solvent is tetrahydrofuran (THF), halogenated hydrocarbon, N, dinethylformamide, 1, and 4-dioxane, arene, ketone or esters solvent also can adopt the binary mixture of above-mentioned solvent.
A kind of preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit is characterized in that, may further comprise the steps:
1) with multipolymer
Be dissolved in organic solvent with the unsaturated monomer that can carry out radical polymerization and be mixed with solution, wherein the proportioning of multipolymer and unsaturated monomer is 0.001～0.1g/mL, and the mass concentration of polymeric reaction solution is 10～100wt%.
2) under the nitrogen protection with above-mentioned solution polymerization 5min～50h under 60 ℃～140 ℃ temperature, after reaction finishes, reaction soln is poured in the precipitation agent, obtain throw out;
3) throw out is separated drying, obtain containing the segmented copolymer of alpha-methyl styrol structural unit.
Above-mentioned solvent is tetrahydrofuran (THF), trichloromethane, methylene dichloride, N, dinethylformamide, 1, and 4-dioxane, arene, ketone or esters solvent also can adopt the binary mixture of above-mentioned solvent.
A kind of preparation method who contains the multipolymer and the polyolefine fusion-grafting multipolymer of alpha-methyl styrol structural unit is characterized in that, may further comprise the steps:
Polyolefine and above-mentioned multipolymer are pre-mixed evenly according to 100/15～100/50 mass ratio, carry out melting graft reaction then, controlled temperature is 160～230 ℃, and the time is 10～30min.
A kind of application that contains the multipolymer of alpha-methyl styrol structural unit, it is characterized in that, this multipolymer directly is added in the co-mixing system of one of polyolefine and nylon, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, wood powder, glass fibre and lime carbonate, talcum powder, plays the original position compatibilization.
The characterization method that the inventive method relates to product comprises:
(1) characterization method that contains α-Jia Jibenyixigongjuwu has:
1. use gel permeation chromatography (GPC) to measure the molecular weight and the molecular weight distribution of multipolymer.
2. adopt infrared spectra (FTIR) and nucleus magnetic resonance (
1H-NMR) molecular structure and the analysis multipolymer that characterizes multipolymer formed.
3. adopt thermogravimetry (TGA) to characterize the thermostability of multipolymer.
(2) characterization method of polypropylene grafted thing has:
1. adopt the generation of the qualitative sign graft reaction of infrared spectra.
2. adopt wide-angle x-ray diffraction (XRD) and differential scanning calorimetric (DSC) to characterize the crystal property of grafts.
3. adopt thermogravimetry (TGA) to characterize the thermal characteristics of grafts.
(3) characterization method of original position Compatibilized blends has:
1. the observation of blend morphology structure: the blend batten is gone up its fracture morphology of observation in scanning electronic microscope (SEM) or transmission electron microscope (TEM) after the brittle failure in liquid nitrogen.
2. the test of blend mechanical property: the blend particulate material for preparing on the forcing machine is prepared into the standard batten on injector, and then on corresponding instrument, tests stretching, bending and impact property.
The multipolymer that contains alpha-methyl styrol structural unit in the inventive method is as follows to the principle of polypropylene co-mixing system original position compatibilization: in the melt blending process, at first, depolymerization takes place in the multipolymer that contains alpha-methyl styrol structural unit when being heated to certain temperature, form free radical; Simultaneously, DeR can take place in polypropylene under high temperature and conversion unit shear extrusion effect repeatedly, thereby forms polypropylene macromolecular chain free radical; Then, the free radical of multipolymer depolymerization formation and polypropylene macromolecular chain free radical carry out coupling and form polypropylene grafted thing; This grafts is owing to some reactive group (as epoxy group(ing), hydroxyl, carboxylic acid group or anhydride group etc.) that has on the molecular chain on the multipolymer segment, can with the reaction-ity group reaction on the disperse phase, thereby the phase interface place at blend forms the macromole docking structure with consistency, reduce two-phase interface tension force, promote the mutual entanglement between the different components macromole simultaneously, promote the refinement of phase structure in the intermingling material and stable thus, finally reached the purpose that improves the blend mechanical property.
Description of drawings:
Gained copolymer p AG is in deuterated acetone among Fig. 1 embodiment 1
1The H-NMR spectrogram.
The infrared spectrum of PAG and PP melting graft reaction different time products therefrom among Fig. 2 embodiment 9.
(a) PP, (b) t=10 minute, (c) t=15 minute, (d) t=20 minute, (e) t=25 minute.
The infrared spectrum of PASM and PP melting graft reaction different time products therefrom among Fig. 3 embodiment 10.(a) t=10 minute, (b) t=15 minute, (c) t=25 minute
The SEM photo of different PAG content blend PP/PA6/PAG among Fig. 4 embodiment 11.
(a)PP/PA6＝80/20，(b)PP/PA6/PAG＝80/20/1，(c)PP/PA6/PAG＝80/20/3，(d)PP/PA6/PAG＝80/20/5
The SEM photo of PP/PA6/PASM among Fig. 5 embodiment 12 (80/20/3) blend.
(a)PP/PA6＝80/20，(b)PP/PA6/PASM3＝80/20/3
Embodiment
(1) contains multipolymer synthetic of alpha-methyl styrol structural unit
In four-hole boiling flask, add initiator Diisopropyl azodicarboxylate (AIBN) successively, monomer alpha-methyl styrene (AMS), glycidyl methacrylate (GMA), solvents tetrahydrofurane, initiator and total monomeric mass ratio are 0.04: 1 in solution, solution quality concentration is 25%, and the mol ratio of AMS and GMA is 1: 2.The logical nitrogen of this solution is driven oxygen seal and place water-bath after 20 minutes.Be reflected at nitrogen atmosphere and be added with under the churned mechanically situation and carry out, the control bath temperature is 50 ± 1 ℃, and polymerization reaction time is 30h.Reaction finishes, with gained solution methanol extraction, and centrifugation, vacuum-drying is to constant weight.It is 35.6% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=2.85 * 10
3, M
w=3.64 * 10
3, M
v=3.78 * 10
3
Fig. 1 be the gained multipolymer nuclear-magnetism (
1H-NMR) spectrogram.Wherein the absorption peak at δ=7.29ppm and 7.20ppm place is the chemical shift of phenyl ring hydrogen on the AMS structural unit, the absorption peak at δ=4.32ppm and 3.80ppm place then correspond respectively to link to each other with ester group on the GMA structural unit-OCH
2Last two proton chemical shifts, the absorption peak of δ=3.28ppm belongs to the methyne-CH on the epoxy group(ing), and the absorption peak of δ=2.82ppm and 2.71ppm belongs to methylene radical-CH on the epoxy group(ing) respectively
2Two protons, and the absorption peak at δ=1.95ppm and 1.84ppm place corresponds respectively on the copolymer chain-CH
2Two protons in the group, near the several peaks 1ppm then are side group-CH
3In three proton chemical shifts.
1H-NMR spectrum analysis result has confirmed that resulting polymers is the multipolymer of AMS and GMA.
In there-necked flask, add initiator benzoyl peroxide (BPO) successively, monomer alpha-methyl styrene, glycidyl methacrylate, solvent ethyl acetate, initiator and total monomeric mass ratio are 0.01: 1 in solution, solution quality concentration is 60%, and the mol ratio of AMS and GMA is 1: 10.The logical nitrogen of this solution is driven oxygen seal and place water-bath after 20 minutes.Be reflected at nitrogen atmosphere and be added with under the churned mechanically situation and carry out, in the reaction process, bath temperature is 75 ± 1 ℃, reaction times 10h.Reaction finishes, gained solution precipitated with normal hexane, and suction filtration, vacuum-drying is to constant weight.It is 60.7% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=1.23 * 10
4, M
w=1.96 * 10
4, M
v=2.33 * 10
4
Embodiment 3
In four-hole boiling flask, add initiator A IBN successively, monomer alpha-methyl styrene, maleic anhydride (MAH) and vinylbenzene (St) and solvent butanone.The mass ratio of initiator and monomer maleic anhydride is 0.04: 1 in solution, the total mass concentration of monomer is 60%, a mole proportioning is [AMS]/[St+MAH]=1: 1 between the monomer, and wherein the mol ratio of monomer M AH and St is 1: 1, the control bath temperature is 75 ± 1 ℃, reaction times 0.1h, other reaction conditions is with embodiment 1.Reaction finishes, with the reaction solution methanol extraction, and suction filtration, vacuum-drying is to constant weight.It is 1.53% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=0.93 * 10
4, M
w=1.64 * 104, M
v=4.16 * 10
4
Embodiment 4
In there-necked flask, add initiator K successively
2S
2O
8-FeSO
4Monomer alpha-methyl styrene, methyl methacrylate (MMA), emulsifier sodium lauryl sulfate and deionized water, wherein the mass ratio of initiator and monomer total amount is 0.02: 1, the mass ratio of water and monomer total amount is 70/30, the mol ratio of monomer A MS and MMA is 1: 5, and the mass ratio of monomer summation is 0.01: 1 in emulsifying agent and the polymerization system.The logical nitrogen of solution is driven oxygen seal and place water-bath after 20 minutes.Be reflected at nitrogen atmosphere and be added with under the churned mechanically situation and carry out, the control bath temperature is 70 ± 1 ℃, and the reaction times is 20h.Reaction finishes, and reaction soln is poured in a large amount of methyl alcohol precipitated, suction filtration, vacuum-drying is to constant weight.It is 60.7% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=1.23 * 10
4, M
w=1.96 * 10
4, M
v=2.33 * 10
4
In there-necked flask, add initiator A IBN successively, monomer alpha-methyl styrene, vinyl acetate (VAc), the pure and mild deionized water of polyethylene of dispersing agent, wherein the mass ratio of initiator and monomer total amount is 0.01: 1, the mass ratio of water and monomer total amount is 85/15, the mol ratio of AMS and VAc is 1: 3, and the mass percent of polyvinyl alcohol in deionized water is 1%.The logical nitrogen of this solution is driven oxygen seal and place water-bath after 20 minutes.Be reflected at nitrogen atmosphere and be added with under the churned mechanically situation and carry out, the control bath temperature is 70 ± 1 ℃, and the reaction times is 8h.Reaction finishes, and reaction soln is poured in a large amount of methyl alcohol precipitated, suction filtration, vacuum-drying is to constant weight.It is 18.5% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=2.25 * 10
4, M
w=3.68 * 10
4, M
v=3.54 * 10
4
(2) contain the polymerization of the multipolymer trigger monomer of alpha-methyl styrol structural unit
Embodiment 6
Add after the mixed that the copolymer p AG and the monomers methyl methacrylate of alpha-methyl styrene and glycidyl methacrylate are pressed 0.01g/mL in the test tube, seal behind the logical nitrogen deoxygenation 20min, place water-bath.The control bath temperature is 90 ± 1 ℃, and the reaction times is 40min.Reaction finishes the back and takes out test tube, with the ice-water bath cooling, the reaction in test tube thing is taken out rapidly, with the tetrahydrofuran (THF) dissolving, pours into then in a large amount of methyl alcohol and precipitates, and separates, and vacuum-drying is to constant weight.It is 10.18% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=2.51 * 10
5, M
w=4.80 * 10
5, M
v=4.42 * 10
5
Add after the mixed that the copolymer p AM and the monomer styrene of alpha-methyl styrene and methyl methacrylate are pressed 0.03g/mL in the test tube, seal behind the logical nitrogen deoxygenation 20min, place water-bath.The control bath temperature is 100 ± 1 ℃, and the reaction times is 2h.Reaction finishes the back and takes out test tube, with the ice-water bath cooling, the reaction in test tube thing is taken out rapidly, with the tetrahydrofuran (THF) dissolving, pours into then in a large amount of acetone and precipitates, and separates, and vacuum-drying is to constant weight.It is 30.56% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=1.19 * 10
5, M
w=2.68 * 10
5, M
v=2.46 * 10
5
Embodiment 8
Copolymer p AG, monomer vinyl acetate and the solvent ethyl acetate of alpha-methyl styrene and glycidyl methacrylate are added there-necked flask successively, wherein the proportioning of copolymer p AG and monomer vinyl acetate is 0.03g/mL, the mass ratio of monomer vinyl acetate and solvent ethyl acetate is 30/100, and logical nitrogen deoxygenation 20min is placed in the water-bath.Be reflected at nitrogen atmosphere and be added with under the churned mechanically situation and carry out, the control bath temperature is 70 ± 1 ℃, and the reaction times is 20h.After reaction finishes, reaction soln poured in a large amount of normal hexanes precipitate, separate, vacuum-drying is to constant weight.It is 12.18% that weighting method is calculated monomer conversion, and GPC method determining molecular weight obtains the average molecular numerical quantity of multipolymer, is respectively M
n=1.56 * 10
3, M
w=2.45 * 10
3, M
v=3.36 * 10
3
(3) contain the multipolymer and the polyacrylic fusion-grafting of alpha-methyl styrol structural unit
Low-molecular weight copolymer (PAG) 8g and the 40gPP of institute's synthetic alpha-methyl styrene and glycidyl methacrylate among the embodiment 1 are pre-mixed evenly, the Brabender that adds preheating then plastifies in the instrument and carries out melting graft reaction, controlled temperature is 190 ℃, rotor speed is 30r/min, controlling reaction time is respectively 10,15,20 and 25 minutes.Again graft product is carried out purifying according to following process: the 1g reaction product is added be equipped with in the round-bottomed flask of 30ml dimethylbenzene, reflux is to dissolving fully; Pour in the acetone then and precipitate, the oligopolymer that wherein has neither part nor lot in reaction is dissolved in the acetone and is removed.The purifying after product is done the Infrared spectroscopy (see figure 2), show among the figure, compare with PP before the reaction, the FTIR spectrogram of PP is at 1729cm behind the graft reaction
-1About and 704cm
-1About all obviously have new absorption peak to occur, correspond respectively to GMA and go up the stretching vibration of ester carbonyl group and the flexural vibration absorption peak that AMS goes up single-substituted ring, GMA unit and AMS unit in this explanation oligopolymer all have been grafted on the PP macromolecular chain.In addition, it can also be seen that from Fig. 2 that along with the prolongation of graft reaction time, the absorption peak of ester carbonyl group and the absorption peak of phenyl ring are all increasing gradually, the size and the length in reaction times of this explanation percentage of grafting are closely-related.
Embodiment 10
After the synthetic AMS/MAH/St of institute terpolymer (being designated as PASM) 10g and 40gPP mix in container among the embodiment 2, pour in the Haake torque rheometer that is preheating to design temperature and carry out fusion-grafting, controlled temperature is 230 ℃, rotor speed is 50r/min, controlling reaction time is 10,15 and 25 minutes.Reaction product is carried out purifying according to the purge process among the embodiment 3, and the purifying after product is done Infrared spectroscopy, the results are shown in Figure 3.Compare with pure PP, melting graft reaction is more than 10 minutes the time, and the FTIR spectrogram of products therefrom is respectively at 1713cm
-1, 1780cm
-1, 1855cm
-1And 700cm
-1Near new absorption peak has all obviously appearred, and along with the prolongation in reaction times, absorption peak is increasing.Near 1780cm-1 and the 1855cm-1 absorption peak is respectively the asymmetric and symmetrical stretching vibration absorption peak of carbonyl on the MAH five-ring (C=O), near the 700cm-1 absorption peak then is the charateristic avsorption band of single-substituted ring, and this shows has anhydride group and phenyl ring to be grafted on the PP macromolecular chain respectively.Near 1713cm-1 absorption peak then is the absorption peak of the carbonyl of PP oxidized back generation.
(4) contain of the original position increase-volume of the multipolymer of alpha-methyl styrol structural unit to polypropylene/nylon 6 mixing system
Embodiment 11
With synthetic AMS/GMA copolymer p AG among polypropylene, nylon 6 and the embodiment 2 respectively according to 80/20/1,80/20/3 and 80/20/5 mass ratio mixes, add then and carry out the blend experiment on the Haake torque rheometer that has been preheating to design temperature, the control blend time is 10min, temperature is 210 ℃, and rotor speed is 50r/min.With the brittle failure in liquid nitrogen of blend batten,, the results are shown in Figure 4 with going up its fracture morphology of observation in scanning electronic microscope (SEM) behind the formic acid etching section.As can be seen, (Fig. 4 a) compares, and when only adding 1wt%PAG in blend, just has significantly " compatibilization effect " appearance (Fig. 4 b), and the particle size of disperse phase PA6 is reduced to below 1～2 μ m, and is little more a lot of than simple blend with simple blend.Along with the increase of PAG consumption in the co-mixing system, the size of disperse phase PA6 further reduces in the blend.When the consumption of PAG is 3wt% (Fig. 4 c), the size of PA6 phase is reduced to below the 1 μ m; And when the consumption of PAG is increased to 5wt% (Fig. 4 d), the particle size of PA6 phase is little of the degree that is difficult to basically differentiate, and blend is become be difficult to distinguish the homogeneous system of island, marine facies.
Embodiment 12
The preparation of the synthetic AMS/St/MAH of institute terpolymer PASM original position increase-volume PP/PA6 co-mixing system sample is carried out on the Haake torque rheometer among the embodiment 3, material proportion is PP/PA6/PASM=80/20/3, the control blend time is 10min, and temperature is 230 ℃, and rotor speed is 50r/min.Reaction is pressed into thin slice with the blend sample after finishing, and cuts into batten again, then with batten brittle failure in liquid nitrogen, with observing its fracture morphology by SEM behind the formic acid etching section, the results are shown in Figure 5.The stereoscan photograph of each blend among paired observation Fig. 5, can clearly be seen that, compare with the SEM photo of simple blend PP/PA6 shown in Fig. 5 a, the terpolymer PASM that adds a small amount of (3wt%) in the PP/PA6 co-mixing system just can reduce PP and PA6 biphase interfacial tension effectively, make that the consistency of PP and PA6 is significantly improved (Fig. 5 b) in the co-mixing system, formed the very little dispersion particle (＜2 μ m) of size.
Claims (2)
1. a preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit is characterized in that, may further comprise the steps:
1) with multipolymer
Be dissolved in organic solvent with the unsaturated monomer that can carry out radical polymerization and be mixed with solution, wherein the proportioning of multipolymer and unsaturated monomer is 0.001～0.1g/mL, and the mass concentration of polymeric reaction solution is 10～100wt%; R is and the structural unit of alpha-methyl styrene reactivity ratio less than 1 unsaturated monomer in the formula, and these monomers are selected from one of methacrylic acid, glycidyl methacrylate, hydroxyethyl methylacrylate, methyl methacrylate, maleic anhydride, vinyl cyanide, vinyl acetate, vinylchlorid, vinylbenzene and derivative thereof;
2) under the nitrogen protection with above-mentioned solution polymerization 5min～50h under 60 ℃～140 ℃ temperature, after reaction finishes, reaction soln is poured in the precipitation agent, obtain throw out;
3) throw out is separated drying, obtain containing the segmented copolymer of alpha-methyl styrol structural unit.
2. the preparation method who contains the segmented copolymer of alpha-methyl styrol structural unit according to claim 1, it is characterized in that, solvent is tetrahydrofuran (THF), trichloromethane, methylene dichloride, N, dinethylformamide, 1,4-dioxane, arene, ketone or esters solvent perhaps adopt the binary mixture of above-mentioned solvent.
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| CN102746443B (en) * | 2012-07-18 | 2014-08-13 | 江苏柏鹤涂料有限公司 | Polymer for electrooptical material, dispersed liquid crystal film and method for preparing polymer |
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