CN108752523A - The poly- N of super high molecular weight, N- dimethacrylamide are prepared by free radical polymerization - Google Patents
The poly- N of super high molecular weight, N- dimethacrylamide are prepared by free radical polymerization Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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Abstract
The present invention relates to free radical polymerizations to obtain high-molecular-weight poly N, N- dimethacrylamide (PDMAAm), by adjusting persulfate, methacrylic acid 2- (N, TMSDMA N dimethylamine base) ethyl ester (being denoted as DMAEMA), sodium chloride (NaCl) concentration, catalyst structure and concentration, and reaction temperature, it obtains heavy polymer with higher, avoid being crosslinked.Include the following steps：Polymerizable redox system, which is constituted, with persulfate-DMAEMA causes N in the aqueous solution containing a certain amount of high oxidation state transition metal salt complex (copper or iron) and NaCl, N- dimethacrylamide (DMAAm) free radical polymerization, it is more than 10 to obtain viscosity-average molecular weight in not less than 40 DEG C reaction 60min or more6Long chain branching high molecular weight PDMAAm.Raw material of the present invention is common, mild condition, and institute is all commercially available product using raw material, cheap, is easy to get；Easy to operate, environmental pollution is small, has wide industrial applications foreground.
Description
Technical field
The invention belongs to prepare heavy polymer field, it is related to N,N-DMAA (being denoted as DMAAm)
Aqueous free radical combined polymerization more particularly to (is denoted as with persulfate-methacrylic acid 2- (N, TMSDMA N dimethylamine base) ethyl ester
DMAEMA it) constitutes polymerizable redox system and is containing a certain amount of high oxidation state transition metal salt complex compound (such as copper or iron
Salt) with the free radical polymerization that causes DMAAm in the aqueous solution of halide ion (such as chlorion or bromide ion), to form long-chain branch
Change high-molecular-weight poly N, N- dimethacrylamide (PDMAAm).
Background technology
N,N-DMAA (being denoted as DMAAm) is common one of water-soluble nonionic unsaturated monomer, by
The poly- N that free-atom aqueous solution or reverse emulsion polymerization are formed, N- dimethacrylamide (being denoted as PDMAAm) type is various, structure is more
Sample is widely used in the excellent hygroscopicity of water treatment field, antistatic property, dispersibility, compatibility and adhesive property etc., can be wide
It is general to be used for the necks such as chemical fibre, plastics, papermaking, printing and dyeing, adhesive, coating, photograph, printing, cosmetics, medical and health and oilfield chemistry
Domain, having broad application prospects, (synthesis and its application study progress of Yang little Hua, N,N-DMAA polymer are answered
With chemical industry 2009,38:1509-1912).It is more than 10 that the free radical polymerization of DMAAm, which can be easily obtained average relative molecular mass,5's
DMAAm based polyalcohols (wherein DMAAm contents are not less than 80mol.%), but due to free radical termination between radicals etc., it is difficult at present
With obtain higher molecular weight DMAAm/copolymer.Also there is no at present and obtain molecular weight by free radical polymerization is more than 106's
The report of DMAAm based polyalcohols.
It is apparent that thirsting for forming higher molecular weight if being made of a macromolecular (i.e. hyperbranched polymer) multiple chains
DMAAm polymer.But it is formed while generating branched chain if generating branched structure with the methods of chain tra nsfer new
Primary group of free radicals, and increase since the low molecular weight stage, therefore be unfavorable for obtaining heavy polymer.(N.O'Brien,
A.McKee,D.C.Sherrington,A.T.Slark,A.Titterton,Facile,versatile and cost
effective route to branched vinyl polymers,Polymer 2000,41,6027–6031；
F.Isaure,P.A.G.Cormack,D.C.Sherrington Facile synthesis of branched water-
soluble poly(dimethylacrylamide)s in conventional and parallel reactors using
free radical polymerisation Reactive&Functional Polymers 66(2006)65–79).Therefore
Triggering mechanism again rather than chain tra nsfer mechanism based on reversible activation should be used, to build hyperbranched polymer.On the other hand, it answers
Cause monomer polymerization from macromolecular chain, rather than cause polymerization from the decomposition of small molecule initiator, otherwise the latter persistently divides
Solution will be constantly be generated new low-molecular weight polymer, not high so as to cause products therefrom average molecular weight.
In preceding a invention, we are FeCl3Complex compound oxidation methyl acrylic acid 2- (N, TMSDMA N dimethylamine under air conditions
Base) ethyl ester (being denoted as DMAEMA) cause DMAAm free radical polymerization, due to FeCl3Play the part of oxidant, halogen source and ATRP simultaneously to urge
Agent role, to form super high molecular weight highly branched chain PDMAAm, (Zhai Guangqun, Chen Qi are a kind of to prepare high molecular weight N, N- dimethyl
The method of acrylamide copolymer, CN 201810038429.8).But iron salt concentration is generally more than 10 in this method-3mol L-1,
Cause later stage catalyst removal relatively difficult.If three of the above role detached, thirst for reducing iron salt concentration.In the present invention
In, we are halogen source, Cu by oxidant, halogen of persulfateII/FeIIIComplex compound only plays the part of ATRP catalyst roles, to
So that 10 can be less than in transition metal salt concentration-3mol L-1Lower catalysis polymerization, reaction process speed, and do not formed
Insoluble matter, the viscosity-average molecular weight of products therefrom can be more than 1.5 × 10 under high conversion7。
Invention content
The purpose of the present invention is to provide a kind of methods obtaining high molecular weight PDMAAm using free radical polymerization, pass through tune
The concentration of persulfate, DMAEMA, NaBr, catalyst structure and the conditions such as concentration and reaction temperature are saved, that is, have higher polymerization
Rate, also obtains heavy polymer, also avoids ultimately forming cross-linked network.
The technical solution adopted in the present invention is to specifically include following steps：
(1) batch mixing
The good catalyst solution mother liquor of water, configured in advance, DMAEMA, DMAAm are added portionwise in certain temperature water-bath
In the reactor of constant temperature, it is water-soluble that stirring makes each component that the good sodium peroxydisulfate of a small amount of configured in advance (NaPS) be added after mixing
Liquid starts to react after stirring.
(2) heating polymerization
According to process conditions, reaction is started to warm up after a certain period of time to improve reaction speed, the molecular weight of polymer with
Polymerization be continuously improved.After to be polymerized, it is firstly added water/ethyl alcohol to biphenol (5.0wt.%) containing polymerization inhibitor
(v/v 1/1) solution is inhibited in time with diluting reaction solution, reduction viscosity.Then it is water-soluble that 70 DEG C of NaOH is added dropwise
Liquid (20wt.%), until white gum polymer is precipitated.It is dry in 70 DEG C of air dry oven after polymer with water is cleaned
It is dried for 24 hours, to remove moisture content in 70 DEG C of vacuum drying chamber after 12h.
The molecular weight of gained copolymer sample is measured by single-point viscosity method in the present invention, is as follows：Configuration
25mL aqueous solutions of polymers (concentration=0.50-0.70g L-1), it is measured in 40 DEG C and measures pure solvent and polymer solution respectively
Delivery time.The intrinsic viscosity ([η]) of the polymer is calculated according to following formula：
Then by Mark-Houwink equation calculation polymer viscosity average molecular weighs, as follows：
[η]=kMν α (2)
Wherein k=0.02mL g-1, α=0.65 (M.Kurata, X Tsunashima, Viscosity-molecular
weight relationships and unperturbed dimensions of linear chain molecules,in
Polymer Handbook,4thEdition；Eds.:J.Brandrup,E.H.Immergut,E.A.Grulke；Wiley,
Pergamon,2003；VII/10-12).
The beneficial effects of the present invention are：The present invention using commercially available cheap and to the common raw material that air moisture content is stablized,
In air atmosphere, aqueous free radical polymerization is carried out.The reaction can form molecular weight 10 with fast speed6-107Copolymer, and
Transition metal salt catalyst concn used is less than 10-3mol L-1.Compared with other free radical polymerisation process being reported,
The method is simple and efficient, and operation is simple, and of less demanding to reaction condition, environmental pollution is small.
Specific implementation method
The present invention is elaborated further with reference to specific embodiment, the specific process parameter of following embodiment is answered
It is considered as the materialization to invention content, and it is non-limiting or reduce the scope.
Embodiment 1：
The aqueous solution that total volume is 250mL is configured, the wherein initial concentration of DMAAm (is denoted as [DMAAm]0) it is 4.375mol
L-1, DMAEMA initial concentration (be denoted as [DMAEMA]0) it is 0.295mol L-1, NaPS initial concentration (be denoted as [NaPS]0) be
8.0×10-4mol L-1、Fe(NO3)3Initial concentration (be denoted as [Fe (NO3)3]0) it is 10-5mol L-1, ethylenediamine tetra-acetic acid two
The initial concentration of sodium (is denoted as [EDTA]0) it is 2 × 10-5mol L-1, NaCl initial concentration (be denoted as [NaCl]0)1.0×10- 2mol L-1.4h is reacted in 40 DEG C, then in 60 DEG C of reaction 2h, then in 70 DEG C of reaction 1h, then in 90 DEG C of reaction 2h.By institute
PDMAAm precipitation separation is obtained, it is 6.87 × 10 to measure gained PDMAAm through viscosity method5。
Embodiment 2：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 2h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 6.61 × 106。
Embodiment 3：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 4h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 8.97 × 106。
Embodiment 4：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 6h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 1.03 × 107。
Embodiment 5：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 9h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 1.37 × 107。
Embodiment 6：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 12h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 1.58 × 107。
Embodiment 7：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 15h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 1.79 × 107。
Embodiment 8：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 18h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 1.83 × 107。
Embodiment 9：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.295mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[Fe(NO3)3]0It is 10-5mol L-1、[EDTA]0It is 2 × 10-5mol
L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in 70 DEG C react 1h, with
2h is reacted in 90 DEG C afterwards, then in 100 DEG C of reaction 21h.By gained PDMAAm precipitation separation, gained PDMAAm is measured through viscosity method
It is 2.21 × 107。
Embodiment 10：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、CuSO4Initial concentration (be denoted as [CuSO4]0) it is 10-5mol L-1、
Three (N, N- dimethylaminoethyl) amine (Me6TREN initial concentration) (is denoted as [Me6TREN it is) 2 × 10-5mol L-1、[NaCl]0
It is 1.0 × 10-2mol L-1.4h is reacted in 40 DEG C, then in 60 DEG C of reaction 2h.By gained PDMAAm precipitation separation, through viscosity method
It is 1.36 × 10 to measure gained PDMAAm7。
Embodiment 11：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、CuSO4Initial concentration (be denoted as [CuSO4]0) it is 10-5mol L-1、
Three (N, N- dimethylaminoethyl) amine (Me6TREN initial concentration) (is denoted as [Me6TREN it is) 2 × 10-5mol L-1、[NaCl]0
It is 1.0 × 10-2mol L-1.4h is reacted in 40 DEG C, then in 60 DEG C of reaction 2h, then in 80 DEG C of reaction 2h.By gained PDMAAm
Precipitation separation, it is 1.71 × 10 to measure gained PDMAAm through viscosity method7。
Embodiment 12：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h.By gained PDMAAm precipitation separation, measuring gained PDMAAm through viscosity method is
2.19×107。
Embodiment 13：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 6h.By gained PDMAAm precipitation separation, through viscosity method
It is 2.29 × 10 to measure gained PDMAAm7。
Embodiment 14：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 8h.By gained PDMAAm precipitation separation, through viscosity method
It is 2.74 × 10 to measure gained PDMAAm7。
Embodiment 15：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 11h.By gained PDMAAm precipitation separation, through viscosity method
It is 3.12 × 10 to measure gained PDMAAm7。
Embodiment 16：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 14h.By gained PDMAAm precipitation separation, through viscosity method
It is 3.40 × 10 to measure gained PDMAAm7。
Embodiment 17：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 17h.By gained PDMAAm precipitation separation, through viscosity method
It is 4.04 × 10 to measure gained PDMAAm7。
Embodiment 18：
The aqueous solution that total volume is 250mL is configured, wherein [DMAAm]0For 4.375mol L-1、[DMAEMA]0For
0.291mol L-1、[NaPS]0It is 8.0 × 10-4mol L-1、[CuSO4]0It is 10-5mol L-1、[Me6TREN]0Initial concentration
It is 2 × 10-5mol L-1、[NaCl]0It is 1.0 × 10-2mol L-1.In 40 DEG C react 4h, then in 60 DEG C react 2h, then in
80 DEG C are reacted 2h, then in 100 DEG C of reaction 2h, then in 100 DEG C of reaction 23h.By gained PDMAAm precipitation separation, through viscosity method
It is 4.21 × 10 to measure gained PDMAAm7。
Comparative example 1
As a comparison, it is not added with high oxidation state transition metal salt complex compound and halide ion, DMAEMA is only aoxidized with NaPS
Cause the general radical polymerization of DMAAm, the aqueous solution that configuration total volume is 50mL, wherein [DMAAm]0For 4.375mol L-1、
[DMAEMA]0For 0.291mol L-1、[NaPS]0It is 10-3mol L-1.After reacting at room temperature 1.0h, 2.0h and 4.0h, it will polymerize
Object Precipitation extracts for 24 hours in Soxhlet extractor by reflux solvent of water after drying to constant weight, and by insoluble matter, drying to constant weight
After measure gel content.Gel content is respectively 17.5%, 32.5% and 46.2%.
Claims (2)
1. obtaining high-molecular-weight poly N, N- dimethacrylamide using free radical polymerization the purpose of the present invention is to provide a kind of
(PDMAAm) method, it is characterised in that：
(1) (referred to as by methacrylic acid 2- (N, N- dimethylamino) ethyl esters (abbreviation DMAEMA) and N, N- dimethacrylamide
DMAAm binary aqueous free radical polymerization) is made, by adjusting persulfate, DMAEMA, the concentration of villaumite, catalyst knot
The conditions such as structure and concentration and reaction temperature obtain heavy polymer, also avoid ultimately forming cross-linked network；
(2) complex compound formed with cupric salt and three (N, N- dimethylaminoethyls) (is denoted as CuII/Me6) or trivalent TREN
The complex compound that molysite is formed with disodium ethylene diamine tetraacetate (is denoted as FeIII/ EDTA) catalyst；
(3) free radical polymerization of the present invention carries out under air conditions, is not necessarily to deoxygenation；
(4) free radical polymerization of the present invention, range of reaction temperature are 40-100 DEG C；
(5) free radical polymerization of the present invention, reaction time are no less than 4h.
2. such as the obtained PDMAAm of claim 1, viscosity-average molecular weight is more than 1.0 × 106, and with polymerization reaction time extend and
Increased to over 4.0 × 107。
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| CN111533836A (en) * | 2020-05-13 | 2020-08-14 | 常州大学 | Self-initiated free radical polymerization of N-isopropylacrylamide |
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| CN102516430A (en) * | 2011-12-06 | 2012-06-27 | 江门市慧信净水材料有限公司 | Method for preparing polyacrylamide by activecontrollable free radical polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102516430A (en) * | 2011-12-06 | 2012-06-27 | 江门市慧信净水材料有限公司 | Method for preparing polyacrylamide by activecontrollable free radical polymerization |
Non-Patent Citations (1)
| Title |
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| XIUTING WANG，ETAL.: "Redox initiated aqueous radical polymerization of N,N-dimethylacrylamide in the presence of poly(tertiary amine) as a multifunctional reducing agent", 《POLYMER BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111533836A (en) * | 2020-05-13 | 2020-08-14 | 常州大学 | Self-initiated free radical polymerization of N-isopropylacrylamide |
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