CN103360550A - Cellulose-graft-polyisoprene copolymer and preparation method thereof - Google Patents
Cellulose-graft-polyisoprene copolymer and preparation method thereof Download PDFInfo
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- CN103360550A CN103360550A CN2013103425206A CN201310342520A CN103360550A CN 103360550 A CN103360550 A CN 103360550A CN 2013103425206 A CN2013103425206 A CN 2013103425206A CN 201310342520 A CN201310342520 A CN 201310342520A CN 103360550 A CN103360550 A CN 103360550A
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Abstract
The invention provides a cellulose-graft-polyisoprene copolymer and a preparation method thereof. Cellulose and isoprene are taken as starting raw materials. Firstly, the cellulose is modified in an ionic liquid to prepare a cellulose macroinitiator; and then homogeneous charge transfer-atom transfer free radical polymerization is performed to prepare the cellulose-graft-polyisoprene copolymer. The invention provides the cellulose-graft-polyisoprene copolymer crosslinked at the tail end of a side chain and the preparation method thereof. The preparation method is characterized in that a ligand with higher catalytic activity and a reducing agent are used, then free radical coupling can be terminated at the tail end of the side chain of a copolymer, namely polyisoprene, obtained by polymerization, and then the cellulose-graft-polyisoprene copolymer crosslinked at the tail end of the side chain can be further obtained. The copolymer has excellent mechanical properties and very high application value and prospects, for example, the copolymer can be used for artificial skin.
Description
Technical field
The present invention relates to the biomimetic material technical field, be specifically related to a kind of biomimetic material multipolymer and preparation method thereof.
Background technology
Nature has magical creativity, it with simple raw material (Mierocrystalline cellulose, xylogen, albumen etc.) thus being integrated into perfect microtexture has created panoramic natural biologic material with special performance, such as shell, bamboo, bone, skin, muscle etc.The marrow of biomimetic material is exactly to learn to natural, and the microtexture by mimic biology body material prepares and possesses the Novel bionic material that has close or identical performance with organism material, and its importance is self-evident.Now, biomimetic material has become one of most important and the most popular research field.Success of scientists opened various biomimetic materials, such as sea cucumber skin (Capadona, J.R., Shanmuganathan, K., Tyler, D.J., Rowan, S.J.﹠amp; Weder, C.Science319,1370-1374, (2008)), artificial spider silk (Cranford, S.W., Tarakanova, A., Pugno, N.M.﹠amp; Buehler, M.J.Nature482,72-U91, (2012)), artificial-muscle (Lv, S.et al.Designed biomaterials to mimic the mechanical properties of muscles.Nature465,69-73, (2010)), artificial skin (Takei, K.et al.Nature Mater.9,821-826, (2010)) etc.
Existing disclosed biomaterial for artificial skin comprises: chitin, hyaluronate sodium, Nano chitosan etc.; use the skin biomimetic material of this material preparation to possess the performance that approaches with skin; as keep the moisture content of body; the protection body exempts from bacterial invasion; and have certain temperature sensitivity, yet these materials have very large gap with skin on microtexture and mechanical property.
The Main Tissues that embodies the skin mechanical property is skin corium.And skin corium is to organically combine the three-dimensional net structure that forms by the collagen fabric of rigidity and soft elastin.In order to prepare the biomimetic material that possesses the skin mechanics performance, at first should select suitable material to imitate respectively collagen protein and elastin.Mierocrystalline cellulose is a kind of natural polymer of uniqueness, has good biocompatibility, degradability, thermostability and recyclability.The researchist finds, Mierocrystalline cellulose becomes the structural constituent of two kinds of modal loads of occurring in nature together with collagen protein, they have close mechanical property (Fratzl, P.Cellulose and collagen:From fibres to tissues.Curr.Opin.Colloid Interface Sci.8,32-39, (2003)).Natural rubber (a kind of natural polymer) has and the similar snappiness of elastin.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of Mierocrystalline cellulose-grafting-polyisoprene copolymers.
Another object of the present invention provides a kind of method for preparing Mierocrystalline cellulose-grafting-polyisoprene copolymers.
In order to realize purpose of the present invention, concrete scheme of the present invention is as follows:
At first, the invention provides a kind of Mierocrystalline cellulose-grafting-polyisoprene copolymers, its structural formula is as follows:
Wherein, R is Br or cellulose chain (cellulose); The value of n is the integer of 300≤n≤800; M is the integer more than or equal to 1, and x is that 0.90, y is that 0.04, z is 0.06.
Further, the invention provides a kind of method for preparing described Mierocrystalline cellulose-grafting-polyisoprene copolymers, it is that the monomer isoprene is grafted to the multipolymer that cellulosic backbone obtains by charge transfer-atom transition free radical polymerization reaction, and this multipolymer R is Br.
Preferably, the starting raw material of described multipolymer comprises following component, counts by weight:
0.1～1.0 part of Mierocrystalline cellulose;
15～30 parts of isoprene;
69～84 parts of solvents;
Catalyzer 5*10
-4Part
1 part of reductive agent;
0.5 part of part.
Preferably, described catalyzer is cupric bromide; Described reductive agent is copper wire; Described part be 2,2'-second bipyridine or 4,4 '-dinonyl-2, the 2'-second bipyridine; Described solvent is that volume ratio is the DMF of 1:2 and the mixed solvent of Isosorbide-5-Nitrae-dioxane.
Preferably, described Mierocrystalline cellulose is any one or the two or more mixture in wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp, and the content of cellulose in described wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp is 90-100%; The described cellulosic polymerization degree is 300-800.Preferred, described Mierocrystalline cellulose is the wood pulp element, and its viscometric degree of polymerization is 650, by cellulose dissolution is recorded with Ubbelohde viscometer in cupriethylene diamine solution.
Preferably, described Mierocrystalline cellulose is the cellulose macromolecule initiator through the atom transfer radical polymerization initiator modification, and its preparation method comprises following concrete preparation process:
(1) extracting cellulose 1-5 part, 1-allyl group-3 Methylimidazole villaumite ionic liquid 50-80 part, 50-90 ℃ vacuum-drying 12-36 hour;
(2) described Mierocrystalline cellulose and the ionic liquid stated of step (1) mixed 60-90 ℃ of dissolving;
(3) obtain light yellow transparent solution with adding the DMF dilution after the cooling of step (2) mixing solutions;
(4) under the ice-water bath condition, in the described solution of step (3), slowly drip 2-bromine isobutyl acylbromide 10-15 part;
(5) after dropping process is finished, room temperature reaction 24-40 hour, and product is deposited in obtains white cotton-shaped product, suction filtration-washed several times with water in the water;
(6) the white cotton-shaped product that step (5) is obtained obtained the cellulose macromolecule initiator at 40-60 ℃ of vacuum-drying 20-40 hour.
Described Mierocrystalline cellulose is preferably the wood pulp element, and its viscometric degree of polymerization is 650, by cellulose dissolution is recorded with Ubbelohde viscometer in cupriethylene diamine solution.
Further, the synthetic method of Mierocrystalline cellulose-grafting provided by the invention-polyisoprene copolymers, specifically comprise the steps: to obtain the cellulose macromolecule initiator with atom transferred free radical initiator modified-cellulose, 0.1～1.0 part of described cellulose macromolecule initiator is dissolved in 69-84 part solvent, add 15～30 parts of isoprene monomers, the catalyzer of trace, part and reductive agent; This polymeric solution is put into the heavy wall pressure bottle, and 110-130 ℃ of reaction of sealing is 72-120 hour behind the logical argon gas, makes Mierocrystalline cellulose-grafting-polyisoprene.The product of gained is faint yellow viscoelastic solid.
More specifically, the preparation method of described Mierocrystalline cellulose-grafting-polyisoprene copolymers comprises the steps:
(1) 0.1～1.0 part of described cellulose macromolecule initiator is dissolved in the mixed solvent of 20 parts of DMFs and 40 parts of Isosorbide-5-Nitrae-dioxane;
(2) in the described solution of step (1), add 5*10-4 part cupric bromide, 0.5 part 2,2'-second bipyridine (English name 2,2'-dipyridyl are called for short bpy) or 4,4 '-dinonyl-2, the 2'-second bipyridine (English name 4,4 '-dinonyl-2,2'-dipyridyl, be called for short dnbpy), 1 part of copper wire and 15～30 parts of isoprene;
(3) the described reaction soln of step (2) is added in the heavy wall pressure bottle, logical argon gas 5 minutes, sealing, 110-130 ℃ was reacted 72～120 hours;
(4) the described product of step (3) is diluted the rear neutral alumina pillar of crossing with tetrahydrofuran (THF), precipitate in acetone, the rear 40-60 ℃ of vacuum-drying of washing 24 hours obtains Mierocrystalline cellulose-grafting-polyisoprene copolymers.Described Mierocrystalline cellulose-grafting-polyisoprene copolymers manifests the three-dimensional net structure of micro/nano-scale, referring to Fig. 2.Described Mierocrystalline cellulose-grafting-polyisoprene copolymers is viscoelastic material, mechanical property a little less than.
In order to strengthen the mechanical property of this multipolymer, the present invention also provides the preparation method of another kind of Mierocrystalline cellulose-grafting-polyisoprene copolymers, it is grafted to the monomer isoprene on the cellulosic backbone by charge transfer-atom transition free radical polymerization reaction first, then the crosslinked Mierocrystalline cellulose-grafting of the side chain terminal that obtains by the coupled reaction between the polyisoprene chain end-polyisoprene copolymers, this multipolymer R is Br or cellulose chain.
Further, the starting raw material of described multipolymer comprises following component, counts by weight:
0.8～4 part of Mierocrystalline cellulose;
16～19.2 parts of isoprene;
80 parts of solvents;
Catalyzer 2*10
-4Part;
Reductive agent 1.5*10
-3Part;
Preferably, described catalyzer is cupric bromide, and described reductive agent is xitix, and described part is N, N, N', N'', N''-five methyl diethylentriamine; Described solvent is that volume ratio is the DMF of 1:1 and the mixed solvent of Isosorbide-5-Nitrae-dioxane.
Preferably, described Mierocrystalline cellulose is any one or the two or more mixture in wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp, and the content of cellulose in described wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp is 90-100%; The described cellulosic polymerization degree is 300-800; Preferred wood pulp element.
Preferably, described Mierocrystalline cellulose is the cellulose macromolecule initiator through the atom transfer radical polymerization initiator modification.
Further, the synthetic method of the crosslinked Mierocrystalline cellulose-grafting of side chain terminal provided by the invention-polyisoprene copolymers, it comprises following concrete steps: obtain the cellulose macromolecule initiator with atom transferred free radical initiator modified-cellulose, 1.0～5.2 parts of described cellulose macromolecule initiators are dissolved in 70-90 part solvent, add 15.7～19.0 parts of isoprene monomers, the catalyzer of trace, part and reductive agent; This polymeric solution is put into the special type bottle, and 50-90 ℃ of reaction of sealing is 10-48 hour behind the logical argon gas, makes the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene.The product of gained is faint yellow block rectangular parallelepiped.
More specifically, the crosslinked Mierocrystalline cellulose-grafting of described side chain terminal-polyisoprene copolymers, its preparation method comprises following concrete preparation process:
(1) 1.0～5.2 parts of described cellulose macromolecule initiators is dissolved in the mixed solvent of 40 parts of DMFs and 40 parts of Isosorbide-5-Nitrae-dioxane;
(2) in the described solution of step (1), add 2*10
-4Part cupric bromide, 1.8*10
-3Part N, N, N', N'', N''-five methyl diethylentriamine (English name Pentamethyldiethylenetriamine is called for short PMDETA), 1.5*10
-3Part xitix (English name ascorbic acid) and 15.7～19.0 parts of isoprene;
(3) the described reaction soln of step (2) is added in the special type bottle, logical argon gas 5 minutes, sealing, 50-90 ℃ was reacted 48 hours;
(4) the described product of step (3) is washed rear 50-90 ℃ of vacuum-drying 24 hours with tetrahydrofuran (THF), obtain crosslinked Mierocrystalline cellulose-grafting-polyisoprene, its cutting is cut into the dumbbell shape batten to be used for mechanical treatment and mechanical test.
Crosslinked Mierocrystalline cellulose-the grafting of described side chain terminal-polyisoprene copolymers, its mechanical property parameters is as follows: Young's modulus is 51MPa～293MPa, and breaking tenacity is 3.9MPa～22.8MPa, and elongation at break is respectively 126%～374%.
Beneficial effect of the present invention is as follows:
The present invention is integrated into the three-dimensional net structure with similar collagen protein and elastin formation by the Polymer Synthesizing method with Mierocrystalline cellulose and natural rubber, and this structure is given the mechanical property of the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene copolymers excellence.As, possess the intensity that approaches with skin, elongation at break.In addition, the natural polymers such as the good Mierocrystalline cellulose of this multipolymer biocompatibility and natural rubber form, thereby possess excellent biocompatibility.This multipolymer is at biomedicine field, and especially there is very widely application prospect in the artificial skin field.
Description of drawings
For the more complete the present invention that understands, now carry out by reference to the accompanying drawings following explanation:
The nucleus magnetic hydrogen spectrum of Fig. 1 display fibers element-grafting-polyisoprene copolymers 1.
The transmission electron microscopy electromicroscopic photograph of Fig. 2 display fibers element-grafting-polyisoprene copolymers 1.
Fig. 3 Mierocrystalline cellulose, the solid-state nmr spectrogram of cellulose macromolecule initiator and embodiment 7 described samples.
Fig. 4 shows the stress-strain curve of the crosslinked Mierocrystalline cellulose-grafting of embodiment 7,8,9 described side chain terminal-polyisoprene copolymers.
Fig. 5 shows the stress-strain curve by the artificial skin that shows embodiment 7,8,9 preparations.
Fig. 6 shows the stress-strain curve of skin.
Embodiment
The reagent that uses in following examples is all bought from market, and described solvent must underpressure distillation behind anhydrous magnesium sulfate drying before using, and described isoprene needed parlkaline aluminum oxide pillar before using.
The preparation of embodiment 1 cellulose macromolecule initiator 1
Be prepared as follows based on wood pulp element macromole evocating agent 1: get wood pulp element 2g, 50g ionic liquid (1-allyl group-3 Methylimidazole villaumite) was 80 ℃ of dissolvings 2 hours.Add and obtain the glassy yellow clear solution after the 20mL DMF mixes.Under the condition of ice-water bath, in mentioned solution, slowly drip 2-bromine isobutyl acylbromide 7.6mL, be added dropwise to complete rear room temperature reaction 36 hours.After reaction finishes, product precipitated in water obtain white cotton-shaped product.After repeatedly washing, made the cellulose macromolecule initiator in 24 hours 40-60 ℃ of lower vacuum-drying.Chemical shift is that 160.8 peak is the initiation point (referring to Fig. 3) of atom transfer radical polymerization in the solid-state nmr carbon spectrum of cellulose macromolecule initiator.
The preparation of embodiment 2 cellulose macromolecule initiators 2
Be prepared as follows based on Cotton Pulp cellulose macromolecule initiator 2: its preparation method is with embodiment 1, and difference is that the Mierocrystalline cellulose of selecting is the Cotton Pulp Mierocrystalline cellulose.
The preparation of embodiment 3 cellulose macromolecule initiators 3
Be prepared as follows based on hemp dissolving pulp cellulose macromolecule initiator 3: its preparation method is with embodiment 1, and difference is that the Mierocrystalline cellulose of selecting is the hemp dissolving pulp Mierocrystalline cellulose.
The preparation of embodiment 4 Mierocrystalline celluloses-grafting-polyisoprene copolymers 1
With 300mg cellulose macromolecule initiator 1,22.3mg cupric bromide, 244.8mg4,4 '-dinonyl-2, the 2'-second bipyridine, the 20mL isoprene, 10mL DMF and 20mL1,4-dioxane wiring solution-forming, put into the heavy wall pressure bottle, add 20cm, the copper wire of diameter 0.5mm, logical argon gas 5 minutes, sealing, 110-130 ℃ was reacted 72-120 hour, product precipitates in acetone with the rear neutral alumina pillar of crossing of tetrahydrofuran (THF) dilution again, the rear 40-60 ℃ of vacuum-drying of washing 24 hours, obtaining content of cellulose is 10.6 % by weight, and polyisoprene content is the Mierocrystalline cellulose-grafting-polyisoprene copolymers of 89.4 % by weight.The nucleus magnetic hydrogen spectrum (referring to Fig. 1) of embodiment 4 samples, embodiment 4 samples are three-dimensional net structure: the cellulose nanospheres of rigidity is dispersed in (referring to Fig. 2) in the polyisoprene body.
The preparation of embodiment 5 Mierocrystalline celluloses-grafting-polyisoprene copolymers 2
Be prepared as follows Mierocrystalline cellulose-grafting-polyisoprene copolymers 2: its preparation method is with embodiment 4, and difference is that the consumption of cellulose macromolecule initiator 1 is 150mg.Obtaining content of cellulose is 6.6 % by weight, and polyisoprene content is the Mierocrystalline cellulose-grafting-polyisoprene copolymers of 93.4 % by weight.
The preparation of embodiment 6 Mierocrystalline celluloses-grafting-polyisoprene copolymers 3
Be prepared as follows Mierocrystalline cellulose-grafting-polyisoprene copolymers 3: its preparation method is with embodiment 4, difference is that used initiator is cellulose macromolecule initiator 2, consumption is 30mg, obtaining content of cellulose is 1.6 % by weight, and polyisoprene content is the Mierocrystalline cellulose-grafting-polyisoprene copolymers of 98.4 % by weight.
The product of embodiment 4,5,6 gained is Mierocrystalline cellulose-grafting-polyisoprene copolymers, its difference is that the length of polyisoprene side chain of polymkeric substance of gained is different, because of the cellulosic material that embodiment 6 is used different, the length of its cellulosic backbone also from embodiment 4,5 different.
The preparation of the crosslinked Mierocrystalline cellulose-grafting of embodiment 7 side chain terminal-polyisoprene copolymers 1
Be prepared as follows the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene polymers 1: with 1200mg cellulose macromolecule initiator 1,4.5mg cupric bromide, 40 μ L PMDETA, the 35mg xitix, the 8mL isoprene, 8mL N, dinethylformamide and 8mL1,4-dioxane wiring solution-forming is put into the flask of specified shape, logical argon gas 5 minutes, sealing, 70 ℃ were reacted 48 hours, and product washs rear 70 ℃ of vacuum-dryings 24 hours with tetrahydrofuran (THF), obtaining content of cellulose is 20.3 % by weight, and polyisoprene content is the crosslinked Mierocrystalline cellulose-grafting of the side chain terminal of 79.7 % by weight-polyisoprene.The relative value that the middle chemical shift of the solid-state nmr carbon spectrum (referring to Fig. 3) of embodiment 7 samples is 160.8 peaks is little than the cellulose macromolecule initiator, prove that coupled reaction occurs some active point that causes, realize crosslinked, thereby obtain the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene copolymers.This sample is cut into thick 0.5mm, wide 2mm, the dumbbell shape batten of long 15mm is to be used for mechanical test.Its stress-strain curve is referring to Fig. 4.
The preparation of the crosslinked Mierocrystalline cellulose-grafting of embodiment 8 side chain terminal-polyisoprene copolymers 2
Be prepared as follows the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene copolymers 2: its preparation method is with embodiment 7, and difference is that the consumption of cellulose macromolecule initiator 1 is 960mg.Obtaining content of cellulose is 14.7 % by weight, and polyisoprene content is the crosslinked Mierocrystalline cellulose-grafting of the side chain terminal of 85.3 % by weight-polyisoprene.This sample is cut into thick 0.5mm, wide 2mm, the dumbbell shape batten of long 15mm is to be used for mechanical test.Its stress-strain curve is referring to Fig. 4.
The preparation of the crosslinked Mierocrystalline cellulose-grafting of embodiment 9 side chain terminal-polyisoprene copolymers 3
Be prepared as follows the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene copolymers 3: its preparation method is with embodiment 7, and difference is that used initiator is cellulose macromolecule initiator 3, and consumption is 600mg.Obtaining content of cellulose is 8.7 % by weight, and polyisoprene content is the crosslinked Mierocrystalline cellulose-grafting of the side chain terminal of 93.3 % by weight-polyisoprene.This sample is cut into thick 0.5mm, wide 2mm, the dumbbell shape batten of long 15mm is to be used for mechanical test.Its stress-strain curve is referring to Fig. 4.
Application examples 1 makes artificial skin with embodiment 7,8,9 multipolymer, tests the performance perameter of this artificial skin
The multipolymer that the present invention obtains is comprised of natural polymers such as the good Mierocrystalline cellulose of biocompatibility and natural rubbers, and it possesses excellent biocompatibility.Above-mentioned experimental example is possessed with skin near mechanical property by the artificial skin of multipolymer of the present invention preparation as can be known, comprises initial modulus, breaking tenacity, elongation at break etc.
The above only is preferred implementation of the present invention, it is to be noted, these embodiment only are not used in for explanation the present invention and limit the scope of the invention, and, after having read content of the present invention, the relevant technical staff in the field can make various changes or modification to the present invention, and these equivalent form of values fall into the application's appended claims limited range equally.
Claims (10)
1. Mierocrystalline cellulose-grafting-polyisoprene copolymers, its structural formula is as follows:
Wherein, R is Br or cellulose chain; The value of n is the integer of 300≤n≤800; M is the integer more than or equal to 1, and x is that 0.90, y is that 0.04, z is 0.06.
2. method for preparing the described Mierocrystalline cellulose-grafting of claim 1-polyisoprene copolymers, it is characterized in that, it is that the monomer isoprene is grafted to the multipolymer that cellulosic backbone obtains by charge transfer-atom transition free radical polymerization reaction, and this multipolymer R is Br.
3. method according to claim 2 is characterized in that, the starting raw material of described multipolymer comprises following component, counts by weight:
0.1～1.0 part of Mierocrystalline cellulose;
15～30 parts of isoprene;
69～84 parts of solvents;
Catalyzer 5*10
-4Part;
1 part of reductive agent;
0.5 part of part.
4. method according to claim 2 is characterized in that, described catalyzer is cupric bromide; Described reductive agent is copper wire; Described part be 2,2'-second bipyridine or 4,4 '-dinonyl-2, the 2'-second bipyridine; Described solvent is that volume ratio is the DMF of 1:2 and the mixed solvent of Isosorbide-5-Nitrae-dioxane; Described Mierocrystalline cellulose is any one or the two or more mixture in wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp, and the content of cellulose in described wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp is 90-100%; The described cellulosic polymerization degree is 300-800.
5. the described method of any one according to claim 2～4, it is characterized in that, the method specifically comprises the steps: to obtain the cellulose macromolecule initiator with atom transferred free radical initiator modified-cellulose, 0.1～1.0 part of described cellulose macromolecule initiator is dissolved in 69-84 part solvent, add 15～30 parts of isoprene monomers, the catalyzer of trace, part and reductive agent; This polymeric solution is put into the heavy wall pressure bottle, and 110-130 ℃ of reaction of sealing is 72-120 hour behind the logical argon gas, makes Mierocrystalline cellulose-grafting-polyisoprene.
6. preparation method who prepares the described Mierocrystalline cellulose-grafting of claim 1-polyisoprene copolymers, it is grafted to the monomer isoprene on the cellulosic backbone by charge transfer-atom transition free radical polymerization reaction first, then the crosslinked Mierocrystalline cellulose-grafting of the side chain terminal that obtains by the coupled reaction between the polyisoprene chain end-polyisoprene copolymers, this multipolymer R is Br or cellulose chain.
7. method according to claim 6 is characterized in that, the starting raw material of described multipolymer comprises following component, counts by weight:
0.8～4 part of Mierocrystalline cellulose;
16～19.2 parts of isoprene;
80 parts of solvents;
Catalyzer 2*10
-4Part;
Reductive agent 1.5*10
-3Part;
Ligand 1 .8*10
-3Part.
8. method according to claim 5 is characterized in that, described catalyzer is cupric bromide, and described reductive agent is xitix, and described part is N, N, N', N'', N''-five methyl diethylentriamine; Described solvent is that volume ratio is the DMF of 1:1 and the mixed solvent of Isosorbide-5-Nitrae-dioxane; Described Mierocrystalline cellulose is any one or the two or more mixture in wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp, and the content of cellulose in described wood pulps, the Rice ﹠ peanut milk dregs of rice, Cotton Pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, bagasse pulp or the hemp dissolving pulp is 90-100%; The described cellulosic polymerization degree is 300-800.
9. the described method of any one according to claim 6～8, it is characterized in that, it comprises following concrete steps: obtain the cellulose macromolecule initiator with atom transferred free radical initiator modified-cellulose, 1.0～5.2 parts of described cellulose macromolecule initiators are dissolved in 70-90 part solvent, add 15.7～19.0 parts of isoprene monomers, the catalyzer of trace, part and reductive agent; This polymeric solution is put into the special type bottle, and 50-90 ℃ of reaction of sealing is 10-48 hour behind the logical argon gas, makes the crosslinked Mierocrystalline cellulose-grafting of side chain terminal-polyisoprene.
10. according to claim 4 or 8 described methods, it is characterized in that described Mierocrystalline cellulose is the cellulose macromolecule initiator through the atom transfer radical polymerization initiator modification, its preparation method comprises following concrete steps:
(1) extracting cellulose 1-5 part, 1-allyl group-3 Methylimidazole villaumite ionic liquid 50-80 part, 50-90 ℃ vacuum-drying 12-36 hour;
(2) described Mierocrystalline cellulose and the ionic liquid stated of step (1) mixed 60-90 ℃ of dissolving;
(3) obtain light yellow transparent solution with adding the DMF dilution after the cooling of step (2) mixing solutions;
(4) under the ice-water bath condition, in the described solution of step (3), slowly drip 2-bromine isobutyl acylbromide 10-15 part;
(5) after dropping process is finished, room temperature reaction 24-40 hour, and product is deposited in obtains white cotton-shaped product, suction filtration-washed several times with water in the water;
(6) the white cotton-shaped product that step (5) is obtained obtained the cellulose macromolecule initiator at 40-60 ℃ of vacuum-drying 20-40 hour.
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| CN103145918A (en) * | 2013-01-18 | 2013-06-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose-g-resin acid grafted copolymer |
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| CN104562847A (en) * | 2014-12-17 | 2015-04-29 | 广西大学 | Method for improving paper strength |
| CN104611984A (en) * | 2014-12-17 | 2015-05-13 | 广西大学 | Preparation method of ATRP method modified paper pulp fiber |
| CN106215907A (en) * | 2016-08-22 | 2016-12-14 | 鲁东大学 | A kind of magnetic cellulose base poly ion liquid type adsorbent and preparation method thereof |
| CN106215907B (en) * | 2016-08-22 | 2018-09-18 | 鲁东大学 | A kind of magnetic cellulose base poly ion liquid type adsorbent and preparation method thereof |
| CN109734844B (en) * | 2018-12-20 | 2020-07-07 | 安徽农业大学 | High-toughness flexible transparent glass material and preparation method thereof |
| CN109734844A (en) * | 2018-12-20 | 2019-05-10 | 安徽农业大学 | A kind of high tenacity flexible and transparent glass material and preparation method thereof |
| CN109369853A (en) * | 2018-12-24 | 2019-02-22 | 王春华 | A kind of preparation method of cellulose base elastic material |
| CN111187385A (en) * | 2019-08-26 | 2020-05-22 | 中国科学技术大学 | Cellulose-based bottle-brush-shaped thermoplastic elastomer and preparation method thereof |
| CN111187385B (en) * | 2019-08-26 | 2021-07-06 | 中国科学技术大学 | Cellulose-based bottle-brush-shaped thermoplastic elastomer and preparation method thereof |
| CN110918067A (en) * | 2019-12-09 | 2020-03-27 | 河北科技大学 | Grafted cellulose adsorbent and preparation method and application thereof |
| CN110918067B (en) * | 2019-12-09 | 2022-08-26 | 河北科技大学 | Grafted cellulose adsorbent and preparation method and application thereof |
| CN110975329A (en) * | 2019-12-11 | 2020-04-10 | 安徽大学 | Polymer modified straw based on agricultural waste straw and preparation method and application thereof |
| CN111732698A (en) * | 2020-06-30 | 2020-10-02 | 中国科学技术大学 | Application of bottle brush-shaped polymer elastomer and bionic skin |
| CN115386148A (en) * | 2022-08-11 | 2022-11-25 | 上海科邦医用乳胶器材有限公司 | Natural medical rubber gloves and preparation method thereof |
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