CN102167782B - Method for grafting polymer in double bond position of natural rubber by adopting atom transfer radical polymerization (ATRP) - Google Patents
Method for grafting polymer in double bond position of natural rubber by adopting atom transfer radical polymerization (ATRP) Download PDFInfo
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- CN102167782B CN102167782B CN201110004883XA CN201110004883A CN102167782B CN 102167782 B CN102167782 B CN 102167782B CN 201110004883X A CN201110004883X A CN 201110004883XA CN 201110004883 A CN201110004883 A CN 201110004883A CN 102167782 B CN102167782 B CN 102167782B
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- atrp
- natural rubber
- double bond
- epoxy natural
- nucleophilic reagent
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Abstract
The invention belongs to the technical field of the modification of natural rubber and particularly relates to a method for grafting polymer in the double bond position of natural rubber by adopting the atom transfer radical polymerization (ATRP). The method comprises the following steps: partially epoxidized natural rubber reacts with halogenated nucleophilic reagent, a side group with active halogen atom is introduced to the double bond position of the natural rubber molecular chain to obtain an ATRP macromolecular initiator, a polymer chain is grafted through ATRP to prepare natural rubber (NR) graft copolymer. The technology in the invention is simple; by controlling the action conditions, the positions of the grafted chains of the NR graft copolymer on the main chain and the density, length and length uniformity of the grafted chain can be effectively controlled; and the grafted chains are distributed in double bond position of the NR molecular chain, thus the performances of the NR graft copolymer and the uniformity of the product can be increased.
Description
Technical field
The invention belongs to tree elastomer modification technology field, be specifically related to the method for a kind of employing ATRP (ATRP) graftomer on the tree elastomer position of double bond.
Background technology
Through polymer graft modification tree elastomer (NR), not only can improve the performance of NR itself, the graft copolymer of generation uses as strengthening agent and expanding material, can also increase the shock strength and the interfacial bond power of polymer blending material.
At present, the polymer graft modification of NR mainly is through radical polymerization, on the α-reactive hydrogen of NR molecular chain and position of double bond, forms allyl radical and alkyl diradical as grafting active site, causes the second monomer generation graft copolymerization.Polymer graft chain major part is distributed on α-reactive hydrogen position of NR, few part is also arranged on position of double bond.Carry out graft copolymerization through radical polymerization and have following drawback: one, radical produces the NR radical except causing NR; Also trigger monomer produces free polymer readical; The former forms grafted chain at the trigger monomer polymerization, and the latter perhaps forms grafted chain with the NR combined with radical, perhaps forms the monomer homopolymer through chain transfer and chain termination; This will cause the grafting efficiency of polymkeric substance low, even formation " homopolymer microcell ".Two, radical polymerization causes, increases soon, is prone to take place the characteristics of chain termination and chain transfer slowly, makes polyreaction be difficult to control, causes polymerisate to present wide distribution, and molecular weight is uncontrollable, sometimes even branching, crosslinked etc. can take place.Therefore; When carrying out the graft copolymerization of NR, can't control distribution and length and the length homogeneity of grafted chain of grafted chain on the NR molecular chain, and form crosslinked easily through radical polymerization; The performance that this certainly will influence the NR graft copolymer causes consistency of product poor.
The epoxidation of NR is meant through chemical modification, on the position of double bond of rubber molecular chain, connects epoxy group(ing), obtains epoxy natural rubber (ENR).Owing to have good reaction activity between epoxy group(ing) and nucleophilic reagent, can make ENR as a kind of reactive intermediate, for the further chemical modification of NR on position of double bond provides condition through the chemical reaction of epoxy group(ing) and other functional group's materials.
(ATRP) is applied to one of mode of graft copolymerization with ATRP; Be on main polymer chain, to introduce band ATRP reactive halogen (mainly to refer to chlorine or bromine; The side group of atom down together), the preparation macromole evocating agent causes the second monomer generation graft copolymerization through the ATRP method.This method has following advantage: one, carry out owing to chainpropagation only causes point at ATRP; Can through the controlling polymers main chain cause the position and the number of point (being the active halo atom) with ATRP; Position and the density thereof of control grafted chain on main chain, and do not have the homopolymer generation.Two, therefore the molecular weight of ATRP resulting polymers, when being applied to graft copolymerization, can reach the purpose of controlling grafted chain length through controlling the second monomeric consumption and transformation efficiency with the transformation efficiency linear growth.Three, the ATRP initiator system has quick initiation, quick reversibly inactivated characteristics, and the gained polymerisate demonstrates narrow polydispersity index (1.0＜M
w/ M
n＜1.5, M wherein
wBe meant weight-average molecular weight and M
nBe meant number-average molecular weight), can control the length homogeneity of grafted chain thus.
Summary of the invention
The objective of the invention is to the deficiency of prior art and a kind of ATRP of employing is provided the method for graftomer on the tree elastomer position of double bond; Through the control reaction conditions; Position, the density of grafted chain and length and the length homogeneity of grafted chain of grafted chain in the NR graft copolymer on main chain controlled, thus the performance and the consistency of product of raising NR graft copolymer.
The know-why that the present invention adopted: utilize the reactive behavior between epoxide group and nucleophilic reagent; Reaction through ENR and halo nucleophilic reagent; On the position of double bond of NR molecular chain, introduce the side group of band ATRP reactive halogen atom, through the NR macromole evocating agent of the synthetic different halogen atom loadings of control reaction conditions; Through ATRP grafted polymer on the position of double bond of NR molecular chain, the density of grafted chain is through using the NR macromole evocating agent control of different halogen atom loadings again, and the length of grafted chain and length homogeneity are controlled by the ATRP reaction conditions.
The technical scheme that the present invention adopted:
A kind of method that adopts ATRP graftomer on the tree elastomer position of double bond, carry out according to following steps:
(1) mol ratio according to epoxidation unit in the epoxy natural rubber (ENR) and halo nucleophilic reagent is 0.5～2.0: 1; The epoxidation unit in the epoxy natural rubber and the weight ratio of catalyzer are 5.0～20.0: 1; Epoxy natural rubber (latex or solution state), halo nucleophilic reagent and one of catalyzer adding are furnished with in the Schlenk flask of magnetic agitation; Under protection of inert gas; Place 25～90 ℃ oil bath to react, reaction 0.1～20h obtains halogen atom loading (mol ratio of polyisoprene units in halogen atom and the tree elastomer) and is 1%～60% NR macromole evocating agent.Said halo nucleophilic reagent is meant at the halogenated carboxylic acid class nucleophilic reagent that has active substituent on the alpha-carbon or the halogenated carboxylic acid class nucleophilic reagent of the R-X key a little less than on alpha-carbon, containing; Wherein active substituent is aryl, carbonyl or allyl group; R is meant N, S or O, and X is meant Cl or Br.Said catalyzer is meant the basic cpd that the reaction between the epoxy group(ing) of epoxy natural rubber and carboxylic-acid nucleophilic reagent is had katalysis, the tetramethyl ammonium of preferred NaOH, KOH or this halo nucleophilic reagent.
The state of said epoxy natural rubber is latex or solution state.
Said epoxy natural rubber latex is meant that epoxidation level is 1%～60% epoxy natural rubber latex.
Said epoxy natural rubber latex before adding other reaction reagents by Na
2CO
3Regulate pH value to 7～10.
Said epoxy natural rubber is meant epoxy natural rubber solution, by the dried glue of epoxy natural rubber with fully dissolve as the THF of solvent or methylene dichloride after make.
Said halo nucleophilic reagent can be 2-bromo acid, 2 bromopropionic acid, to bromo methyl acid and at least a in the carboxyl benzene sulfonyl chloride.
(2) mol ratio according to the halogen atom in the NR macromole evocating agent of preparation in the step (1) and ATRP catalyzer, ligand is 1～1.5: 1～1.5: 1～3; NR macromole evocating agent, ATRP catalyzer and ligand are joined in the Schlenk flask of being furnished with magnetic agitation together; With diaphragm of rubber sealed reaction flask tightly, the degassing and charge into rare gas element under vacuum.Introduce the solvent and second monomer through syringe then, place 25～110 ℃ oil bath to react, the ATRP reaction takes place in system under emulsion or solution state; After reaction finished, polymerisate obtained the NR graft copolymer of grafted chain on position of double bond through deposition, washing and vacuum drying.Said ATRP catalyzer is CuX, FeX
2, CuX
2Or FeX
3, wherein X refers to Cl or Br, the type of X is consistent with the type of halogen atom in the halo nucleophilic reagent.Said ligand is meant that one or more contain the ligand of N-or P-, is coordinated on the transition metal (Fe or Cu) with σ-key or π-key, and preferred ligand is 2; 2 '-bipyridine (bpy), 4,4 '-two (five-nonyl)-2,2 '-bipyridine (dNbpy), 4; 4 '-di-n-butyl-2,2 '-bipyridine (dTbpy), N, N; N ', N ", N "-a kind of in five methyl diethylentriamine (PMDETA), triphenylphosphine (TPP) or the tributylphosphine (TBUP) or mix.Said second monomer is meant vinylbenzene, TEB 3K, methylacrylic acid or vinyl cyanide etc.
Said solvent is meant the organic solvent that can dissolve the tree elastomer macromole evocating agent, preferred toluene or THF.
The Nomenclature Composition and Structure of Complexes to reaction product characterizes, and its testing method is following:
(1) mensuration of halogen atom loading in the NR macromole evocating agent:
With the proton nmr spectra of Bruker AV 400 type nmr determination NR macromole evocating agents (
1H-NMR), CDCl
3Make solvent.The halogen atom loading is obtained by computes:
Tt is meant the halogen atom loading in the NR macromole evocating agent, I
X, I
OxiraneAnd I
C=CRepresentative supports the unitary oxyethane ring of epoxidation and 1 in the C atom, NR of halogenation nucleophilic reagent, the proton absorption peak strength of C=C in the 4-polyisoprene units respectively.
(2) sign of the mean length of grafted chain and length homogeneity:
The NR graft copolymer is carried out ozone degradation; Make the rubber hydrocarbon molecular chain degradation discharge grafted chain for the lower molecular weight segment, gained grafted chain polymkeric substance is measured grafted chain molecular weight of polymer and MWD with Waters150 type gel chromatograph (GPC) after the Suo Shi extracting; 25 ℃ of column temperatures; THF is a leacheate, and flow velocity 1mL/min, monodisperse polystyrene are calibration standard.Pass through number-average degree of polymerization
With molecular weight polydispersity index M
w/ M
nCharacterize the mean length and the length homogeneity of grafted chain,
Big more expression grafted chain is long more, M
w/ M
nThe length of more little expression grafted chain is homogeneous more.
Technology of the present invention is simple; Through the control reaction conditions; Effectively position, the density of grafted chain and length and the length homogeneity of grafted chain of grafted chain in the NR graft copolymer on main chain controlled, thus the performance and the consistency of product of raising NR graft copolymer.
Description of drawings
Fig. 1 is the synthetic route chart of NR macromole evocating agent.
Fig. 2 is the route map of ATRP method grafted polymer on the NR position of double bond.
Embodiment
With indefiniteness embodiment the present invention is described further below.
Embodiment one
(1) gets 1g38.6%ENR (epoxidation level=38.6%) fully dissolving in the 10mL methylene dichloride; Join in the Schlenk flask of being furnished with magnetic agitation with the tetramethyl ammonium of 0.869g2-bromo acid (BIBA) and 0.0437g2-bromo acid, under nitrogen protection, place 60 ℃ oil bath to react 24h; After reaction finishes; Precipitate in product and the excessive methanol, and dissolve repeatedly-precipitate through methylene chloride, throw out in 35 ℃ of following vacuum-dryings to constant weight.Gained macromole evocating agent BIBA-NR warp
1H-NMR analyzes, and records halogen atom loading T
t=20.3%.
(2) with 1gBIBA-NR and 0.269gCuBr, 0.325gN, N, N '; N "; N "-five methyl diethylentriamine (PMDETA) adds in the Schlenk flask of being furnished with magnetic agitation together, with diaphragm of rubber sealed reaction flask tightly, and the degassing and charge into argon gas under vacuum.Introduce 20ml toluene and 10g TEB 3K (MMA) through syringe then, place 90 ℃ oil bath to react 24h.After reaction finished, polymerisate to constant weight, obtained NR-g-PMMA through methanol extraction, distilled water wash and 50 ℃ of vacuum dryings after the Suo Shi extracting of acetone as solvent.Grafted chain gets through gpc analysis
M
w/ M
n=1.41.
Embodiment two
(1) 38.6%ENR latex being diluted to dried containing is 5%, and through Na
2CO
3Adjust pH to 8.20g ENR latex joins in the Schlenk flask of being furnished with magnetic agitation carboxyl benzene sulfonyl chloride (CSBA) and 0.0437gNaOH with 2.296g; Under nitrogen protection; Place 30 ℃ oil bath to react 24h, reaction precipitates in product and the excessive methanol after finishing; And through zero(ppm) water and methyl alcohol repetitive scrubbing, residuum in 35 ℃ of following vacuum-dryings to constant weight.Gained macromole evocating agent CSBA-NR warp
1H-NMR analyzes, and records halogen atom loading T
t=27.2%.
(2) with 1gCSBA-NR and 0.201gCuCl, 0.351gN, N, N '; N "; N "-five methyl diethylentriamine (PMDETA) adds in the Schlenk flask of being furnished with magnetic agitation together, with diaphragm of rubber sealed reaction flask tightly, and the degassing and charge into argon gas under vacuum.Introduce 20ml toluene and 10g TEB 3K (MMA) through syringe then, place 90 ℃ oil bath to react 24h.After reaction finished, polymerisate to constant weight, obtained NR-g-PMMA through methanol extraction, distilled water wash and 50 ℃ of vacuum dryings after the Suo Shi extracting of acetone as solvent.Grafted chain gets through gpc analysis
M
w/ M
n=1.67.
Embodiment three
(1) 38.6%ENR latex being diluted to dried containing is 5%, and through Na
2CO
3Adjust pH to 8.20g ENR latex joins in the Schlenk flask of being furnished with magnetic agitation bromo methyl acid (BPTA) and 0.0437gNaOH with 2.238g; Under nitrogen protection; Place 30 ℃ oil bath to react 48h, reaction obtains macromole evocating agent BPTA-NR emulsion after finishing.Precipitate in portion of product product and the excessive methanol, and through zero(ppm) water and methyl alcohol repetitive scrubbing, to constant weight, gained BPTA-NR is used for residuum in 35 ℃ of following vacuum-dryings
1H-NMR analyzes, and records halogen atom loading T
t=23.9%.
(2) directly in the BPTA-NR emulsion that obtains, inject 10g vinylbenzene (St); Tightly seal the Schlenk flask with diaphragm of rubber; Under vacuum the degassing and charge into argon gas, add 0.178gCuBr, 0.508g 4,4 '-two (five-nonyl)-2 subsequently; 2 '-bipyridine (dNbpy) places 60 ℃ oil bath to react.After reaction finished, polymerisate to constant weight, obtained NR-PSt through methanol extraction, distilled water wash and 50 ℃ of vacuum dryings after the Suo Shi extracting of acetone as solvent.Grafted chain gets through gpc analysis
M
w/ M
n=1.74.
Claims (6)
1. a method that adopts ATRP graftomer on the tree elastomer position of double bond is characterized in that, carries out according to following steps:
(1) mol ratio according to epoxidation unit in the epoxy natural rubber and halo nucleophilic reagent is 0.5～2.0: 1; The epoxidation unit in the epoxy natural rubber and the weight ratio of catalyzer are 5.0～20.0: 1; Epoxy natural rubber, halo nucleophilic reagent and one of catalyzer adding are furnished with in the Schlenk flask of magnetic agitation; Under protection of inert gas; Place 25～90 ℃ oil bath to react, reaction 0.1～20h obtains the halogen atom loading and is 1%～60% NR macromole evocating agent; Said halo nucleophilic reagent is meant at the halogenated carboxylic acid class nucleophilic reagent that has active substituent on the alpha-carbon or the halogenated carboxylic acid class nucleophilic reagent of the R-X key a little less than on alpha-carbon, containing; Wherein active substituent is aryl, carbonyl or allyl group; R is meant N, S or O; X is meant Cl or Br, and is concrete, and the halo nucleophilic reagent is 2-bromo acid, 2 bromopropionic acid, to bromo methyl acid and at least a in the carboxyl benzene sulfonyl chloride; Said catalyzer is NaOH, KOH or tetramethyl ammonium;
(2) mol ratio according to the halogen atom in the NR macromole evocating agent of preparation in the step (1) and ATRP catalyzer, ligand is 1～1.5: 1～1.5: 1～3; NR macromole evocating agent, ATRP catalyzer and ligand are joined in the Schlenk flask of being furnished with magnetic agitation together; With diaphragm of rubber sealed reaction flask tightly; The degassing and charge into rare gas element under vacuum; Introduce the solvent and second monomer through syringe then, place 25～110 ℃ oil bath to react, the ATRP reaction takes place in system under emulsion or solution state; After reaction finished, polymerisate obtained the NR graft copolymer of grafted chain on position of double bond through deposition, washing and vacuum drying; Said ATRP catalyzer is CuX, FeX
2, CuX
2Or FeX
3, wherein X refers to Cl or Br, the type of X is consistent with the type of halogen atom in the halo nucleophilic reagent; Said ligand is 2,2 '-bipyridine, 4,4 '-two (five-nonyl)-2,2 '-bipyridine, 4; 4 '-di-n-butyl-2,2 '-bipyridine, N, N; N ', N ", N "-a kind of in five methyl diethylentriamine, triphenylphosphine or the tributylphosphine or mix; Said second monomer is meant vinylbenzene, TEB 3K, methylacrylic acid or vinyl cyanide.
2. the method for employing ATRP according to claim 1 graftomer on the tree elastomer position of double bond, it is characterized in that: the state of said epoxy natural rubber is latex or solution state.
3. the method for employing ATRP according to claim 2 graftomer on the tree elastomer position of double bond, it is characterized in that: said epoxy natural rubber latex is meant that epoxidation level is 1%～60% epoxy natural rubber latex.
4. the method for employing according to claim 2 ATRP graftomer on the tree elastomer position of double bond is characterized in that: said epoxy natural rubber latex before adding other reaction reagents by Na
2CO
3Regulate pH value to 7～10.
5. the method for employing according to claim 2 ATRP graftomer on the tree elastomer position of double bond is characterized in that: said epoxy natural rubber solution be by the dried glue of epoxy natural rubber with fully dissolve as the THF of solvent or methylene dichloride after make.
6. the method for employing ATRP according to claim 1 graftomer on the tree elastomer position of double bond, it is characterized in that: said solvent is toluene or THF.
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| CN102633912B (en) * | 2012-03-20 | 2014-07-02 | 暨南大学 | Preparation method for quaternary ammonium or quaternary phosphonium modified chlorinated natural rubber |
| CN102627705B (en) * | 2012-03-30 | 2014-06-25 | 暨南大学 | Preparation method for quaternary phosphonium modified epoxidized natural rubber |
| CN110776588B (en) * | 2019-11-04 | 2022-12-09 | 青岛科技大学 | Method for preparing chloride of polymer containing unsaturated double bond structural unit and method for preparing polymer brush by using chloride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125749A (en) * | 1994-08-11 | 1996-07-03 | 威姆伯利橡胶制品公司 | Coating composition, method of using it and article coated with same |
| CN1798782A (en) * | 2003-06-02 | 2006-07-05 | 株式会社普利司通 | Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire |
| WO2007066689A1 (en) * | 2005-12-07 | 2007-06-14 | Bridgestone Corporation | Rubber composition and tire using same |
| EP2119730A1 (en) * | 2008-05-13 | 2009-11-18 | Sumitomo Rubber Industries, Ltd. | Modified natural rubber, method for producing modified natural rubber, rubber composition, and tire |
| WO2009139347A1 (en) * | 2008-05-14 | 2009-11-19 | 電気化学工業株式会社 | Adhesive film |
| CN101831034A (en) * | 2010-05-11 | 2010-09-15 | 中国热带农业科学院农产品加工研究所 | Natural rubber/N-vinyl pyrrolidone graft copolymer and preparation method thereof |
-
2011
- 2011-01-10 CN CN201110004883XA patent/CN102167782B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125749A (en) * | 1994-08-11 | 1996-07-03 | 威姆伯利橡胶制品公司 | Coating composition, method of using it and article coated with same |
| CN1798782A (en) * | 2003-06-02 | 2006-07-05 | 株式会社普利司通 | Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire |
| WO2007066689A1 (en) * | 2005-12-07 | 2007-06-14 | Bridgestone Corporation | Rubber composition and tire using same |
| EP2119730A1 (en) * | 2008-05-13 | 2009-11-18 | Sumitomo Rubber Industries, Ltd. | Modified natural rubber, method for producing modified natural rubber, rubber composition, and tire |
| WO2009139347A1 (en) * | 2008-05-14 | 2009-11-19 | 電気化学工業株式会社 | Adhesive film |
| CN101831034A (en) * | 2010-05-11 | 2010-09-15 | 中国热带农业科学院农产品加工研究所 | Natural rubber/N-vinyl pyrrolidone graft copolymer and preparation method thereof |
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