CN101831040B - Amphipathilic block copolymer and preparation method thereof - Google Patents
Amphipathilic block copolymer and preparation method thereof Download PDFInfo
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- CN101831040B CN101831040B CN201010157403.9A CN201010157403A CN101831040B CN 101831040 B CN101831040 B CN 101831040B CN 201010157403 A CN201010157403 A CN 201010157403A CN 101831040 B CN101831040 B CN 101831040B
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Abstract
The invention discloses an amphipathilic block copolymer and a preparation method thereof. The preparation method comprises the following steps of: synthesizing polyvinyl pyrrolidone with low molecular weight and narrow molecular weight distribution through reverse atom transfer radical polymerization reaction of N-vinyl pyrrolidone, and further obtaining the block copolymer with low molecular weight distribution through atom transfer radical polymerization reaction of ethenyltriethoxy silane at certain temperature by using macromolecules as an initiator, using ferrous chloride or cuprous chloride as a catalyst and using triphenylphosphine or bipyridine as an organic ligand. The amphipathilic block copolymer has the following structure, wherein X is chlorine atom, the average molecular weight of the block copolymer is in a range of 5,000 to 16,000, and the molecular weight distribution coefficient of the block copolymer is between 1.25 and 1.4.
Description
Technical field
The present invention relates to a kind of amphipathic nature block polymer and preparation method thereof.
Background technology
The preparation of segmented copolymer mainly can be by continuous living control polymerization, realize with the approach such as Macromolecular coupling reaction of functional group.Active free radical polymerization is wide because of applicable monomeric species, reaction conditions is gentle easy to control, become the important method of the segmented copolymer of preparation compound with regular structure, wherein, activity/controlled radical polymerization that atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP) get up as developed recently, have the advantage of living polymerization and radical polymerization concurrently, become one of effective way of preparation macromonomer, segmented copolymer.
Polyvinylpyrrolidone (PVP) is widely used in the various fields such as medicine, food, daily-use chemical industry because have good adsorptivity, film-forming properties, cementability and biocompatibility and good thermostability.Polysiloxane (such as polyvinyl triethoxysilane VTES) has good thermostability, and biocompatibility, anti-oxidant, ultraviolet light character and good chain snappiness are widely used in filed of daily-use chemical industry.As seen, polysiloxane and polyvinylpyrrolidone have complementarity in performance, can predict, and the segmented copolymer that both form has potential purposes in fields such as biological medicine material, daily-use chemical industries.
Summary of the invention
The object of the present invention is to provide a kind of amphipathic nature block polymer that is formed by NVP and two kinds of components of vinyltriethoxysilane and based on two step synthesis methods of controllable free-radical polymerisation.This segmented copolymer can be used as potential polymeric surface active agent, biological medical polymer material.
Amphipathic nature block polymer provided by the invention has following structure:
Wherein: X is the chlorine atom; The average molecular weight range of segmented copolymer is 5000～16000, and the molecular weight distribution coefficient of segmented copolymer is between 1.25～1.4.
The present invention also provides a kind of preparation method of amphipathic nature block polymer, and this preparation method was divided into for two steps:
The first step: prepare macromole evocating agent by reverse atom transfer radical polymerization, this macromole evocating agent has following structure:
Wherein: X is the chlorine atom; The average molecular weight range of macromole evocating agent is 1500～4000, molecular weight distribution coefficient 1.18～1.36;
The initiator system that adopts in the macromole evocating agent preparation is initiator Diisopropyl azodicarboxylate, catalyzer iron(ic) chloride, part triphenylphosphine or initiator Diisopropyl azodicarboxylate, catalyzer cupric chloride, part bipyridine; The monomer N-vinyl pyrrolidone;
Second step: the preparation of amphipathic nature block polymer, with the synthetic macromole evocating agent of the first step as initiator, catalyzer iron protochloride, part triphenylphosphine or catalyzer cuprous chloride, part bipyridine; Monomer vinyl triethoxyl silane, solvent are pimelinketone.
Initiator in the first step wherein: catalyzer: part: the mol ratio of monomer is 1～2: 1～2: 2～4: 30～60, and in 5～8 hours reaction times, temperature of reaction is 70 ℃～80 ℃; Initiator in the second step: catalyzer: part: the mol ratio of monomer is 1～2: 1～2: 2～4: 100～200; Vinyltriethoxysilane: the volume ratio of solvent is 10～30: 70: 90; In 10～15 hours reaction times, temperature of reaction is 55 ℃～65 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 5000～16000, and the molecular weight distribution coefficient of segmented copolymer is between 1.25～1.4
Amphipathic nature block polymer of the present invention can be used as potential polymeric surface active agent, the purposes of biological medical polymer material.
Embodiment
Below in conjunction with embodiment the present invention is made further and to specify.
Embodiment 1
The first step, macromole evocating agent preparation: initiator Diisopropyl azodicarboxylate, catalyzer iron(ic) chloride, part triphenylphosphine, wherein, initiator: catalyzer: part: monomer (NVP) is 1: 1: 2: 30 (mol ratios), in 5 hours reaction times, temperature of reaction is 80 ℃.The molecular-weight average that gel permeation chromatography records macromole evocating agent is 1721, molecular weight distribution coefficient 1.28.
Second step: with the synthetic macromole evocating agent of the first step as initiator, catalyzer iron protochloride, part triphenylphosphine, wherein, monomer vinyl triethoxyl silane, solvent are pimelinketone.Initiator: catalyzer: part: monomer is 1: 1: 2: 100 (mol ratios), vinyltriethoxysilane: solvent is 10: 90 (volume ratio).In 10 hours reaction times, temperature of reaction is 55 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 6213, the molecular weight distribution coefficient 1.26 of segmented copolymer.
Embodiment 2
The first step, macromole evocating agent preparation: initiator Diisopropyl azodicarboxylate, catalyzer iron(ic) chloride, part triphenylphosphine, wherein, initiator: catalyzer: part: monomer (NVP) is 1: 1: 2: 60 (mol ratios), in 8 hours reaction times, temperature of reaction is 70 ℃.The molecular-weight average that gel permeation chromatography records macromole evocating agent is 3805, molecular weight distribution coefficient 1.22.
Second step: with the synthetic macromole evocating agent of the first step as initiator, catalyzer iron protochloride, part triphenylphosphine, wherein, monomer vinyl triethoxyl silane, solvent are pimelinketone.Initiator: catalyzer: part: monomer is 1: 2: 4: 200 (mol ratios), vinyltriethoxysilane: solvent is 20: 80 (volume ratio).In 15 hours reaction times, temperature of reaction is 60 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 14867, the molecular weight distribution coefficient 1.32 of segmented copolymer.
Embodiment 3
The first step, macromole evocating agent preparation: initiator Diisopropyl azodicarboxylate, catalyzer cupric chloride, part bipyridine, wherein, initiator: catalyzer: part: monomer (NVP) is 1: 1: 2: 60 (mol ratios), in 8 hours reaction times, temperature of reaction is 80 ℃.The molecular-weight average that gel permeation chromatography records macromole evocating agent is 3527, molecular weight distribution coefficient 1.21.
Second step: with the synthetic macromole evocating agent of the first step as initiator, catalyzer cupric chloride, part bipyridine, wherein, monomer vinyl triethoxyl silane, solvent are pimelinketone.Initiator: catalyzer: part: monomer is 1: 1: 2: 200 (mol ratios), vinyltriethoxysilane: solvent is 20: 80 (volume ratio).In 15 hours reaction times, temperature of reaction is 55 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 15332, the molecular weight distribution coefficient 1.27 of segmented copolymer.
Embodiment 4
The first step, macromole evocating agent preparation: initiator Diisopropyl azodicarboxylate, catalyzer cupric chloride, part bipyridine, wherein, initiator: catalyzer: part: monomer (NVP) is 1: 1: 2: 40 (mol ratios), in 6 hours reaction times, temperature of reaction is 80 ℃.The molecular-weight average that gel permeation chromatography records macromole evocating agent is 2253, molecular weight distribution coefficient 1.27.
Second step: with the synthetic macromole evocating agent of the first step as initiator, catalyzer cupric chloride, part bipyridine, wherein, monomer vinyl triethoxyl silane, solvent are pimelinketone.Initiator: catalyzer: part: monomer is 1: 2: 4: 100 (mol ratios), vinyltriethoxysilane: solvent is 30: 70 (volume ratio).In 12 hours reaction times, temperature of reaction is 65 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 9425, the molecular weight distribution coefficient 1.37 of segmented copolymer.
Embodiment 4
The first step, macromole evocating agent preparation: initiator Diisopropyl azodicarboxylate, catalyzer cupric chloride, part bipyridine, wherein, initiator: catalyzer: part: monomer (NVP) is 1: 2: 4: 30 (mol ratios), in 6 hours reaction times, temperature of reaction is 70 ℃.The molecular-weight average that gel permeation chromatography records macromole evocating agent is 1820, molecular weight distribution coefficient 1.21.
Second step: with the synthetic macromole evocating agent of the first step as initiator, catalyzer cupric chloride, part bipyridine, wherein, monomer vinyl triethoxyl silane, solvent are pimelinketone.Initiator: catalyzer: part: monomer is 1: 2: 4: 150 (mol ratios), vinyltriethoxysilane: solvent is 10: 90 (volume ratio).In 15 hours reaction times, temperature of reaction is 55 ℃.
The average molecular weight range that gel permeation chromatography records segmented copolymer is 12146, the molecular weight distribution coefficient 1.30 of segmented copolymer.
Claims (2)
1. amphipathic nature block polymer is characterized in that this amphipathic nature block polymer has following structure:
Wherein: X is the chlorine atom; The average molecular weight range of segmented copolymer is 5000～16000, and the molecular weight distribution coefficient of segmented copolymer is between 1.25～1.4.
2. the preparation method of an amphipathic nature block polymer claimed in claim 1 is characterized in that this preparation method was divided into for two steps:
The first step: prepare macromole evocating agent by reverse atom transfer radical polymerization, this macromole evocating agent has following structure:
Wherein: X is the chlorine atom; The average molecular weight range of macromole evocating agent is 1500～4000, molecular weight distribution coefficient 1.18～1.36;
The initiator system that adopts in the macromole evocating agent preparation is initiator Diisopropyl azodicarboxylate, catalyzer iron(ic) chloride, part triphenylphosphine or initiator Diisopropyl azodicarboxylate, catalyzer cupric chloride, part bipyridine, the monomer N-vinyl pyrrolidone, initiator wherein: catalyzer: part: the mol ratio of monomer is 1～2: 1～2: 2～4: 30～60, in 5～8 hours reaction times, temperature of reaction is 70 ℃～80 ℃;
Second step: the preparation of amphipathic nature block polymer, with the synthetic macromole evocating agent of the first step as initiator, catalyzer iron protochloride, part triphenylphosphine or catalyzer cuprous chloride, part bipyridine; Monomer vinyl triethoxyl silane, solvent are pimelinketone, wherein initiator: catalyzer: part: the mol ratio of monomer is 1～2: 1～2: 2～4: 100～200; Vinyltriethoxysilane: the volume ratio of solvent is 10: 90 or 20: 80 or 30: 70; In 10～15 hours reaction times, temperature of reaction is 55 ℃～65 ℃.
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