CN102225990A - Poly((methyl)acrylic acid-b-butadiene) block copolymer and preparation method thereof - Google Patents
Poly((methyl)acrylic acid-b-butadiene) block copolymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a poly((methyl)acrylic acid-b-butadiene) block copolymer and a preparation method thereof. The preparation method comprises the following steps: adding 0.5-10 weight parts of amphiphilic macromolecular reversible addition breakage chain transfer reagent to 20-80 weight parts of water so as to form a water phase; transferring the water phase and 0.001-0.05 weight part of initiator into a high-pressure reaction kettle, carrying out nitrogen introduction and oxygen discharge for 10-30 minutes in the process of stirring, vacuuming, and repeating the operations 2-3 times; and adding 5-30 weight parts of butadiene, heating to 60-80 DEG C, polymerizing for 3-20 hours, cooling and discharging. The process flow of the method is simple in equipment, the process is environmentally-friendly and energy-saving, and the product poly((methyl)acrylic acid-b-butadiene) block copolymer has good application prospects in the fields of adhesives, compatilizers, dispersing agents and the like.
Description
Technical field
The present invention relates to a kind of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer and preparation method thereof.
Background technology
In the processing of multiple elastomerics such as rubber articles or thermoplastic elastomer, need to add mineral fillers such as carbon black, lime carbonate, kaolinite usually,, also can reduce cost simultaneously to improve the rigidity and the thermotolerance of resilient material; In addition, in some applications, metal, inorganic surfaces such as building stones need nonpolar polymkeric substance such as polyethylene or polypropylene as coating.In these cases, when inorganic materials and polymer blending or be attached on a time-out, both interfacial tensions are excessive, a little less than the avidity, cause mechanical property not strong, layering or phenomenon of rupture take place in processing and use usually, therefore need a kind of compatilizer to connect the two.The effect of compatilizer is exactly to improve the dispersity of mineral filler in polymkeric substance on the one hand, reduces interfacial tension on the other hand, makes the inconsistent blend of thermodynamics become the blend of process compatible.
Segmented copolymer particularly contains the segmented copolymer of strong polar group, is often used as the compatilizer of blend polymer.At present, segmented copolymer adopts the method preparation of active anionic polymerization more, but, because the limitation of this method, also can't be contained strong polarity unit and nonpolar unitary segmented copolymer simultaneously by direct polymerization, it contains polar block and non-polar blocks simultaneously to yet there are no any segmented copolymer compatilizer, for example poly-((methyl) vinylformic acid-b-divinyl).1998, Graeme Moad and Ezio Rizzardo etc. found RAFT active free radical polymerization (RAFT), and subsequently, people are applied to the preparation of various polymkeric substance and block polymer always in exploration.Development through more than ten years, RAFT active free radical polymerization method can be applied in the polymerization of multiple important monomer, styrenic for example, (methyl) esters of acrylic acid, ammonia ester class, dienes, vinyl acetate or the like, and polymkeric substance has narrower molecular weight distribution and higher chain extension activity, wherein, polystyrene, polymkeric substance such as butyl polyacrylate can also reach the high molecular more than 100,000.In addition, the RAFT active free radical polymerization also has been successfully applied to emulsion system, and this certainly will will accelerate its industrialized paces greatly.
The method of the invention is exactly to adopt RAFT living radical emulsion polymerisation process to prepare novel poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer first, this segmented copolymer has strong polarity (methyl) vinylformic acid block component and nonpolar polybutadiene block to be formed, and can be used as the dispersion agent of the mineral filler of the compatilizer of blend of polar polymer/non-polar polymer or non-polar polymer.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide and take a kind of brand-new Technology to prepare poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer first.
The chemical structure of general formula of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer is: AA
N1-St
N2-Bd
N3-R, wherein AA is methacrylic acid or acrylic acid units, and St is a styrene units, and Bd is a butadiene unit, and R is an alkyl trithio ester group, the mean polymerisation degree of each block is respectively n
1=20～60, n
2=3～6, n
3=20～500.
The preparation method of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer segmented copolymer is:
The amphiphilic macromole RAFT reagent of 0.5～10 weight part is added in 20～80 weight parts waters, forms water; Water and 0.001～0.05 weight part initiator are moved into autoclave together, and logical nitrogen deoxygenation is 10～30 minutes in the stirring, vacuumizes, repeat 2～3 times, add 5～30 weight parts of butadiene, heat temperature raising to 60～80 ℃, polyreaction 3～20 hours, cooling discharging.
The chemical structure of general formula of described amphiphilic macromole RAFT reagent is:
AA is an acrylic acid units, methacrylic acid unit, and St is a styrene units, and C is the alkyl of carbon number from four to 12, and R is the isopropyl acid base, acetoxyl, 2-itrile group acetoxyl, 2-glycine base.Wherein m and n are respectively the mean polymerisation degree of (methyl) acrylic acid units and styrene units, m=20～60, n=3～6.
Described amphiphilic macromole RAFT reagent is molecular weight at 1000～6000 amphiphilic oligopolymer.
Described initiator is a Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4,4'-azo (4-cyanopentanoic acid), azo two isobutyl imidazoline salt hydrochlorates, azo di-isopropyl tetrahydroglyoxaline, dibenzoyl peroxide, dicumyl peroxide, tertbutyl peroxide or di-t-butyl peroxide.
The present invention has realized the successful preparation of poly-((methyl) vinylformic acid-b-divinyl) first, the RAFT emulsion polymerization technique has following advantage: 1) blanketing effect of letex polymerization can not react interparticle free radical, greatly reduce the termination speed that increases free radical, thereby letex polymerization has the rate of polymerization height, the characteristics that molecular weight is big; 2) the emulsion aqueous systems has advantages such as viscosity is low, heat transfer is fast, pollution is little, is the first-selected system that polymerization industry generates; 3) the RAFT active free radical polymerization can participate in synthesizing of segmented copolymer chain more monomer, has effectively increased the kind of polymkeric substance and has strengthened polymer properties; 4) the RAFT active free radical polymerization has also reduced the harsh requirement to material equipment, has saved cost greatly, is the first-selected system that polymerization industry generates.
Description of drawings
Fig. 1 is in poly-(vinylformic acid-b-divinyl) segmented copolymer of RAFT emulsion preparation, the GPC molecular weight distribution of segmented copolymer is along with the variation diagram (per-cent is represented the transformation efficiency of divinyl among the figure, and macroRAFT1 represents parents' macromole RAFT reagent) of butadiene conversion.
Embodiment
The chemical structure of general formula of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer is: AA
N1-St
N2-Bd
N3-R, wherein AA is methacrylic acid or acrylic acid units, and St is a styrene units, and Bd is a butadiene unit, and R is an alkyl trithio ester group, the mean polymerisation degree of each block is respectively n
1=20～60, n
2=3～6, n
3=20～500.
The preparation method of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer segmented copolymer is: the amphiphilic macromole RAFT reagent of 0.5～10 weight part is added in 20～80 weight parts waters, forms water; Water and 0.001～0.05 weight part initiator are moved into autoclave together, and logical nitrogen deoxygenation is 10～30 minutes in the stirring, vacuumizes, repeat 2～3 times, add 5～30 weight parts of butadiene, heat temperature raising to 60～80 ℃, polyreaction 3～20 hours, cooling discharging.
The chemical structure of general formula of described amphiphilic macromole RAFT reagent is:
AA is an acrylic acid units, methacrylic acid unit, and St is a styrene units, and C is the alkyl of carbon number from four to 12, and R is the isopropyl acid base, acetoxyl, 2-itrile group acetoxyl, 2-glycine base.Wherein m and n are respectively the mean polymerisation degree of (methyl) acrylic acid units and styrene units, m=20～60, n=3～6.
Described amphiphilic macromole RAFT reagent is molecular weight at 1000～6000 amphiphilic oligopolymer.
Described initiator is a Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4,4'-azo (4-cyanopentanoic acid), azo two isobutyl imidazoline salt hydrochlorates, azo di-isopropyl tetrahydroglyoxaline, dibenzoyl peroxide, dicumyl peroxide, tertbutyl peroxide or di-t-butyl peroxide.
Amphiphilic macromole RAFT reagent chemical structure skeleton symbol used in the embodiment of the invention is as follows, by vinylformic acid with styrene copolymerizedly obtain to dodecyl-2-isopropyl acid three thioesters, and polymerizing acrylic acid degree (n wherein
1) be 27, styrene polymerization degree (n
2) be 5, polymkeric substance by hydrogen nuclear magnetic resonance spectroscopy (
1H NMR) analysis obtains, and structure is as follows:
Adopt the sulfuric acid dilute solution that poly-(vinylformic acid-b-divinyl) segmented copolymer latex is carried out breakdown of emulsion, the copolymer products that obtains carries out heat drying under vacuum.
Polybutadiene block polymerization degree n in poly-(vinylformic acid-b-divinyl) segmented copolymer
3Can according to proton nmr spectra (
1H NMR) analysis obtains.
Embodiment 1
The amphiphilic macromole RAFT reagent of 0.8 weight part is added in 30 weight parts waters, forms water; Water and 0.01 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 10 weight parts of butadiene, heat temperature raising to 70 ℃, polymerization 4 hours, cooling discharging.
As shown in Figure 1, GPC detects and shows that gained block copolymer amount increases with transformation efficiency, has confirmed the successful grafting of polybutadiene block, and this method is successfully gathered (vinylformic acid-b-divinyl) segmented copolymer.
Embodiment 2
The amphiphilic macromole RAFT reagent of 0.8 weight part is added in 20 weight parts waters, forms water; Water and 0.01 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 10 weight parts of butadiene, heat temperature raising to 70 ℃, polymerization 10 hours, cooling discharging.
Embodiment 3
The amphiphilic macromole RAFT reagent of 2 weight parts is added in 30 weight parts waters, forms water; Water and 0.02 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 10 weight parts of butadiene, heat temperature raising to 70 ℃, polymerization 10 hours, cooling discharging.
Embodiment 4
The amphiphilic macromole RAFT reagent of 2 weight parts is added in 50 weight parts waters, forms water; Water and 0.02 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 15 weight parts of butadiene, heat temperature raising to 70 ℃, polymerization 10 hours, cooling discharging.
Embodiment 5
The amphiphilic macromole RAFT reagent of 2 weight parts is added in 50 weight parts waters, forms water; Water and 0.02 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 15 weight parts of butadiene, heat temperature raising to 70 ℃, polyase 13 hour, cooling discharging.
Embodiment 6
The amphiphilic macromole RAFT reagent of 4 weight parts is added in 80 weight parts waters, forms water; Water and 0.05 weight part AIBN are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 30 weight parts of butadiene, heat temperature raising to 70 ℃, polymerization 8 hours, cooling discharging.
Embodiment 7
The amphiphilic macromole RAFT reagent of 0.5 weight part is added in 20 weight parts waters, forms water; Water and 0.001 weight part initiator are moved into autoclave together, and logical nitrogen deoxygenation is 10 minutes in the stirring, vacuumizes, and repeats 2 times, adds 5 weight parts of butadiene, heat temperature raising to 60 ℃, polyreaction 20 hours, cooling discharging.
Embodiment 8
The amphiphilic macromole RAFT reagent of 10 weight parts is added in 80 weight parts waters, forms water; Water and 0.05 weight part initiator are moved into autoclave together, and logical nitrogen deoxygenation is 30 minutes in the stirring, vacuumizes, and repeats 3 times, adds 30 weight parts of butadiene, heat temperature raising to 80 ℃, polyreaction 3 hours, cooling discharging.
Claims (5)
1. one kind is gathered ((methyl) vinylformic acid-b-divinyl) segmented copolymer, it is characterized in that: the chemical structure of general formula of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer is: AA
N1-St
N2-Bd
N3-R, wherein AA is methacrylic acid or acrylic acid units, and St is a styrene units, and Bd is a butadiene unit, and R is an alkyl trithio ester group, the mean polymerisation degree of each block is respectively n
1=20～60, n
2=3～6, n
3=20～500.
2. the preparation technology of poly-((methyl) vinylformic acid-b-divinyl) segmented copolymer segmented copolymer as claimed in claim 1, it is characterized in that: the amphiphilic macromole RAFT reagent of 0.5～10 weight part is added in 20～80 weight parts waters, forms water; Water and 0.001～0.05 weight part initiator are moved into autoclave together, and logical nitrogen deoxygenation is 10～30 minutes in the stirring, vacuumizes, repeat 2～3 times, add 5～30 weight parts of butadiene, heat temperature raising to 60～80 ℃, polyreaction 3～20 hours, cooling discharging.
3. the preparation method of a kind of RAFT letex polymerization according to claim 2 is characterized in that the chemical structure of general formula of described amphiphilic macromole RAFT reagent is:
AA is an acrylic acid units, methacrylic acid unit, St is a styrene units, and C is the alkyl of carbon number from four to 12, and R is the isopropyl acid base, acetoxyl, 2-itrile group acetoxyl, 2-glycine base, wherein m and n are respectively the mean polymerisation degree of (methyl) acrylic acid units and styrene units, m=20～60, n=3～6.
4. the preparation method of a kind of RAFT letex polymerization according to claim 2 is characterized in that described amphiphilic macromole RAFT reagent is molecular weight at 1000～6000 amphiphilic oligopolymer.
5. the preparation method of a kind of RAFT letex polymerization according to claim 2, it is characterized in that described initiator is a Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 4,4'-azo (4-cyanopentanoic acid), azo two isobutyl imidazoline salt hydrochlorates, azo di-isopropyl tetrahydroglyoxaline, dibenzoyl peroxide, dicumyl peroxide, tertbutyl peroxide or di-t-butyl peroxide.
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|---|---|---|---|---|
| WO2013135112A1 (en) * | 2012-03-15 | 2013-09-19 | 浙江大学 | Poly((meth)acrylic acid-b-styrene-b-butadiene-b-styrene) block copolymer latex and preparation method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880364A (en) * | 2010-06-25 | 2010-11-10 | 浙江大学 | Styrene/butadiene amphiphilic block copolymer nano rubber latex and preparation method thereof |
| CN101955555A (en) * | 2010-09-30 | 2011-01-26 | 浙江大学 | Implementation method of reversible addition fragmentation chain emulsion polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101880364A (en) * | 2010-06-25 | 2010-11-10 | 浙江大学 | Styrene/butadiene amphiphilic block copolymer nano rubber latex and preparation method thereof |
| CN101955555A (en) * | 2010-09-30 | 2011-01-26 | 浙江大学 | Implementation method of reversible addition fragmentation chain emulsion polymerization |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013135112A1 (en) * | 2012-03-15 | 2013-09-19 | 浙江大学 | Poly((meth)acrylic acid-b-styrene-b-butadiene-b-styrene) block copolymer latex and preparation method therefor |
| WO2013134965A1 (en) * | 2012-03-15 | 2013-09-19 | 浙江大学 | Poly((meth)acrylic acid-b-styrene-b-butadiene-b-styrene) block copolymer latex and preparation method therefor |
| US9328234B2 (en) | 2012-03-15 | 2016-05-03 | Zhejiang University | Poly((meth)acrylic acid-b-styrene-b-butadiene-b-styrene) block copolymer latex and method for preparing the same |
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