CN105801759A - Preparation method of carboxylic polyisoprene rubber - Google Patents
Preparation method of carboxylic polyisoprene rubber Download PDFInfo
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- CN105801759A CN105801759A CN201610205034.3A CN201610205034A CN105801759A CN 105801759 A CN105801759 A CN 105801759A CN 201610205034 A CN201610205034 A CN 201610205034A CN 105801759 A CN105801759 A CN 105801759A
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- polyisoprene rubber
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- carboxylated
- maleic anhydride
- polyisoprene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
Abstract
The invention discloses a preparation method of carboxylic polyisoprene rubber. After organic peroxide used as an initiator, maleic anhydride used as a carboxylation agent and polyisoprene are subjected to a reaction for a certain period of time under certain conditions, a proper solvent is selected, a reaction product is washed for multiple times, the excessive initiator and carboxylation agent are removed, and carboxylic polyisoprene is obtained after drying. A carboxylic polymer is colorless and transparent in appearance and good in bonding performance to metals and fibers, can be used as an adhesive, a pressure-sensitive adhesive and a sealant and can also be used for preparing modified latex.
Description
Technical field
The present invention relates to a kind of functionalized method, the preparation method being specifically related to a kind of carboxylated polyisoprene rubber.
Background technology
Polyolefin is typical non-polar polymeric material, and its surface tension is relatively low, and the compatibility with other materials such as polar polymer, inorganic filler and metal is poor, during compound use, need to add compatilizer to reduce interfacial tension, increases interfacial adhesion.Polyolefin is carried out grafting modification, it is carried out grafting of polar monomers, namely it is grafted on polyolefin macromolecular chain by the reaction monomers with polar functional group, make its polar, utilize polarity and the reactivity of polar group, improve the deficiency in its performance, increase again new character simultaneously, conventional grafting method carrys out improved polyalkene, reaction monomers is generally unsaturated acids and derivant etc. thereof, such as maleic anhydride, acrylic acid, mercaptoethanol etc., the grafting method technique adopted is more complicated, not easily grasp, and it is uneconomical, fusion-grafting production efficiency is high, but reaction is not exclusively, residual reaction monomer is more, product is easily made to produce bubble, the defects such as variable color, the percent grafting of solid phase grafting is not easy to improve.Huang et al. have studied the click chemistry reaction of the sulfydryl-double bond to polyisoprene (PI).Under the ultraviolet light irradiation of 365nm, double bond and 3-sulfydryl-1,2-propylene glycol reacts, hydroxyl is incorporated on PI main chain, bromine group macromole evocating agent is incorporated in PI side chain by the reaction adopting bromo isobutyl acylbromide and hydroxyl, causes styrene or acrylate tert-buthyl polymerization by ATRP method, obtains " V " the type side chain graft comb copolymer to polyisoprene main chain, achieve modifiying polyisoprene, expand the use scope of polyisoprene.The bright grade of Petrochina Lanzhou Petrochemical Company Chen Ji with tertiary butyl dimethyl Si base propyl lithium be initiator, hexamethylene for solvent, CO2For " block " reagent, adopt the synthesis of anionic polymerization method high by 1,4-structural content, Narrow Molecular Weight Distribution Alpha-hydroxy-ω-carboxy terminatedpolybutadiene (HO-PB-COOH), and with Fourier transform infrared spectroscopy, nuclear magnetic resonance, NMR and gel permeation chromatography, its backbone structure, molecular weight distribution and average functionality have been characterized.Luo Yanling etc. are with peroxide of glutaric acid for initiator, acetone/dehydrated alcohol is solvent, reasonably combined by initiator original amounts and rate of addition, reaction temperature and response time, obtains narrow molecular weight distribution, viscosity is low, yield is high end carboxyl butyronitrile liquid rubber (CTBN).
Carboxylated polyisoprene can adopt end carboxyl or two kinds of methods of grafting carboxylated compound.The preparation of end carboxyl polymer needs the living chain utilizing polymer and functional compound to be obtained by reacting end functional group, needs introducing blocking group and side reaction more in the reaction, is unfavorable for commercial production.
Summary of the invention
For making up the deficiencies in the prior art, the present invention provides a kind of reaction condition gentle, it is easy to control, the preparation method of simple to operate and carboxylated polyisoprene rubber without side reaction.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of carboxylated polyisoprene rubber: it is characterized in that and comprises the following steps:
(1) graft reaction: be sequentially added into polyisoprene rubber, maleic anhydride in reaction vessel, in reaction vessel, non-polar solven is added after adopting the air in nitrogen displacement reaction container, stirring is lower fully dissolves, at 30-130 DEG C, the oil solution of organic peroxide is joined in reaction vessel, react 2-48h;
(2) purifying products: add solvent in the product of step (1), precipitate out polymer, adopt a large amount of solvent that polymer is washed, dry through normal-temperature vacuum, obtain carboxylated product, measure maleic anhydride grafting ratio.
The preparation method of the carboxylated polyisoprene rubber of the present invention, polyisoprene rubber described in step (1) is liquid rubber, and molecular weight is 5000-100000.
The preparation method of the carboxylated polyisoprene rubber of the present invention, described organic peroxide is the one in benzoyl peroxide (BPO), cumyl peroxide (DCP), methyl ethyl ketone peroxide (MEPK), peroxidized t-butyl perbenzoate (TBPB), the peroxidating isooctyl acid tert-butyl ester (TBPO), the 1-10% that quality is polyisoprene rubber that organic peroxide adds.
The preparation method of the carboxylated polyisoprene rubber of the present invention, the solvent of described organic peroxide oil solution is the one in benzene,toluene,xylene, acetone, oxolane, alcohol, ether.
The preparation method of the carboxylated polyisoprene rubber of the present invention, the 1-20% that quality is polyisoprene rubber that in step (1), maleic anhydride adds.
The preparation method of the carboxylated polyisoprene rubber of the present invention, non-polar solven described in step (1) is the one in normal hexane, hexamethylene, toluene, dimethylbenzene.
The preparation method of the carboxylated polyisoprene rubber of the present invention, in step (1) in the mixed solution of polyisoprene rubber, maleic anhydride and non-polar solven composition, solution solid content is 10%-70%.
The preparation method of the carboxylated polyisoprene rubber of the present invention, solvent described in step (2) is acetone, ethanol, methanol, ether etc., and polymer is washed 5-15 time by solvent, it is preferable that 8-10 time.
The invention has the beneficial effects as follows: the method that the present invention obtains carboxylated polyisoprene by solution grafting; directly utilizing polyisoprene and carry out grafting with maleic anhydride, the method need not increase protective group in course of reaction, simple to operate; reaction condition is gentle, without side reaction.The graft obtained can be used as binding agent, compatilizer, improve the compatibility etc. of polymer and other polar materials, gained carboxylated polymers appearance colorless is transparent, good with metal and fibre adhesion, can be used as binding agent, pressure sensitive adhesive and fluid sealant, can also be used for preparing modified latex, widen its application further.
Accompanying drawing explanation
Accompanying drawing 1 is the infrared spectrum of carboxylated polyisoprene prepared by the present invention.
Detailed description of the invention
Embodiment 1
In the 100ml there-necked flask with stirring, it is sequentially added into 20g polyisoprene and 0.6g maleic anhydride (MAH), after the displacement of system nitrogen, add toluene 40g, dissolve after completely, heated and stirred 30min under 45 DEG C of conditions, adds the toluene solution of the initiator benzoyl peroxide containing 0.4g (BPO), reacts 4h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and BPO washing with acetone, repeated washing 5 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 2.11% to the percent grafting of polyisoprene.
Embodiment 2
In the round-bottomed flask of 100mL, it is sequentially added into 20g polyisoprene and 0.6g maleic anhydride (MAH), after the displacement of system nitrogen, add normal hexane 40g, dissolve after completely, in the water-bath of 50 DEG C after heated and stirred 30min, add the acetone soln of the initiator peroxidized t-butyl perbenzoate containing 0.4g (TBPB), react 6h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and TBPB washing with acetone, repeated washing 8 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 1.45% to the percent grafting of polyisoprene.
Embodiment 3
In the round-bottomed flask of 100mL, it is sequentially added into 20g polyisoprene and 0.6g maleic anhydride (MAH), after the displacement of system nitrogen, add dimethylbenzene 40g, dissolve after completely, in the water-bath of 50 DEG C after heated and stirred 30min, add the tetrahydrofuran solution of the initiator benzoyl peroxide containing 0.6g (BPO), react 4h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and BPO washing with acetone, repeated washing 10 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 2.77% to the percent grafting of polyisoprene.
Embodiment 4
In the round-bottomed flask of 100mL, it is sequentially added into 20g polyisoprene and 0.8g maleic anhydride MAH, after the displacement of system nitrogen, add toluene 40g, dissolve after completely, in the water-bath of 60 DEG C after heated and stirred 30min, the benzene adding the initiator benzoyl peroxide containing 0.4g (BPO) dissolves, and reacts 12h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and BPO washing with acetone, repeated washing 6 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 3.85% to the percent grafting of polyisoprene.
Embodiment 5
The round-bottomed flask of 100mL is sequentially added into 40g polyisoprene and 2g maleic anhydride (MAH), after the displacement of system nitrogen, add dimethylbenzene 40g, dissolve after completely, in the water-bath of 60 DEG C after heated and stirred 30min, add the acetone soln of the initiator benzoyl peroxide containing 1.6g (BPO), react 16h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and BPO washing with acetone, repeated washing 6 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 5.74% to the percent grafting of polyisoprene.
Embodiment 6
The round-bottomed flask of 100mL is sequentially added into 40g polyisoprene and 4g maleic anhydride (MAH), after the displacement of system nitrogen, add toluene 40g, dissolve after completely, in the water-bath of 60 DEG C after heated and stirred 30min, add the benzole soln of the initiator methyl ethyl ketone peroxide containing 0.8g (MEPK), react 6h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and MEPK washing with acetone, repeated washing 10 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 3.04% to the percent grafting of polyisoprene.
Embodiment 7
In the round-bottomed flask of 100mL, it is sequentially added into 30g polyisoprene and 2g maleic anhydride (MAH), after the displacement of system nitrogen, add dimethylbenzene 40g, dissolve after completely, in the water-bath of 70 DEG C after heated and stirred 30min, add the acetone soln of the initiator cumyl peroxide containing 0.4g (DCP), react 13h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and DCP washing with acetone, repeated washing 12 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 4.26% to the percent grafting of polyisoprene.
Embodiment 8
In the round-bottomed flask of 100mL, it is sequentially added into 40g polyisoprene and 4g maleic anhydride (MAH), after the displacement of system nitrogen, add dimethylbenzene 40g, dissolve after completely, in the water-bath of 90 DEG C after heated and stirred 30min, add the benzole soln of the initiator peroxidating isooctyl acid tert-butyl ester containing 0.8g (TBPO), react 8h.After having reacted, precipitate out the carboxylated polyisoprene rubber of polymer, unreacted MAH and TBPO washing with acetone, repeated washing 15 times with acetone.Product is dried to constant weight through vacuum drying oven.The mensuration of percent grafting adopts chemical analysis, and calculating MAH is 4.33% to the percent grafting of polyisoprene.
Claims (8)
1. the preparation method of a carboxylated polyisoprene rubber, it is characterised in that: comprise the following steps:
(1) in reaction vessel, polyisoprene rubber, maleic anhydride it are sequentially added into, in reaction vessel, non-polar solven is added after adopting the air in nitrogen displacement reaction container, stirring is lower fully dissolves, at 30-130 DEG C, the oil solution of organic peroxide is joined in reaction vessel, react 2-48h;
(2) in the product of step (1), add solvent, precipitate out polymer, adopt a large amount of solvent that polymer is washed, dry through normal-temperature vacuum, obtain carboxylated product, measure maleic anhydride grafting ratio.
2. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterised in that: polyisoprene rubber described in step (1) is liquid rubber, and molecular weight is 5000-100000.
3. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterized in that: described organic peroxide is the one in benzoyl peroxide, cumyl peroxide, methyl ethyl ketone peroxide, peroxidized t-butyl perbenzoate, the peroxidating isooctyl acid tert-butyl ester, the 1-10% that quality is polyisoprene rubber that organic peroxide adds.
4. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1 or 3, it is characterised in that: the solvent of described organic peroxide oil solution is the one in benzene,toluene,xylene, acetone, oxolane, alcohol, ether.
5. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterised in that: the 1-20% that quality is polyisoprene rubber that in step (1), maleic anhydride adds.
6. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterised in that: non-polar solven described in step (1) is the one in normal hexane, hexamethylene, toluene, dimethylbenzene.
7. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterised in that: in step (1) in the mixed solution of polyisoprene rubber, maleic anhydride and non-polar solven composition, solution solid content is 10%-70%.
8. the preparation method of a kind of carboxylated polyisoprene rubber according to claim 1, it is characterised in that: solvent described in step (2) is acetone, ethanol, methanol, ether etc., and polymer is washed 5-15 time by solvent.
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Cited By (6)
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CN106349867A (en) * | 2016-08-25 | 2017-01-25 | 马鞍山采石矶涂料有限公司 | Graphene reinforced epoxy resin anticorrosion coating and preparation method thereof |
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CN108586666A (en) * | 2018-02-12 | 2018-09-28 | 濮阳林氏化学新材料股份有限公司 | A kind of industrialized process for preparing of maleic anhydride grafting polyisoprene |
CN109776733A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Polarity diene polymer and preparation method thereof |
CN110337457A (en) * | 2017-02-24 | 2019-10-15 | 日本瑞翁株式会社 | The manufacturing method of polymer-modified latex |
CN112574617A (en) * | 2020-11-30 | 2021-03-30 | 江苏科技大学 | Quick-drying water-based ink composition and preparation method and application thereof |
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Cited By (8)
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CN106349867A (en) * | 2016-08-25 | 2017-01-25 | 马鞍山采石矶涂料有限公司 | Graphene reinforced epoxy resin anticorrosion coating and preparation method thereof |
CN106433115A (en) * | 2016-09-27 | 2017-02-22 | 宁夏宝塔石化科技实业发展有限公司 | Modified liquid rubber toughed nylon material for bearing retainer and preparation method |
CN110337457A (en) * | 2017-02-24 | 2019-10-15 | 日本瑞翁株式会社 | The manufacturing method of polymer-modified latex |
CN110337457B (en) * | 2017-02-24 | 2021-10-19 | 日本瑞翁株式会社 | Process for producing modified polymer latex |
CN109776733A (en) * | 2017-11-13 | 2019-05-21 | 中国石油化工股份有限公司 | Polarity diene polymer and preparation method thereof |
CN109776733B (en) * | 2017-11-13 | 2021-12-31 | 中国石油化工股份有限公司 | Polar diene polymer and preparation method thereof |
CN108586666A (en) * | 2018-02-12 | 2018-09-28 | 濮阳林氏化学新材料股份有限公司 | A kind of industrialized process for preparing of maleic anhydride grafting polyisoprene |
CN112574617A (en) * | 2020-11-30 | 2021-03-30 | 江苏科技大学 | Quick-drying water-based ink composition and preparation method and application thereof |
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Application publication date: 20160727 |