CN105801759A - Preparation method of carboxylic polyisoprene rubber - Google Patents
Preparation method of carboxylic polyisoprene rubber Download PDFInfo
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- polyisoprene rubber
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- maleic anhydride
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- 229920001195 polyisoprene Polymers 0.000 title claims abstract description 67
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 15
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- -1 isooctyl acid tert-butyl ester Chemical compound 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000004816 latex Substances 0.000 abstract description 2
- 229920000126 latex Polymers 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- 230000021523 carboxylation Effects 0.000 abstract 2
- 238000006473 carboxylation reaction Methods 0.000 abstract 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 | Method for producing modified polymer 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 |
| CN116285777A (en) * | 2023-01-10 | 2023-06-23 | 北京理工大学 | A kind of self-healing adhesive based on metal ion-polymer coordination bond and preparation method thereof |
| CN116355137A (en) * | 2023-04-06 | 2023-06-30 | 四川大学 | Rubber with high mechanical property, high adhesive property and recoverable property |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016360A (en) * | 2007-01-18 | 2007-08-15 | 武汉工程大学 | Solid phase preparation method for simultaneously increasing polarity and graft degree of polyolefin |
| CN101223201A (en) * | 2005-07-11 | 2008-07-16 | 朗盛公司 | Liquid maleated butyl rubber |
| CN105418844A (en) * | 2015-12-31 | 2016-03-23 | 山东大学 | Novel preparation method for hydroxide radical containing liquid rubber |
-
2016
- 2016-04-05 CN CN201610205034.3A patent/CN105801759A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101223201A (en) * | 2005-07-11 | 2008-07-16 | 朗盛公司 | Liquid maleated butyl rubber |
| CN101016360A (en) * | 2007-01-18 | 2007-08-15 | 武汉工程大学 | Solid phase preparation method for simultaneously increasing polarity and graft degree of polyolefin |
| CN105418844A (en) * | 2015-12-31 | 2016-03-23 | 山东大学 | Novel preparation method for hydroxide radical containing liquid rubber |
Non-Patent Citations (2)
| Title |
|---|
| 刘大华主编: "《合成橡胶工业手册》", 30 December 1991 * |
| 马金红等: "UV 固化液体聚异戊二烯橡胶改性物的合成", 《江西师范大学学报(自然科学版)》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 | Method for producing modified polymer latex |
| CN110337457B (en) * | 2017-02-24 | 2021-10-19 | 日本瑞翁株式会社 | Method 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 |
| CN116285777A (en) * | 2023-01-10 | 2023-06-23 | 北京理工大学 | A kind of self-healing adhesive based on metal ion-polymer coordination bond and preparation method thereof |
| CN116285777B (en) * | 2023-01-10 | 2025-11-07 | 北京理工大学 | Self-repairing binder based on metal ion-polymer coordination bond and preparation method thereof |
| CN116355137A (en) * | 2023-04-06 | 2023-06-30 | 四川大学 | Rubber with high mechanical property, high adhesive property and recoverable property |
| CN116355137B (en) * | 2023-04-06 | 2025-09-12 | 四川大学 | A recyclable rubber with high mechanical properties, high adhesive properties |
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