CN108822255A - Norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization - Google Patents

Norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization Download PDF

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Publication number
CN108822255A
CN108822255A CN201810758811.6A CN201810758811A CN108822255A CN 108822255 A CN108822255 A CN 108822255A CN 201810758811 A CN201810758811 A CN 201810758811A CN 108822255 A CN108822255 A CN 108822255A
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hept
ene
phenylmaleimide
ring
amylene
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胡敏杰
李正辉
王志强
李勰
杨建平
胡爱珠
陈斌
房江华
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Ningbo University of Technology
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings

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  • Organic Chemistry (AREA)
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Abstract

The present invention relates to a kind of norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization, it is characterised in that includes the following steps：According to molar ratio 1：1：1 takes polymerized monomer norborneol alkenes, amylene class and N-phenylmaleimide to be added in autoclave, and solvent dissolution is added；Then initiator is added, is reacted 1~4 hour under 90~150 DEG C, 0.1~6MPa pressure；The initiator includes metachloroperbenzoic acid and sodium peroxide, and metachloroperbenzoic acid and sodium peroxide molar ratio are 0.1：1~1：0.1, the dosage of the initiator is the 0.1%~1.5% of polymerized monomer total weight；The product that reaction obtains is poured into ethanol solution, obtained precipitates washed with EtOH, norbornene class, amylene class and N-phenylmaleimide terpolymer are obtained after vacuum drying.

Description

Norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization
Technical field
The present invention relates to high polymer field more particularly to a kind of norborneol alkenes, amylene class and N- benzyl maleimide Amine method for ternary polymerization.
Background technique
Disclosed in Chinese patent ZL 201510217365.4《Norborneol alkenes, styrene and N-phenylmaleimide Ternary polymerization catalyst and method for ternary polymerization》Using nickel-lithium complex catalyst norborneol alkenes, styrene and N- Phenyl maleimide terpolymerization；Disclosed in Chinese patent ZL 201610850217.0《Norborneol alkenes, hexafluoro third Alkene and N-phenylmaleimide ternary polymerization catalyst and method for ternary polymerization》Using molybdenum-titanium complex catalyst Norborneol alkenes, hexafluoropropene and N-phenylmaleimide terpolymerization；Application No. is 201611106424.1 China Provided by patent application《Norborneol alkenes, vinylacetate and N-phenylmaleimide ternary polymerization catalyst and three First copolymerization process》Using Ni-Ti complex compound catalyst catalysis norborneol alkenes, vinylacetate and N-phenylmaleimide three First combined polymerization；Provided by Chinese patent application application No. is 201611106421.8《Norborneol alkenes, tetrafluoroethene and N- Phenyl maleimide ternary polymerization catalyst and method for ternary polymerization》Using palladium-titanium complex catalyst norborneol Alkenes, tetrafluoroethene and N-phenylmaleimide terpolymerization；Application No. is 201710543303.1 Chinese patent Shens Please be disclosed《Norborneol alkenes, maleic anhydride and N-phenylmaleimide ternary polymerization catalyst and ternary polymerization side Method》Using palladium-titanium complex catalyst norborneol alkenes, maleic anhydride and N-phenylmaleimide terpolymerization； Disclosed in Chinese patent application application No. is 201710809938.1《Norborneol alkenes, cyclohexene and N- phenyl Malaysia acyl Imines ternary polymerization catalyst and method for ternary polymerization》Using tungsten-titanium complex catalyst norborneol alkenes, cyclohexene With N-phenylmaleimide terpolymerization.The above patent uses complex catalyst catalytic polymerization, and combined polymerization is required in nothing It is carried out under the conditions of oxygen anhydrous response, reaction environment requires high；And obtained copolymer cementability also needs to further increase.
Summary of the invention
The technical problem to be solved by the present invention is to the status for the prior art, to provide a kind of reaction condition mild and altogether Norborneol alkenes, amylene class and the N-phenylmaleimide three that polymers cementability is good, molecular weight is larger and molecular dispersivity is big First copolymerization process.
The present invention solves technical solution used by above-mentioned technical problem：The norborneol alkenes, amylene class and N- phenyl Maleimide method for ternary polymerization, it is characterised in that include the following steps：
According to molar ratio 1：1：1 takes polymerized monomer norborneol alkenes, amylene class and N-phenylmaleimide to be added to height It presses in kettle, solvent dissolution is added；Then initiator is added, is reacted 1~4 hour under 90~150 DEG C, 0.1~6MPa pressure；
The initiator includes metachloroperbenzoic acid and sodium peroxide, metachloroperbenzoic acid and sodium peroxide molar ratio It is 0.1：1~1：0.1, the dosage of the initiator is the 0.1%~1.5% of polymerized monomer total weight；
The solvent be selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes, Hexamethylene or cyclohexanone；The amount ratio of the sum of molal quantity of each polymerized monomer and the solvent is 0.03 mole：20 milliliters；
The product that reaction obtains is poured into ethanol solution, obtained precipitates washed with EtOH, after vacuum drying to obtain the final product To norborneol alkenes, amylene class and N-phenylmaleimide terpolymer.
Preferably, the metachloroperbenzoic acid and sodium peroxide molar ratio are 1.0~1.4.
Preferably, the metachloroperbenzoic acid and sodium peroxide molar ratio are 1:0.8；The initiator amount is polymerization The 0.7~1.0% of total monomer weight.
In above-mentioned each scheme, penta vinyl monomer is selected from 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene.
The Norbornene derivative preferably be selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept-2-ene", 5- methyl bicyclic [2,2,1] hept-2-ene", 7- methyl bicyclic [2,2,1] hept-2-ene", two ring of 1- ethyl [2,2,1] hept-2-ene", 5- Two ring of ethyl [2,2,1] hept-2-ene", 5,5- dimethyl, two ring [2,2,1] hept-2-ene", two ring of 1- phenyl [2,2,1] hept-2-ene", Two ring of 5- phenyl [2,2,1] hept-2-ene", two ring of 5- vinyl [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene" -5- formic acid Methyl esters or two rings [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
Compared with prior art, the present invention causes norborneol alkenes, amylene class and N- benzene using special initiator combination Base maleimide ternary is free-radical polymerized, do not have under the conditions of anhydrous and oxygen-free operation, risk it is small, reaction condition is mild, and The copolymer of preparation has preferable molecular weight dispersion, is catalyzed norbornene analog copolymer with metal complex in background technique The general Mw/Mn of molecular weight dispersion is 2 or so, and application No. is 201810339071.2 Chinese patents《Norborneol alkenes, N- benzene Base maleimide and 2,3,4,5,6- pentafluorostyrene method for ternary polymerization》Molecular weight of copolymer dispersibility Mw/Mn is on 3 left sides The right side, and norborneol alkenes prepared by the present invention, amylene class and N-phenylmaleimide molecular weight of copolymer dispersibility Mw/Mn reach To 5 or more, the cementability of copolymer is improved, and molecular weight of copolymer is 104Grade or more.
Specific embodiment
Present invention is further described in detail with reference to embodiments.
Embodiment 1
By 0.01 mole of two ring [2,2,1] hept-2-ene", 0.01 mole of 1- amylene and 0.01 mole of N-phenylmaleimide It is added in autoclave, 20ml benzene is added to dissolve.It is that 0.1: 1 preparation causes by metachloroperbenzoic acid and sodium peroxide molar ratio Agent, amount of initiator are the 0.4% of two rings [2,2,1] hept-2-ene", 1- amylene and N-phenylmaleimide three's total weight, will Initiator is added in above-mentioned autoclave.Constant temperature reacts 3 hours under 120 DEG C, 6MPa pressure.Product, which is poured into ethanol solution, to be made altogether Polymers precipitating, precipitates washed with EtOH；To get to two rings [2,2,1] hept-2-ene", 1- amylene and N- phenyl after vacuum drying Maleimide terpolymer.Calculating reaction yield is 48.2%.
The calculation method of reaction yield is terpolymer weight/total comonomer weight × 100%.
The binary and terpolymer molecular weight dispersion in background technique in embodiment 1 are measured through gel permeation chromatograph Mw/Mn is respectively less than 2.3-3.2, and this example product molecular weight of copolymer dispersibility Mw/Mn is 5.3, molecular weight MW=2.4 × 104。
The terpolymer molecular weight dispersion of following each embodiment preparations is similar with embodiment 1；Molecular weight dispersion Between 5.0~5.8, molecular weight MW1.8 × 104-6.5×104Between.
Embodiment 2
By 0.01 mole of 1- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of 3- Methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml toluene is added to dissolve.By metachloroperbenzoic acid and sodium peroxide molar ratio It is 0.3: 1, amount of initiator is 1- methyl bicyclic [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide three Above-mentioned initiator is added in above-mentioned autoclave the 0.1% of person's total weight, and it is small that constant temperature reacts 3 under 90 DEG C, 0.1MPa pressure When.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get 1- methyl bicyclic is arrived [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 51.7%.
Embodiment 3
By 0.01 mole of 5- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of 4-methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml tetrahydrofuran is added to dissolve.It rubs by metachloroperbenzoic acid and sodium peroxide , than being 0.5: 1, amount of initiator is 5- methyl bicyclic [2,2,1] hept-2-ene", 4-methyl-1-pentene and N- benzyl maleimide for you The 0.5% of amine three's total weight, initiator is added in above-mentioned autoclave.It is small that constant temperature reacts 4 under 150 DEG C, 0.7MPa pressure When.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get 5- methyl bicyclic is arrived [2,2,1] hept-2-ene", 4-methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 65.5%.
Embodiment 4
By 0.01 mole of 7- methyl bicyclic [2,2,1] hept-2-ene", 0.01 mole of 4-methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, adds 20ml petroleum ether dissolution.By metachloroperbenzoic acid and sodium peroxide mole Than being 0.7: 1, amount of initiator is 7- methyl bicyclic [2,2,1] hept-2-ene", 4-methyl-1-pentene and N-phenylmaleimide Above-mentioned initiator is added in above-mentioned autoclave the 0.6% of three's total weight.It is small that constant temperature reacts 3 under 130 DEG C, 5MPa pressure When.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get 7- methyl bicyclic is arrived [2,2,1] hept-2-ene", 4-methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 74.6%.
Embodiment 5
By 0.01 mole of two ring of 1- ethyl [2,2,1] hept-2-ene", 0.01 mole of 3- Methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml methyl phenyl ethers anisole is added to dissolve.By metachloroperbenzoic acid and sodium peroxide mole Than being 0.9: 1, amount of initiator is two ring of 1- ethyl [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide Above-mentioned initiator is added in above-mentioned autoclave the 0.7% of three's total weight.Constant temperature reacts 2.5 under 140 DEG C, 1MPa pressure Hour.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get 1- ethyl two is arrived Ring [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 85.8%.
Embodiment 6
By 0.01 mole of two ring of 5- ethyl [2,2,1] hept-2-ene", 0.01 mole of 1- amylene and 0.01 mole of N- phenyl Malaysia Acid imide is added in autoclave, adds 20ml Isosorbide-5-Nitrae-dioxane dissolution.By metachloroperbenzoic acid and sodium peroxide molar ratio It is 1: 1, amount of initiator is two ring of 5- ethyl [2,2,1] hept-2-ene", 1- amylene and N-phenylmaleimide three's total weight 0.8%, above-mentioned initiator is added in above-mentioned autoclave.Constant temperature reacts 3 hours under 130 DEG C, 4MPa pressure.Product is poured into second Precipitate copolymer in alcoholic solution, precipitates washed with EtOH is dried in vacuo to get two ring of 5- ethyl [2,2,1] hept- 2- is arrived Alkene, 1- amylene and N-phenylmaleimide terpolymer.Calculating reaction yield is 89.5%.
Embodiment 7
By 0.01 mole of 5,5- dimethyl, two ring [2,2,1] hept-2-ene", 0.01 mole of 1- amylene and 0.01 mole of N- phenyl Maleimide is added in autoclave, adds 20ml 1, the dissolution of 2- dichloroethanes.It rubs by metachloroperbenzoic acid and sodium peroxide You are than being 1: 0.9, amount of initiator 5, two ring of 5- dimethyl [2,2,1] hept-2-ene", 1- amylene and N-phenylmaleimide three Above-mentioned initiator is added in above-mentioned autoclave the 0.9% of person's total weight.Constant temperature reacts 2 hours under 140 DEG C, 4MPa pressure. Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, and vacuum drying is to get to 5,5- dimethyl, two ring [2,2,1] hept-2-ene", 1- amylene and N-phenylmaleimide terpolymer.Calculating reaction yield is 92.5%.
Embodiment 8
By 0.01 mole of two ring of 1- phenyl [2,2,1] hept-2-ene", 0.01 mole of 3- Methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml hexamethylene is added to dissolve.By metachloroperbenzoic acid and sodium peroxide mole Than being 1: 0.8, amount of initiator is two ring of 1- phenyl [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide Above-mentioned initiator is added in above-mentioned autoclave the 0.9% of three's total weight.It is small that constant temperature reacts 3 under 140 DEG C, 3MPa pressure When.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get two ring of 1- phenyl is arrived [2,2,1] hept-2-ene", 3- Methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 94.7%.
Embodiment 9
By 0.01 mole of two ring of 5- phenyl [2,2,1] hept-2-ene", 0.01 mole of 4-methyl-1-pentene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml cyclohexanone is added to dissolve.By metachloroperbenzoic acid and sodium peroxide mole Than being 1: 0.6, amount of initiator is two ring of 5- phenyl [2,2,1] hept-2-ene", 4-methyl-1-pentene and N-phenylmaleimide Above-mentioned initiator is added in above-mentioned autoclave the 1.0% of three's total weight.Constant temperature reacts 2 under 100 DEG C, 0.9MPa pressure Hour.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, is dried in vacuo to get 5- phenyl two is arrived Ring [2,2,1] hept-2-ene", 4-methyl-1-pentene and N-phenylmaleimide terpolymer.Calculating reaction yield is 87.3%.
Embodiment 10
By 0.01 mole of two ring of 5- vinyl [2,2,1] hept-2-ene", 0.01 mole of 1- amylene and 0.01 mole of N- phenyl horse Carry out acid imide to be added in autoclave, 20ml cyclohexanone is added to dissolve.It is 1 by metachloroperbenzoic acid and sodium peroxide molar ratio: 0.4, amount of initiator is two ring of 5- vinyl [2,2,1] hept-2-ene", 1- amylene and N-phenylmaleimide three's total weight 1.2%, above-mentioned initiator is added in above-mentioned autoclave.Constant temperature reacts 2.5 hours under 120 DEG C, 2MPa pressure.Product is poured into Precipitate copolymer in ethanol solution, precipitates washed with EtOH is dried in vacuo to get two ring of 5- vinyl [2,2,1] hept- is arrived 2- alkene, 1- amylene and N-phenylmaleimide terpolymer.Calculating reaction yield is 76.9%.
Embodiment 11
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- methyl formate, 0.01 mole of 1- amylene and 0.01 mole of N- benzene Base maleimide is added in autoclave, and 20ml benzene is added to dissolve.It is 1 by metachloroperbenzoic acid and sodium peroxide molar ratio: 0.2, amount of initiator is two rings [2,2,1] hept-2-ene" -5- methyl formate, 1- amylene and N-phenylmaleimide three's gross weight Above-mentioned initiator is added in above-mentioned autoclave the 1.5% of amount.Constant temperature reacts 3.5 hours under 110 DEG C, 1MPa pressure.Product Being poured into ethanol solution precipitates copolymer, precipitates washed with EtOH, and vacuum drying is to get to two rings [2,2,1] hept- 2- Alkene -5- methyl formate, 1- amylene and N-phenylmaleimide terpolymer.Calculating reaction yield is 65.5%.
Embodiment 12
By 0.01 mole of two ring [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 0.01 mole of 1- amylene and 0.01 mole of N- Phenyl maleimide is added in autoclave, and 20ml toluene is added to dissolve.By metachloroperbenzoic acid and sodium peroxide molar ratio It is 1: 0.1, amount of initiator is two rings [2,2,1] hept-2-ene" -5- formic acid spy butyl ester, 1- amylene and N-phenylmaleimide three Above-mentioned initiator is added in above-mentioned autoclave the 0.3% of person's total weight.It is small that constant temperature reacts 3 under 110 DEG C, 0.8MPa pressure When.Product, which is poured into ethanol solution, precipitates copolymer, precipitates washed with EtOH, and vacuum drying is to get to two rings [2,2,1] Hept-2-ene" -5- formic acid spy butyl ester, 1- amylene and N-phenylmaleimide terpolymer.Calculating reaction yield is 56.7%.

Claims (5)

1. norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization, it is characterised in that include the following steps：
According to molar ratio 1：1：1 takes polymerized monomer norborneol alkenes, amylene class and N-phenylmaleimide to be added to autoclave In, solvent dissolution is added；Then initiator is added, is reacted 1~4 hour under 90~150 DEG C, 0.1~6MPa pressure；
The initiator includes metachloroperbenzoic acid and sodium peroxide, and metachloroperbenzoic acid and sodium peroxide molar ratio are 0.1：1~1：0.1, the dosage of the initiator is the 0.1%~1.5% of polymerized monomer total weight；
The solvent is selected from benzene, toluene, tetrahydrofuran, petroleum ether, methyl phenyl ethers anisole, 1,4- dioxane, 1,2- dichloroethanes, hexamethylene Alkane or cyclohexanone；The amount ratio of the sum of molal quantity of each polymerized monomer and the solvent is 0.03 mole：20 milliliters；
The product that reaction obtains is poured into ethanol solution, obtained precipitates washed with EtOH, is dropped after vacuum drying Borneol alkenes, amylene class and N-phenylmaleimide terpolymer.
2. norborneol alkenes according to claim 1, amylene class and N-phenylmaleimide method for ternary polymerization, special Sign is the metachloroperbenzoic acid and sodium peroxide molar ratio is 1.0~1.4.
3. norborneol alkenes according to claim 2, amylene class and N-phenylmaleimide method for ternary polymerization, special Sign is the metachloroperbenzoic acid and sodium peroxide molar ratio is 1:0.8；The initiator amount is polymerized monomer gross weight The 0.7~1.0% of amount.
4. according to claim 1 to norborneol alkenes, amylene class described in 3 any claims and N-phenylmaleimide three First copolymerization process, it is characterised in that penta vinyl monomer is selected from 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene.
5. norborneol alkenes according to claim 4, amylene class and N-phenylmaleimide method for ternary polymerization, special Sign is that the Norbornene derivative is selected from two rings [2,2,1] hept-2-ene", 1- methyl bicyclic [2,2,1] hept-2-ene", 5- first Two ring of base [2,2,1] hept-2-ene", 7- methyl bicyclic [2,2,1] hept-2-ene", two ring of 1- ethyl [2,2,1] hept-2-ene", 5- ethyl Two rings [2,2,1] hept-2-ene", 5,5- dimethyl, two ring [2,2,1] hept-2-ene", two ring of 1- phenyl [2,2,1] hept-2-ene", 5- benzene Two ring of base [2,2,1] hept-2-ene", two ring of 5- vinyl [2,2,1] hept-2-ene", two rings [2,2,1] hept-2-ene" -5- methyl formate Or two ring [2,2,1] hept-2-ene" -5- formic acid spy's butyl ester.
CN201810758811.6A 2018-07-11 2018-07-11 Norborneol alkenes, amylene class and N-phenylmaleimide method for ternary polymerization Withdrawn CN108822255A (en)

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