CN101012292B - Polyolefin containing polar group and preparing method thereof - Google Patents
Polyolefin containing polar group and preparing method thereof Download PDFInfo
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- CN101012292B CN101012292B CN200710055276XA CN200710055276A CN101012292B CN 101012292 B CN101012292 B CN 101012292B CN 200710055276X A CN200710055276X A CN 200710055276XA CN 200710055276 A CN200710055276 A CN 200710055276A CN 101012292 B CN101012292 B CN 101012292B
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Abstract
The invention discloses a polyolefin with polar group, whose structural formula is displayed as right upper formula, wherein x is CH2 or CH2CH2; n and m is natural number from 0 to infinity; R is as right lower formula; the solvent is allocated by carbon disulfide, tetrachloroethane, nitrobenzene or their composition; the catalyst is Lewis acid (AlCl3 and ZnCl2); the annular diacid anhydride and ethane and allylpropone benzene or ethane and allyl butyl benzene are reacted to make the product through Friedel-Crafts reaction; The fusing point of copolymer is improved by 3 deg, which reduces contact angle of polyolefin by 10 deg.
Description
Technical field
The present invention relates to a kind of polar functionalities Polyolefin and its preparation method, is to utilize the Friedel-Crafts acylation reaction that polar group is introduced polyolefine.
Background technology
Polyolefine is typical non-polar polymeric material, this feature limits its application in some aspects.Introducing polar group or molecule segment can change its physical and chemical performance effectively in the polyolefine macromole, as give its wetting ability, dyeability, colourability, impressionability, consistency with polar polymer, increase the surface tension of goods and to the clinging power (but sprayability) of polar material etc., improve its added value, widen range of application.Ethene and some polar monomer (as acrylate, vinyl acetate) can under high pressure carry out radical copolymerization, but the polymeric reaction condition harshness, the one-time investment of equipment is big, and the structure of product is complicated, unstable properties.People wish to realize with the polycoordination technology of industrial widespread use the controlled copolymerization of alkene and polar monomer always, new function polyolefine material with the obtained performance excellence, but owing to the functional group in the polar monomer can make its inactivation with traditional Z igler-Natta and metallocene catalyst active centre ion coordination, thereby the coordination copolymerization of alkene and polar monomer is a comparatively thing of difficulty, though the Lewis acidity of the late transition metal catalyst that immediate development is got up decreases, the nitrogen in the polar monomer, oxygen heteroatom still makes its catalytic activity, molecular weight of copolymer significantly reduces.
Summary of the invention
For overcoming the shortcoming of prior art, obtain the polyolefine of the polar functionalities of excellent performance, the invention discloses a kind of polar functionalities Polyolefin and its preparation method.
One of the object of the invention provides the polar functionalities polyolefine, and its structural formula is as follows:
In this structural formula, x represents CH
2Or CH
2CH
2, m, n are respectively 0 to infinitely-great natural number, and R is
Two of the object of the invention provides polar functionalities preparation of polyolefins method.
Its reaction process is as follows:
X represents CH
2Or CH
2CH
2, m, n are respectively 0 to infinitely-great natural number, and R is
Reactant 1 is the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene, and reactant 2 is respectively Succinic anhydried, Pyroglutaric acid, 3-oxa-Pyroglutaric acid, two ring [221]-5-heptene-2,3-dicarboxylic acid anhydride, phthalic anhydride, chloro-benzoic anhydride or nitro phthalic anhydride.All connecting these two kinds of polar groups of carbonyl and carboxyl on the polyolefine of the polar functionalities that all obtain simultaneously.
The polymerization procedure and the condition of synthesizing ethylene and allyl benzene or ethene and alkene butylbenzene multipolymer are as follows:
(1) ethene and allyl benzene or ethene and alkene butylbenzene multipolymer-" polyolefine intermediate " is synthetic
The present invention has synthesized makes the catalyst deactivation heteroatoms a kind of not containing, but compound with regular structure and contain the polyolefine of the functional groups that is easy to modification.Two indenes zirconium rac-Et (ind) of ethyl bridging have been selected in the polymerization process
2ZrCl
2As catalyzer, structure is as follows:
This catalyzer is under the effect of the methylaluminoxane (MMAO) of promotor modification, and zirconium becomes the positively charged ion catalytic active center, and simultaneously because two indenes ring angles are moderate, so its copolymerized ability is strong, the regular and narrow distribution of gained copolymer structure.Utilize this catalyzer to carry out ethene and allyl benzene or its catalytic activity of alkene butylbenzene copolymerization not second to ethylene homo, gained multipolymer phenyl ring content is controlled and be uniformly distributed on the main polymer chain.
The exsiccant reactor is put in 40 ℃ of water-baths, after purging 5 minutes with ethylene gas, add toluene, toluene mL wherein: two indenes Zr catalyst μ mol of ethyl bridging are 14: 1, after ethylene gas is saturated, add allyl benzene, wherein allyl benzene: the mol ratio of two indenes Zr catalysts of ethyl bridging is 6: 1; Or add alkene butylbenzene, wherein alkene butylbenzene: the mol ratio of two indenes Zr catalysts of ethyl bridging is 2: 1; The two indenes Zr catalysts that add the ethyl bridging, the methylaluminoxane of modification (MMAO), methylaluminoxane wherein: the mol ratio of two indenes Zr catalysts of ethyl bridging is 2000: 1, begin to stir, continuing to feed ethene and keep ethylene pressure is 1 normal atmosphere, reaction 30min, reaction solution is poured into the ethanolic soln that contains 10%V/V hydrochloric acid, ethanol solution hydrochloride mL: Zr catalyst μ mol is 50: 1, filter the back with ethanol wash obtain leach thing three times, leach thing and under vacuum state, dry by the fire to dry basic benzene or ethene and alkene butylbenzene multipolymer.
(2), utilize the Friedel-Crafts acylation reaction that polar group is introduced ethene and allyl benzene or ethene and alkene butylbenzene multipolymer, preparation polar functionalities polyolefine
Under nitrogen protection; with ethene and allyl benzene multipolymer or ethene and alkene butylbenzene multipolymer dithiocarbonic anhydride, oil of mirbane, tetrachloroethane or the dissolving of their mixed solvent; wherein; dithiocarbonic anhydride, oil of mirbane, tetrachloroethane or their mixed solvent cumulative volume mL: side-chain benzene ring content mmol is 40: 1 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene, adds AlCl then
3, AlCl wherein
3Mmol: side-chain benzene ring content mmol is 2-6 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene: 1; Or adding ZnCl
2, ZnCl wherein
2Mmol: side-chain benzene ring content mmol is 4: 1 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene; Cyclic acid anhydride is dissolved in above-mentioned dithiocarbonic anhydride, oil of mirbane, in tetrachloroethane or their mixed solvent, obtain cyclic acid anhydride solution, solvent volume amount used herein is the dithiocarbonic anhydride that foregoing dissolve ethylene and allyl benzene multipolymer or ethene and alkene butylbenzene multipolymer are used, oil of mirbane, 1/2 of the volume of tetrachloroethane or their mixed solvent, described cyclic acid anhydride is a Succinic anhydried, Pyroglutaric acid, 3-oxa-Pyroglutaric acid, two ring [221]-5-heptene-2, the 3-dicarboxylic acid anhydride, phthalic anhydride, chloro-benzoic anhydride or nitro phthalic anhydride, wherein, the mol ratio of side-chain benzene ring is 1: 1 in the multipolymer of cyclic acid anhydride and ethene and allyl benzene or ethene and alkene butylbenzene, at 10-50 ℃, divide 11 batches of equivalent to add reaction system cyclic acid anhydride solution, added a collection of every 5 minutes, begin to finish from beginning to add acid anhydrides solution to reaction, total coreaction 1-2 hour, in reaction solution, add hydrochloric acid, frozen water mixed solution termination reaction, wherein the hydrochloric acid volume equals frozen water volume sum, and hydrochloric acid, solvent for use is a dithiocarbonic anhydride in frozen water mixed solution cumulative volume and the reaction, oil of mirbane, the cumulative volume of tetrachloroethane or their mixed solution equates, stirring is spent the night, use the separating funnel separatory then, wash organic phase twice with aqueous hydrochloric acid again, concentrate organic phase, add ethanol sedimentation, filter, leach thing and under 60 ℃, be evacuated to drying, obtain the polar functionalities polyolefine.
Below be the polyolefinic nuclear-magnetism characteristic peak ownership of described cyclic acid anhydride and ethene and allyl benzene or ethene and alkene butylbenzene multipolymer generation acidylate gained polar functionalities, the polyolefine that has obtained polar functionalities really be described:
Polyolefine with Pyroglutaric acid acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2): δ 3.008 (C
H 2CH
2CH
2COOH), 2.054 (C
H 2CH
2COOH), 2.465 (C
H 2COOH);
Polyolefine with Succinic anhydried acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2): δ 3.232 (C
H 2CH
2COOH), 2.738 (C
H 2COOH);
Polyolefine with phthalic anhydride acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.008 (Ha), 7.519 (Hb), 7.573 (Hc), 7.329 (Hd);
Polyolefine with 3-oxa-Pyroglutaric acid acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2): δ 4.308 (OC
H 2COOH);
With two ring [221]-5-heptene-2, the polyolefine of 3-dicarboxylic acid anhydride acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 3.587 (Ha);
X is CH
2Or CH
2CH
2
Polyolefine with alpha-chloro phthalic anhydride acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 7.682 (Ha);
Polyolefine with β-chloro-benzoic anhydride acidylate gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.132 (Ha);
Polyolefine with α-oil of mirbane anhydride acylation gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.246 (Ha), 8.300 (Hb);
Polyolefine with β-oil of mirbane anhydride acylation gained polar functionalities
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.837 (Ha).
Beneficial effect: under high acidylate rate; the polyolefinic fusing point of polar functionalities can improve 3 ℃ than parent multipolymer fusing point; main is not degraded and the generation of crosslinked phenomenon in the acylation process; not only kept the original premium properties of multipolymer parent; and raising is also arranged for wetting ability with the consistency of polar material; the polar functionalities polyolefine wetting ability of comparing with the parent multipolymer all increases, and water has reduced by 10 ° at the contact angle of polar functionalities polyolefin surfaces with comparing at the contact angle on multipolymer parent surface.
Embodiment
Embodiment 1
Exsiccant 500mL there-necked flask is put in 40 ℃ of waters, after purging 5 minutes with ethylene gas, add toluene 112mL, after ethylene gas is saturated, add the 48mmol allyl benzene, add two indenes Zr catalyst 4.86mg (8 μ mol) of ethyl bridging, add methylaluminoxane (MMAO) 8mL of the modification of 2mol/L, begin to stir, continuing to feed ethene and keep ethylene pressure is 1 normal atmosphere.Behind the reaction 30min reaction solution is poured in the ethanolic soln that 400mL contains 10% (V/V) hydrochloric acid, filtered the back and give a baby a bath on the third day after its birth time with ethanol, 60 ℃ of following vacuum-drying 24 hours obtains ethene and allyl benzene multipolymer.By each calculated by peak area of nuclear-magnetism as can be known on the main chain per 100 carbon atom side chains contain 3.85 of phenyl ring.
Embodiment 2
Exsiccant 500mL there-necked flask is put in 40 ℃ of waters, after purging 5 minutes with ethylene gas, add toluene 112mL, after ethylene gas is saturated, add 16mmol alkene butylbenzene, add two indenes Zr catalyst 4.86mg (8 μ mol) of ethyl bridging, add methylaluminoxane (MMAO) 8mL of the modification of 2mol/L, begin to stir, continuing to feed ethene and keep ethylene pressure is 1 normal atmosphere.Behind the reaction 30min reaction solution is poured in the ethanolic soln that 400mL contains 10% (V/V) hydrochloric acid, filtered the back and give a baby a bath on the third day after its birth time with ethanol, 60 ℃ of following vacuum-drying 24 hours obtains ethene and alkene butylbenzene multipolymer.By each calculated by peak area of nuclear-magnetism as can be known on the main chain per 100 carbon atom side chains contain 6.48 of phenyl ring.
Embodiment 3
In the 250mL there-necked flask, take by weighing ethene and allyl benzene multipolymer 0.5g (contains phenyl ring 1.1mmol, per 100 carbon of main chain contain 3.85 of phenyl ring) and aluminum trichloride (anhydrous) 0.59g (4.4mmol), add dithiocarbonic anhydride 40mL, solution is heated to boiling, polymkeric substance is fully dissolved, be cooled to 10 ℃ then, after stirring 10min, beginning 11 batches of equivalent of branch adds with 20mL dithiocarbonic anhydride dissolved 0.13g (1.1mmol) Pyroglutaric acid solution, because of Pyroglutaric acid solvability in dithiocarbonic anhydride relatively poor, therefore need in ultrasonic wave, fully vibrate so that Pyroglutaric acid fully dissolves, a collection of every adding in 5 minutes, 5min is continued to stir in the reinforced back that finishes, and the reaction times is total to 1h, in reaction solution, add hydrochloric acid, frozen water mixed solution 60mL termination reaction, wherein the hydrochloric acid volume equals the frozen water cumulative volume.Stirring is spent the night, and uses the separating funnel separatory then, washes twice with aqueous hydrochloric acid again, concentrates organic phase, adds ethanol sedimentation, filters the gained solid 60 ℃ of following vacuum-dryings, gets polar functionalities polyolefine 0.49g.
1H?NMR(Cl
2D
2CCD
2Cl
2)：δ3.008(-C
H 2CH
2CH
2COOH)，2.054(C
H 2H
2COOH)，2.465(C
H 2COOH)。By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.18 carboxyl.
Embodiment 4
Modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.53g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.23 carboxyls.
Embodiment 5
Modification is carried out under 50 ℃, and other gets polar functionalities polyolefine 0.57g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 2.96 carboxyls.
Embodiment 6
Modification is carried out under 30 ℃, and solvent for use is an oil of mirbane, and other gets polar functionalities polyolefine 0.51g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.82 carboxyl.
Embodiment 7
Modification is carried out under 30 ℃, and solvent for use is oil of mirbane and tetrachloroethane mixed solution, and both add with the equal-volume ratio, and other gets polar functionalities polyolefine 0.49g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.31 carboxyl.
Embodiment 8
Modification is carried out under 30 ℃, with the anhydrous ZnCl of 0.60g (4.4mmol)
2Replace anhydrous AlCl
3, other gets polar functionalities polyolefine 0.52g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.93 carboxyl.
Embodiment 9
Modification is carried out under 30 ℃, with 0.42g ethene and alkene butylbenzene multipolymer (contain phenyl ring 1.1mmol, per 100 carbon of main chain contain 6.48 of phenyl ring) replace ethene and allyl benzene multipolymer other with embodiment 3, must polar functionalities polyolefine 0.43g.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 2.33 carboxyls.
Embodiment 10
Modification is carried out under 50 ℃, and the aluminum trichloride (anhydrous) add-on is 0.29g (2.2mmol), and other gets polar functionalities polyolefine 0.57g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.54 carboxyls.
Embodiment 11
Modification is carried out under 50 ℃, and the aluminum trichloride (anhydrous) add-on is 0.88g (6.6mmol), and other gets polar functionalities polyolefine 0.59g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 3.07 carboxyls.
Embodiment 12
Modification is carried out under 50 ℃, and reaction is extended for 2h total time, and other gets polar functionalities polyolefine 0.60g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 3.16 carboxyls.
Embodiment 13
With the Pyroglutaric acid among Succinic anhydried 0.11g (1.1mmol) the replacement embodiment 3, other gets polar functionalities polyolefine 0.51g with embodiment 3.
1H?NMR(Cl
2D
2CCD
2Cl
2)：δ3.232?(-C
H 2CH
2COOH)，2.738(C
H 2COOH)。By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.28 carboxyl.
Embodiment 14
With the Pyroglutaric acid among Succinic anhydried 0.11g (1.1mmol) the replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.53g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.79 carboxyls.
Embodiment 15
With the Pyroglutaric acid among Succinic anhydried 0.11g (1.1mmol) the replacement embodiment 3, modification is carried out under 50 ℃, and other gets polar functionalities polyolefine 0.57g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 3.42 carboxyls.
Embodiment 16
With the Pyroglutaric acid among Succinic anhydried 0.11g (1.1mmol) the replacement embodiment 3, modification is carried out under 50 ℃, and reaction is extended for 2h total time, and other gets polar functionalities polyolefine 0.58g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 3.60 carboxyls.
Embodiment 17
With the Pyroglutaric acid among phthalic anhydride 0.16g (1.1mmol) the replacement embodiment 3, other gets polar functionalities polyolefine 0.52g with embodiment 3.
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.008 (Ha), 7.519 (Hb), 7.573 (Hc), 7.329 (Hd).By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.20 carboxyl.
Embodiment 18
With the Pyroglutaric acid among phthalic anhydride 0.16g (1.1mmol) the replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.55g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.43 carboxyls.
Embodiment 19
With the Pyroglutaric acid among phthalic anhydride 0.16g (1.1mmol) the replacement embodiment 3, modification is carried out under 50 ℃, and other gets polar functionalities polyolefine 0.60g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 2.52 carboxyls.
Embodiment 20
With the Pyroglutaric acid among phthalic anhydride 0.16g (1.1mmol) the replacement embodiment 3, modification is carried out under 50 ℃, and the reaction times is extended for 2h, and other gets polar functionalities polyolefine 0.64g with embodiment 3.By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 3.56 carboxyls.
Embodiment 21
With the Pyroglutaric acid among 3-oxa-Pyroglutaric acid 0.13g (1.1mmol) the replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.53g with embodiment 3.
1HNMR(Cl
2D
2CCD
2Cl
2)：δ4.308(-OC
H 2COOH)。By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.38 carboxyls.
Embodiment 22
With two ring [221]-5-heptene-2,3-dicarboxylic acid anhydride 0.18g (1.1mmol) replaces the Pyroglutaric acid among the embodiment 3, and modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.53g with embodiment 3.
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 3.587 (Ha).
By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 0.96 carboxyl.
Embodiment 23
With the Pyroglutaric acid among alpha-chloro phthalic anhydride 0.20g (1.1mmol) the replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.54g with embodiment 3.
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 7.682 (Ha).By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.22 carboxyls.
Embodiment 24
With the Pyroglutaric acid among β-chloro-benzoic anhydride 0.20g (1.1mmol) replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.58g with embodiment 3.
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.132 (Ha).By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.63 carboxyls.
Embodiment 25
With the Pyroglutaric acid among α-nitro phthalic anhydride 0.21g (1.1mmol) replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.61g with embodiment 3.
1H NMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.246 (Ha), 8.300 (Hb).By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.78 carboxyls.
Embodiment 26
With the Pyroglutaric acid among β-nitro phthalic anhydride 0.21g (1.1mmol) replacement embodiment 3, modification is carried out under 30 ℃, and other gets polar functionalities polyolefine 0.57g with embodiment 3.
1HNMR (Cl
2D
2CCD
2Cl
2) (See Figure): δ 8.837 (Ha).By nuclear-magnetism as can be known, per 100 carbon atoms of main chain, side chain contains 1.59 carboxyls.
Claims (2)
1. the polyolefine of polar functionalities is characterized in that, its structural formula is as follows:
In this structural formula, x represents CH
2Or CH
2CH
2, m, n are respectively 0 to infinitely-great natural number, and R is
2. the polyolefinic preparation method of polar functionalities as claimed in claim 1 is characterized in that, step and condition are as follows:
(1) ethene and allyl benzene or ethene and alkene butylbenzene multipolymer-" polyolefine intermediate " is synthetic
Two indenes zirconiums of having selected the ethyl bridging are as catalyzer, and structural formula is as follows:
The exsiccant reactor is put in 40 ℃ of water-baths, after purging 5 minutes with ethylene gas, add toluene, toluene mL wherein: two indenes Zr catalyst μ mol of ethyl bridging are 14: 1, after ethylene gas is saturated, add allyl benzene, wherein allyl benzene: the mol ratio of two indenes Zr catalysts of ethyl bridging is 6: 1; Or add alkene butylbenzene, wherein alkene butylbenzene: the mol ratio of two indenes Zr catalysts of ethyl bridging is 2: 1; The two indenes Zr catalysts that add the ethyl bridging, the methylaluminoxane of modification, methylaluminoxane wherein: the mol ratio of two indenes Zr catalysts of ethyl bridging is 2000: 1, begin to stir, continuing to feed ethene and keep ethylene pressure is 1 normal atmosphere, reaction 30min, reaction solution is poured into the ethanolic soln that contains 10%V/V hydrochloric acid, hydrochloride ethanol liquid mL: Zr catalyst μ mol is 50: 1, filtering the back gives a baby a bath on the third day after its birth time with ethanol, leach thing and under vacuum state, dry by the fire, obtain ethene and allyl benzene or ethene and alkene butylbenzene multipolymer to dry;
(2), utilize the Friedel-Crafts acylation reaction that polar group is introduced ethene and allyl benzene or ethene and alkene butylbenzene multipolymer, preparation polar functionalities polyolefine
Under nitrogen protection; with ethene and allyl benzene multipolymer or ethene and alkene butylbenzene multipolymer dithiocarbonic anhydride, oil of mirbane, tetrachloroethane or the dissolving of their mixed solvent; wherein; dithiocarbonic anhydride, oil of mirbane, tetrachloroethane or their mixed solvent cumulative volume mL: side-chain benzene ring content mmol is 40: 1 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene, adds AlCl then
3, AlCl wherein
3Mmol: side-chain benzene ring content mmol is 2-6 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene: 1; Or adding ZnCl
2, ZnCl wherein
2Mmol: side-chain benzene ring content mmol is 4: 1 in the multipolymer of ethene and allyl benzene or ethene and alkene butylbenzene; Cyclic acid anhydride is dissolved in above-mentioned dithiocarbonic anhydride, oil of mirbane, in tetrachloroethane or their mixed solvent, obtain cyclic acid anhydride solution, solvent volume amount used herein is the dithiocarbonic anhydride that foregoing dissolve ethylene and allyl benzene multipolymer or ethene and alkene butylbenzene multipolymer are used, oil of mirbane, 1/2 of the volume of tetrachloroethane or their mixed solvent, described cyclic acid anhydride is a Succinic anhydried, Pyroglutaric acid, 3-oxa-Pyroglutaric acid, two ring [221]-5-heptene-2, the 3-dicarboxylic acid anhydride, phthalic anhydride, chloro-benzoic anhydride or nitro phthalic anhydride, wherein, the mol ratio of side-chain benzene ring is 1: 1 in the multipolymer of cyclic acid anhydride and ethene and allyl benzene or ethene and alkene butylbenzene, at 10-50 ℃, divide 11 batches of equivalent to add reaction system cyclic acid anhydride solution, added a collection of every 5 minutes, begin to finish from beginning to add acid anhydrides solution to reaction, total coreaction 1-2 hour, in reaction solution, add hydrochloric acid, frozen water mixed solution termination reaction, wherein the hydrochloric acid volume equals frozen water volume sum, and hydrochloric acid, solvent for use is a dithiocarbonic anhydride in frozen water mixed solution cumulative volume and the reaction, oil of mirbane, the cumulative volume of tetrachloroethane or their mixed solution equates, stirring is spent the night, use the separating funnel separatory then, wash organic phase twice with aqueous hydrochloric acid again, concentrate organic phase, add ethanol sedimentation, filter, leach thing and under 60 ℃, be evacuated to drying, obtain the polar functionalities polyolefine.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181482A1 (en) * | 1984-10-03 | 1986-05-21 | Nippon Petrochemicals Co., Ltd. | Novel ethylene copolymers |
| US6391451B1 (en) * | 1999-09-07 | 2002-05-21 | Basf Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
| US6750289B2 (en) * | 1998-05-18 | 2004-06-15 | Shell Oil Company | Functionalized thermoplastic elastomer |
| US6803107B2 (en) * | 1999-09-07 | 2004-10-12 | Basf Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
-
2007
- 2007-01-26 CN CN200710055276XA patent/CN101012292B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181482A1 (en) * | 1984-10-03 | 1986-05-21 | Nippon Petrochemicals Co., Ltd. | Novel ethylene copolymers |
| US6750289B2 (en) * | 1998-05-18 | 2004-06-15 | Shell Oil Company | Functionalized thermoplastic elastomer |
| US6391451B1 (en) * | 1999-09-07 | 2002-05-21 | Basf Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
| US6803107B2 (en) * | 1999-09-07 | 2004-10-12 | Basf Aktiengesellschaft | Surface-treated superabsorbent polymer particles |
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|---|---|
| CN101012292A (en) | 2007-08-08 |
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