CN101012292B - Polar group-containing polyolefin and its preparation method - Google Patents

Abstract

该结构式中，x代表CH₂或CH₂CH₂，m，n分别为0到无穷大的自然数，R为

以二硫化碳、四氯乙烷、硝基苯或它们的混合物为溶剂，以路易斯酸(AlCl₃、ZnCl₂)为催化剂，利用环状二酸酐与乙烯与烯丙烯苯或乙烯与烯丁基苯共聚物发生Friedel-Crafts酰基化反应制备出同时含有羰基和羧基极性基团的聚烯烃。在高酰化率下，含极性基团聚烯烃的熔点较母体共聚物熔点可提高3℃，酰化过程中没有降解和交联现象发生，对于亲水性和与极性物质的相容性也有提高，水在含极性基团聚烯烃表面的接触角与在共聚物母体表面的接触角相比较降低了10°。The polyolefin containing polar group of the present invention, its structural formula is as follows:

In this structural formula, x represents CH ₂ or CH ₂ CH ₂ , m and n are natural numbers from 0 to infinity respectively, and R is

Using carbon disulfide, tetrachloroethane, nitrobenzene or their mixtures as solvents, using Lewis acid (AlCl ₃ , ZnCl ₂ ) as a catalyst, the copolymerization of cyclic dianhydrides with ethylene and allyl benzene or ethylene and allyl benzene Polyolefins containing both carbonyl and carboxyl polar groups were prepared by Friedel-Crafts acylation reaction. At a high acylation rate, the melting point of the polyolefin containing polar groups can be increased by 3°C compared with the melting point of the parent copolymer, and there is no degradation and crosslinking during the acylation process, which is good for hydrophilicity and compatibility with polar substances There is also an improvement, and the contact angle of water on the surface of the polyolefin containing polar groups is reduced by 10° compared with the contact angle on the surface of the copolymer matrix.

Description

Polar group-containing polyolefin and its preparation method

technical field

The invention relates to a polyolefin containing polar groups and a preparation method thereof. The polar group is introduced into the polyolefin by Friedel-Crafts acylation reaction.

Background technique

Polyolefin is a typical non-polar polymer material, which limits its application in some aspects. Introducing polar groups or molecular segments into polyolefin macromolecules can effectively change its physical and chemical properties, such as endowing it with hydrophilicity, dyeability, colorability, printability, and compatibility with polar polymers Sex, increase the surface tension of the product and the adhesion to polar substances (sprayability), etc., increase its added value, and broaden the scope of application. Ethylene and some polar monomers (such as acrylate, vinyl acetate) can be free radically copolymerized under high pressure, but the polymerization reaction conditions are harsh, the one-time investment in equipment is large, the structure of the product is complex, and the performance is unstable. People have always hoped to realize the controllable copolymerization of olefins and polar monomers by using coordination polymerization technology widely used in industry to obtain new functionalized polyolefin materials with excellent performance, but due to the functional groups in polar monomers It can coordinate with the active center ion of traditional Zigler-Natta and metallocene catalysts to deactivate them, so the coordination copolymerization of olefins and polar monomers is a relatively difficult thing, although the recently developed post-transition metal catalysts The Lewis acidity of the polar monomer is reduced, but the nitrogen and oxygen heteroatoms in the polar monomer still make its catalytic activity and the molecular weight of the copolymer greatly reduced.

Contents of the invention

In order to overcome the disadvantages of the prior art and obtain a polyolefin containing a polar group with excellent performance, the invention discloses a polyolefin containing a polar group and a preparation method thereof.

One of object of the present invention is to provide polyolefin containing polar groups, its structural formula is as follows:

In this structural formula, x represents CH ₂ or CH ₂ CH ₂ , m and n are natural numbers from 0 to infinity respectively, and R is

The second object of the present invention is to provide a preparation method for polyolefins containing polar groups.

Its reaction process is as follows:

x represents CH ₂ or CH ₂ CH ₂ , m and n are natural numbers from 0 to infinity respectively, and R is

Reactant 1 is a copolymer of ethylene and allylbenzene or ethylene and butylbenzene, and reactant 2 is succinic anhydride, glutaric anhydride, 3-oxaglutaric anhydride, bicyclo[2.2.1 ]-5-heptene-2,3-dicarboxylic anhydride, phthalic anhydride, chlorophthalic anhydride or nitrophthalic anhydride. All the obtained polar group-containing polyolefins are simultaneously connected with two kinds of polar groups, carbonyl group and carboxyl group.

The polymerization steps and conditions of synthesizing ethylene and allylbenzene or ethylene and allylbenzene copolymer are as follows:

(1) Synthesis of ethylene and allylbenzene or ethylene and butylbenzene copolymer - "polyolefin intermediate"

The invention synthesizes a polyolefin that does not contain heteroatoms that deactivate the catalyst, but has a regular structure and contains functional groups that are easily modified. In the polymerization process, ethyl-bridged bis-indene zirconium rac-Et(ind) ₂ ZrCl ₂ was selected as the catalyst, and the structure is as follows:

Under the action of cocatalyst-modified methylaluminoxane (MMAO), zirconium becomes the cationic catalytic active center, and because the angle between the two indene rings is moderate, its copolymerization ability is strong, and the obtained copolymer has a regular structure and The distribution is narrow. The catalytic activity of the catalyst for copolymerization of ethylene and allylbenzene or allylbenzene is no less than that of ethylene homopolymerization, and the benzene ring content of the obtained copolymer is controllable and uniformly distributed on the polymer main chain.

The dry reactor was placed in a water bath at 40°C, and after being purged with ethylene gas for 5 minutes, toluene was added, wherein the ratio of toluene mL:ethyl-bridged bisindene zirconium catalyst μmol was 14:1. After the ethylene gas was saturated, ethylene was added. Propylbenzene, wherein the mol ratio of allylbenzene:ethyl bridged bisindene zirconium catalyst is 6:1; or add allylbenzene, wherein allylbenzene:ethyl bridged bisindene zirconium catalyst The mol ratio is 2: 1; Add the bis-indene zirconium catalyst of ethyl bridging, the modified methyl aluminoxane (MMAO), wherein the mol ratio of methyl aluminoxane: the bis indene zirconium catalyst of ethyl bridging is 2000:1, start stirring, continue to feed ethylene and keep the ethylene pressure at 1 atmosphere, react for 30min, pour the reaction solution into ethanol solution containing 10% V/V hydrochloric acid, hydrochloric acid ethanol solution mL:zirconium catalyst μmol is 50:1 , After filtering, wash the filtrate three times with ethanol, and dry the filtrate under vacuum to dryness, based on benzene or ethylene and butylbenzene copolymer.

(2) Using Friedel-Crafts acylation reaction to introduce polar groups into copolymers of ethylene and allylbenzene or ethylene and butylbenzene to prepare polyolefins containing polar groups

Under the protection of nitrogen, dissolve the copolymer of ethylene and allylbenzene or the copolymer of ethylene and butylbenzene with carbon disulfide, nitrobenzene, tetrachloroethane or their mixed solvents, wherein carbon disulfide, nitrobenzene, tetrachloride The total volume of ethyl chloride or their mixed solvents mL: the side chain benzene ring content in the copolymer of ethylene and allylbenzene or ethylene and allylbenzene in mmol is 40:1, then add AlCl ₃ , wherein AlCl ₃ mmol: The content of side chain benzene ring in the copolymer of ethylene and allylbenzene or ethylene and allylbenzene is 2-6:1 in mmol; or ZnCl ₂ is added, wherein ZnCl ₂ mmol: ethylene and allylbenzene or ethylene and alkene The side chain benzene ring content mmol in the copolymer of butylbenzene is 4: 1; The cyclic anhydride is dissolved in the above-mentioned carbon disulfide, nitrobenzene, tetrachloroethane or their mixed solvents to obtain a cyclic anhydride solution, where Used solvent volume is 1% of the volume of carbon disulfide, nitrobenzene, tetrachloroethane or their mixed solvents used for dissolving ethylene and allylbenzene copolymer or ethylene and allylbenzene copolymer as described above /2, the cyclic acid anhydride is succinic anhydride, glutaric anhydride, 3-oxaglutaric anhydride, bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, phthalic anhydride, Chlorophthalic anhydride or nitrophthalic anhydride, wherein, the molar ratio of the cyclic anhydride to the copolymer of ethylene and allylbenzene or ethylene and allylbenzene is 1:1, and at 10-50°C, the The cyclic acid anhydride solution is added to the reaction system in 11 batches in equal amounts, and one batch is added every 5 minutes. From the beginning of adding the acid anhydride solution to the end of the reaction, the total reaction time is 1-2 hours, and the reaction solution is terminated by adding hydrochloric acid and ice-water mixture. Reaction, wherein hydrochloric acid volume is equal to the sum of ice-water volume, and hydrochloric acid, ice-water mixed liquid total volume are equal to the total volume of solvent used in the reaction, i.e. carbon disulfide, nitrobenzene, tetrachloroethane or their mixed solution, stirred overnight, Then use a separating funnel to separate the liquid, then wash the organic phase twice with aqueous hydrochloric acid, concentrate the organic phase, add ethanol to precipitate, filter, and vacuum the filtrate to dryness at 60°C to obtain a polyolefin containing a polar group.

The following is the NMR characteristic peak assignment of the polar group-containing polyolefin obtained by the acylation of the cyclic anhydride with ethylene and allylbenzene or ethylene and allylbenzene copolymer, indicating that the polar group-containing polyolefin has indeed been obtained. Polyolefin:

Polar group-containing polyolefin obtained by acylation with glutaric anhydride ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ): δ3.008 ( -CH ₂ CH ₂ CH ₂ COOH), 2.054 ( CH ₂ CH ₂ COOH), 2.465 ( CH ₂ COOH);

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with succinic anhydride: δ3.232 ( -CH ₂ CH ₂ COOH), 2.738 ( CH ₂ COOH);

¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) of polyolefins containing polar groups obtained by acylation with phthalic anhydride (see the figure below): δ8.008 (Ha), 7.519 (Hb), 7.573 (Hc), 7.329 (Hd);

X为CH₂或CH₂CH₂

X _{is CH2} or _CH2CH2

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with 3-oxaglutaric anhydride: δ4.308 (-OC H ₂ COOH);

¹ H NMR (Cl 2 D 2 CCD _{2 Cl 2 )} of polyolefins containing polar groups obtained by acylation of bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride (see below Figure): δ3.587 (Ha);

X _{is CH2} or _CH2CH2

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with α-chlorophthalic anhydride (see the figure below): δ7.682 (Ha);

X为CH₂或CH₂CH₂

X _{is CH2} or _CH2CH2

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with β-chlorophthalic anhydride (see the figure below): δ8.132 (Ha);

X为CH₂或CH₂CH₂

X _{is CH2} or _CH2CH2

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with α-nitrophthalic anhydride (see the figure below): δ8.246 (Ha), 8.300 (Hb);

X为CH₂或CH₂CH₂

X _{is CH2} or _CH2CH2

Polar group-containing polyolefin ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) obtained by acylation with β-nitrophthalic anhydride (see the figure below): δ8.837 (Ha).

X为CH₂或CH₂CH₂

X _{is CH2} or _CH2CH2

Beneficial effects: at a high acylation rate, the melting point of polyolefin containing polar groups can be increased by 3°C compared with the melting point of the matrix copolymer, and more importantly, there is no degradation and crosslinking during the acylation process, not only retaining the copolymer matrix The original excellent performance, and the hydrophilicity and compatibility with polar substances are also improved. Compared with the parent copolymer, the hydrophilicity of polyolefins containing polar groups has been improved, and water in the polyolefins containing polar groups The contact angle on the olefin surface was reduced by 10° compared to the contact angle on the copolymer matrix surface.

Detailed ways

Example 1

Put a dry 500mL three-neck flask in water at 40°C, and after purging it with ethylene gas for 5 minutes, add 112mL of toluene. After the ethylene gas is saturated, add 48mmol of allylbenzene, and add 4.86mg of ethyl-bridged bis-indene zirconium catalyst (8 μmol), add 8 mL of 2 mol/L modified methylalumoxane (MMAO), start stirring, continue to feed ethylene and keep the ethylene pressure at 1 atmosphere. After reacting for 30 minutes, the reaction solution was poured into 400 mL ethanol solution containing 10% (V/V) hydrochloric acid, filtered, washed three times with ethanol, and vacuum-dried at 60° C. for 24 hours to obtain a copolymer of ethylene and allylbenzene. According to the calculation of each peak area of NMR, it can be known that every 100 carbon atom side chains on the main chain contain 3.85 benzene rings.

Example 2

Put a dry 500mL three-neck flask in water at 40°C, and after purging it with ethylene gas for 5 minutes, add 112mL of toluene. After the ethylene gas is saturated, add 16mmol of butylbenzene, and add 4.86mg of ethyl-bridged bisindene zirconium catalyst (8 μmol), add 8 mL of 2 mol/L modified methylalumoxane (MMAO), start stirring, continue to feed ethylene and keep the ethylene pressure at 1 atmosphere. After reacting for 30 minutes, the reaction solution was poured into 400 mL ethanol solution containing 10% (V/V) hydrochloric acid, filtered, washed three times with ethanol, and vacuum-dried at 60° C. for 24 hours to obtain a copolymer of ethylene and butylbenzene. According to the calculation of each peak area of NMR, it can be known that every 100 carbon atom side chains on the main chain contain 6.48 benzene rings.

Example 3

In a 250 mL three-necked flask, weigh 0.5 g of ethylene and allylbenzene copolymer (containing 1.1 mmol of benzene rings, 3.85 benzene rings per 100 carbons in the main chain) and 0.59 g (4.4 mmol) of anhydrous aluminum trichloride, Add 40 mL of carbon disulfide, heat the solution to boiling to fully dissolve the polymer, then cool down to 10°C, stir for 10 minutes, and start adding 0.13 g (1.1 mmol) of glutaric anhydride solution dissolved in 20 mL of carbon disulfide in equal amounts in 11 batches. Glutaric anhydride has poor solubility in carbon disulfide, so it needs to be fully oscillated in an ultrasonic wave to fully dissolve glutaric anhydride, add a batch every 5 minutes, continue to stir for 5 minutes after the addition, and the reaction time is 1 hour in total. Add 60 mL of hydrochloric acid and ice-water mixture to terminate the reaction, wherein the volume of hydrochloric acid is equal to the total volume of ice-water. Stir overnight, then separate the liquid with a separatory funnel, wash twice with aqueous hydrochloric acid, concentrate the organic phase, add ethanol for precipitation, filter the resulting solid and dry it in vacuum at 60°C to obtain 0.49 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ): δ 3.008 ( -CH ₂ CH ₂ CH ₂ COOH), 2.054 ( CH ₂ H ₂ COOH), 2.465 ( CH ₂ COOH). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.18 carboxyl groups.

Example 4

The modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.53 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.23 carboxyl groups.

Example 5

The modification was carried out at 50° C., and the others were the same as in Example 3 to obtain 0.57 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 2.96 carboxyl groups.

Example 6

The modification was carried out at 30° C., and the solvent used was nitrobenzene. Others were the same as in Example 3, and 0.51 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.82 carboxyl groups.

Example 7

The modification was carried out at 30° C., and the solvent used was a mixture of nitrobenzene and tetrachloroethane. The two were added in an equal volume ratio. Others were the same as in Example 3, and 0.49 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.31 carboxyl groups.

Example 8

The modification was carried out at 30° C., and 0.60 g (4.4 mmol) of anhydrous ZnCl ₂ was used instead of anhydrous AlCl ₃ . Others were the same as in Example 3 to obtain 0.52 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.93 carboxyl groups.

Example 9

The modification is carried out at 30°C, with 0.42g of ethylene and allylbenzene copolymer (containing 1.1mmol of benzene rings, 6.48 benzene rings per 100 carbons in the main chain) to replace the ethylene and allylbenzene copolymer. Others are implemented in the same way Example 3, 0.43 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 2.33 carboxyl groups.

Example 10

The modification was carried out at 50° C., and the amount of anhydrous aluminum trichloride added was 0.29 g (2.2 mmol). Others were the same as in Example 3, and 0.57 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.54 carboxyl groups.

Example 11

The modification was carried out at 50° C., and the amount of anhydrous aluminum trichloride added was 0.88 g (6.6 mmol). Others were the same as in Example 3, and 0.59 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 3.07 carboxyl groups.

Example 12

The modification was carried out at 50° C., and the total reaction time was extended to 2 hours. Others were the same as in Example 3, and 0.60 g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 3.16 carboxyl groups.

Example 13

Replace glutaric anhydride in Example 3 with 0.11 g (1.1 mmol) of succinic anhydride, and the others are the same as in Example 3 to obtain 0.51 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ): δ 3.232 ( -CH ₂ CH ₂ COOH), 2.738 ( CH ₂ COOH). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.28 carboxyl groups.

Example 14

0.11 g (1.1 mmol) of succinic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.53 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.79 carboxyl groups.

Example 15

0.11 g (1.1 mmol) of succinic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 50° C., and the others were the same as in Example 3 to obtain 0.57 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 3.42 carboxyl groups.

Example 16

Replace glutaric anhydride in Example 3 with 0.11 g (1.1 mmol) of succinic anhydride, modify at 50° C., and extend the total reaction time to 2 hours. Others are the same as in Example 3 to obtain 0.58 g of polyolefin containing polar groups. . It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 3.60 carboxyl groups.

Example 17

Phthalic anhydride 0.16g (1.1mmol) was used to replace glutaric anhydride in Example 3, and the others were the same as in Example 3 to obtain 0.52g of polar group-containing polyolefin. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see figure below): δ8.008 (Ha), 7.519 (Hb), 7.573 (Hc), 7.329 (Hd). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.20 carboxyl groups.

Example 18

0.16 g (1.1 mmol) of phthalic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.55 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.43 carboxyl groups.

Example 19

0.16 g (1.1 mmol) of phthalic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 50° C., and the others were the same as in Example 3 to obtain 0.60 g of polyolefin containing polar groups. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 2.52 carboxyl groups.

Example 20

Phthalic anhydride 0.16g (1.1mmol) was used instead of glutaric anhydride in Example 3, the modification was carried out at 50°C, and the reaction time was extended to 2h. Others were the same as in Example 3, and 0.64g of polyolefin containing polar groups was obtained. It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 3.56 carboxyl groups.

Example 21

0.13 g (1.1 mmol) of 3-oxaglutaric anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.53 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ): δ 4.308 (-OC H ₂ COOH). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.38 carboxyl groups.

Example 22

Use 0.18 g (1.1 mmol) of bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride to replace the glutaric anhydride in Example 3. The modification is carried out at 30 ° C, and the others are the same as the implementation Example 3, 0.53 g of polyolefin containing polar groups was obtained. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see the figure below): δ3.587 (Ha).

It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 0.96 carboxyl groups.

Example 23

0.20 g (1.1 mmol) of α-chlorophthalic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.54 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see the figure below): δ7.682 (Ha). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.22 carboxyl groups.

Example 24

0.20 g (1.1 mmol) of β-chlorophthalic anhydride was used to replace the glutaric anhydride in Example 3. The modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.58 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see figure below): δ8.132 (Ha). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.63 carboxyl groups.

Example 25

0.21 g (1.1 mmol) of α-nitrophthalic anhydride was used instead of glutaric anhydride in Example 3, and the modification was carried out at 30°C. Others were the same as in Example 3 to obtain 0.61 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see figure below): δ 8.246 (Ha), 8.300 (Hb). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.78 carboxyl groups.

Example 26

0.21 g (1.1 mmol) of β-nitrophthalic anhydride was used to replace the glutaric anhydride in Example 3, the modification was carried out at 30° C., and the others were the same as in Example 3 to obtain 0.57 g of polyolefin containing polar groups. ¹ H NMR (Cl ₂ D ₂ CCD ₂ Cl ₂ ) (see the figure below): δ8.837 (Ha). It can be seen from NMR that for every 100 carbon atoms in the main chain, the side chain contains 1.59 carboxyl groups.

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.