CN115612004A - Polyolefin with multifunctional side group and preparation method thereof - Google Patents

Polyolefin with multifunctional side group and preparation method thereof Download PDF

Info

Publication number
CN115612004A
CN115612004A CN202110787490.4A CN202110787490A CN115612004A CN 115612004 A CN115612004 A CN 115612004A CN 202110787490 A CN202110787490 A CN 202110787490A CN 115612004 A CN115612004 A CN 115612004A
Authority
CN
China
Prior art keywords
polyolefin
peroxide
multifunctional
side group
polyethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110787490.4A
Other languages
Chinese (zh)
Other versions
CN115612004B (en
Inventor
陈商涛
石行波
荔栓红
胡清
张振莉
杜斌
蔡玉东
张勇杰
胡雁鸣
周光远
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202110787490.4A priority Critical patent/CN115612004B/en
Publication of CN115612004A publication Critical patent/CN115612004A/en
Application granted granted Critical
Publication of CN115612004B publication Critical patent/CN115612004B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a polyolefin with multifunctional side groups and a preparation method thereof, wherein the polyolefin with the multifunctional side groups has a structure shown in a formula (I):
Figure DDA0003159626380000011
wherein R is 1 And R 2 Same or different, eachIs independently selected from-H, -CH 3 ，‑CH 2 CH 3 ，‑CH 2 CH 2 CH 3 -one or more of Ph; r 3 Selected from-H, -Br, -Cl, -F, -CH 3 ，‑CH 2 CH 3 ，‑OCH 3 -one or more of Ph; m is an integer of 20 to 30000; n is an integer of 1 to 3000. The side group functionalized polyolefin provided by the invention has a definite molecular structure, adjustable and controllable functionalized side group content and multiple functional characteristics, and specifically comprises the following components: fluorescence property, polarity, oxidation resistance, compatibilization property and the like, and has important potential application in the aspect of preparing novel polyolefin-based high-performance materials.

Description

Polyolefin with multifunctional side group and preparation method thereof
Technical Field
The invention belongs to the technical field of new polymer materials, and particularly relates to polyolefin with multifunctional side groups and a preparation method thereof.
Background
Polyolefin belongs to typical carbon-based polymers, has rich raw materials, low price, easy processing and forming and excellent comprehensive performance, and can be suitable for the fields of packaging, home appliances, automobiles, decoration, buildings and the like, thereby being a high polymer material with the largest output and very wide application. Of these, polyethylene and polypropylene are the most important, the main categories being polyethylene and some copolymers based on ethylene, and also polypropylene and some polypropylene copolymers. The general polyolefin material has a molecular structure consisting of simple saturated hydrocarbon units and lacks polar groups, so that the properties of polyolefin such as printing property, compatibility and the like are poor, and the application range of the general polyolefin material is limited to a certain extent.
By means of functionalization reaction, polar/reactive functional groups are introduced into the polyolefin side groups, and the side group functionalized polyolefin can be obtained. By optimizing the functional group of the side group, the functionalized polyolefin of the side group with characteristic functional characteristics can be obtained, the comprehensive performance of the polyolefin can be obviously improved by the functionalization of the side group, and the application field of the polyolefin is widened. The functional characteristics include, but are not limited to: reactivity, polarity, better printing and dyeing performance, anti-oxidation performance, capacity-increasing characteristic and the like.
The side group functionalized polyolefin can be obtained by a pre-functionalization method and a post-functionalization method. The most representative of the pre-functionalization method is an olefin/polar monomer copolymerization method, which is currently difficult to balance in the aspects of catalyst activity, polar monomer content, polymer molecular weight, comprehensive cost and the like, and related researches are in a laboratory stage. The preparation of maleic anhydride or alkenyl siloxane grafted polyolefins based on a melt free radical grafting process is currently a relatively mature post-functionalization route in the industry. However, the mechanism of the melt free radical grafting process is complex, obvious side reactions are accompanied, the functionalized structure of the obtained side group is not clear, and the function of the obtained side group functionalized polyolefin is single.
Limited by the reaction inertia of polyolefin, the traditional post-functionalization method for preparing the side group functionalized polyolefin continues to use a melt free radical grafting mechanism, the reaction conditions are harsh, and the side reaction is difficult to control, so that the performance of the side group functionalized polyolefin is poor. Hydrocarbon activation is an emerging polyolefin functionalization scheme, and a plurality of documents are reported at present. However, most reaction routes are complex and have poor practicability, and the industrial prospect is not achieved.
Chinese patent CN03142815.0 discloses a method for preparing functional polyolefin resin, which mechanically mixes polyolefin resin pre-irradiated by electron beam or gamma-ray with functional monomer and electron-donating reagent; the polyolefin resin and the functional monomer are subjected to grafting reaction in a molten state by a reactive extrusion method. The weight ratio of the grafting rate of the functionalized polyolefin resin prepared by the method is 0.1-10%, the weight ratio of the grafting efficiency is 40-80%, the adhesion with metal or materials such as polyamide and polyester is good, and the peel strength of the functionalized polyolefin resin is adjustable within the range of 2-20N/mm.
And as Chinese patent CN201501273907.X, a fully degradable plastic film with a fluorescent effect and a preparation method thereof are disclosed, the method uses corn starch, nano montmorillonite, peanut oil, tetrabutyl titanate, ramie flax, tributyl citrate, white carbon black, strontium aluminate, carboxymethyl cellulose, natural rubber, stearic acid, strontium aluminate and polyvinyl alcohol to perform hot melt extrusion blow molding in an extruder to form a film, and the fluorescent plastic is obtained.
However, the preparation steps of the functional material are still complicated, and the stability of the fluorescence effect still needs to be improved.
Disclosure of Invention
The invention aims to provide polyolefin with multifunctional side groups, and aims to overcome the defect that the function of side group functionalized polyolefin is single in the prior art.
The invention also aims to provide a preparation method of the polyolefin with the multifunctional side group, so as to solve the problem that the steps are complicated and complicated when the functionalized polyolefin with the side group is prepared in the prior art.
To achieve the above objects, the present invention provides a polyolefin with multifunctional pendant groups having the structure of formula (I):
Figure BDA0003159626360000031
wherein R is 1 And R 2 Are the same or different and are each independently selected from-H, -CH 3 ，-CH 2 CH 3 ，-CH 2 CH 2 CH 3 -one or more of Ph;
R 3 selected from-H, -Br, -Cl, -F, -CH 3 ，-CH 2 CH 3 ，-OCH 3 -one of Ph;
m is an integer of 20 to 30000;
n is an integer of 1 to 3000.
The polyolefin with the multifunctional side group has the number average molecular weight of 600-500000g/mol and the polydispersity index of 1-8.
In order to achieve the above object, the present invention also provides a method for preparing a polyolefin with multifunctional side groups, which comprises dissolving a polyolefin in an organic solvent or performing a functionalization reaction with a functionalizing agent in a molten state to obtain a polyolefin with multifunctional side groups, wherein the polyolefin has a structure represented by formula (II):
Figure BDA0003159626360000032
wherein R is 1 And R 2 Are the same or different and are each independently selected from the group consisting of-H, -CH 3 ，-CH 2 CH 3 ，-CH 2 CH 2 CH 3 -one or more of Ph;
m is an integer of 20 to 30000;
n is an integer of 1 to 3000;
the functionalization reagent has a structure shown in formula (III):
Figure BDA0003159626360000041
wherein R is 3 Selected from-H, -Br, -Cl, -F, -CH 3 ，-CH 2 CH 3 ，-OCH 3 -one of Ph.
The above reaction process can be carried out under the action of a catalyst or without any catalyst, and the formula is as follows:
Figure BDA0003159626360000042
the preparation method of the polyolefin with multifunctional side groups comprises the step of carrying out the functionalization reaction in the presence of a catalyst, wherein the catalyst is one or more of tert-butyl peroxybenzoate, dicumyl peroxide, dibenzoic acid peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxy (2-ethylhexanoate), cyclohexanone peroxide, diacetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, azobisisoheptonitrile, dimethyl azobisisobutyrate, di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, azobispiperidine, 4' -azobisanisole, azobisisobutyronitrile, azobiscyclohexanecarbonitrile and bis (2, 4-dichlorobenzoyl) peroxide.
The preparation method of the polyolefin with the multifunctional side group comprises the step of preparing a polyolefin with the multifunctional side group, wherein the organic solvent is one or more of toluene, benzene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylformamide, tetrachloroethane, naphthalene, decahydronaphthalene, heptane, decane, cyclohexane, dodecane, octadecane and dotriacontane.
The invention relates to a preparation method of polyolefin with multifunctional side groups, wherein the polyolefin is one or more of polyethylene, polypropylene, polybutylene and polystyrene.
The preparation method of the polyolefin with multifunctional side groups comprises the following steps of (1) preparing a functionalized reagent, wherein the mass ratio of the functionalized reagent to the polyolefin is 1; the mass ratio of the polyolefin to the organic solvent is 1.
The preparation method of the polyolefin with multifunctional side groups comprises the following steps of 1, 0.1-10, preferably 1, of the molar ratio of the functionalizing agent to the catalyst.
The invention relates to a preparation method of polyolefin with multifunctional side groups, which comprises the following steps: under the protection of inert gas, polyolefin is dissolved in organic solvent and reacts with functional reagent at 70-180 ℃ for 0.1-30h, the reaction temperature is preferably 90-150 ℃, and the reaction time is preferably 0.2-15h.
The invention relates to a preparation method of polyolefin with multifunctional side groups, which comprises the following steps: under the protection of inert gas or vacuum condition, melting polyolefin, adding a functional reagent, and reacting with the functional reagent at 120-250 ℃ for 0.1-10h, wherein the reaction temperature is preferably 150-220 ℃, and the reaction time is preferably 0.1-3h.
The above reaction may be carried out in a reaction vessel conventional in the art, and preferably, may be carried out in a flask or a screw extruder.
The invention has the beneficial effects that:
the side group functionalized polyolefin provided by the invention has a definite molecular structure, adjustable and controllable functionalized side group content and multiple functional characteristics, and specifically comprises the following components: fluorescence property, polarity, oxidation resistance, compatibilization property and the like, and has important potential application in the aspect of preparing polyolefin-based high-performance new materials. The preparation method is a practical method for preparing multifunctional polyolefin by one step by using hydrocarbon activation reaction of polyolefin side groups under the conditions of no metal catalysis, no solvent or less solvent. The preparation method of the side group functionalized polyolefin provided by the invention is simple to operate, can be carried out in the presence of a molten or small amount of organic solvent, and has the advantages of controllable side reaction, reasonable cost and strong practicability.
Drawings
FIG. 1 is an IR spectrum of a side group functionalized polyethylene prepared in example 1;
FIG. 2 is a graph comparing the carbonyl indices of the side group functionalized polyethylene prepared in example 5 with that of the unfunctionalized polyethylene;
FIG. 3 is a fluorescent spectrum of the side group functionalized polyethylene prepared in example 2;
FIG. 4 is a graph of the thermal weight loss of the side group functionalized polyethylene prepared in example 2;
fig. 5A and 5B are graphs showing the compatibilization effect of the side group functionalized polyethylene prepared in example 3.
Detailed Description
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as one skilled in the art will be able to make certain insubstantial modifications and variations of this invention based on the teachings set forth herein.
Example 1
In a 150ml two-necked flask, 10g of polyethylene (number average molecular weight Mn =1500g/mol, polydispersity PDI = 2.5), 2g of chromone, 0.8g of dibenzoyl peroxide and 0.3g of azobisisobutyronitrile were added, 80ml of o-dichlorobenzene was added, purged with nitrogen, heated to 100 ℃ and stirred to dissolve them sufficiently. And continuously stirring for reaction for 8 hours, precipitating a polymer by using a large amount of alcohol, filtering, repeatedly washing by using the alcohol, and drying in vacuum at 50 ℃ for 12 hours to obtain the side group functionalized polyethylene.
The infrared spectrum shown in figure 1 shows successful grafting of the chromones onto the pendant polyethylene groups. 1 H NMR characterization determined 9wt% chromone grafting, number average molecular weight Mn =1470g/mol, and polydispersity PDI =2.8.
Example 2
In a 50ml two-necked flask, 8g of polyethylene (number average molecular weight Mn =2700g/mol, polydispersity PDI = 1.4), 5g of 4-methoxychromone and 1g of cyclohexanone peroxide were charged, 5ml of heptane was added, and after purging with nitrogen, the mixture was stirred and mixed uniformly at room temperature, and then heated to 130 ℃ and stirred to melt the polyethylene. And continuously stirring for reaction for 2h, repeatedly washing with a large amount of alcohol, and vacuum-drying at 50 ℃ for 12h to obtain the side group functionalized polyethylene. 1 H NMR characterization determined that the 4-methoxychromone grafting was 11wt%, the number average molecular weight Mn =2640g/mol, and the polydispersity number PDI =1.8.
Example 3
50g of linear low density polyethylene (number average molecular weight Mn =120000g/mol, polydispersity PDI = 2.2), 5g of 3-fluorochromone and 7g of azobiscyclohexanecarbonitrile were charged into a 250ml two-neck flask, purged with nitrogen, stirred and mixed homogeneously at room temperature, and then heated to 160 ℃ to melt the polyethylene with stirring. And continuously stirring for reaction for 0.3h, repeatedly washing with a large amount of alcohol, and vacuum drying at 50 ℃ for 12h to obtain the side group functionalized polyethylene. 1 H NMR characterization determined that the 3-fluorochromone grafting was 1.2wt%, the number average molecular weight Mn =126000g/mol, and the polydispersity PDI =2.6.
Example 4
150g of polyethylene (number average molecular weight)Mn =12000g/mol, polydispersity PDI = 2.2), 5g of 3-chlorochromone, 10g of chromone and 6g of dicumyl peroxide, purging with nitrogen, stirring at room temperature, mixing homogeneously, subsequently heating to 160 ℃ and stirring to melt the polyethylene. And continuously stirring for reaction for 0.3h, repeatedly washing with a large amount of alcohol, and vacuum drying at 50 ℃ for 12h to obtain the side group functionalized polyethylene. 1 H NMR characterization confirmed that the total grafting ratio of 3-chlorochromone to chromone was 4.3wt%, the number average molecular weight Mn =12600g/mol, and the polydispersity number PDI =2.6.
Example 5
500g of polyethylene (the number average molecular weight Mn =236000g/mol, the polydispersity number PDI = 4.3), 25g of chromone and 10g of dilauroyl peroxide are uniformly stirred and mixed at room temperature, then the mixture is extruded by a double-screw extruder under the vacuum condition, the temperature of the extruder is 190 ℃, extruded sample strips are cooled by water, granulated, repeatedly washed by a large amount of alcohol, and then dried for 12 hours at 50 ℃ in vacuum, so that the side group functionalized polyethylene is obtained. 1 H NMR characterization determined that the chromone grafting ratio was 1.4wt%, the number average molecular weight Mn =248000g/mol, and the polydispersity number PDI =4.9.
Example 6
500g of polypropylene (number average molecular weight Mn =37000g/mol, polydispersity number PDI = 5.1), 25g of chromone and 10g of dilauroyl peroxide are uniformly mixed at room temperature, then extruded by a twin-screw extruder under the vacuum condition, the temperature of the extruder is 220 ℃, extruded sample strips are water-cooled, granulated, repeatedly washed by a large amount of alcohol, and then dried under vacuum at 50 ℃ for 12 hours to obtain the side group functionalized polypropylene. 1 Characterization by H NMR showed that the chromone grafting was 2.4wt%.
Example 7
500g of polypropylene (number average molecular weight Mn =84000g/mol, polydispersity number PDI = 4.5), 25g of chromone and 10g of di-tert-butyl peroxide are uniformly mixed at room temperature, then extruded by a twin-screw extruder under the vacuum condition, the temperature of the extruder is 220 ℃, extruded sample strips are cooled by water, granulated, repeatedly washed by a large amount of alcohol, and then dried in vacuum at 50 ℃ for 12 hours to obtain the side group functionalized polypropylene. 1 Characterization by H NMR showed that the chromone grafting was 1.7wt%.
Example 8
The antioxidant property of the prepared side group functionalized polyethylene is identified according to the following scheme. 150g of each of the side group functionalized polyethylene (chromone grafted polyethylene) obtained in example 5 and the commercial polyethylene (trademark LD100BW, melt index of 2.1g/10 min) were uniformly mixed at high speed at room temperature, and then melt-extruded and blended by a twin-screw extruder at 180 ℃, and after cooling and dicing, a polyethylene blend, which is marked as A-PE, was obtained. And (3) carrying out melt extrusion on the commercial polyethylene LD100BW by the same extruder under the same condition, cooling and pelletizing to obtain the processed polyethylene, which is marked as B-PE. A-PE and B-PE are respectively aged for 30 days by artificial thermal oxidation at 130 ℃ in an air atmosphere, carbonyl indexes (ratio of absorbance of an absorption peak of 1718 wave number to absorbance of an absorption peak of 2915 wave number in an infrared spectrum) of the A-PE and the B-PE are periodically measured, and the result is shown in figure 2, the increase rate of the carbonyl index of the B-PE is obviously higher than that of the A-PE, so that the chromone grafted polyethylene has better antioxidation.
Example 9
The fluorescence property of the prepared side group functionalized polyethylene and the tracing effect of the prepared side group functionalized polyethylene on common polyethylene are identified according to the following scheme. The side group functionalized polyethylene obtained in example 2 was examined using UV spectroscopy and determined to have the strongest UV absorption at 337 nm. The fluorescence spectra of the side group functionalized polyethylene (f-PE) obtained in example 2 and the virgin polyethylene (p-PE) used in example 2 were measured by fluorescence spectroscopy using 420nm as an excitation wavelength, and the results are shown in FIG. 3, which shows that f-PE has a distinct fluorescence peak and p-PE has no fluorescence peak. The f-PE obtained in the example 2 and the common polyethylene HDPE are blended according to the weight ratio of 1/100, and the fluorescence spectra of the HDPE/f-PE blend and the HDPE are measured, and the blend has an obvious fluorescence peak, which indicates that the f-PE can be used as a fluorescence tracer of the HDPE.
Example 10
The antioxidant effect of the prepared side group functionalized polyethylene is identified according to the following scheme. Thermogravimetric analysis of the side group functionalized polyethylene (f-PE) obtained in example 1 and the virgin polyethylene (p-PE) used in example 1 showed an increase in the initial decomposition temperature of 45 deg.C (air atmosphere, 10 deg.C/min) for f-PE compared to p-PE. Blending the f-PE obtained in the example 1 and common polyethylene LDPE in a weight ratio of 1/10, measuring the thermal weight loss curve of the obtained LDPE/f-PE blend and LDPE, and finding that the initial decomposition temperature of the blend is improved by 20 ℃ compared with that of LDPE as shown in figure 4, which indicates that the f-PE can be used as an antioxidant of LDPE.
Example 11
The compatibilization effect of the prepared side group functionalized polyethylene is identified according to the following scheme. The side group functionalized polyethylene (f-PE) obtained in example 3 is used as a compatibilizer of a blending system of linear low density polyethylene LLDPE and polystyrene PS to respectively prepare two blends of LLDPE/PS/f-PE (80/20/5) and LLDPE/PS (80/20). Scanning electron microscopy results are shown in figure 5, which shows a significant reduction in the dispersed phase size of the PS in the brittle fracture surface of the LLDPE/PS/f-PE blend. The blending system of the f-PE and the linear low density polyethylene LLDPE and the polystyrene PS which can be compatibilized is proved.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.

Claims (10)

1. A polyolefin having pendant multifunctional groups, characterized by having the structure of formula (I):
Figure FDA0003159626350000011
wherein R is 1 And R 2 Are the same or different and are each independently selected from-H, -CH 3 ，-CH 2 CH 3 ，-CH 2 CH 2 CH 3 -one or more of Ph;
R 3 selected from-H, -Br, -Cl, -F, -CH 3 ，-CH 2 CH 3 ，-OCH 3 -one of Ph;
m is an integer of 20 to 30000;
n is an integer of 1 to 3000.
2. The polyolefin with pendant multifunctional groups of claim 1 having a number average molecular weight of from 600 to 500000g/mol and a polydispersity index of from 1 to 8.
3. The method for preparing polyolefin with multifunctional side group according to claim 1 or 2, wherein the polyolefin is dissolved in an organic solvent or is subjected to a functionalization reaction with a functionalizing agent in a molten state to obtain polyolefin with multifunctional side group, wherein the polyolefin has a structure represented by formula (II):
Figure FDA0003159626350000012
wherein R is 1 And R 2 Are the same or different and are each independently selected from the group consisting of-H, -CH 3 ，-CH 2 CH 3 ，-CH 2 CH 2 CH 3 -one or more of Ph;
m is an integer of 20 to 30000;
n is an integer of 1 to 3000;
the functionalizing agent has a structure shown in a formula (III):
Figure FDA0003159626350000021
wherein R is 3 Selected from-H, -Br, -Cl, -F, -CH 3 ，-CH 2 CH 3 ，-OCH 3 -one of Ph.
4. The method of claim 3, wherein the functionalization reaction is carried out in the presence of a catalyst selected from the group consisting of t-butyl peroxybenzoate, dicumyl peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl peroxy (2-ethylhexanoate), cyclohexanone peroxide, diacetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, azobisisoheptonitrile, dimethyl azobisisobutyrate, di-t-butyl azodicarboxylate, diisopropyl azodicarboxylate, azobisformyldipiperidine, 4' -azobisanisole, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and bis (2, 4-dichlorobenzoyl) peroxide.
5. The method of claim 3, wherein the organic solvent is one or more of toluene, benzene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, dimethylformamide, tetrachloroethane, naphthalene, decahydronaphthalene, heptane, decane, cyclohexane, dodecane, octadecane, and dotriacontane.
6. The method of claim 3, wherein the polyolefin is one or more of polyethylene, polypropylene, polybutylene, and polystyrene.
7. The process for the preparation of polyolefins with multifunctional pendant groups according to claim 3, wherein the mass ratio of the functionalizing agent to the polyolefin is 1; the mass ratio of the polyolefin to the organic solvent is 1.
8. The process for the preparation of polyolefins with multifunctional side groups according to claim 4, wherein the molar ratio of functionalizing agent to catalyst is 1.
9. The method of claim 3, wherein the method comprises the steps of: under the protection of inert gas, polyolefin is dissolved in organic solvent and reacts with functional reagent at 70-180 ℃ for 0.1-30h, the reaction temperature is preferably 90-150 ℃, and the reaction time is preferably 0.2-15h.
10. The method of claim 3, wherein the method comprises the steps of: under the protection of inert gas or vacuum condition, melting polyolefin, adding functional reagent, and reacting with the functional reagent at 120-250 deg.C for 0.1-10h, preferably 150-220 deg.C, and preferably 0.1-3h.
CN202110787490.4A 2021-07-13 2021-07-13 Polyolefin with multifunctional side group and preparation method thereof Active CN115612004B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110787490.4A CN115612004B (en) 2021-07-13 2021-07-13 Polyolefin with multifunctional side group and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110787490.4A CN115612004B (en) 2021-07-13 2021-07-13 Polyolefin with multifunctional side group and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115612004A true CN115612004A (en) 2023-01-17
CN115612004B CN115612004B (en) 2024-08-09

Family

ID=84855355

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110787490.4A Active CN115612004B (en) 2021-07-13 2021-07-13 Polyolefin with multifunctional side group and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115612004B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107955100A (en) * 2017-12-07 2018-04-24 万华化学集团股份有限公司 A kind of method and its continuous producing method for pinpointing Functional Polyolefins
CN108359057A (en) * 2018-01-26 2018-08-03 河南工程学院 A kind of functional polyolefin and preparation method thereof
CN111499778A (en) * 2020-04-29 2020-08-07 中国科学技术大学 Antibacterial polyolefin material and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107955100A (en) * 2017-12-07 2018-04-24 万华化学集团股份有限公司 A kind of method and its continuous producing method for pinpointing Functional Polyolefins
CN108359057A (en) * 2018-01-26 2018-08-03 河南工程学院 A kind of functional polyolefin and preparation method thereof
CN111499778A (en) * 2020-04-29 2020-08-07 中国科学技术大学 Antibacterial polyolefin material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JINCAN ZHAO: "Metal-Free Oxidative C(sp3)− H Bond Functionalization of Alkanes and Conjugate Addition to Chromones", 《ORGANIC LETTERS》, no. 16, pages 5342 *

Also Published As

Publication number Publication date
CN115612004B (en) 2024-08-09

Similar Documents

Publication Publication Date Title
US11530281B2 (en) Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof
CN108440761B (en) Non-release type high-molecular antibacterial master batch containing guanidyl side chain as well as preparation method and application thereof
CN101357968A (en) Maleic anhydride-grafted polypropylene material and preparation method thereof
CN112920565A (en) High-melt-strength biodegradable polyester material and preparation method thereof
CN108341940B (en) Preparation method of efficient gel-free long-chain branched polylactic acid
CN115612004A (en) Polyolefin with multifunctional side group and preparation method thereof
CN101107297A (en) Process for preparing trioxepane composition and use thereof in crosslinking polymers
CN113563696B (en) Preparation method of modified polyethylene terephthalate
CN101696254B (en) Method for improving melt strength of polypropylene by using fullerene
CN115093656A (en) Wear-resistant modified PVC material and synthesis process
EP3545036B1 (en) Compatibilised polyolefin and polyphenylene oxide and/or polystyrene composition
Akbari et al. Copolymer of acrylonitrile/acrylic acid film dendrigrafted with citric acid: Host/guest properties of dendrigraft/dye complexes in relation to acrylic acid content
CN113817186A (en) Siloxane crosslinked polyethylene with repeatable processability and preparation method thereof
CN115109173B (en) Cyclic siloxane grafted polyethylene and preparation method thereof
CN117089140B (en) Modified PP composite material and preparation method thereof
Tang et al. Synthesis and crystallization behavior of (PP-MA)-g-PEO
CN114058158B (en) Aliphatic aromatic copolyester foaming composition, aliphatic aromatic copolyester foaming sheet and preparation method thereof
KR102675143B1 (en) Surface modification compatibilizer for improving mechanical strength of waste plastics and manufacturing method of waste plastic composites using the same
KR101328913B1 (en) Method for preparation of modified polyolefin for polyolefin compatibilizer
CN116178629B (en) Hydroxylation modified POE and preparation method and application thereof
CN114044961B (en) Photodegradable environment-friendly plastic packaging bag and production process thereof
CN109679027B (en) High melt strength propylene polymer and preparation method thereof
CN117186308A (en) In-situ compatibilization high-performance polyolefin blend and preparation method thereof
US20080161498A1 (en) Polypropylene derivatives and preparation thereof
CN117362963A (en) High-performance degradable plastic and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant