A process for the preparation of an isobutylene or derivative thereof-maleic anhydride alternating copolymer

Abstract

The application provides application of a Lewis acid in preparation of an isobutylene or derivative thereof-maleic anhydride alternating copolymer. The application also provides a preparation method of the isobutylene or derivative thereof-maleic anhydride alternating copolymer. The application uses a Lewis acid as a cocatalyst together with a free radical initiator in a catalytic system for copolymerization of isobutyl and derivatives thereof and maleic anhydride, can significantly improve copolymerization activity of isobutylene and derivatives thereof and maleic anhydride, reduces polymerization temperature, shortens polymerization reaction time, reduces energy consumption, significantly improves production efficiency, inhibits chain transfer reaction phenomenon, and improves molecular weight of the copolymer. Moreover, the preparation process is simple, the condition is mild, controllability is strong, and is beneficial to industrial application and commercial popularization.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of maleic anhydride and isobutene or its derivative alternating copolymer material, and relates to application of a Lewis acid in preparation of an isobutene or its derivative-maleic anhydride alternating copolymer and a preparation method of the isobutene or its derivative-maleic anhydride alternating copolymer. BACKGROUND

[0002] The copolymer of isobutene and its derivative and maleic anhydride is an amphoteric polymer, the isobutene and its derivative structural unit in the structure has strong lipophilicity, and the maleic anhydride structural unit has good hydrophilicity, and is commonly used as a dispersant, is efficient and has good thermal stability. Can be used as a viscosity reducer of a drilling fluid, a cement slurry, a pesticide dispersant and a water treatment agent and the like; is used as a high water-absorbing resin after crosslinking, has a large water absorption and is durable and stable; in addition, can be used as an adhesive and a colloidal agent and the like.

[0003] So far, the copolymerization of isobutene and its derivative and maleic anhydride mainly adopts a free radical polymerization method, but there are problems of high reaction temperature, long polymerization time and low production efficiency. For example, in the literature Industrial Wastewater Treatment, 2013, 33, 56-59, isobutene and maleic anhydride are copolymerized by continuously dropping an azo free radical initiator (1% of input amount) at 60-80 DEG C, the reaction is terminated after 4 hours, and the product yield reaches about 70%. The literature Makromol. Chem. 1986, 187, 1593-1596 also uses a free radical initiator to initiate the alternating copolymerization of maleic anhydride and isobutene.

[0004] Therefore, how to more efficiently prepare the isobutene or its derivative-maleic anhydride alternating copolymer, solve the above problems existing in the isobutene or its derivative-maleic anhydride alternating copolymer, and expand the application field of the isobutene or its derivative-maleic anhydride alternating copolymer have become one of the focuses of many front-line researchers in the field. SUMMARY

[0005] In view of this, the technical problem to be solved by the application is to provide application of a Lewis acid in preparation of an isobutene or its derivative-maleic anhydride alternating copolymer and a preparation method of the isobutene or its derivative-maleic anhydride alternating copolymer. When the Lewis acid and the free radical initiator are used in the copolymerization catalytic system for simultaneously initiating the copolymerization of isobutene and its derivative and maleic anhydride, the copolymerization activity is greatly improved. Under the same conditions, the introduction of the Lewis acid can greatly improve the yield of the polymer, and the molecular weight of the prepared copolymer is also significantly improved; moreover, the preparation process is simple, the conditions are mild, and the controllability is strong, which is beneficial to industrial application and commercial popularization.

[0006] The application provides application of a Lewis acid in preparation of an isobutylene or derivative-maleic anhydride alternating copolymer.

[0007] Preferably, the isobutylene or derivative-maleic anhydride alternating copolymer is an alternating copolymer with a copolymerization ratio of isobutylene or derivative to maleic anhydride being 1:1;

[0008] The isobutylene derivative includes one or more of 2-methyl-1-butene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-undecene and limonene;

[0009] The preparation mode includes free radical copolymerization;

[0010] The molar ratio of the isobutylene or derivative to maleic anhydride is (0.5-1000):1.

[0011] Preferably, the Lewis acid includes an organic boron compound;

[0012] The preparation mode includes free radical copolymerization under the condition of the Lewis acid and a free radical initiator;

[0013] The Lewis acid acts as a cocatalyst;

[0014] The molar ratio of the maleic anhydride to the Lewis acid is (0.1-5000):1.

[0015] Preferably, the general formula of the organic boron compound is BR 1 R 2 R 3 ; wherein, R 1 , R 2 and R 3 are the same or different, the R 1 -R 3 are each independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl;

[0016] The application specifically refers to application of improving copolymerization activity and increasing the molecular weight of the isobutylene or derivative-maleic anhydride alternating copolymer.

[0017] Preferably, the alkyl includes alkyl with a carbon atom number of 1-30;

[0018] The aryl includes aryl with a carbon atom number of 6-12;

[0019] The molar ratio of the maleic anhydride to the free radical initiator is (50-5000):1;

[0020] The preparation mode specifically includes, under the joint action of the Lewis acid and the free radical initiator and the condition of no water and no oxygen.

[0021] Preferably, the radical initiator includes an azo-based radical initiator and / or a peroxide-based radical initiator;

[0022] The azo-based radical initiator includes one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, azobisdimethylamino isobutyronitrile, and dimethyl azobis isobutyrate;

[0023] The peroxide-based radical initiator includes one or more of dibenzoyl peroxide, lauryl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, diisopropyl peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, diethoxyethyl peroxydicarbonate, tert-butyl peroxyneodecanoate, alpha-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, acetyl cyclohexyl sulfonyl peroxide, diisobutyryl peroxide, 2,4,4-trimethylpentyl-2-peroxybenzyloxyacetate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, and benzoyl peroxide / N,N-dimethylaniline.

[0024] The present application provides a preparation method of an isobutene or its derivative-maleic anhydride alternating copolymer, including the following steps:

[0025] Under the action of a Lewis acid and in anhydrous and oxygen-free conditions, isobutene or its derivative and maleic anhydride monomers are subjected to a copolymerization reaction to obtain an isobutene or its derivative-maleic anhydride alternating copolymer.

[0026] Preferably, the molar ratio of the isobutene or its derivative to the maleic anhydride is (0.5-1000):1;

[0027] The raw material of the copolymerization reaction further includes an organic solvent;

[0028] The organic solvent includes one or more of petroleum ether, n-hexane, cyclohexane, cyclopentane, toluene, xylene, chlorobenzene, decaline, dichloromethane, and dichloroethane.

[0029] Preferably, the Lewis acid includes an organic boron compound;

[0030] The organic boron compound includes one or more of triethyl boron, tripropyl boron, tributyl boron, tri-sec-butyl boron, triamyl boron, trihexyl boron, ethyl diphenyl boron, triphenyl boron, tri-p-fluorophenyl boron, tri-o-fluorophenyl boron, tris(2,6-difluorophenyl)boron, tris(2,4,6-trifluorophenyl)boron, tris(pentafluorophenyl)boron, and tris(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)boron.

[0031] Preferably, the copolymerization temperature is 20-150°C;

[0032] The copolymerization time is 0.1-24 hours;

[0033] The copolymerization further comprises a filtering and / or drying step.

[0034] The application provides application of a Lewis acid in preparation of isobutene or its derivative-maleic anhydride alternating copolymer. The application also provides a preparation method of isobutene or its derivative-maleic anhydride alternating copolymer. Compared with the prior art, the application is directed to the problems of the prior isobutene or its derivative-maleic anhydride alternating copolymer, i.e. the isobutene or its derivative-maleic anhydride alternating copolymer can be prepared at a high yield only under a free radical initiator, at a high temperature and for a long time, and the problems of time consumption, energy consumption and low production efficiency, etc. The application creatively applies the Lewis acid in the free radical copolymerization preparation process of the alpha olefin / maleic anhydride alternating copolymer.

[0035] When the Lewis acid cocatalyst and the free radical initiator are simultaneously used to initiate the isobutene or its derivative and maleic anhydride copolymerization catalytic system, the copolymerization activity is greatly improved. That is, under the same conditions, the introduction of the Lewis acid can greatly improve the yield of the polymer. Moreover, the molecular weight of the prepared copolymer is also significantly improved.

[0036] When the Lewis acid cocatalyst and the free radical initiator are simultaneously used to initiate the isobutene or its derivative and maleic anhydride copolymerization catalytic system, the copolymerization activity is greatly improved. That is, under the same conditions, the introduction of the Lewis acid can greatly improve the yield of the polymer. Moreover, the molecular weight of the prepared copolymer is also significantly improved.

[0037] The experimental results show that when the Lewis acid cocatalyst and the free radical initiator are introduced into the isobutene or its derivative and maleic anhydride copolymerization process, the high-activity copolymerization of isobutene or its derivative and maleic anhydride can be realized at a lower temperature, the production energy consumption is reduced, the production efficiency is improved, the chain transfer effect is inhibited, and the molecular weight of the copolymer is improved. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 DSC spectrum of the isobutene-maleic anhydride alternating copolymer prepared in Example 6 of the application. DETAILED DESCRIPTION

[0039] In order to further understand the application, the preferred embodiments of the application are described below in combination with examples, but it should be understood that the description is only for further illustrating the features and advantages of the application, and is not a limitation on the claims of the application.

[0040] The all raw materials of the present application are not particularly limited in source, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0041] The all raw materials of the present application are not particularly limited in purity, and the present application preferably adopts analytical purity or conventional purity requirements in the field of polyolefin materials.

[0042] The expression of the substituent groups in the present application is not particularly limited, and all adopt the expression well known to those skilled in the art, and those skilled in the art can correctly understand its meaning based on common sense according to its expression.

[0043] The all raw materials of the present application are all conventional grades or abbreviations in the art, and each grade and abbreviation is clear and explicit in its related field of use, and those skilled in the art can purchase or prepare them according to the conventional method based on the grade, abbreviation and corresponding use.

[0044] The present application provides the application of Lewis acid in the preparation of isobutene or its derivative-maleic anhydride alternating copolymer.

[0045] In the present application, the isobutene or its derivative-maleic anhydride alternating copolymer is preferably an alternating copolymer of isobutene or its derivative and maleic anhydride with a copolymerization ratio of 1:1, i.e. a strictly alternating copolymer. The isobutene or its derivative-maleic anhydride alternating copolymer is an isobutene-maleic anhydride alternating copolymer or an isobutene derivative-maleic anhydride alternating copolymer.

[0046] In the present application, the isobutene derivative preferably includes one or more of 2-methyl-1-butene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-undecene and limonene, and more preferably is 2-methyl-1-butene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-undecene or limonene.

[0047] In the present application, the preparation method preferably includes free radical copolymerization.

[0048] In the present application, the Lewis acid preferably includes an organic boron compound.

[0049] In the present application, the preparation method preferably includes free radical copolymerization under the conditions of Lewis acid and free radical initiator.

[0050] In the present application, the Lewis acid is preferably used as a cocatalyst.

[0051] In the present application, the molar ratio of the maleic anhydride to the Lewis acid is preferably (0.1-5000):1, more preferably (1-3000):1, more preferably (10-2000):1, and more preferably (50-1000):1.

[0052] In the present application, the general formula of the organic boron compound is preferably BR 1 R 2 R 3 ; wherein R 1 , R 2 and R 3 are the same or different, and each of R 1 -R 3 is independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl.

[0053] In the present application, the application is particularly preferably the application of improving the copolymerization activity and increasing the molecular weight of the isobutylene or its derivative and maleic anhydride alternating copolymer.

[0054] In the present application, the alkyl group includes an alkyl group with a carbon atom number of preferably 1-30, more preferably 5-25, and more preferably 10-20.

[0055] In the present application, the aryl group includes an aryl group with a carbon atom number of preferably 6-12, more preferably 7-11, and more preferably 8-10.

[0056] In the present application, the molar ratio of the maleic anhydride to the radical initiator is preferably (50-5000):1, more preferably (500-4000):1, and more preferably (1000-3000):1.

[0057] In the present application, the preparation method particularly preferably includes, under the joint action of the Lewis acid and the radical initiator and in the absence of water and oxygen.

[0058] In the present application, the radical initiator preferably includes an azo-based radical initiator and / or a peroxide-based radical initiator, and more preferably an azo-based radical initiator or a peroxide-based radical initiator.

[0059] In the present application, the azo-based radical initiator preferably includes one or more of azobisisobutyronitrile, azobisisoheptyl nitrile, azobisdimethoxyisopropyl nitrile, and dimethyl azobis isobutyrate, and more preferably azobisisobutyronitrile, azobisisoheptyl nitrile, azobisdimethoxyisopropyl nitrile, or dimethyl azobis isobutyrate.

[0060] In the present application, the peroxide-based radical initiator preferably includes one or more of dibenzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-p-menthane, t-butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, acetyl cyclohexyl sulfonyl peroxide, diisobutyryl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, and benzoyl peroxide / N,N-dimethylaniline, more preferably dibenzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-p-menthane, t-butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, acetyl cyclohexyl sulfonyl peroxide, diisobutyryl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, or benzoyl peroxide / N,N-dimethylaniline.

[0061] The present application provides a method for preparing an isobutylene or derivative thereof-maleic anhydride alternating copolymer, comprising the steps of:

[0062] After isobutylene or derivative thereof and maleic anhydride monomers are subjected to a copolymerization reaction under the action of a Lewis acid and in anhydrous and oxygen-free conditions, an isobutylene or derivative thereof-maleic anhydride alternating copolymer is obtained.

[0063] In the present application, the molar ratio of isobutylene or derivative thereof to maleic anhydride is preferably (0.5-1000):1, more preferably (1-500):1, more preferably (2-200):1, more preferably (10-100):1, and more preferably (10-50):1.

[0064] In the present application, the raw material for the copolymerization reaction also preferably includes an organic solvent.

[0065] In the present application, the organic solvent preferably includes one or more of petroleum ether, n-hexane, cyclohexane, cyclopentane, toluene, xylene, chlorobenzene, decaline, dichloromethane, and dichloroethane, more preferably petroleum ether, n-hexane, cyclohexane, cyclopentane, toluene, xylene, chlorobenzene, decaline, dichloromethane, or dichloroethane.

[0066] In the present application, the Lewis acid preferably includes an organic boron compound.

[0067] In the present application, the organic boron compound preferably includes one or more of triethyl boron, tripropyl boron, tributyl boron, tri-sec-butyl boron, triamyl boron, trihexyl boron, ethyl diphenyl boron, triphenyl boron, tri-p-fluorophenyl boron, tri-o-fluorophenyl boron, tri(2,6-difluorophenyl)boron, tri(2,4,6-trifluorophenyl)boron, tri(pentafluorophenyl)boron, and tri(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)boron, and more preferably triethyl boron, tripropyl boron, tributyl boron, tri-sec-butyl boron, triamyl boron, trihexyl boron, ethyl diphenyl boron, triphenyl boron, tri-p-fluorophenyl boron, tri-o-fluorophenyl boron, tri(2,6-difluorophenyl)boron, tri(2,4,6-trifluorophenyl)boron, tri(pentafluorophenyl)boron, or tri(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)boron.

[0068] In the present application, the temperature of the copolymerization is preferably 20-150°C, more preferably 50-120°C, and more preferably 80-90°C.

[0069] In the present application, the time of the copolymerization is preferably 0.1-24 hours, more preferably 1-20 hours, more preferably 5-15 hours, and more preferably 9-10 hours.

[0070] In the present application, the copolymerization is preferably further followed by a filtration and / or drying step, and more preferably a filtration or drying step.

[0071] The present application is a complete and detailed overall technical solution, which better improves the molecular weight of isobutylene or its derivative-maleic anhydride alternating copolymer, further reduces the polymerization temperature, polymerization reaction time, and energy consumption in the preparation process, better improves the monomer conversion rate and production efficiency, and the preparation method of the above-mentioned isobutylene or its derivative-maleic anhydride alternating copolymer can specifically include the following contents:

[0072] In a high-pressure reaction kettle, under anhydrous and anaerobic conditions, maleic anhydride, a free radical initiator, a Lewis acid catalyst promoter, and an organic solvent (or no solvent for bulk polymerization) are stirred uniformly;

[0073] Isobutene gas or an isobutene derivative monomer is introduced into the high-pressure kettle, and copolymerization is carried out under the conditions of a pressure of 0.01-0.5 MPa and a polymerization temperature of 20-150°C;

[0074] After the reaction is completed, the reaction mixture is filtered, the filter cake is collected, and vacuum drying is performed to obtain an isobutylene and its derivative-maleic anhydride alternating copolymer.

[0075] Specifically, the Lewis acid catalyst promoter is organic boron.

[0076] Specifically, the organic boron is BR 1 R 2 R 3(B represents the element boron), where R 1 R 2 and R 3 The same or different, respectively selected from alkyl, phenyl, and aryl groups with substituents; preferably R 1 R 2 and R 3 Whether the groups are the same or different, they are selected from alkyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 12 carbon atoms, and substituted aryl groups; preferred R 1 R 2 and R 3 Whether the carbon atoms are the same or different, the alkyl group can be 2 to 20, and the aryl or substituted aryl group can be 6 to 8; more preferably, the alkyl group can be 2 to 12, and the aryl or substituted aryl group can be 6; preferably, the alkyl group has 2 to 6 carbon atoms, and the aryl or substituted aryl group has 6 to 7 carbon atoms; preferably: triethylboron, tripropylboron, tributylboron, trisec-butylboron, tripentylboron, trihexylboron, ethyldiphenylboron, triphenylboron, tri-p-fluorophenylboron, tri-o-fluorophenylboron, tri(2,6-difluorophenyl)boron, tri(2,4,6-trifluorophenyl)boron, tri(pentafluorophenyl)boron, tri(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)boron.

[0077] Specifically, the isobutylene and its derivatives are preferably: isobutylene, 2-methyl-1-butene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-undecene, and limonene.

[0078] Specifically, the organic solvent can be any solvent, as long as it is inert in the polymerization reaction. Such solvents may include one or more mixtures of petroleum ether, n-hexane, cyclohexane, cyclopentane, toluene, xylene, chlorobenzene, decahydronaphthalene, dichloromethane, dichloroethane, etc.

[0079] Specifically, the radical initiator can be appropriately selected from the azo-based radical initiators, peroxide-based radical initiators and the like in the prior art. As the azo-based radical initiator, azobisisobutyronitrile (AIBN), azobisisoheptyl nitrile, azobisdimethoxyisopropyl nitrile, dimethyl azobis isobutyrate (AIBME) and the like can be listed. As the peroxide-based radical initiator, dibenzoyl peroxide (BPO), lauryl peroxide (LPO), di-tert-butyl peroxide (DTBP), dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, diisopropyl peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, diethoxyethyl peroxydicarbonate and the like percarbonate compounds; tert-butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate and the like peroxyester compounds; acetyl cyclohexyl sulfonyl peroxide, diisobutyryl peroxide; 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicyclohexyl peroxydicarbonate, benzoyl peroxide / N,N-dimethylaniline and the like can be listed, which can be one or more of the above initiators.

[0080] Specifically, maleic anhydride: radical initiator = (5000-50):1 (molar ratio); maleic anhydride: Lewis acid = (5000-0.1):1 (molar ratio).

[0081] Specifically, there is no special requirement for the monomer concentration, and the polymerization can be carried out in a bulk polymerization or in a relatively dilute solution.

[0082] Specifically, the molar ratio of isobutene and its derivatives to maleic anhydride = (1000-0.5):1.

[0083] Specifically, the polymerization time is 0.1-24 hours, and most preferably 1-5 hours.

[0084] Specifically, the reaction temperature is 20-150°C, and most preferably 50-100°C.

[0085] The above content of the present application provides the application of Lewis acid in the preparation of isobutene or its derivatives-maleic anhydride alternating copolymer and a preparation method of isobutene or its derivatives-maleic anhydride alternating copolymer. The present application applies Lewis acid in the free radical copolymerization preparation process of α-olefin / maleic anhydride alternating copolymer. When the Lewis acid and the radical initiator are used simultaneously to initiate the copolymerization catalytic system of isobutene and its derivatives and maleic anhydride, the copolymerization activity is greatly improved. That is, under the same conditions, the introduction of Lewis acid can greatly improve the yield of the polymer. Moreover, the molecular weight of the prepared copolymer is also significantly improved.

[0086] The application uses the Lewis acid as a cocatalyst together with the radical initiator in the isobutyl and its derivatives and maleic anhydride copolymerization catalytic system, which can significantly improve the copolymerization activity of isobutene and its derivatives and maleic anhydride, reduce the polymerization temperature, shorten the polymerization reaction time, reduce the energy consumption, significantly improve the production efficiency, inhibit the chain transfer reaction phenomenon and improve the molecular weight of the copolymer.

[0087] The experimental results show that the introduction of the Lewis acid and the radical initiator into the isobutene and its derivatives and maleic anhydride copolymerization process can realize the high-activity copolymerization of isobutene and its derivatives and maleic anhydride at a lower temperature, reduce the production energy consumption, improve the production efficiency, inhibit the chain transfer effect and improve the molecular weight of the copolymer.

[0088] In order to further illustrate the application, the application of the Lewis acid provided by the application in the preparation of isobutene or its derivative-maleic anhydride alternating copolymer and a preparation method of isobutene or its derivative-maleic anhydride alternating copolymer are described in detail in the following examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the application, and detailed implementation modes and specific operation processes are given, which are only for further illustrating the features and advantages of the application, and are not a limitation on the claims of the application, and the protection scope of the application is not limited to the following examples.

[0089] The application does not have special limitations on the sources of the raw materials in the following examples, and the raw materials can be prepared by the preparation methods well known to those skilled in the art or purchased on the market.

[0090] Performance test method and standard

[0091] The molecular weight of the polymer is tested by using a normal temperature gel chromatograph at 40 DEG C, using DMF as a mobile phase (containing 0.5wt% NnBu4Br) and using standard polystyrene as a reference sample.

[0092] The glass transition temperature of the polymer is tested by using a differential scanning calorimeter (DSC), and the temperature rising and falling rate is 10 DEG C / min, and the scanning range is 25-300 DEG C.

[0093] Example 1

[0094] Maleic anhydride (50 mmol), AIBN (0.5 mmol), co-catalyst tris(pentafluorophenyl)boron (B(C6F5)3, 1 mmol) and 10 mL of toluene were charged into a reaction vessel under anhydrous and anaerobic conditions, followed by isobutene (51 mmol) and the polymerization vessel was then placed in an oil bath at 60°C for 6 minutes. Then, the reaction was terminated by adding methanol and dried in a vacuum oven at 60°C to constant weight to obtain a white solid powder 7.7 grams with 100% conversion (calculated based on the conversion of maleic anhydride) and Mw= 16.2 x 104, Mn= 8.1 x 103, Mz= 2.01 x 104, Tg= 216. n 4 w n g

[0095] Examples 2 to 5

[0096] Referring to Table 1, Table 1 is a summary of the polymerization conditions and results of Examples 1 to 5 and Comparative Examples of the present application.

[0097] Examples 2 to 5 and Comparative Examples 1 to 3 were the same as Example 1 except for the conditions described in the table.

[0098] Table 1

[0099]

[0100] Example 6

[0101] Maleic anhydride (50 mmol), benzoyl peroxide / N,N-dimethylaniline (0.35 mmol), co-catalyst tris(pentafluorophenyl)boron (B(C6F5)3, 1 mmol) and 10 mL of toluene were charged into a reaction vessel under anhydrous and anaerobic conditions, followed by isobutene (50 mmol) and the polymerization vessel was then placed in an oil bath at 20°C for 24 minutes. Then, the reaction was terminated by adding methanol and dried in a vacuum oven at 60°C to constant weight to obtain a white solid powder 6.8 grams with 88% conversion (calculated based on the conversion of maleic anhydride) and Mw= 31.3 x 104, Mn= 15.6 x 103, Mz= 2.35 x 104, Tg= 216. n 4 w n g

[0102] Examples 7 to 17

[0103] Referring to Table 2, Table 2 is a summary of the polymerization conditions and results of Examples 6 to 17 of the present application.

[0104] ​​​​​​​​​​Examples 7-17 and Comparative Example 4 were prepared under the same polymerization conditions as Example 6 except for the conditions described in the table.

[0105] Table 2

[0106]

[0107]

[0108] See Figure 1 , Figure 1 DSC thermogram of isobutylene-maleic anhydride alternating copolymer D prepared in accordance with Example 6 of the present application.

[0109] The above detailed the application of the Lewis acid provided by the present application in the preparation of isobutylene or its derivative-maleic anhydride alternating copolymer, a method for preparing an isobutylene or its derivative-maleic anhydride alternating copolymer. The principles and modes of operation of this application have been described in terms of particular embodiments. The specification and examples are only intended to illustrate the method of the present application and the core idea, including the best mode, and also enable any person skilled in the art to practice the present application, including the manufacture and use of any devices or systems, and the implementation of any combined method. It should be noted that for those skilled in the art, certain improvements and modifications can be made to the present application without departing from the principles of the present application, and these improvements and modifications also fall within the scope of protection of the claims of the present application. The scope of protection of the present application is defined by the claims, and can include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. Application of Lewis acids in the preparation of isobutylene or its derivatives-maleic anhydride alternating copolymers; The isobutylene or its derivative-maleic anhydride alternating copolymer is an alternating copolymer of isobutylene or its derivative and maleic anhydride in a copolymerization ratio of 1:1; The Lewis acid includes organoboron compounds; The preparation method involves free radical copolymerization under the conditions of Lewis acid and free radical initiator.

2. The application according to claim 1, characterized in that, The isobutylene derivatives include one or more of 2-methyl-1-butene, 2-methyl-1-heptene, 2-methyl-1-octene, 2-methyl-1-undecene, and limonene; The molar ratio of isobutylene or its derivative to maleic anhydride is (0.5~100):

1.

3. The application according to claim 1, characterized in that, The Lewis acid is used as a cocatalyst; The molar ratio of maleic anhydride to Lewis acid is (0.1~5000):

1.

4. The application according to claim 3, characterized in that, The general formula of the organoboron compound is BR 1 R 2 R 3 Among them, R 1 R 2 and R 3 The same or different, the R 1 ~R 3 Each is independently selected from substituted or unsubstituted alkyl groups and substituted or unsubstituted aryl groups; The specific application is to enhance copolymerization activity and increase the molecular weight of isobutylene or its derivatives in alternating copolymers with maleic anhydride.

5. The application according to claim 4, characterized in that, The alkyl group includes alkyl groups having 1 to 30 carbon atoms; The aryl group includes aryl groups having 6 to 12 carbon atoms; The molar ratio of maleic anhydride to free radical initiator is (50~5000):1; The preparation method specifically includes the combined action of Lewis acid and free radical initiator under anhydrous and oxygen-free conditions.

6. The application according to claim 3, characterized in that, The free radical initiator includes azo-based free radical initiators and / or peroxide-based free radical initiators; The azo-based free radical initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azodimethoxyisoheptanenitrile, and dimethyl azobisisobutyrate; The peroxide-based free radical initiators include one or more of the following: benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl pervalerate, diisopropyl peroxide, bis(2-ethylhexyl) peroxide, diethoxyethyl peroxide, tert-butyl peroxyneodecanate, α-cumyl peroxyneodecanate, tert-butyl peroxyneodecanate, acetylcyclohexylsulfonyl peroxide, diisobutyryl peroxide 2,4,4-trimethylpentyl-2-peroxyphenoxyacetic acid ester, methyl ethyl ketone peroxide, cyclohexanone peroxide, dicyclohexyl peroxide, and benzoyl peroxide / N,N-dimethylaniline.

7. A method for preparing an alternating copolymer of isobutylene or its derivatives with maleic anhydride, characterized in that, Includes the following steps: Under the action of Lewis acid and under anhydrous and oxygen-free conditions, isobutylene or its derivatives and maleic anhydride monomers are copolymerized to obtain an alternating copolymer of isobutylene or its derivatives and maleic anhydride. The isobutylene or its derivative-maleic anhydride alternating copolymer is an alternating copolymer of isobutylene or its derivative and maleic anhydride in a copolymerization ratio of 1:1; The Lewis acid includes organoboron compounds; The preparation method involves free radical copolymerization under the conditions of Lewis acid and free radical initiator.

8. The preparation method according to claim 7, characterized in that, The molar ratio of isobutylene or its derivative to maleic anhydride is (0.5~1000):1; The raw materials for the copolymerization reaction also include organic solvents; The organic solvent includes one or more of petroleum ether, n-hexane, cyclohexane, cyclopentane, toluene, xylene, chlorobenzene, decahydronaphthalene, dichloromethane, and dichloroethane.

9. The preparation method according to claim 7, characterized in that, The organoboron compounds include one or more of triethylboron, tripropylboron, tributylboron, trisec-butylboron, tripentylboron, trihexylboron, ethyldiphenylboron, triphenylboron, tri-p-fluorophenylboron, tri-o-fluorophenylboron, tri(2,6-difluorophenyl)boron, tri(2,4,6-trifluorophenyl)boron, tri(pentafluorophenyl)boron, and tri(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)boron.

10. The preparation method according to claim 7, characterized in that, The copolymerization temperature is 20~150℃; The copolymerization time is 0.1 to 24 hours; The copolymerization process also includes filtration and / or drying steps.

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