CN1803888A - Method for preparing polyether imide copolymer by bisubstituted compound and bisphenol - Google Patents

Abstract

The disclosed polyetherimide copolymer is copolymerized in dichloro-benzenes with the material with disubstituted phthalimide, diamine as NH2-R-NH2 and proper NH2-R-NH2 and 4, 4-dichlorodiphenyl sulfone. This invention reduces cost, simplifies process, and can recover the solvent conveniently.

Description

Method for preparing polyetherimide copolymer with double substituted compound and bisphenol

technical field

The invention belongs to a method for preparing a polyetherimide copolymer from a disubstituted compound and bisphenol.

Background technique

As a polymer material, polyetherimide has attracted much attention due to its unique properties and wide application prospects. However, due to the high cost of polyimide synthesized from dianhydride and diamine as monomers, polyetherimide Its application in a wider range is limited. The direct synthesis method using substituted phthalic anhydride as raw material without dianhydride can reduce its cost. As early as 1974, General Electric Company of the United States (GE Co.) just disclosed the patent (US pat. The obtained polyetherimide molecular weight of the method is low, is difficult to apply. In 1997, the company disclosed a method for synthesizing high molecular weight polyetherimide by first preparing bisphenol disodium salt, but the yield of bisphenol was only 50%, so it did not reduce its production cost the goal of. Polyetherimides can also be prepared from bis-nitrophthalimides and bisphenols, but except for individual varieties, the molecular weight of the resulting polymerization is also low (Polymer Science Journal: Polymer Chemistry Edition, 1980, Vol, 18 , 3069-3080. Journal of Polymer Science: Polymer Chemistry Edition, 1980, Vol, 18, 3069-3080). Therefore, it is very important to seek a method for directly synthesizing high-molecular-weight polyetherimide copolymers from lower-priced bis-chlorinated compounds and bis-substituted phthalimides in high yields to reduce costs significantly.

Contents of the invention

In order to seek a method for directly synthesizing high-molecular-weight polyetherimide copolymers from lower-priced bis-chlorinated compounds and bis-substituted phthalimides in high yields. The object of the present invention is to provide a kind of method that disubstituted phthalimide, 4,4-dichlorodiphenyl sulfone and bisphenol prepare polyetherimide copolymer, reduce polyetherimide by this method preparation cost.

The advantage of the present invention is that there is no need to synthesize bisphenolate separately, and after completing the salt-forming reaction between bisphenol and alkali in the reflux process, add disubstituted phthalimide and 4,4-dichlorobisphenyl to the system Sulfone is polymerized in diphenyl sulfone to obtain polyetherimide copolymer.

The chemical reaction formula of the present invention is as follows:

The preparation method of the present invention is to adopt any compound of the following raw material components and 4,4-dichlorodiphenyl sulfone to copolymerize in diphenyl sulfone to obtain a disubstituted compound and bisphenol to prepare a polyetherimide copolymer:

(1). Disubstituted phthalimide:

Bis(4-X substituted phthalimide)                                                                          

Bis(3-X substituted phthalimide)

where X = Cl, Br, F, _NO2

(2). Diamine: NH ₂ -R-NH ₂ is selected from the following diamines:

m-phenylenediamine 4,4`-biphenylenediamine 4,4`-diamino-diphenoxy-4``,4```-biphenyl

4,4`-Diaminodiphenyl ether

3,3`-dimethyl-4,4`-diamino-diphenylmethane p-phenylenediamine

4,4`-Diamino-diphenyl sulfide

4,4`-Diamino-diphenyl isopropane 4,4`-Diamino-diphenyl-4``,4```-phenylene ether

(3). Bisphenol

2,2-Bis(4-hydroxyphenyl)isopropane Hydroquinone Bis(4-hydroxyphenyl)methane

Hydroquinone 4,4-Dihydroxydiphenyl Ether 4,4-Dihydroxydiphenyl Sulfide

4,4'-Dihydroxydiphenylsulfone 4,4'-Dihydroxydiphenylphenylmethane 4,4'-Dihydroxybenzophenone

The alkali used is: sodium carbonate, potassium carbonate, potassium hydroxide or sodium hydroxide; using diphenyl sulfone as a solvent;

The synthesis steps and conditions are as follows:

The mass ratio of bisphenol, disubstituted phthalimide and 4,4-dichlorodiphenyl sulfone to diphenyl sulfone is 1:2-10; bisphenol: disubstituted phthalimide and 4,4 -Dichlorodiphenylsulfone (molar ratio) is 1:1, the ratio of disubstituted phthalimide and 4,4-dichlorodiphenylsulfone is arbitrary; bisphenol: base (molar ratio) is 1 : 2～2.2, wherein the concentration of NaOH or KOH solution is 40%; Na ₂ CO ₃ or K ₂ CO ₃ is an anhydrous compound, weigh the bisphenol component according to the above ratio and add it into a three-necked container, pass nitrogen Deoxygenation, add water-carrying agent xylene, reflux with water for 2 to 15 hours, add disubstituted phthalimide and 4,4-dichlorodiphenyl sulfone according to the above ratio, and polymerize at 160°C to 300°C for 2 -20 hours; pour the resulting polymer solution into 3% dilute hydrochloric acid in a thin stream, filter, and grind; extract the solvent with acetone or ethanol to obtain a disubstituted compound and bisphenol to prepare polyetherimide copolymerization things. Its intrinsic viscosity is 0.1~1.0dl/g.

The beneficial effects of the present invention are as follows:

Provided is a method for preparing polyetherimide copolymer from disubstituted phthalimide, 4,4-dichlorodiphenyl sulfone and bisphenol, and the method can reduce the preparation cost of polyetherimide. Moreover, there is no need to synthesize bisphenolate alone, but directly complete the salt-forming reaction between bisphenol and alkali in the reflux process, and then add disubstituted phthalimide and 4,4-dichlorodiphenyl sulfone to the system in dichlorodiphenyl sulfone Polymerized in phenylsulfone to obtain polyetherimide copolymer. The solvent diphenyl sulfone used in this method can be recovered and reused conveniently.

Detailed ways:

Example 1:

Add 0.01 moles (2.28g) of bisphenol A, 14.7 grams of diphenylsulfone and 0.02 moles (2.0g) of 40% NaOH solution into a three-neck flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 2 hours Afterwards, add 0.009 mole (4.761g) of 4,4'-bis(4-chlorophthalimide) diphenyl ether, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone, at 160 ℃ polymerization reaction for 20 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.32dL/g.

Example 2:

Add 0.01 moles (2.28g) of bisphenol A, 45 grams of diphenyl sulfone and 0.02 moles (2.0g) of 40% NaOH solution into a three-neck flask, pass nitrogen to remove oxygen, add 40 milliliters of xylene, and reflux with water for 4 hours After that, add 0.009 mole (4.761g) of 4,4'-bis(4-chlorophthalimide) diphenyl ether, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone at 300 ℃ polymerization reaction for 2 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with acetone, and the intrinsic viscosity of the obtained polymer was 0.65dL/g.

Example 3

Add 0.01 moles (2.28g) of bisphenol A, 45 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH solution into a three-neck flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 4 hours Finally, add 0.009 mole (4.932g) of 4,4'-bis(4-nitrophthalimide) diphenyl ether, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone, in Polymerization at 180°C for 200 hours. The obtained polymer solution was poured into 3% dilute hydrochloric acid in a trickle, filtered and ground. The solvent was extracted with acetone and ethanol, and the intrinsic viscosity of the obtained polymer was 0.47dL/g.

Example 4:

Add 0.01 moles (2.28g) of bisphenol A, 80 grams of diphenyl sulfone and 0.022 moles (2.2g) of 40% NaOH into a three-neck flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 4 hours , add 0.009 mole (5.544g) of 4,4'-bis(4-bromophthalimide) diphenyl ether, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone, at 250°C Polymerization was carried out for 3 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.25dL/g.

Example 5:

Add 0.01 moles (1.10g) of hydroquinone, 45 grams of diphenyl sulfone and 0.021 moles (2.1g) of 40% NaOH into a three-necked flask, remove oxygen and nitrogen, add 25 milliliters of xylene, and bring water under reflux for 4 hours Finally, add 0.009 mole (4.446g) of 4,4'-bis(3-fluorophthalimide) diphenyl ether, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone at 190°C Polymerization was carried out for 4 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with acetone and ethanol, and the intrinsic viscosity of the obtained polymer was 0.61dL/g.

Embodiment 6:

Add 0.01 moles (2.28g) of bisphenol A, 45 grams of diphenyl sulfone and 0.02 moles (2.0g) of 40% NaOH into a three-neck flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 4 hours , add 0.007 mole (3.836g) of 4,4'-bis(3-nitrophthalimide) diphenyl ether, 0.003 mole (0.861g) of 4,4-dichlorodiphenyl sulfone, at 200 ℃ polymerization reaction for 20 hours. The obtained polymer solution has been poured into 3% dilute hydrochloric acid in a trickle, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 1.0dL/g.

Embodiment 7:

Add 0.01 moles (2.0g) of 4,4-dihydroxydiphenylmethane, 50 grams of diphenyl sulfone and 0.02 moles (2.76g) of K ₂ CO ₃ into the three-necked flask, remove oxygen and nitrogen, and add 25 milliliters of xylene After reflux with water for 15 hours, add 0.008 mole (4.384g) of 4,4'-bis(3-nitrophthalimide) diphenyl ether, 0.002 mole (0.574g) of 4,4-dichloro Substituted diphenyl sulfone, polymerized at 250°C for 6 hours. The obtained polymer solution was poured into 3% dilute hydrochloric acid in a trickle, filtered and ground. The solvent was extracted with acetone and ethanol, and 40 grams of diphenyl sulfone was recovered. The intrinsic viscosity of the obtained polymer was 0.47 dL/g.

Embodiment 8:

Add 0.01 moles (2.14g) of 4,4-dihydroxybenzophenone, 45 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH into the three-necked flask, pass nitrogen to remove oxygen, and add 25 milliliters of xylene , after refluxing with water for 10 hours, add 0.005 mole (2.73g) of 4,4'-bis(3-nitrophthalimide) diphenylmethane, 0.005 mole (1.435g) of 4,4-dichloro Substituted diphenyl sulfone, polymerized at 250°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with acetone, and the intrinsic viscosity of the obtained polymer was 0.42dL/g.

Embodiment 9:

Add 0.01 moles (2.02g) of 4,4-dihydroxydiphenyl ether, 25 grams of diphenyl sulfone and 0.02 moles (2.76g) of K ₂ CO ₃ into the three-necked flask, pass nitrogen to remove oxygen, and add 25 milliliters of xylene , after reflux with water for 4 hours, add 0.001 mole (5.74g) of 3,3'-dimethyl-4,4'-bis(3-nitrophthalimide) diphenylmethane, 0.009 mole (2.583 g) 4,4-dichlorodiphenyl sulfone, polymerized at 250°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.56dL/g.

Example 10:

0.01 moles (1.10g) of resorcinol, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH solution were added to the there-necked flask, nitrogen was passed through to remove oxygen, 25 milliliters of xylene was added, and water was brought back to flow for 4 After 1 hour, add 0.003 mol (4.879g) of 4,4`-bis(4-chlorophthalimide)diphenoxy-4,4``-biphenyl, 0.007 mol (2.009g) of 4, 4-Dichlorodiphenylsulfone, polymerized at 200°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.41dL/g.

Example 11:

Add 0.01 moles (2.18g) of 4,4'-dihydroxydiphenyl sulfide, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH into the three-necked flask, pass nitrogen to remove oxygen, and add 25 ml Xylene, after refluxing with water for 4 hours, add 0.009 mole (3.933g) of N,N-m-phenyl-bis(4-chlorophthalimide), 0.001 mole (0.287g) of 4,4-bis Chlorodiphenyl sulfone, polymerized at 250°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.21dL/g.

Example 12:

Add 0.01 moles (2.76g) of 4,4-dihydroxy-diphenylphenylmethane, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH solution into the three-necked flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, after reflux with water for 4 hours, add 0.009 mole (5.589g) of 4,4`-bis(4-chlorophthalimide)diphenyl-4``,4```-benzene Diether, 0.001 mole (0.287g) of 4,4-dichlorodiphenylsulfone, polymerized at 250°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.28dL/g.

Example 13:

Add 0.01 mole (1.10g) of hydroquinone, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH solution into the three-necked flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and bring water under reflux for 12 After one hour, add 0.008 mole (4.104g) of 4,4'-bis(4-chlorophthalimide) biphenyl, 0.002 mole (0.574g) of 4,4-dichlorodiphenyl sulfone, in Polymerization at 240°C for 12 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with acetone, and the intrinsic viscosity of the obtained polymer was 0.27dL/g.

Example 14:

Add 0.01 moles (2.18g) of 4,4-dihydroxydiphenylsulfide, 50 grams of diphenyl sulfone and 0.02 (2g) moles of 40% NaOH into a three-necked flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, After refluxing with water for 15 hours, add 0.009 mol (3.825g) of 4,4'-bis(4-chlorophthalimide)diphenyl sulfone, 0.001 mol (0.287g) of 4,4-dichlorobis Phenylsulfone, polymerized at 220°C for 6 hours. The obtained polymer solution was poured into 3% dilute hydrochloric acid in a trickle, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.39dL/g.

Example 15:

Add 0.01 moles (1.10g) of hydroquinone, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH into a three-necked flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 4 hours Finally, add 0.009 mol (4.995g) of 3,3'-dimethyl-bis(3-chlorophthalimide)-4,4'-diphenylmethane, 0.001 mol (0.287g) of 4,4 -Dichlorodiphenylsulfone, polymerized at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.63dL/g.

Example 16:

Add 0.01 mole (1.10g) of hydroquinone, 50 grams of diphenylsulfone and 0.02 moles (2.8g) of 40% KOH solution into the three-necked flask, remove oxygen and nitrogen, add 25 milliliters of xylene, and bring water under reflux for 12 Hours later, add 0.007 mol (3.815g) of 4,4'-bis(4-chlorophthalimide)-diphenylsulfide, 0.003 mol (0.867g) of 4,4-dichlorodiphenyl sulfone , Polymerized at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and 38 grams of diphenyl sulfone was recovered, and the intrinsic viscosity of the obtained polymer was 0.40 dL/g.

Example 17:

Add 0.01 mole (1.10g) of hydroquinone, 35 grams of diphenylsulfone and 0.02 moles (2.8g) of 40% KOH solution into the there-necked flask, remove oxygen and nitrogen, add 25 milliliters of xylene, and bring water under reflux for 4 After 1 hour, add 0.009 mol (4.995g) of 3,3'-dimethyl-bis(4-chlorophthalimide) diphenylmethane, 0.001 mol (0.287g) of 4,4-dichlorobis Phenylsulfone, polymerized at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.59dL/g.

Example 18:

Add 0.01 mole (1.10g) of hydroquinone, 50 grams of diphenylsulfone and 0.02 moles (2.0g) of 40% NaOH solution into the there-necked flask, pass nitrogen to deoxygenate, add 25 milliliters of xylene, bring water under reflux for 4 After one hour, add 0.008 mole (3.496g) of N,N-p-phenyl-bis(4-chlorophthalimide), 0.002 mole (0.574g) of 4,4-dichlorodiphenyl sulfone, in Polymerization at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and 40 grams of diphenyl sulfone was recovered, and the intrinsic viscosity of the obtained polymer was 0.29 dL/g.

Example 19:

Add 0.01 mole (1.10g) of hydroquinone, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH solution into the three-necked flask, remove oxygen and nitrogen, add 25 milliliters of xylene, and bring water under reflux for 4 After one hour, add 0.009 mol (4.995g) of 4,4'-bis(4-chlorophthalimide) diphenylisopropane, 0.001 mol (0.287g) of 4,4-dichlorodiphenyl sulfone , Polymerized at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with acetone and ethanol, and the intrinsic viscosity of the obtained polymer was 0.43dL/g.

Example 20:

Add 0.01 moles (1.10g) of hydroquinone, 50 grams of diphenyl sulfone and 0.02 moles (2.12g) of Na ₂ CO ₃ into the three-necked flask, remove oxygen and nitrogen, add 25 milliliters of xylene, bring water back to 4 After one hour, add 0.009 mole (3.825g) of 4,4'-bis(3-chlorophthalimide) diphenyl sulfone, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone, in Polymerization at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.13dL/g.

Example 21:

Add 0.01 moles (1.10g) of hydroquinone, 50 grams of diphenyl sulfone and 0.02 moles (2.8g) of 40% KOH into a three-necked flask, pass nitrogen to remove oxygen, add 25 milliliters of xylene, and reflux with water for 4 hours Finally, add 0.009 mole (4.743g) of 4,4'-bis(4-chlorophthalimide)-diphenylmethane, 0.001 mole (0.287g) of 4,4-dichlorodiphenyl sulfone, in Polymerization at 230°C for 6 hours. The resulting polymer solution was poured into 3% dilute hydrochloric acid in a thin stream, filtered and ground. The solvent was extracted with ethanol, and the intrinsic viscosity of the obtained polymer was 0.33dL/g.

Claims (1)

1. bisubstituted compound and bis-phenol prepare the method for polyether imide copolymer, it is characterized in that: be any one compound and 4 that adopts following starting material component, the copolymerization in sulfobenzide of 4-dichloro-sulfobenzide obtains bisubstituted compound and bis-phenol prepares polyether imide copolymer:

(1). two replacement phthalimides:

Two (4-X replaces for phthalimide), 3-X replaced phthalimide, and 4-X replaces phthalimide

X=Cl wherein, Br, F, NO ₂

Two (3-X replaces phthalimide)

(2). diamine: NH ₂-R-NH ₂Be selected from following diamines:

Mphenylenediamine 4,4`-benzidine 4,4`-diamino-two phenoxy groups-4``, 4```-biphenyl

4,4`-diaminodiphenyl oxide 4,4`-diamino-ditane

3,3`-dimethyl-4,4`-diamino-ditane Ursol D

4,4`-diamino-diphenyl sulfide 4,4`-diamino-sulfobenzide

4, the different propane 4 of 4`-diamino-phenylbenzene, 4`-diamino-phenylbenzene-4``, 4```-benzene diether

(3). bis-phenol

2, two (4-hydroxy phenyl) methane of two (4-hydroxy phenyl) the different propane Resorcinol of 2-

Resorcinol 4,4-dihydroxy diphenyl ether 4,4-dihydroxyl diphenyl sulfide

4,4 '-dihydroxy diphenylsulphone 4,4 '-dihydroxyl diphenyl benzene methylmethane 4,4 '-dihydroxy benzophenone

Used alkali is: yellow soda ash, salt of wormwood, potassium hydroxide or sodium hydroxide; The employing sulfobenzide is a solvent;

Synthesis step and condition are as follows:

Bis-phenol and two phthalimides, 4 that replace, 4-dichloro-sulfobenzide quality and with the quality proportioning of sulfobenzide be 1: 2-10; Bis-phenol: two replacement phthalimides and 4,4-dichloro-sulfobenzide (mol ratio) is 1: 1; Bis-phenol: alkali (mol ratio) is 1: 2～2.2, and wherein NaOH or KOH strength of solution are 40%; Na ₂CO ₃Or K ₂CO ₃Be anhydrous compound, take by weighing the bis-phenol component and it is joined in three mouthfuls of containers by said ratio, letting nitrogen in and deoxidizing, add band aqua dimethylbenzene, reflux and be with water 2～15 hours, add two phthalimides and 4 that replace by said ratio, 4-dichloro-sulfobenzide, 160 ℃～300 ℃ polyreaction 2-20 hour; The polymers soln of gained poured into the thread shape contain in 3% the dilute hydrochloric acid, filter, grind; Extract solvent with acetone or alcohol, obtain bisubstituted compound and bis-phenol prepares polyether imide copolymer.