DERIVATIZED POLYIMIDES AND METHODS OF MAKING AND USING

Abstract

The present invention provides comb polymer compositions comprising phosphorus acid group containing backbone polymers of six-membered cyclic methacrylic imide having one or more side chain ether group containing N-substituent chosen from an ether group, a polyether group, an etheramine group, a polyetheramine group, an ether group crosslinking the backbone polymer chains, and a polyether group crosslinking the backbone polymer chains. The backbone polymers comprise from 60 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units, regardless of their form, and from 7.5 to 95 wt. % of such polymerized units as methacrylic anhydride groups or six-membered cyclic methacrylic imide groups.

Claims

1. A comb polymer composition comprising a phosphorus acid group containing, backbone polymer of six-membered cyclic methacrylic imide having one or more side chain ether group containing N-substituent on a six-membered cyclic methacrylic imide chosen from an ether group, a polyether group, an etheramine group, a polyetheramine group, an ether group crosslinking the backbone polymer chains, and a polyether group crosslinking the backbone polymer chains, and, further, having at least one group chosen from a methacrylic acid group in polymerized form, its quaternary ammonium carboxylate its metal carboxylate, an ester side chain group, and anamide side chain group, wherein the side chain group is chosen from a hydrophobic ester or amide side chain, a polyether ester side chain, a polyether amide side chain, group, and combinations thereof, wherein the backbone polymer comprises from 60 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units, regardless of their form.

2. The comb polymer compositions as claimed in claim 1, wherein the backbone polymer comprises a hypophosphite group containing backbone polymer.

3. The comb polymer compositions as claimed in claim 1, wherein the backbone polymer comprises from 90 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units, regardless of their form.

4. The comb polymer compositions as claimed in claim 1, wherein from 7.5 to 95 wt. % of the methacrylic acid polymerized units are in the form of methacrylic anhydride groups or six-membered cyclic methacrylic imide groups which are formed from the methacrylic anhydride groups, as determined by titration of the backbone polymers containing methacrylic anhydride groups prior to forming the six-membered cyclic methacrylic imide groups to determine the total number methacrylic anhydride groups therein.

5. The comb polymer compositions as claimed in claim 4, wherein from 60 to 70 wt. %, of the methacrylic acid polymerized units are in the form of six-membered cyclic methacrylic imide groups or methacrylic anhydride groups.

6. The comb polymer compositions as claimed in claim 1, wherein the phosphorus acid group containing backbone polymers of six-membered cyclic methacrylic imide of the present invention, excluding the weight of any side chain groups or salt groups in the backbone polymers, have a weight average molecular weight (Mw) of from 1,000 to 25,000.

7. The comb polymer compositions as claimed in claim 1, wherein the phosphorus acid group containing backbone polymers of six-membered cyclic methacrylic imide further containing one or more methacrylic anhydride group or six-membered cyclic methacrylic anhydride group.

8. The comb polymer compositions as claimed in claim 1, wherein the phosphorus acid group containing backbone polymers of six-membered cyclic methacrylic imide of the present invention have one or more hypophosphite group and comprise from 1 to 20 wt. % of the hypophosphite compound or its salts in polymerized form, based on the total weight of reactants used to make the backbone polymer.

9. The comb polymer compositions as claimed in claim 1, wherein the ether group containing N-substituent is chosen from an ethoxy group, a propoxy group, a diethylene glycol, a dipropylene glycol, a polyether of ethylene oxide repeat units, preferably, a polyether of at least 90 wt. % of ethylene oxide repeat units, a polyether of propylene oxide repeat units, a polyether having ethylene oxide and propylene oxide units, and mixtures and combinations thereof.

10. The comb polymer compositions as claimed in claim 1, wherein the comb polymer has an Mw of from 1200 to 1,500,000 as determined as that of the backbone polymer in fully hydrolyzed form prior to the formation of any six-membered cyclic methacrylic imide groups thereon by GPC against a polyacrylic acid standard plus the total amount of any N-substituent groups, salts, quaternary ammonium groups, ester side chain groups, or amide side chain groups reacted with or contained in the backbone polymer as determined by N-substituent group yield, ester side chain yield, and amide side chain yield from any alcohol or amine compound as determined by NMR

11. A method for making comb polymers which are phosphorus acid group containing backbone polymers of six-membered cyclic methacrylic imide having one or more ether group containing N-substituents chosen from an ether group, a polyether group, an etheramine group, a polyetheramine group, an ether group crosslinking the backbone polymer chains, and a polyether group crosslinking the backbone polymer chains comprising: aqueous solution polymerizing a monomer mixture of methacrylic acid and/or its salt with one or more phosphorus acid compound to form a precursor polymer having methacrylic acid polymerized units; drying the precursor polymer in a melt at from 175 to 250° C., to form a methacrylic anhydride group containing backbone polymer having from 7.5 to 70 wt. % of the methacrylic acid polymerized units in the form of methacrylic anhydride, as determined by titration of the backbone polymer; reacting in a fluid medium, at from 0 to 220° C. the methacrylic anhydride group containing backbone polymer with one or more ether group containing amine compound in a molar amount of amine not to exceed the moles of methacrylic anhydride in the methacrylic anhydride group containing backbone polymer, as determined by titration, to form at least one ether group containing amic acid group, and then reacting in a fluid medium the ether group containing amic acid group with a neighboring methacrylic acid group on the backbone polymer at from 100 to 240° C. to form ether group containing N-substituents and six-membered cyclic methacrylic imide groups on the backbone polymer.

Description

EXAMPLES

[0104] The following examples illustrate the present invention. Unless otherwise indicated, all parts and percentages are by weight and all temperatures are in ° C.

[0105] Test Methods: In the Examples that follow, the following test methods were used:

[0106] Titration: The number of methacrylic anhydride groups present on a backbone polymer and the number of carboxylic acid groups present on a given precursor polymer or backbone polymer as a percentage of total methacrylic acid polymerized units in the polymer was determined by titration. First, the total free carboxylic acid content was measured by hydrolysis of the anhydride. A 0.1-0.2 g of each material was measured and put in a 20 ml glass vial. To this, 10 ml of deionized (DI) water was added and the closed vial was heated in 60° C. oven for 12 h. After 12 h, the vial was titrated against 0.5 N KOH (aq.) to determine acid number of the thus hydrolyzed polymethacrylic anhydride polymer (the total free carboxylic groups in the polymer). Next, the anhydride content was determined by reacting the same pMAAn material in its unhydrolyzed state with methoxy propyl amine (MOPA). MOPA opens the anhydride and reacts with one side, the other side is converted back to a carboxylic acid. For each polymer tested, 0.1-0.2 g of each pMAAn material along with 10 ml of tetrahydrofuran (THF) and 0.2-0.3 g of MOPA was added to a 20 ml glass vial equipped a with magnetic stirrer bar. The vial was closed and the mixture was stirred at room temperature overnight (about 18-20 h). Following this 10 ml of DI water was added and mixture was titrated against 0.5 N HCL (aq.) to determine the anhydride content. Titration was used to determine the overall disappearance of carboxylic acid in the polymer which indicates the conversion of carboxylic acid groups to anhydride. The calculated percentage of COOH (acid groups) converted into anhydride=(mols of anhydride in 1 g of polymer sampled)/(Total mols of —COOH in 1 g of hydrolyzed polymer sampled)*100. Instrument: Titralab TIM865 Titration Manager (Radiometer Analytical SAS, France); Reagents: 0.5 N KOH. 0.5 N HCl, Tetrahydrofuran (Sigma Aldrich. St Louis, Mo.).

[0107] Methacrylic Imide Content Verified by FTIR: For each polymethacrylic imide group containing polymer, the conversion of methacrylic anhydride groups in a corresponding methacrylic anhydride polymer into methacrylic imide groups was confirmed qualitatively by FTIR of the methacrylic imide group containing polymer itself.

[0108] FTIR: Methods A) or B) as described, above.

Synthesis Example 1

Methacrylic Anhydride Group Containing Backbone Polymer With 66.7 Wt. % of Methacrylic Anhydride Groups

[0109] Spray dried hypophosphite group containing polymethacrylic acid having an Mw of ˜5K was heated under vacuum (pressure 17 mm Hg). for 4 hrs. at 200° C. The spray dried material remains melted at about 185° C. and the melt is not agitated during the dehydration process. After cooling under vacuum the now solid mass is crushed and stored in anhydrous conditions. The resulting backbone polymer material has 66.7% of the polymerized methacrylic acid content been converted to anhydride, as determined by titration. The material contains equal moles of anhydride functionality and carboxylic functionality.

Synthesis Example 2

Methacrylic Anhydride Group Containing Backbone Polymer With 92.3 Wt. % of Methacrylic Anhydride Groups

[0110] The polymer was manufactured as described in U.S. Pat. No. 8,859,686, except that this material was subject to a second heat stage. A Haake PolyLab System™ (Model P300) mixer (Thermo-Fisher Scientific, Waltham, Ma.) comprising control of temperature and rotor speed, was used, made up of a Haake Rheomix™ 600P mixer fitted with a R600 bowl (120 mL chamber volume, excluding rotors; about 65 mL volume with rotors installed), in turn fitted with co-rotating (Rheomix™ 3000E) roller rotors (Thermo-Fisher) geared at a 3:2 ratio, a Haake Rheocord™ used to measure the torque established between the rotors, and Polylab™ Monitor V 4.18 control software provided as part of the system and used to control rotor speed, temperature and record torque, equipment and melt temperature. A mixing bowl was made of 301 stainless steel—DIN 1.4301 (SS-301, Deutsches Institut für Normung e.V., Berlin, DE, 2014); the rotors were made of 316 stainless steel—DIN 1.4408 (SS-316, 2014)).

[0111] A 35 g sample of powdered, spray dried hypophosphite group containing polymethacrylic acid (pMAA) having an Mw of ˜5K was introduced to the mixing bowl which was stabilized at 185° C. via a removable funnel. The screw speed was set to 50 PRM. The bowl temperature set points (i.e., all three) were set to 190° C. After the polymer had melted, shown by a spike in torque, a second 15 g batch of the pMAA was added; this was accompanied by a second torque spike. A nitrogen purge was implemented after the second batch of pMAA had melted to prevent the light powder from being blown out of the chamber; mixing was then continued at 190° C. for 10 minutes. Thereafter, the temperature was raised to 225° C. and run for 30 minutes. Rotor speed was reduced to 3 RPM and the immediately thereafter Haake bowl was removed while hot and the polymer inside removed and cooled before packaging. This step was done in ambient conditions and thus the hot material was exposed to moisture in the atmosphere. The material was removed from the bowl while still in a softened state. After cooling, the material removed from the Haake bowl was, in all cases, very brittle, with a fibrous texture. A second batch was made as above and the batches combined The combined methacrylic anhydride backbone polymer (pMAAn) batches were remixed in clean a Haake bowl as follows:

[0112] The Haake bowl was stabilized at 185° C., 35 g of powdered pMAAn (combined batches were ground together with mortar and pestal) was introduced to the bowl via the removable funnel. The screw speed was set to 50 PRM. The bowl temperature set points (i.e., all three) were set to 190° C. After the pMAAn backbone polymer had melted, shown by a spike in torque, the second 15 g batch of pMAAn was added; this was accompanied by a second torque spike. A nitrogen purge was implemented, and—mixing continued at 190° C. for 10 minutes. Then, the temperature was raised to 225° C. and run for 30 minutes; the rotor speed was reduced to 3 RPM and the immediately thereafter Haake bowl removed while hot and the polymer inside removed and cooled before packaging.

[0113] Titration of the resulting polymethylacrylic anhydride backbone polymer was found to contain 92.28 wt. % anhydride (i.e., of the original carboxylic acid, 7.72% remained as acid, the remainder being in anhydride form), based on the total weight of methacrylic acid polymerized units in the polymer.

Example 1

Reaction of Poly(methacrylic acid-co-methacrylic anhydride) of Synthesis Example 2 With Polyetheramine (˜19 EO Groups)

[0114] Into a 3-neck, 250 mL round bottom flask with Dean-Stark trap and condenser under a gentle nitrogen stream along with a magnetic stir bar was loaded anhydrous 1-methyl-2-pyrrolidone (100 ml) and the poly(methacrylic-co-methacrylic anhydride) of Synthesis Example 2 (1.535 grams). The apparatus was insulated, placed in a variable transformer regulated heating mantle sitting on a magnetic stir plate. Flask was gently warmed to dissolve polymer and is then cooled to room temperature. A Jeffamine™ M1000 polyetheramine (Huntsman Int'l LLC, 7.40 grams) was injected into the flask and stirred at room temperature under nitrogen for 72 hours. Toluene was loaded into the apparatus with 20 ml added to the Dean Stark trap and 25 ml added to the flask. Toluene was refluxed for 2.5 hours and then distilled and drained from the Dean-Stark trap. The resulting mixture was added to diethyl ether with product settling. Diethyl ether was decanted and product was reslurried in fresh diethyl ether with ether layer decanted four times more. Product was dried in a 70° C. vacuum oven. Dried product was mixed with KBr to prepare a pellet for FTIR per method B, disclosed above.

Example 2

Reaction of Poly(Methacrylic Acid-Co-Methacrylic Anhydride) of Synthesis Example 1 With Polyetheramine (˜19 EO Groups)

[0115] Into a 3-neck, 500 mL roundbottom flask with Dean-Stark trap and condenser under a gentle nitrogen stream along with a magnetic stir bar was loaded 1-methyl-2-pyrrolidione (278.7 grams) and toluene. Apparatus was insulated, placed in variable transformer regulated heating mantle sitting on a magnetic stir plate. Toluene was distilled into the Dean-Stark trap and subsequently drained. Flask was cooled under nitrogen to room temperature and the poly(methacrylic-co-methacrylic anhydride) (10.69 grams) was added to flask with flask contents warmed to about 180° C. to dissolve the polymer. Flask's contents are cooled to about room temperature with warm JEFFAMINE™ M1000 (40.04 grams) polyetheramine (Huntsman) injected into the flask and stirred overnight at room temperature. Toluene (45 mL) was added to the flask and flask was warmed to reflux for 5 hours into the Dean-Stark trap, then toluene was drained off. Reaction mixture was cooled to room temperature. Remaining solvent was stripped from product in warm vacuum oven with product being a clear, light yellow, viscous liquid while warm.

Example 3

Reaction of Poly(Methacrylic Acid-Co-Methacrylic Anhydride) of Synthesis Example 1 With Polyetheramine (˜19 EO Groups) (Alternative Method)

[0116] Into a 3-neck, 100 mL roundbottom flask with magnetic stir bar and fitted with inlet adaptor, stopper, and Dean-Stark trap with condenser and outlet adaptor was loaded N,N-dimethylacetamide (50 mL) and toluene (15 mL) with apparatus under a slow nitrogen sweep. Toluene was distilled and drained from the Dean-Stark trap. Poly(methacrylic acid-co-methacrylic anhydride, 2.10 grams, was added to the flask and warmed to dissolve in the N,N-dimethylacetamide to a temp of about 120° C. and then cooled. To the ambient temperature solution was added the Jeffamine™ M1000 (6.90 grams) polyetheramine was added. Mixture was stirred overnight at ambient temperature. Toluene was placed in the flask (10 mL) as well as filling the Dean-Stark trap. Toluene was refluxed for about 9 hours with toluene and water drained from the trap. Product solution has solvent removed in a 100° C. vacuum oven. Inherent viscosity of product=0.111 dL/g (30.0° C., 0.50 g/dL, N-methyl-2-pyrrolidinone).

Example 4

Reaction of Poly(Methacrylic Acid-Co-Methacrylic Anhydride) of Synthesis Example 1 With Polyetheramine (˜19 EO Groups) and a bis-amine polyether (˜4 PO groups)

[0117] Into a 3-neck, 100 mL roundbottom flask with magnetic stir bar and fitted with inlet adaptor, stopper, and Dean-Stark trap with condenser and outlet adaptor was loaded N,N-dimethylacetamide (50 mL) and toluene (15 mL) with apparatus under slow nitrogen sweep. Toluene was distilled and drained from the Dean-Stark trap. Poly(methacrylic acid-co-methacrylic anhydride)(50/50 mole/mole, 2.10 grams) was added to the flask and warmed to dissolve in the N,N-dimethylacetamide to a temp of about 120° C. and then cooled. To the ambient temperature solution was added Jeffamine™ D230 (0.196 grams) bis-amino polyether (Huntsman) and 6.5 hours later Jeffamine™ M1000 (6.94 grams) polyetheramine was added to the solution. Mixture was stirred overnight at ambient temperature. Toluene was placed in the flask (10 mL) as well as filling the Dean-Stark trap. Toluene was refluxed for about 9 hours with toluene and water drained from the trap. Product solution has solvent removed in a 100° C. vacuum oven. Inherent viscosity of product=0.124 dL/g (30.0° C., 0.50 g/dL, N-methyl-2-pyrrolidinone).

[0118] Example 4 demonstrates the increasing of molecular weight by use of small amount of a bis-amine polyether (Jeffamine™ D230 polymer) comprising a propylene oxide polyether. The increase in molecular weight was demonstrated by measuring inherent viscosity. Example 3 was a direct comparison as the method of reacting was the same except no D230 was used. The inherent viscosity increased from 0.111 dL/g (example 2) to 0.124 dL/g (example 3) indicating that an increase in molecular weight occurred which amounted to more than a 10% increase.

[0119] All FTIR spectra for all examples are shown in the Table, below with all examples done by method B with Comparative Example 1, done as KBr pellet sample, and Examples 3 and 4, done as polytetrafluoroethylene (PTFE) card sample.

TABLE-US-00001 TABLE FTIR Data from Comb Polymers Example #1 Example #3 Example #4 Band Strength Assignment Band Strength Assignment Band Strength Assignment 1801 W Cyclic 1801 W Cyclic anhydride anhydride C═O C═O 1759 S Cyclic 1759 S Cyclic anhydride anhydride C═O C═O 1718 M Imide C═O 1723 S Imide C═O 1720 S Imide C═O 1670 S Imide C═O 1671 VS Imide C═O 1672 VS Imide C═O In Table 1, above, VS = very strong, S = Strong, M = Medium and W = weak, indicating to a degree the amount of each functional group shown. As the Table shows, all inventive comb polymers comprise at least a cyclic methacrylic imide group. In Examples 3 and 4, the stronger imide signals suggest a preferred higher imide yield than in Example 1.

Example 5

Reaction of the Backbone Polymer of Synthesis Example 1 With ˜10% Polyetheramine (˜19 EO Groups)

[0120] Into a 3-neck, 100 ml roundbottom flask with magnetic stir bar and fitted with inlet adaptor, stopper, and Dean-Stark trap with condenser and outlet adaptor was loaded N,N-dimethylacetamide (50 ml) and toluene (15 ml) with apparatus under slow nitrogen sweep. Toluene was distilled and drained from the Dean-Stark trap. The poly(methacrylic acid-co-methacrylic anhydride)(50/50 mole/mole, 2.10 grams) of Synthesis Example 1 was added to the flask and warmed to dissolve in the N,N-dimethylacetamide at about 120° C. To the ambient temperature solution was added Jeffamine™ M1000 polyetheramine (Huntsman Int'l. LLC, 0.87 grams) was added to the solution. Mixture was stirred overnight at ambient temperature. Toluene was placed in the flask (10 mL) as well as filling the Dean-Stark trap. The mixture was refluxed for about 9 hours with toluene (at ˜110° C.) and water drained from the trap. Product solution has solvent removed in a 100° C. vacuum oven leaving a glassy solid with recovered yield of 2.75 grams. Solution of final product was cast on a PTFE card for FTIR collection by method B.

[0121] The FTIR showed strong anhydride bands, which are stronger than the imide bands; and, also shows a strong carboxylic acid peak. Because less polyetheramine or amine reactant was used in example 5 than in Example 4, the imides in the Example 5 comb polymer were not as pronounced as in the Example 4 comb polymer. See Table 2, below.

TABLE-US-00002 TABLE 2 FTIR Results Example Band (cm.sup.−1) Strength Assignment 1 1718 M Imide C═O 1670 S Imide C═O 3 1801 W Cyclic anhydride C═O 1760 S Cyclic anhydride C═O 1723 S Imide C═O 1671 VS Imide C═O 4 1801 W Cyclic anhydride C═O 1759 S Cyclic anhydride C═O 1720 S Imide C═O 1672 VS Imide C═O 5 1801 S Cyclic anhydride C═O 1759 VS Cyclic anhydride C═O 1730 M Imide C═O 1701 W-Shldr Carboxylic acid C═O 1672 W-Shldr Imide C═O

[0122] As shown in Table 2, above, the presence of strong imide peaks at about 1670 cm.sup.−1 and also at above 1720 cm.sup.−1 indicates the presence of six-membered cyclic methacrylic imide group containing polymers in inventive Examples 3, 4 and 5. The FTIR analysis of the polymer of Example 1 did not result in as strong a six-membered cyclic methacrylic acid imide signal; however, the analysis does confirm the presence of such groups.