AMPHIPHILIC COMB POLYMERS CONTAINING METHACRYLIC ANHYDRIDE

Abstract

The present invention provides amphiphilic comb polymer compositions of phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic alkyl, aryl, cycloalkyl or polyolefin ester or amide side chain groups formed on the backbone polymers and comprising from 75 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units, wherein in the backbone polymer from 20 to less than 70 wt. %, preferably from 50 to 67 wt. % of the methacrylic acid polymerized units comprise methacrylic anhydride groups as determined by titration of the backbone polymer. As polymeric additives, the polymers can compatibilize polyolefins and polar polymers like polyesters.

Claims

1. An amphiphilic comb polymer composition comprising one or more phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic ester or amide side chains formed on the backbone polymers, wherein the backbone polymer comprises from 75 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units, and, further wherein, in the backbone polymer from 20 to less than 70 wt. % of the methacrylic acid polymerized units comprise methacrylic anhydride groups as acid polymerized units, all methacrylic anhydride percentages as determined by titration of the backbone polymer prior to the formation of any ester or amide side chains

2. The amphiphilic comb polymer composition as claimed in claim 1, wherein at least one of the one or more phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic ester or amide side chains comprises from 90 to 100 wt. %, based on the total weight of monomers used to make the backbone polymer, of methacrylic acid polymerized units.

3. The amphiphilic comb polymer composition as claimed in claim 1, wherein in at least one of the one or more phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic ester or amide side chains, from 50 to 67 wt. % of the methacrylic acid polymerized units in the backbone polymer comprises methacrylic anhydride as acid polymerized units, all methacrylic anhydride percentages as determined by titration.

4. The amphiphilic comb polymer composition as claimed in claim 1, wherein at least one of the one or more the phosphorus acid group containing backbone polymers in the amphiphilic comb polymers have a weight average molecular weight (Mw) of from 1,000 to 25,000.

5. The amphiphilic comb polymer composition as claimed in claim 1, wherein at least one of the one or more phosphorus acid group containing backbone polymers in the amphiphilic comb polymers comprise from 2 to 20 wt. %, of a phosphite compound, a hypophosphite compound or its salts, based on the total weight of reactants used to make the backbone polymer.

6. The amphiphilic comb polymer composition as claimed in claim 1, wherein the hydrophobic side chains are chosen from compounds having an average of from 1 to 500 carbons, cycloaliphatic hydrocarbons having an average of from 1 to 500 carbons, aryl hydrocarbons having an average of from 1 to 500 carbons, polyolefins, and their combinations, linked to the backbone polymer via an ester or amide group.

7. The amphiphilic comb polymer composition as claimed in claim 1, wherein the phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic side chains comprises powders, pellets, granules, or suspensions thereof in non-aqueous carriers, such as oils, e.g., vegetable oils, glycols, polyglycols, ethers, glycol ethers, glycol esters and alcohols.

8. The amphiphilic comb polymer composition as claimed in claim 1, further comprising one or more polyolefins, copolymers of polyethylene, or thermoplastic polyolefins (TPO).

9. The amphiphilic comb polymer composition as claimed in claim 8, further comprising an acrylic emulsion polymer, a polyamide polymer, a polyester polymer or a copolymer comprising vinyl alcohol.

10. The amphiphilic comb polymer composition as claimed in claim 8, wherein the compositions comprise from 0.1 to 35 wt. % in total of the one or more phosphorus acid group containing backbone polymers of methacrylic anhydride having hydrophobic side chains and one or more hydrophobic group containing alcohol or amine compound.

11. A method for making amphiphilic comb polymers of phosphorus acid group, containing backbone polymers of methacrylic anhydride having hydrophobic ester or amide side chains comprising: aqueous solution polymerizing a monomer mixture of one or more phosphorus acid compound and/or its salt and methacrylic acid and/or its salt to form a precursor backbone polymer having methacrylic acid polymerized units; drying the precursor backbone polymer at from 175 to 250° C. to form a melt of the backbone polymer of methacrylic anhydride; and, grafting one or more hydrophobic group containing alcohol or amine compound onto the backbone polymer, the alcohol or amine compound chosen from a C.sub.1 to C.sub.500 alkyl group containing alcohol compound, a C.sub.1 to C.sub.500 alkyl group containing amine compound, a C.sub.1 to C.sub.500 cycloaliphatic group containing alcohol compound, a C.sub.1 to C.sub.500 cycloaliphatic group containing amine compound, a C.sub.1 to C.sub.500 alkyl aryl group containing alcohol compound, a C.sub.1 to C.sub.500 alkyl aryl group containing amine compound, a polyolefin alcohol compound, and a polyolefin amine compound, to form hydrophobic ester or amide side chains.

Description

SYNTHESIS EXAMPLE 1: METHACRYLIC ANHYDRIDE GROUP CONTAINING POLYMERS WITH OCTADECANOL (C.SUB.18.) HYDROPHOBIC SIDE CHAINS

[0074] A 5,000 Mw hypophosphite pMAA solution homopolymer of 42 wt. % solids was dried at 150° C. for 1.5 hours. The dried pMAA was pulverized and put in an oven at 200° C. for 30 minutes to convert to the anhydride. Previous methacrylic anhydride group containing polymers made in this way contain from 55 to 60 wt. % of the methacrylic acid polymerized units in the form of anhydride groups. See U.S. Patent Publication No. 2014/0323743 to Rand. Then, 60.5 grams of octadecanol (99% w/w, Aldrich Chemicals, St. Louis, Mo.) and 40.0 g (100% solids) of the polymethacrylic anhydride polymer were charged to a 500 mL 3-neck flask equipped with a with stirrer, thermocouple, and a condenser under a slight N.sub.2 gas blanket. A Jack-o-matic™ stand (Glas-Col, Terre Haute, Ind.) and heating mantle was used to heat the reactor. The slight nitrogen blanket was put on the reactor and the mixture was heated, with stirring initiated when the octadecanol melted. The reaction was carried out at 160° C. for 5 hours then cooled to 80° C. and poured out of the flask; the esterified product contained 33.7% of methacrylic acid polymerized units esterified, as determined by NMR. Perfect 100% yield would have been at 50% esterification.

SYNTHESIS EXAMPLE 2: METHACRYLIC ANHYDRIDE GROUP CONTAINING POLYMERS WITH OCTADECANOL (C.SUB.18.) HYDROPHOBIC SIDE CHAINS

[0075] 54.52 grams of octadecanol (99% w/w, Aldrich Chemicals) and 60.0 g of a 100 wt. % solids polymethacrylic anhydride from synthesis Example 1 were charged to a 500 mL 3-neck flask equipped with a stirrer, thermocouple, and a condenser under a slight N.sub.2 gas blanket. A Jack-o-matic™ stand (Glas-Col, Terre Haute, Ind.) and heating mantle was used to heat the reactor. A slight nitrogen blanket was put on the reactor and the mixture was heated, with stirring initiated when the octadecanol melted. The reaction was carried out at 160° C. for 5 hours after reaching temperature then cooled to 80° C. and poured out of the flask. Yield: 21.29% esterification as determined by NMR. Perfect yield would have been at 30% esterification.

COMPARATIVE SYNTHESIS EXAMPLE 3: METHACRYLIC ACID POLYMERS WITH OCTADECANOL (C.SUB.18.) HYDROPHOBIC SIDE CHAINS

[0076] 50.62 grams of octadecanol (99% w/w, Aldrich Chemicals) and 140.0 g of a hypophosphite group containing polymethacrylic acid (pMAA) having an Mw of 5,000 (solids ˜42 wt. %) were charged to a 500 mL 3-neck flask equipped with a stirrer, thermocouple, and a condenser under a slight N.sub.2 gas blanket. A Jack-o-matic™ stand (Glas-Col, Terre Haute, Ind.) and heating mantle was used to heat the reactor. The slight nitrogen blanket was put on the reactor and the mixture was heated, stirring was initiated when the octadecanol melted. At 106° C., the material separated into two phases, with one being a partly dry, viscous polyacid on the bottom and the other being liquid octadecanol on the top. At this point the reaction was stopped as the mixture was no longer processable. No material could be evaluated for target esterification, thus yield was effectively 0%. Perfect yield would have been at 30% esterification of acid groups.

COMPARATIVE SYNTHESIS EXAMPLE 4: METHACRYLIC ACID POLYMERS WITH OCTADECANOL (C.SUB.18.) HYDROPHOBIC SIDE CHAINS

[0077] 63.99 grams of octadecanol (99% w/w, Aldrich Chemicals) and 80.0 g of spray dried hypophosphite group containing polymethacrylic acid (pMAA) having an Mw of 5,000 (Spray dried, solids ˜90 wt. %) were charged to a 500 mL 3-neck flask equipped with a stirrer, thermocouple, and a condenser under a slight N.sub.2 gas blanket. A Jack-o-matic™ stand (Glas-Col, Terre Haute, Ind.) and heating mantle was used to heat the reactor. The slight nitrogen blanket was put on the reactor and the mixture was heated, stirring was initiated when the octadecanol melted. The reaction was carried out at 160° C. for 5 hours after reaching temperature then cooled to 80° C. and poured out of the flask. Yield: 1.32% esterification as determined by NMR. Perfect yield would have been at 30% esterification.

SYNTHESIS EXAMPLE 5: METHACRYLIC ANHYDRIDE GROUP CONTAINING BACKBONE POLYMER WITH 66.7 WT. % OF METHACRYLIC ANHYDRIDE GROUPS

[0078] 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 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 methacrylic acid polymerized units converted to anhydride, as determined by titration. The resulting material contains equal moles of anhydride functionality and carboxylic acid functionality.

SYNTHESIS EXAMPLE 6: METHACRYLIC ANHYDRIDE GROUP CONTAINING POLYMERS WITH A DISTRIBUTION OF HYDROPHOBIC SIDE CHAINS HAVING AN AVERAGE 50 CARBON ALKYL LENGTH

[0079] 102.68 grams of Unilin™ 700 alcohols having an average length of about C.sub.50 alkyl alcohols (Baker Hughes, 100% solids) and 44.45 g of a 100 wt. % solids polymethacrylic anhydride prepared in the same manner as Synthesis Example 1 were charged to a 500 mL 3-neck flask equipped with a stirrer, thermocouple, and a condenser under a slight N.sub.2 gas blanket. A Jack-o-matic™ stand (Glas-Col, Terre Haute, Ind.) and heating mantle was used to heat the reactor. A slight nitrogen blanket was put on the reactor and the mixture was heated, with stirring initiated when the Unilin™ 700 alcohol melted. The reaction was carried out at 180° C. for 2 hours after reaching temperature then cooled to 80° C. and poured out of the flask. Yield: 10.8% esterification as determined by solid state NMR. Perfect yield would have been 30% esterification of the anhydride groups in the polymethacrylic anhydride.

EXAMPLE 7: COMPATIBILIZATION OF POLYESTER/POLYETHYLENE (PET/PE) BLEND

[0080] A Haake PolyLab System™ (Model P300) mixer (Thermo Fisher Scientific, Tewksbury, Mass.) was used comprising control of temperature and rotor speed and made up of a Haake Rheomix™ 600 P 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 Scientific) geared at a 3:2 ratio, a Haake Rheocord™ used to measure the torque established between the rotors, and a 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 (2014) (SS-301, AK Steel Corp., West Chester, Ohio); the rotors were made of 316 stainless steel—DIN 1.4408 (2014)(SS-316, AK Steel Corp.). All experiments were done with nitrogen padding.

[0081] Materials used included a polyester: Eastapak™ 9921 polymer (Eastman, Kingsport, Tenn.); and a polyethylene: DOWLEX 2045 polymer (Dow Chemical, Midland, Mich.).

[0082] For each experiment, the total weight of material added to the mixing bowl was 50 g. In each case, the PET and PE were of equal weight and were obtained in pellet form. Each mixture of PET and PE was weighed and shaken to mix and fed to the Haake bowl with the rotors rotating at 2 RPM and the bowl temperature at 265° C. The rotor speed was increased up to 10 RPM approximately every 30 seconds after the addition of polymer in the following incremental amounts: 2, 4, 6, 8, and 10 wt. %. Thereafter the torque was increased towards the target rate of 60 RPM in the following increments 20, 30, 40, 50, 60 RPM. At each stage the torque was allowed to stabilize for about 1 minute. Until the torque stabilized at a rotor speed of 60 RPM for 5 minutes, the whole process from adding the polymer typically took about 12-15 minutes, indicating the material was well mixed and the melt was close to the target temperature (265° C.), the required amount of pulverized additive polymer of Synthesis Example 6 was added without reducing the rotor speed. In each experiment in which additive was added, the torque fell rapidly, then rose and stabilized. After stabilizing, the experiment was continued for 5 minutes. At the end of the experiment, the rotor speed was reduced to 3 RPM and the immediately thereafter Haake bowl was removed while hot and the polymer inside removed and cooled while resting in air at room temperature. The material was removed from the bowl while still in a softened state and pressed in to slabs for storage in plastic packaging.

[0083] Each sample was molded on a Carver press model G302H-12-ASTM (Carver MPI, Wabash, Ind.) at 190° C. (temperature program: 6 mins at 20.7 MPa (3,000 psi), 4 mins at 207 MPa (30,000 psi), then cooled at 15° C./min to 35° C.) to form a bar having the nominal dimensions of 63.5 mm×12.7 mm×3.05 mm (2.5″×0.5″×0.120″) then subject to Dynamical Mechanical Spectroscopy (DMS) using an ARES LS Rheometer (TA Instruments, New Castle, Del., USA) at a frequency of 10 rad.Math.sec and a torsion strain of 0.1%. Temperature was ramped at 5° C./min from −100° C. to a maximum of 250° C. or break, whichever came first. A 5 minute delay time was used to allow the sample to equilibrate to the −100° C. initial temperature.

[0084] The results are shown in Table 1, below, and reveal that Inventive Example 7-1 containing 2 wt. % polymer additive, based on total solids, was best compatibilized because the drop in G′ (storage modulus) was shifted to a higher temperature as the more temperature resistant component switched from a discrete to a continuous phase morphology. This change in morphology is an indication of mechanical coupling between the phases during blending. The preferred amount of polymer additive was less than 4% as amount of the additive greater than about 4% (Inventive Examples 7-2, 7-3, and 7-4) showed increase in torque. Comparative Example 7B, in which the additive was poly(meth(acrylic acid anhydride) comprised 66.7% anhydride and no ester showed a large increase in torque, indicative crosslinking of the polyester even though at the same concentration of additive as the in Inventive Example 7-2 and less than the other inventive examples.

TABLE-US-00001 TABLE 2 Dynamical Mechanical Spectroscopy Results In the Table 2, below, T = Temp; G′ = Storage modulus. Compar- Inven- Inven- Inven- Inven- Compar- ative tive tive tive tive ative EXPT# 7A 7-1 7-2 7-3 7-4 7B Additive None PMAAn* 66.7 wt. % Amount of 0 2 4 8 16 2 additive (%) T (C.) at 83.2 91.6 84.4 83.7 87.0 88.1 G′ = 1.0E+08 MPa T(C.) at 117.6 124.7 114.6 113.4 112.4 118.8 G′ = 1.0E+07 MPa Final 469 183 499 459 571 948 torque (mg) *Polymer of Synthesis Example 5 - 66.7 wt. % methacrylic anhydride groups in polymerized form, based on the total weight of methacrylic acid polymerized units in the polymer.

[0085] As shown in Table 2, above, the mechanical coupling of polymer phases reinforced the softened polyethylene phase and delays the drop in storage modulus to a higher temperature. The drop in storage modulus also shifted to a higher temperature as the more temperature resistant polyethylene terephthalate (polyester component) switched from a discrete to a continuous phase morphology. The results are confirmed by AFM images taken from microtomed sections of compression molded plaques of each tested blend, taken at room temperature. The final torque data shows that a 2 wt. % loading of the additive results in substantially less crosslinking of the polyester component than the comparative Examples, especially the pMAAn in Comparative Example 7B. This 2 wt. % loading is in the preferred range of additive proportions.