FORMALDEHYDE FREE MICROSPHERES AND ENCAPSULATION

Abstract

Processes for producing polymer microcapsules using vicinal functional oligomers are also described. The vicinal functional oligomers can be made by polymerizing an acrylate monomer, a styrene monomer, or both in the presence of a chain transfer agent. The vicinal functional oligomers can be reacted with epichlorohydrin to form vicinal epoxies. The vicinal epoxies can be reacted with polyamines to form epoxy polymer microspheres. The vicinal epoxies can be reacted with carbon dioxide in the presence of a catalyst to form vicinal cyclic carbonates. The vicinal cyclic carbonates can be reacted with polyamines to form isocyanate-free polymer microspheres. Polymer microspheres made by the processes are also described.

Claims

1. A process of making polyurethane microspheres comprising: polymerizing an acrylate monomer, or a styrene monomer, or both in the presence of a chain transfer agent to form a vicinal functional oligomer; and reacting the vicinal functional oligomer with an isocyanate and a polyol to form polyurethane polymer microspheres.

2. The process of claim 1 wherein the acrylate monomer comprises acrylic acid, methacrylic acid, methyl methacrylate, t-butyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, N,N-dimethyl amino ethyl methacrylate, acetoacetoxy ethyl methacrylate, or combinations thereof.

3. The process of claim 1 wherein the chain transfer agent is thioglycerol.

4. The process of claim 1 wherein the isocyanate comprises toluene diisocyanate, isophoro diisocyanate, hexamethylene diisocyanate, methylene bisphenyl isocyanate, or combinations thereof.

5. The process of claim 1 wherein the polyol comprises ethylene glycol, 1,4-butane diol, 1,6-hexane diol, 1,3,6-hexane triol, trimethylol propane, poly(tetramethylene) glycol, poly caprolactone diol, poly ethyleneglycol adipate, poly ethyleneglycol succinate, poly ethyleneglycol sabacate, poly ethyleneglycol itoconate, or combinations thereof.

6. The process of claim 1 wherein the vicinal functional oligomer is a polystearyl methacrylate vicinal diol, and the isocyanate is a polyisocyanate.

7. A process of making a vicinal epoxy comprising: polymerizing an acrylate monomer, or a styrene monomer, or both in the presence of a chain transfer agent to form a vicinal functional oligomer; and reacting the vicinal functional oligomer with epichlorohydrin to form the vicinal epoxy.

8. The process of claim 7 further comprising reacting the vicinal epoxy with a polyamine to form epoxy polymer microspheres.

9. The process of claim 7 wherein the vicinal epoxy is reacted with carbon dioxide in presence of a catalyst to form a vicinal cyclic carbonate.

10. The process of claim 9 wherein the catalyst comprises tetrabutyl ammonium bromide, 8-hydroxy quinoline aluminum, 8-hydroxy quinoline iron, 8-hydroxy quinoline vanadium, or combinations thereof.

11. The process of claim 9 further comprising reacting the vicinal cyclic carbonate with a polyamine to form isocyanate-free hydroxyl polyurethane polymer microspheres.

12. The process of claim 8 wherein the polyamine comprises ethylene diamine, 1,3-propane diamine, 1,4-butane diamine, triethylene tetraamine, tetraethylene pentamine, 1,6-hexamethylne diamine, isophorone diamine, polyethylene imine, or combinations thereof.

13. The process of claim 9 wherein reacting the vicinal cyclic carbonate with a polyamine comprises reacting the vicinal cyclic carbonate with the polyamine and a polyfunctional cyclic carbonate, and wherein the vicinal cyclic carbonate is a polystearyl methacrylate vicinal cyclic carbonate.

14. The process of claim 1 wherein the polymer microspheres are spherical and have a particle size between about 0.01 microns and about 500 microns.

15. The process of claim 1 wherein the polymer microspheres encapsulate a solid or liquid active ingredient.

16. The process of claim 15 wherein the active ingredient comprises, benzisothiazolinone, quaternary ammonium salts, epoxy oligomers, acrylic oligomers, isocyanate oligomers, 2,4-dichlorophenoxyacetic acid, sulfentrazone, or combinations thereof.

17-19. (canceled)

20. A vicinal functional oligomer comprising: the reaction product of an acrylate monomer, or a styrene monomer, or both and a chain transfer agent.

21. The oligomer of claim 20 wherein the acrylate monomer comprises acrylic acid, methacrylic acid, methyl methacrylate, t-butyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, N,N-dimethyl amino ethyl methacrylate, acetoacetoxy ethyl methacrylate, or combinations thereof.

22. The oligomer of claim 20 wherein the chain transfer agent is thioglycerol.

Description

EXAMPLES

A: Examples of Making Vicinal Functional Diol

Example 1A: Synthesis of Poly(Stearyl Methacrylate) (PSMA) Thioglycerol (TG)-1

[0044] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 25 g stearyl methacrylate, 3.5 g of thioglycerol, 0.2 g azobisisobutyronitrile, (AIBN), and 28.7 g of toluene were added. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator. The number average molecular weight was characterized by using GPC. The analysis was performed using tetrahydrofuran (THF) as the solvent, a 1 ml/min flow rate, and a testing time of 60 minutes. The chromatogram had three peaks corresponding to molecular weights of 3246, 1096, and 574.

Example 2A: Synthesis of PSMA TG-2

[0045] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 25 g stearyl methacrylate, 1.4 g of thioglyceryl, 0.2 g AIBN, and 26.6 g of toluene were charged. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator. The molecular weight was characterized by using GPC. The analysis was performed using THF as the solvent, 1 ml/min flow rate, and a testing time of 60 minutes. The chromatogram had three peaks corresponding to molecular weights of 4125, 1039, and 635.

Example 3A: Synthesis of PSMA TG-3

[0046] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 25 g stearyl methacrylate, 0.7 g of thioglyceryl, 0.2 g AIBN, and 25.9 g of toluene were added. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator. The molecular weight was characterized by using GPC. The analysis was performed using THF as the solvent, 1 ml/min flow rate, and a testing time of 60 minutes. The chromatogram had one peak corresponding to a molecular weight of 6372.

Example 4A: Synthesis of PSMA TG-4

[0047] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 25 g stearyl methacrylate, 0.35 g of thioglyceryl, 0.2 g AIBN, and 25.55 g of toluene were charged. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator. The molecular weight was characterized by using GPC. The analysis was performed using THF as the solvent, 1 ml/min flow rate, and a testing time of 60 minutes. The chromatogram had one peak corresponding to a molecular weight of 13,086.

Example 5A: Synthesis of Poly(laurylmethacrylate) (PLMA) TG

[0048] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 25 g lauryl methacrylate, 0.7 g of thioglyceryl, 0.2 g AIBN, and 25.9 g of toluene were added. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator. The molecular weight was characterized by using GPC. The analysis was performed using THF as the solvent, a 1 ml/min flow rate, and a testing time of 60 minutes. The chromatogram had one peak corresponding to a molecular weight of 5865.

Example 6A: Synthesis of Poly Dimethyl Amino Ethyl Methacrylate (NN-DMAEA) TG

[0049] In a 100 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry gas inlet, 99.63 g 2-dimethyl amino ethyl methacrylate (NN-DMAEA), 0.11 g of thioglyceryl, 0.21 g AIBN, and 99.3 g of methyl ethyl ketone were added. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature, and the product was isolated by removing the solvent using a Buchi laboratory rotary evaporator.

Example 7A: Synthesis of Poly Glycidyl Methacrylate TG

[0050] In a 250 ml round bottom flask fitted with an overhead stirrer, a thermocouple, a condenser, and a dry inert gas inlet, 50.02 g 2-glycidyl methacrylate, 6.82 g of thioglyceryl, 0.52 g AIBN, and 64.00 g of methyl ethyl ketone were charged. The contents were heated to 60 C. for 16 hours under argon atmosphere. The contents were cooled to room temperature as a clear colorless liquid.

B: Examples of Making Vicinal Functional Epoxides

Example 1B: Synthesis of PSMA Epoxide

[0051] To a 250 ml 3 neck flask equipped with an overhead stirrer, a thermocouple, a condenser, and a gas inlet, 60 g of 5,000 molecular weight PSMA-TG (example 3A), 2.22 g sodium hydroxide (NaOH), 0.54 g (tetrabutyl ammonium bromide, TBAB) and 4.44 g of epichlorohydrin. The contents were heated to 60 C. under argon and allowed to react overnight. The following day, the contents were cooled, and 64.44 g of toluene was added. The mixture was centrifuged at 3000 rpm for 15 minutes to remove any excess NaOH and sodium chloride byproduct.

C: Examples of Making Vicinal Functional Cyclic Carbonates

Example 1C: Synthesis of PSMA Cyclic Carbonate

[0052] The supernatant from example 1B and an additional 1.52 g of TBAB were charged into a 250 ml flask 3 neck flask equipped with an overhead stirrer, a thermocouple, a condenser, and a gas inlet. The flask contents were heated to 60 C., and then CO.sub.2 was bubbled through the material using a fritted gas sparge tube. The reaction was held at 60 C. until the entire amount of epoxy was converted to carbonate. The product was confirmed by H.sup.1 NMR (in CDCl.sub.3) with the disappearance of the epoxy peaks at 2.7, 2.9, and 3.2 ppm.

D: Examples of Making Vicinal Functional Acetyl Acetonate

[0053] When t-butyl acetoacetonate is allowed to react with Vicinal functional oligomers obtained from examples from 1A to 7A and heated in 100 ml 3 neck flask equipped with a magnetic stirrer, a thermocouple, a glass fritted inlet, and a gas outlet bubbler, Vicinal functional acetyl acetonate will be produced.

E: Examples of Making Polyurethane (PU) Microspheres

Example 1E: Preparation of PU Microspheres Using Vicinal Functional Diol Obtained from Example 1A

[0054] In a 250 ml 3-neck flask equipped with a thermocouple, a dry air inlet, a condenser, and a mechanical stirrer, 2.74 g soybean oil based polyol (Cargill X-210), 6.45 g ethylene glycol, 7.3 g PSMA TG-1, 85.28 g mineral oil, and 0.04 g dibutyl tin dilaurate (DBTDL) were added. The reaction contents were heated to 60 C. Once the reaction was at 60 C., 21.3 g of (Toluene diisocyanate, TDI) was added with an addition funnel. Once all the TDI was added, the contents were held at 60 C. overnight. The reaction is complete when the isocyanate peak in the IR has disappeared (2250 cm.sup.1). After the reaction was complete, the contents were washed with petroleum ether or hexane to remove the mineral oil. The contents were filtered, and the solid was dried at room temperature.

Example 2E: Preparation of PU Microspheres Using Vicinal Functional Diol Obtained from Example 2A

[0055] In a 250 ml 3-neck flask equipped with a thermocouple, a dry air inlet, a condenser, and a mechanical stir, 2.76 g (Cargill X-210), 6.46 g ethylene glycol, 7.34 g PSMA-TG-2, 85.23 g mineral oil, and 0.04 g DBTDL were charged. The reaction contents were heated to 60 C. Once the reaction was at 60 C., 20.5 g of TDI was added with an addition funnel. Once all the TDI was added, the contents were held at 60 C. overnight. The reaction is complete when the isocyanate peak in the IR has disappeared (2250 cm.sup.1). After the reaction was complete, the contents were washed with hexane to remove the mineral oil. The contents were filtered, and the solid was dried at room temperature.

Example 3E: Preparation of PU Microspheres Using Vicinal Functional Diol Obtained from Example 3A

[0056] In a 250 ml 3-neck flask equipped with a thermocouple, a dry air inlet, a condenser, and a mechanical stir, 2.7 g (Cargill X-210), 6.5 g ethylene glycol, 7.3 g PSMA-3, 85.2 g mineral oil, and 0.04 g DBTDL were charged. The reaction contents were heated to 60 C. Once the reaction was at 60 C., 20.0 g of TDI was charged with an addition funnel. Once all the TDI was added, the contents were held at 60 C. overnight. The reaction is complete when the isocyanate peak in the IR has disappeared (2250 cm.sup.1). After the reaction was complete, the contents were washed with petroleum ether or hexane to remove the mineral oil. The contents were filtered, and the solid was dried at room temperature.

Example 4E: Preparation of PU Microspheres Using Vicinal Functional Diol Obtained from Example 4A

[0057] In a 250 ml 3-neck flask equipped with a thermocouple, a dry air inlet, a condenser, and a mechanical stir, 2.72 g (Cargill X-210), 6.45 g ethylene glycol, 7.32 g PSMA-TG-4, 85.22 g mineral oil, and 0.04 g DBTDL were charged. The reaction contents were heated to 60 C. Once the reaction was at 60 C., 20.0 g of TDI was added with an addition funnel. Once all the TDI was added, the contents were held at 60 C. overnight. The reaction is complete when the isocyanate peak in the IR has disappeared (2250 cm.sup.1). After the reaction was complete, the contents were washed with petroleum ether or hexane to remove the mineral oil. The contents were filtered, and the solid was dried at room temperature.

F: Examples of Making Poly Epoxide Microspheres

Example 1F: Preparation of Polyepoxide Microspheres Using Vicinal Functional Epoxides Obtained from Example 1B

[0058] 10-75 parts bisphenol A diglycidyl ether, 25-90 parts amine (Ancamine 2739), and 1-25 parts vicinal functional epoxides obtained from Example 1B, 0.1-5 parts DMP-30 were mixed in 100-300 parts mineral oil, and 10-100 parts toluene in a reaction vessel, and allowed to react in the temperature range between 10 C. to 200 C. to produce polyepoxide microspheres.

G: Examples of Making Poly Hydroxyl Urethane Microspheres

[0059] 10-75 parts of cyclic carbonate derived from bisphenol A diglycidyl ether, 25-90 parts amine (Ancamine 2739) and 1-25 parts vicinal functional cyclic carbonates obtained from Example 2C, 0.1-5 parts 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) were mixed in 100-300 parts mineral oil, and 10-100 parts toluene in a reaction vessel, and allowed to react in the temperature range between 10 C. to 200 C. to produce poly hydroxyl urethane microspheres.

H: Examples of Making Polyamide Microspheres

[0060] 10-75 parts of diisocyanates such as toluene diisocyanate, isophone diisocyanate, hexamethylene diisocyanate and the like, 25-90 parts acetoacetylated polyols, such as ethylene glycol, propylene glycol, butane diol, poly ethylene glycol and the like, and 1-25 parts vicinal functional acetyl acetonate from example D are mixed in 100-300 parts mineral oil, and 10-100 parts toluene in a reaction vessel, and allowed to react in the temperature range between 10 C. to 200 C. to produce poly amide microspheres.

[0061] By about, we mean within 10% of the value, or within 5%, or within 1%.

[0062] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims.