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WO2001053359A1 - Gel polymere reticule non hydrosoluble provenant de polymeres hydrosolubles non hydrolyses - Google Patents

Gel polymere reticule non hydrosoluble provenant de polymeres hydrosolubles non hydrolyses Download PDF

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Publication number
WO2001053359A1
WO2001053359A1 PCT/US2001/001448 US0101448W WO0153359A1 WO 2001053359 A1 WO2001053359 A1 WO 2001053359A1 US 0101448 W US0101448 W US 0101448W WO 0153359 A1 WO0153359 A1 WO 0153359A1
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WO
WIPO (PCT)
Prior art keywords
gel
pvp
pvcl
value
water insoluble
Prior art date
Application number
PCT/US2001/001448
Other languages
English (en)
Inventor
Jenn S. Shih
Original Assignee
Isp Investments Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Isp Investments Inc. filed Critical Isp Investments Inc.
Priority to AU2001229523A priority Critical patent/AU2001229523A1/en
Publication of WO2001053359A1 publication Critical patent/WO2001053359A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention concerns water insoluble crosslinked polymer gel coatings or adhesive matrices for active biological, agrochemical, pharmaceutical and personal care components employed to contact animal and plant tissue or to treat an inanimate substrate.
  • the present gels provide water insoluble coatings on paper, wood, glass, mineral and metal surfaces.
  • the present gels provide a durable adhesive base for active biocidal, herbicidal and plant growth regulating components.
  • instant gels can be employed as non- toxic, adhesive matrices for controlled release of active skin and hair care components. Further, these gels are compatible with both acidic and basic components and are thus suitably employed as thickeners, hydrogels or viscosity modifiers in many treatment formulations.
  • Poly(ethyleneimine) is a poiyfunctional amine crosslinking agent referred to as PEI;
  • Poly(N-vinyl pyrrolidone) having a K value of from 10 to 120 is designated as PVP;
  • PVL Poly(N-vinyl lactam), referred to herein as PVL, is a cyclic amide having from 4 to 6 ring carbon atoms which optionally can be substituted with lower alkyl;
  • PVCL Poly(N-vinyl caprolactam) having a K value of from 10 to 120 and
  • N-vinylpyrrolidone and N-caprolactam are referred to as VP and VCL respectively.
  • Water insoluble, ampholitic salts of hydrolyzed PVP and PEI are known and described in U.S. Patent No. 5,306,504 to Lorenz. Although these salts have uses similar to those described herein, they are effective over a restricted pH range of from 7 to 12. Additionally these salts have a limited PEI concentration in the crosslinked product, i.e. between 2.5 and 6.5 wt.%. Because of the ring opening required to form patentee's salt, the hydrolyzed PVP component is prone to crosslink with itself before reacting with PEI. Hence a non-uniform distribution of the PEI crosslinking agent in the water insoluble product results.
  • Another object of this invention is to provide a water insoluble matrix for a disinfectant suitably employed in an adhesive wound dressing, ostomy or denture attachment.
  • Another object is to provide a deformation resistant, water insoluble film coating or cushioning pad on a substrate surface wherein the firmness of the coating or padding can be adapted to meet individual needs of the consumer.
  • Still another object is to provide a water insoluble, adhesive gel matrix for an electron conducting agent useful in attachment to electrodes. Yet another object is to supply a water resistant matrix for cosmetically active agents which can be incorporated in the gel or a gel composition as an individual active agent or as an active agent in a formulation.
  • W and Y are each independently Ci to C alkyl; subscripts x and z each have a value of from 0 to 2 and n has a value of 0 to 100,000.
  • the crosslinked, water insoluble gel adhesive described herein is prepared by reacting polyfunctional PEI in an aqueous mixture of base and non-hydrolyzed cyclic PVL.
  • the PVL reactant is PVP or PVCL which are option-ally substituted on their respective rings with lower alkyl and mixtures of said PVP and PVCL.
  • Each of the lactam reactants can be a polymer containing up to 20 wt.% non-acidic comonomer, such as for example a (meth) acrylate, (meth)acrylamide, styrene and the like.
  • the K value of the PVL is within the range of from 10 to 120, preferably from 25 to 65.
  • unsubstituted PVP, PVCL and PVP/PVCL 40/60-60/40 mixtures and VP/VCL copolymers are preferred.
  • a critical factor in the present invention for inhibiting hydrolysis and ring opening of the cyclic lactam component is the solubilization of the PVL in a basic solution prior to contact with PEI.
  • the PVL is intimately premixed with an aqueous solution containing base sufficient to adjust the pH of the cyclic component to above 7, preferably above 7.5, before contacting with PEI. Additional amounts of base can be added during crosslinking when needed to maintain a basic reaction medium until the crosslinked product is formed. Thereafter, a base or acid can be added to the product so as to provide a pH meeting the specification commensurate with its ultimate use.
  • a pH of from about 6.5 to 7.5 is desirable; most preferably a neutral pH is preferred.
  • the pH of the crosslinked gel can have a pH of from about 3.5 to 14 without sacrifice to stability of the crosslinked gel. Accordingly, pH sensitivity normally associated with PVP/PEI ampholyte salts is overcome.
  • the crosslinking reaction is carried out in aqueous medium at ambient temperature, e.g. below about 32°C, preferably at a temperature between about 18° and about 25°C during which the polymeric reactants are intimately mixed for a period of from about 3 to 60 minutes.
  • the water insoluble, pliant films of the present crosslinked polymer can be formed directly on a substrate by coating the substrate surface with the basic aqueous PVL and PEI mixture and allowing the crosslinking to proceed on the surface. The coated surface is then dried at elevated temperature.
  • the aqueous mixture in the reaction zone contains between about 1 and about 70 wt.% solids, preferably between about 10 and about 30 wt.% solids.
  • the mole ratio of reactant PEI to PVL in the reaction mixture can vary widely and can be controlled between about 1 :5 and about 1 :70, depending upon the firmness desired in the crosslinked product; higher concentrations of PEI providing a firmer, less distortable product.
  • Suitable bases conveniently employed for the PVL premixture include inorganic types such as sodium, potassium and ammonium hydroxides and organic types such as triethanolamine, triethylamine, 2-amino-2-methyl-1- propanol and the like and mixtures of the foregoing bases.
  • plasticizer between about 5 and about 20 wt.%, based on total polymers, can be introduced into the reaction mixture.
  • Suitable plasticizers include gums, glycerine, polyvinyl alcohols, polyethylene- or polypropylene- glycols, etc.
  • the plasticizer can be introduced in the aqueous PVL premixture or in the resulting basic PVL/PEI mixture before, during or after the crosslinking reaction.
  • excipients can be added to the present reaction mixture or gel product. Accordingly up about 15 wt.% of an electrolyte salt such as potassium-, sodium- or magnesium- chloride or acetate can be added for conductive properties in the adhesive gel.
  • an electrolyte salt such as potassium-, sodium- or magnesium- chloride or acetate
  • the PEI ampholytic salt formation resulting from the proton transfer reaction between the amine group of the imine and the carboxyl group of the ring opened PVP described by Lorenz in the '504 patent [supra] is replaced with a hydrogen bonding linkage between an amine group of the imine and the cyclic amide of the non-hydrolyzed PVL. Accordingly, the structure of the present crosslinked polymer is distinguished from that of the patent.
  • the PEI concentration in the present crosslinked polymer which is not dependent on a few random ring opened reaction sites, can be significantly extended to between about 1 :5 to 1 :70 part PEI to parts PVL.
  • the increased number of available crosslinkable sites not only provides for more uniform distribution of the PEI throughout the polymer product but also allows adjustment of physical properties in the product.
  • PEI concentrations at or closely approaching 1 :5 in the present product produces a moldable gel.
  • the higher concentrations of PEI, up to about 1:12, produce a firmer, water insoluble adhesive gel.
  • the crosslinked product fulfills all of the cosmetic, antiseptic, pharmaceutical applications disclosed for the product described in U.S. Patent 5,306,504, which teaching concerning uses is incorporated herein by reference.
  • the present crosslinked polymer has a weight average molecular weight between 10,000 and 2,000,000, preferably between 50,000 and 800,000. This polymer possesses compatibility with a broad spectrum of chemicals and can be combined with electrolytes to provide adhesive conductive gels for electrodes and for use in electron beam technology. Additionally, because of the hydrogen bonding capability of unreacted sites along the PEI chain, instant crosslinked gels affords higher loading of hydrogen bondable drugs and other similarly bondable active components. The hydrogen bonding of such active materials promotes controlled release of the active component over extended time periods. Further, since the present gel is not formed as an ampholytic salt, it is stable over a significantly broader pH range, including a range from about 3 to about 14. The above and many other uses and advantages of the present water insoluble gel are also within the scope of this invention.
  • a mixture of 2 g of non-hydrolyzed PVP K-30 in 8 g of distilled water containing 0.5 g of 10% sodium hydroxide and having a pH of 9.2 was contacted in a glass test tube with 0.5 g of 10% PEI in water under agitation at room temperature.
  • the concentration of water in the reaction mixture was 80 wt.% ( ⁇ 20% solids) and the PEI to PVP weight ratio was 1 :40.
  • the resulting mixture was allowed to stand for 20 minutes during which period a stable, water insoluble, crosslinked PVP/PEI gel was formed.
  • Example 2 The reaction described in Example 1 was repeated except that PVP K- 60 adjusted to a pH of 8.0 and only 0.3 g of 10% PEI in water was substituted for PVP K-30 at pH 9.2 and 0.5 g PEI.
  • the weight ratio of PEI to PVP in this example is 1 :66.6. After shaking for about 3 minutes, the stable, water insoluble, crosslinked gel was immediately formed.
  • a conducting, water insoluble gel was prepared in a 4 ounce glass jar by charging 35 g of non-hydrolyzed 21 % PVP K-60 in water having a pH above 7, 2.5 g magnesium acetate and 12.5 g of PEG 300 and mixing with a homogenizer. To the homogenized mixture, 1.0 g of 10% PEI in water was added dropwise over a period of about 5 minutes while stirring to provide a mole ratio of PEI to PVP of 1 :73.5. After about 10 minutes, a stable, water insoluble gel was formed having a conductance of 3700 mho. EXAMPLE 4
  • a water insoluble gel coating was formed by combining in a 20 ml test tube the reaction mixture of Example 1. After about 2 minutes mixing, this solution was cast on a 2 mil thick Mylar film and dried in an oven at 80°C. The resulting gel coating was water insoluble and dye receptive and was printed with a color printer.
  • Example 1 was repeated, except that PVCL K-40 was substituted for PVP K-30 and 0.7 g of 10% sodium hydroxide was substituted for 0.5 g of 10% NaOH to provide a 20% aqueous solution having a pH of 11.4. After shaking and standing for 5 minutes, a stable, water insoluble gel was formed.
  • Example 1 was repeated except that K-40 poly(N-vinyl pyrrolidone/N- vinyl caprolactam) (wt. ratio 50/50 copolymer) was substituted for PVP K-30 and 0.6 g of 10% NaOH was added to produce a 20% solution of the lactam copolymer having a pH of 10.0. After adding and shaking with the PEI crosslinking agent, the stable, water insoluble gel formed within 5 minutes.
  • Example 1 was repeated except that a K-60 mixture of PVP and PVCL was substituted for K-30 PVP. About 0.6 g of 10% NaOH was added to the mixture to produce a 20% solution of the PVL mixture having a pH of 9.5. After adding PEI crosslinking agent and shaking for about 5 minutes, a stable, water-insoluble gel was formed.
  • Example 2 To the reaction mixture of Example 2, prior to the addition of PEI, was added 2 g of glycerin and the resulting mixture at about 20°C crosslinked within a period of 5 minutes. This product possessed increased tackiness without diminishing the stability of the gel product.
  • Example 1 In Example 1 , 2.5 g of potassium chloride was added to the PVP K-30 aqueous component prior to contact with PEI. Crosslinking of the PVP mixture ensued about 6 minutes after PEI addition at a temperature of about 25°C. The resulting crosslinked product possessed good conductivity suitable for use involving electrodes.
  • Example 1 0.5 g of a pesticide, sodium N-methyl dithiocarbamate - 2-chloroethyl trimethyl ammonium chloride, is added to the PVP prior to contact with PEI and the water insoluble gel of the invention formed after addition of PEI is sprayed as an aqueous suspension on a plant the pesticide is retained on the plant with substantially no seepage to ground water after rain or watering.
  • a pesticide sodium N-methyl dithiocarbamate - 2-chloroethyl trimethyl ammonium chloride
  • Example 10 is repeated, except that an antimicrobial agent, benzyl dimethyl-2-phenoxy-ethyl-ammonium-3-hydroxy-2-naphthoate, is substituted for the pesticide.
  • an antimicrobial agent benzyl dimethyl-2-phenoxy-ethyl-ammonium-3-hydroxy-2-naphthoate
  • the resulting aqueous suspension is sprayed on a wound or wound dressing.
  • Other antimicrobial agents such as for example cetyl trimethyl ammonium bromide, can be substituted herein for the same affect.
  • Example 3 The reaction mixture of Example 3 is coated to a 0.5 mil thickness on a 1.5 mil Mylar film and then dried at elevated temperature at about 45°C. An adhesive water insoluble surface on the Mylar film is obtained.
  • This example can be repeated using a paper substrate in place of Mylar.
  • Example 1 was repeated except that 2 g of 10% PEI in water was substituted to provide a weight ratio of PEI/PVP of 1 :10 an the water insoluble gel was formed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Medicinal Preparation (AREA)

Abstract

La présente invention concerne un gel réticulé non hydrosoluble provenant de polymères hydrosolubles constitué essentiellement de poly(éthylèneimine) et de polymère N-vinyl lactamine cyclique non hydrolysée contenant entre 4 et 6 atomes de carbone dans sa structure cyclique; ce gel présentant des unités de répétition de formule 1, dans laquelle W et Y représentent individuellement C1-C4 alkyle; les indices x et z représentant chacun une valeur comprise entre 0 et 2 et n présente une valeur comprise entre 0 et 100,000.
PCT/US2001/001448 2000-01-18 2001-01-12 Gel polymere reticule non hydrosoluble provenant de polymeres hydrosolubles non hydrolyses WO2001053359A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001229523A AU2001229523A1 (en) 2000-01-18 2001-01-12 Crosslinked water insoluble gel from non-hydrolyzed water soluble polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US48480500A 2000-01-18 2000-01-18
US09/484,805 2000-01-18

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WO2001053359A1 true WO2001053359A1 (fr) 2001-07-26

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WO (1) WO2001053359A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006117382A1 (fr) * 2005-05-04 2006-11-09 Basf Aktiengesellschaft Revetements biocides
WO2010129573A3 (fr) * 2009-05-04 2011-04-07 Beisang Arthur A Matériau de remplissage d'implant et procédé associé
US8084513B2 (en) 2003-12-30 2011-12-27 Beisang Arthur A Implant filling material and method
CN115746487A (zh) * 2022-12-07 2023-03-07 成都理工大学 一种新型有机聚合物气凝胶及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595737A (en) * 1984-06-26 1986-06-17 Basf Aktiengesellschaft Water-soluble terpolymers and their preparation
US5219557A (en) * 1986-12-24 1993-06-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Covering agent for microscopy specimens
US5510004A (en) * 1994-12-01 1996-04-23 Hercules Incorporated Azetidinium polymers for improving wet strength of paper
US5739195A (en) * 1994-09-30 1998-04-14 Basf Aktiengesellschaft Process for preparing aqueous solutions of poly(N-vinyl-ε-caprolactam) and their use
WO1999027900A1 (fr) * 1997-11-28 1999-06-10 Henkel Kommanditgesellschaft Auf Aktien Utilisation de polyethylenimines pour ameliorer les proprietes mecaniques des fibres keratiniques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4595737A (en) * 1984-06-26 1986-06-17 Basf Aktiengesellschaft Water-soluble terpolymers and their preparation
US5219557A (en) * 1986-12-24 1993-06-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Covering agent for microscopy specimens
US5739195A (en) * 1994-09-30 1998-04-14 Basf Aktiengesellschaft Process for preparing aqueous solutions of poly(N-vinyl-ε-caprolactam) and their use
US5510004A (en) * 1994-12-01 1996-04-23 Hercules Incorporated Azetidinium polymers for improving wet strength of paper
WO1999027900A1 (fr) * 1997-11-28 1999-06-10 Henkel Kommanditgesellschaft Auf Aktien Utilisation de polyethylenimines pour ameliorer les proprietes mecaniques des fibres keratiniques

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7976859B2 (en) 2003-12-30 2011-07-12 Beisang Arthur A Implant filling material and method
US7988986B2 (en) * 2003-12-30 2011-08-02 Beisang Arthur A Implant filling material and method
US8084513B2 (en) 2003-12-30 2011-12-27 Beisang Arthur A Implant filling material and method
WO2006117382A1 (fr) * 2005-05-04 2006-11-09 Basf Aktiengesellschaft Revetements biocides
WO2010129573A3 (fr) * 2009-05-04 2011-04-07 Beisang Arthur A Matériau de remplissage d'implant et procédé associé
CN102438670A (zh) * 2009-05-04 2012-05-02 亚瑟·A·贝桑 植入填充材料和方法
AU2010246011B2 (en) * 2009-05-04 2012-12-06 Arthur A. Beisang Iii Implant filling material and method
CN102438670B (zh) * 2009-05-04 2015-05-20 亚瑟·A·贝桑 植入填充材料和方法
CN115746487A (zh) * 2022-12-07 2023-03-07 成都理工大学 一种新型有机聚合物气凝胶及其制备方法

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Publication number Publication date
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