CN112250901A - Application of multifunctional interpenetrating network polymer emulsion in modification of polyurethane soft foam plastic - Google Patents
Application of multifunctional interpenetrating network polymer emulsion in modification of polyurethane soft foam plastic Download PDFInfo
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Abstract
The invention provides an application of multifunctional interpenetrating network polymer emulsion in modification of polyurethane soft foam plastic, in particular relates to an application of polyurethane-polyacrylate interpenetrating network polymer emulsion with a side chain grafted with a quaternary ammonium cation polyether chain, a polyvinylpyrrolidone chain and an alkoxy polyethylene glycol chain in hydrophilic sterilization modification of commercially available polyurethane soft foam plastic, and the polyurethane soft foam plastic with the surface subjected to hydrophilic sterilization modification is used as a medical dressing or a filtering material in an air purifier.
Description
Technical Field
The invention relates to an application of multifunctional interpenetrating network polymer emulsion in modification of polyurethane soft foam plastic, in particular to an application of polyurethane-polyacrylate interpenetrating network polymer emulsion with a side chain grafted with a quaternary ammonium cation polyether chain, a polyvinylpyrrolidone chain and an alkoxy polyethylene glycol chain in hydrophilic sterilization modification of commercially available polyurethane soft foam plastic.
Background
Polyurethanes (PUs) are a generic name for a large class of polymers containing repeating units of urethane (-NHCOO-) in the main chain, usually produced by the polyaddition of polyols and polyisocyanates, and are typically block copolymers; compared with other high polymer materials, the polyurethane material has the characteristics of easy molecular structure design, adjustable performance, good processing performance, various processing modes, excellent mechanical performance and the like. By means of functional modification of polyurethane material, excellent performance of polyurethane is maintained, and unique biological, optoelectromagnetic and thermal and other physical and chemical properties are endowed, so that the method becomes a main method for expanding the application field of polyurethane material. Currently popular polyurethane functionalization methods are: blending modification, coating, grafting, interpenetrating networks, and chemical copolymerization.
Polyurethane products made from different raw materials, formulas and manufacturing processes are also various, and mainly comprise polyurethane elastomers, polyurethane foam plastics, polyurethane fibers, polyurethane coatings, polyurethane adhesives, polyurethane prepolymers and the like. Among them, polyurethane foam is a widely used general material. The open-cell PU soft foam plastic has high elasticity, flexibility, air permeability, adsorption characteristic and good biocompatibility. Recently, the PU soft bag with holes subjected to functional treatmentFoamed plastic is widely applied to manufacturing of medical dressings, and various polyurethane foam dressings are reported at home and abroad, for example, US4773406 and US4773408 adopt a method of adding sodium carboxymethylcellulose, calcium carboxymethylcellulose, pectin, gelatin, guar gum, locust bean gum, collagen and karaya gum to prepare the polyurethane foam dressings with the thickness of 1-10 cm and the density of 0.16-0.8 g/cm3The polyurethane foam dressing of (1). US7022890 uniformly dopes super water absorbents such as starch-grafted sodium acrylate, polyacrylamide, etc. in polyurethane foam to obtain highly water-absorbent polyurethane foam, but since these water-absorbent materials are dispersed in the foam and easily dissolved in water to escape with water, the use is limited. CN1462614 prepares the wound dressing by compounding hydrophilic polyurethane soft foam slice and polyurethane film which is moisture permeable, air permeable, waterproof and bacterium-proof. US4906240 obtains the absorbent layer foam by reacting polyethylene glycol and glycerol with TDI to obtain a prepolymer and then foaming. CN1741824 takes TDI and ethylene oxide/propylene oxide trihydroxy random polymer containing 75% of ethylene oxide as raw materials to prepare prepolymer, and foams obtained by foaming have micropores with the diameter of 10-80 μm, relatively high absorption rate and high moisture permeability, and retain secretion absorbed from wounds in the foams. CN201811511343.9 dimethylolpropionic acid is used as a chain extender in polyurethane prepolymer, chitosan is added in the foaming process, and then the chitosan quaternary ammonium salt-containing antibacterial polyurethane foam dressing is prepared by foaming. CN201810455427.9 also adopts a similar method, and polyhexamethylene guanidine hydrochloride or polyhexamethylene guanidine phosphate is added into a foaming agent for the foaming process of polyurethane prepolymer mixing to prepare the cationic antibacterial polyurethane foam dressing. As is well known to professionals, the addition of a hydrophilic agent, an inorganic antibacterial agent, an organic bactericide and a traditional Chinese medicine extract in the foaming process of the traditional polyurethane plastic can affect the polyurethane foaming technology and process parameters and the physical and mechanical properties of the foam plastic, so that the applicability of the polyurethane plastic is poor. In order to solve the problem, the inventor uses a polyurethane prepolymer of hydroxyl-terminated polyether quaternary ammonium salt and toluene diisocyanate in CN201811305537.3 to perform post-chemical hydrophilic antibacterial modification on a commercial polyurethane foam, so that the water absorption is improved by 50 times, and the water retention is improved12 times, and the mechanical properties of the polyurethane foam before and after modification are hardly changed. However, such polyurethane prepolymers containing quaternary ammonium cations have not high storage stability and, in addition, have serious contamination with volatile organic solvents during the post-chemical modification of polyurethane foams.
It is also known through searching that the antibacterial polyurethane foam dressing on the market at present is to spray a layer of inorganic silver ion antibacterial agent on the surface of the PU foam dressing, but the polyurethane foam dressing with silver-loaded surface has the problems that silver ions are released too fast and are easy to fall off, so that the service life of the dressing is short, and the silver ions directly contact with the skin in the using process and may influence the healing of wounds. Also for human use, ultra-micro TiO is included2The antibacterial polyurethane soft foam dressing is prepared by taking powder, sulfadiazine and silver nitrate as antibacterial agents and adopting a polyurethane soft foam carrier impregnation method or a polyurethane prepolymer method and the like. CN104072798A discloses a nanoparticle modified sponge dressing with antibacterial function, which is obtained by soaking sponge as a base material in a soluble metal salt solution or/and a dispersion of nano metal oxide particles, and treating and combining with ultrasonic waves. The sponge material used by the sponge is polyvinyl acetal sponge, polyurethane sponge, polyether sponge, chitosan sponge, alginate sponge, gelatin sponge, silica gel sponge and the like. CN105536038A discloses a foam-based dressing, which is composed of a base frame made of sheet-like foam dressing and a gel material filled and attached in pores of the base frame, wherein the foam-based dressing contains copper ions, silver ions or nano silver with antibacterial property. CN 108478843A discloses a medical dressing containing a copper coating, wherein the copper coating with biological function is added on the surface of the dressing in a mode of adding copper-carrying microspheres, the copper-carrying microspheres are degradable polymer coated microspheres with the diameter of 5-500nm, and the size of nano-scale copper metal powder is within the range of 10-200 nm. The inorganic antibacterial agent is added into the polyurethane foam dressing by a physical doping or adsorption method, and the polyurethane foam dressing is released and separated out under the action of wound exudate when contacting with a wound surface, so as to achieve the aim of killing bacteria, but the antibacterial agent concentration is reduced along with the time extension in the process, and the antibacterial effect is maintainedOn the other hand, the inorganic antibacterial agent has certain toxicity to human bodies and uncertain safety, so that the polyurethane foam dressing containing the inorganic antibacterial agent has the problems of complex manufacturing process, poor antibacterial durability and poor safety of the inorganic antibacterial agent.
In conclusion, the polyurethane foam dressing is mainly concentrated on the preparation of water absorption or antibacterial materials, and the polyurethane foam dressing has single function and cannot meet the multifunctional requirement of the wound dressing. Therefore, researches and developments of the polyurethane soft foam dressing which has good flexibility, moisture permeability, water absorption, moisture retention, hemostasis, anti-inflammation, detumescence, antibiosis, sterilization, healing promotion and other functions are imperative. The ideal polyurethane soft foam dressing needs to have proper water absorption and can absorb wound exudate in time; the dressing also has certain moisture retention, moisture permeability and air permeability, maintains the moist environment between the wound and the dressing, is not adhered, prevents secondary injury of dry and scabbed wound surfaces, and does not damage new tissues or cause pain of patients due to adhesion when the dressing is replaced; the dressing also can stop bleeding, promote wound healing, sterilize and resist bacteria, and prevent external bacteria from invading the wound through the polyurethane dressing to cause infection or erosion; in addition, the dressing is convenient to use, high in economy, simple and feasible in production process, and can become an ideal dressing.
Disclosure of Invention
The invention provides an application of a multifunctional interpenetrating network polymer emulsion in polyurethane soft foam modification, wherein the multifunctional interpenetrating network polymer emulsion refers to an application of a polyurethane-polyacrylate interpenetrating network polymer emulsion with a side chain grafted with a quaternary ammonium cation polyether chain, a polyvinylpyrrolidone chain and an alkoxy polyethylene glycol chain in hydrophilic sterilization modification of a commercially available polyurethane soft foam commodity.
The invention aims to adopt a simple and easy-to-implement dipping or spraying method to ensure that the cavity of the polyurethane soft foam absorbs the multifunctional interpenetrating network polymer emulsion, and then the polyurethane-polyacrylate interpenetrating network polymer with the side chain grafted with the quaternary ammonium cation polyether chain, the polyvinylpyrrolidone chain and the alkoxy polyethylene glycol chain is uniformly bonded and immobilized on the cavity wall of the polyurethane soft foam after drying. One end of the quaternary ammonium cation polyether chain, the polyvinylpyrrolidone chain and the alkoxy polyethylene glycol chain which are grafted on the side chain of the multifunctional interpenetrating network polymer is fixed on the wall of the polyurethane flexible foam cavity, and the other ends of the quaternary ammonium cation polyether chain, the polyvinylpyrrolidone chain and the alkoxy polyethylene glycol chain are in a suspended state, form a self-assembled hydrogel layer after absorbing moisture when meeting water, are attached to the wall of the polyurethane flexible foam cavity, are not lost and fall off due to washing, vibration, shaking and friction, and ensure the durability and the stability of the medical dressing which is suitable for manufacturing functional medical dressings. Meanwhile, in the process of physically modifying the polyurethane flexible foam by the multifunctional interpenetrating network polymer emulsion, the problem of pollution caused by volatilization of an organic solvent is solved, and the environment-friendly production process of the polyurethane flexible foam dressing is realized.
The invention selects the commercial polyurethane flexible foam as the raw material to be modified and functionalized because the commercial polyurethane flexible foam has mature production process, stable technical index and performance of the product, low production cost and various product types.
The professional is also well aware that the small molecular quaternary ammonium salt and the macromolecular quaternary ammonium salt are widely applied to disinfectants and antibacterial sterilizing materials, and are the first choice for sterilizing and antibacterial functionalization of polyurethane materials. The present inventors rely on the molecular design principle of organic chemistry. The hydroxyl-terminated polyether quaternary ammonium salt is used as a modifier of the polyurethane coating, so that the characteristics of the polyurethane coating, such as antibiosis, sterilization, hydrophilicity, water absorption, moisture retention and the like after meeting water, are improved.
Polyvinylpyrrolidone (PVP) is also well known as a water-soluble polymer, and has the general properties of aqueous polymers, such as colloid protection, film-forming property, adhesion, hygroscopicity, solubilization or aggregation, but its most distinctive feature is its excellent solubility and physiological compatibility. Has no irritation to skin, mucosa, and eye, and has effects in removing toxic substances, stopping bleeding, increasing dissolution concentration, preventing peritoneal adhesion, and promoting blood sedimentation. The invention utilizes a modifier of a hydroxyl-terminated polyvinylpyrrolidone chain modified polyurethane coating according to the molecular design principle of organic chemistry to form a polyurethane coating with a macromolecular side chain and a polyvinylpyrrolidone chain bonded at one end, thereby realizing the characteristics of film forming property, hygroscopicity, moist smoothness and the like of the polyurethane coating after meeting water.
Polyethylene glycol (PEG) is well known to those skilled in the art as an amphiphilic polymer having excellent lubricity, moisture retention, dispersibility,
The adhesive, the antistatic agent, the softening agent and the like can change the biological membrane structure of various cells, so that lipid molecules of plasma membranes at the contact points of two cells are dispersed and recombined, and the cells are fused due to the mutual affinity of the plasma membranes of bilayers at the interface of the two cells and the surface tension effect of the plasma membranes. The invention selects the mono-alkoxy polyethylene glycol as a modifier of the polyurethane coating according to the molecular design principle of organic chemistry to form the polyurethane coating of macromolecular side-linked polyethylene glycol mono-alkyl ether, thereby realizing the characteristics of hydrophilicity, water absorption and moisture retention, lubricity and the like of the polyurethane coating after meeting water.
The invention selects the polyurethane-polyacrylate interpenetrating network polymer with the side chain grafted with the quaternary ammonium cation polyether chain, the polyvinylpyrrolidone chain and the alkoxy polyethylene glycol chain as the functional modifier of the polyurethane soft foam coating, and aims to endow the commercially available polyurethane soft foam plastic with good flexibility, moisture permeability, water absorption, moisture retention, hemostasis, anti-inflammation, detumescence, bacteria resistance, antibiosis, sterilization, healing promotion and other functions and effects; the aqueous emulsion of the interpenetrating network polymer of polyurethane-crosslinked polyacrylate is adopted, aiming at carrying out dipping or spraying processing modification on commercial polyurethane soft foam, the technology is simple and easy to implement, the modification is uniform, and no organic volatile matter is generated in the modification process; the cross-linked polyacrylate is selected as another component in the polyurethane-cross-linked polyacrylate interpenetrating network polymer because the raw materials for preparing the cross-linked polyacrylate are rich in source and low in cost, and the two polymerization techniques of the polyurethane-acrylate interpenetrating network polymer have high suitability.
The embodiment of the application of the multifunctional interpenetrating network polymer emulsion in the modification of the polyurethane soft foam plastic comprises the following steps: and (2) soaking the cleaned and dried polyurethane flexible foam plastic in the multifunctional interpenetrating network polymer emulsion to absorb the multifunctional interpenetrating network polymer emulsion, or uniformly spraying the multifunctional interpenetrating network polymer emulsion on the polyurethane flexible foam plastic, then placing the polyurethane flexible foam plastic in an oven, and drying for 2-72 hours under the condition of controlling the temperature to be 20-80 ℃ to prepare the modified polyurethane flexible foam plastic.
Wherein the relative density of the polyurethane soft foam plastic is 0.16-1.6 g/cm3The diameter of each bubble is 10-1000 mu m, the opening rate is 40-90%, and the moisture permeability under common conditions is 200-20000 g/cm224h of commercial polyurethane flexible foam.
The multifunctional interpenetrating network polymer refers to a polyurethane-polyacrylate multifunctional interpenetrating network polymer with side chains grafted with quaternary ammonium cation polyether chains, polyvinylpyrrolidone chains and oxyl polyethylene glycol chains.
The multifunctional interpenetrating network polymer emulsion is prepared by a sequential polymerization method, and hydroxyl polymer, polymer polyol, a chain extender, polyisocyanate and a catalyst are added into a polymerization kettle at first, and N is2Under protection, controlling the temperature to be 50-90 ℃ to carry out addition polymerization reaction for 2-10 hours, adding a diluent to reduce the viscosity, continuing the addition polymerization reaction for 1-2 hours until the-NCO content in the materials in the polymerization kettle cannot be detected, and reducing the temperature of the materials in the polymerization kettle to room temperature to prepare a multifunctional polyurethane solution; secondly, adding water, olefin monomer, cross-linking agent and initiator into the multifunctional polyurethane solution, stirring and emulsifying for 0.5-2 hours, controlling the temperature to be 20-90 ℃ to carry out chain polymerization for 2-10 hours, reducing the temperature of materials in a polymerization kettle to room temperature after completing the emulsion polymerization of the olefin monomer, and preparing the polyurethane-cross-linked polyacrylate multifunctional interpenetrating network polymer emulsion.
Wherein the mass ratio of the hydroxyl-terminated polymer, the polymer polyol, the polyisocyanate, the chain extender, the catalyst and the diluent is 20-200/30-600/30-600/2-20/0.05-5/30-300;
the mass ratio of the multifunctional polyurethane solution to the water to the olefin monomer to the cross-linking agent to the initiator is 20-200/100-2000/30-300/20-200/0.05-5;
the hydroxyl-terminated polymer refers to one or more than two of hydroxyl-terminated polyether quaternary ammonium salt, hydroxyl-terminated polyvinylpyrrolidone or mono-alkoxy polyethylene glycol.
The hydroxyl-terminated polyether quaternary ammonium salt is a single-ended hydroxyl-terminated polyether quaternary ammonium salt with the mass average molecular weight of 300-6000, and has a structure shown in a formula (1):
wherein R in the general formula (1)1、R2And R3Are respectively selected from substituted or unsubstituted C1~C18One of the hydrocarbon radicals, X-Refers to Cl-Or Br-N is a natural number of 1-200;
the hydroxyl-terminated polyvinylpyrrolidone refers to single-ended hydroxyl-terminated polyvinylpyrrolidone with the mass average molecular weight of 600-6000;
the mono-alkoxy polyethylene glycol refers to polyethylene glycol mono-alkyl ether with a mass-average molecular weight of 600-6000 terminal hydroxyl groups, wherein the alkyl refers to C1~C18One kind of hydrocarbyl.
The polymer polyol refers to one or more of polyether polyol, polyolefin polyol, polyester polyol, polysiloxane polyol and vegetable oil-based polyol with the mass average molecular weight of 150-6000; the polymer polyol is a basic raw material for preparing the polyurethane, and the type of the polymer polyol and the length of a molecular chain of the polymer polyol determine the characteristics of rigidity, hydrolysis resistance, light stability and bonding strength of the cross-linked polyurethane; the length of the molecular chain or different types of the polymer polyol are selected by regulation to obtain the cross-linked polyurethane with expected performance.
The chain extender refers to one of diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 12-dodecanediol, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane or triethanolamine; the small molecular chain extenders contain more than three hydroxyl groups, and after the small molecular chain extenders react with polyisocyanate, the content of hard segments in a polyurethane structure can be improved, and polyurethane chains have a partial cross-linking structural characteristic, so that the hardness and the wear resistance of the polyurethane are improved.
The polyisocyanate refers to one or more than two of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylxylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or trimethylhexane diisocyanate, toluene diisocyanate tripolymer, diphenylmethane diisocyanate tripolymer, 1, 6-hexamethylene diisocyanate tripolymer, isophorone diisocyanate tripolymer and pentamethylene diisocyanate tripolymer;
the catalyst refers to a compound of an organic tin catalyst and an organic amine catalyst;
wherein the organic tin catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, dibutyltin dilauryl sulfide or dibutyltin diacetate;
the organic amine catalyst refers to one of triethylamine, p-dimethylaminopyridine, dimethylethanolamine, N-dimethylformamide, triethylene diamine, dialkyl piperazine, alkyl imidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine carboxylate, dialkyl piperazine carboxylate or alkyl imidazole carboxylate;
the mass ratio of the organic tin catalyst to the organic amine catalyst is 1: 0-1.5.
The diluent refers to an olefin monomer;
the olefin monomer refers to hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, perfluorobutyl acrylate, perfluorooctyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, perfluorobutyl methacrylate, perfluorooctyl methacrylate, isobornyl methacrylate, styrene, 4-vinylpyridine, acrylonitrile, acrylic acid, N-dimethylacrylamide, N-diethylacrylamide, N-diisopropylacrylamide, N-dimethyl-2-methacrylamide, N-diethyl-2-methacrylamide, N-dimethyl-2-methacrylamide, one or more than two of N, N-diisopropyl-2-methacrylamide;
the cross-linking agent is divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 10-hexanediol diacrylate, 1, 10-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, triallyl isocyanurate, N-methylenebisacrylamide, N-methylenebismethacrylamide, bis (ethylene glycol) dimethacrylate, bis (ethylene glycol) diacrylate, bis (ethylene glycol) dimethacrylate, 1, 4-butanediol dimethacrylate, 1, One or more of N, N-dimethyldiallylammonium chloride, N-methyl-N-benzyldiallylammonium chloride, N-ethyl-N-benzyldiallylammonium chloride, or N, N-diethyldiallylammonium chloride;
the initiator is one or more than two of hydrogen peroxide, hydrogen peroxide/ferrous sulfate, ammonium persulfate/ferrous sulfate, potassium persulfate, sodium persulfate/sodium sulfite, azodiisopropylamidine oxazoline hydrochloride, azodiisobutyl amidine hydrochloride, azodimethyl-N-2-hydroxybutyl propionamide, azodicyanic acid, azodiisobutyronitrile, azodiisoheptonitrile, azodiisobutyronitrile dimethyl ester, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, cumene hydroperoxide, tert-butyl hydroperoxide or cyclohexanone peroxide;
the invention has the beneficial effects that:
the multifunctional interpenetrating network polymer of polyurethane-polyacrylate has excellent biocompatibility, hydrophilic, oleophilic and antibacterial functions.
The multifunctional interpenetrating network polymer of polyurethane-polyacrylate is a high molecular surfactant,
One end of the macromolecular antibacterial agent is connected with a quaternary ammonium cation polyether chain, a polyvinylpyrrolidone chain and an alkoxide polyethylene glycol chain on a macromolecular main chain, has relatively higher swinging or stretching freedom degree and free volume, and can form a skin-friendly, lubricating, antibacterial and blocking hydrogel layer by combining self-assembly of water molecules after being dissolved or swelled in water.
And the multifunctional interpenetrating network polymer of polyurethane-polyacrylate is formed by interpenetrating networks of two components, namely the multifunctional polyurethane with strong hydrophilicity and the cross-linked polyacrylate with oleophylic hydrophobicity. The oleophylic and hydrophobic crosslinked polyacrylate has strong adhesiveness and is fixedly carried on the wall of the polyurethane soft foam cavity; through crosslinking or network interpenetration among macromolecular chains, a lubricating antibacterial hydrogel layer formed by dissolving or swelling strongly hydrophilic polyurethane in water is attached to the polyurethane flexible foam and contacts with a wound part of a human body, so that multiple functions of moisture absorption, moisture permeability, wetting, hemostasis, antibacterial sterilization, antibacterial input and wound surface healing assistance are realized.
The multifunctional interpenetrating network polymer emulsion is used for dipping or spraying modified commercial polyurethane soft foam plastic, the technology is simple and easy to implement, the problem of organic solvent volatilization pollution is avoided in the process, and the environment-friendly production process of the polyurethane soft foam dressing is realized.
Detailed Description
For a further understanding of the invention, reference will now be made in detail to the examples which are provided for the purpose of illustration and are intended to provide a further understanding of the invention. Therefore, the application of the multifunctional interpenetrating network polymer emulsion in hydrophilic sterilization modification of polyurethane foam, which is not listed in the examples, should not be construed as limiting the scope of the present invention.
Example 1
Weighing 40 g of 6950F toluene isocyanate trimer with the solid content of about 50% produced by Shandong Vanhua company, adding into a reaction kettle, and adding dried 22 g of polyethylene glycol-2000 monomethyl ether, 30g of single-end hydroxyl polyvinylpyrrolidone with the mass average molecular weight of 2000 and hydroxyl-end polyether with the structure shown as the formula (1-1)Adding 25 g of quaternary ammonium salt, 0.18 g of dibutyltin dilaurate and 0.13 g of triethylene diamine into a reaction kettle, and adding N2Under the protection and stirring, controlling the temperature of materials in the reaction kettle to be 50-65 ℃, and controlling the gradual addition polymerization reaction time to be 2 hours; then adding dried polyether glycol DL-2000D with the mass average molecular weight of 2000, 3.5 g of glycerol and 12 g of toluene diisocyanate (TDI80/20) which are produced by 25 g of Douchongdong blue Star Dong chemical industry Limited liability company, controlling the temperature to be 70-80 ℃ and reacting for 2 hours; when the materials in the reaction kettle are sticky and difficult to stir, adding a mixture of 10 g of hydroxyethyl methacrylate and 30g of butyl methacrylate, continuously stirring for reaction until no-NCO can be detected by a dibutylamine back titration analysis method, and reducing the temperature of the materials in the reaction kettle to room temperature to obtain a multifunctional polyurethane-1 solution for later use;
wherein the structure of the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-1) is shown as follows:
adding 1000 g of deionized water and azodiisopropylamidine into 200 g of the prepared multifunctional polyurethane-1 viscous glue solution
1.5 g of oxazoline hydrochloride, filling nitrogen to remove oxygen for 30 minutes, continuously adding a mixture of 30g of methyl methacrylate, 30g of styrene, 30g of isobornyl acrylate, 30g of ethylene glycol dimethacrylate and 2 g of azobisisobutyronitrile under rapid stirring, gradually increasing the temperature of materials in a reaction kettle to 60-65 ℃ for reaction for 2 hours, and reacting at 80-90 ℃ for 4 hours to prepare the multifunctional interpenetrating network polymer-1 emulsion with the solid content of about 25%.
The relative density is adjusted to be 0.38 g/cm3The diameter of each bubble is 80-200 mu m, the opening rate is 90%, and the moisture permeability under the common condition is 4700 g/cm224h of a commercially available 10 x 2 x 0.2 cm polyurethane flexible foam sheet is placed in ethanol, ultrasonically cleaned for 30 minutes, taken out and dried, then placed in the multifunctional interpenetrating network polymer-1 emulsion for dipping and squeezing, taken out after the emulsion is saturated and absorbed, and placed in an oven for drying for 6 hours at the temperature of 60-65 ℃ to prepare the modified polyurethane flexible foam sheet. The polyurethane before modification is determinedThe saturated water absorption of the flexible foam sheet is 2.38 times, the saturated water absorption of the modified polyurethane flexible foam sheet is 56.03 times, and the moisture permeability is 2650g/cm2·24h。
Example 2
Following the procedure and procedures of example 1, the hydroxyl terminated polyether quaternary ammonium salt of formula (1-1) in example 1 was changed to hydroxyl terminated polyether quaternary ammonium salt of formula (1-2), the toluene diisocyanate trimer was changed to diphenylmethane diisocyanate trimer, and the toluene diisocyanate was changed to diphenylmethane diisocyanate, to produce a multifunctional interpenetrating network polymer-2 emulsion.
Wherein the structure of the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-2) is shown as follows:
the relative density is adjusted to be 0.85 g/cm3The diameter of each bubble is 40-120 mu m, the opening rate is 70-90%, and the moisture permeability under the common condition is 3600 g/cm224h of a commercially available 10 x 2 x 0.2 cm polyurethane flexible foam sheet is placed in ethanol, ultrasonically cleaned for 30 minutes, taken out and dried, then placed in the multifunctional interpenetrating network polymer-1 emulsion for dipping and squeezing, taken out after the emulsion is saturated and absorbed, and placed in an oven for drying for 6 hours at the temperature of 60-65 ℃ to prepare the modified polyurethane flexible foam sheet. The saturated water absorption of the modified polyurethane flexible foam sheet is measured to be 3.83 times, the saturated water absorption of the modified polyurethane flexible foam sheet is 63.55 times, and the moisture permeability is 1030g/cm2·24h。
Example 3
According to the method and the operation steps of the embodiment 1, the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-1) in the embodiment 1 is changed into the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-3), the polyethylene glycol-2000 monomethyl ether is changed into the polyethylene glycol-2000 monolauryl ether, the toluene isocyanate trimer is changed into the diphenylmethane diisocyanate trimer, and the toluene diisocyanate is changed into the diphenylmethane diisocyanate, so that the multifunctional interpenetrating network polymer-3 emulsion is prepared.
Wherein the structure of the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-3) is shown as follows:
the relative density is adjusted to be 0.18 g/cm3The diameter of each bubble is 200-400 mu m, the opening rate is 70-90%, and the moisture permeability under common conditions is 8600 g/cm224h of a commercially available 10 x 2 x 0.2 cm polyurethane flexible foam sheet is placed in ethanol, ultrasonically cleaned for 30 minutes, taken out and dried, then placed in the multifunctional interpenetrating network polymer-1 emulsion for dipping and squeezing, taken out after the emulsion is saturated and absorbed, and placed in an oven for drying for 6 hours at the temperature of 60-65 ℃ to prepare the modified polyurethane flexible foam sheet. The saturated water absorption of the modified polyurethane flexible foam sheet is 1.15 times, the saturated water absorption of the modified polyurethane flexible foam sheet is 76.12 times, and the moisture permeability is 6150g/cm2·24h。
Example 4
According to the method and the operation steps of example 1, the hydroxyl-terminated polyether quaternary ammonium salt of formula (1-1) in example 1 is changed to hydroxyl-terminated polyether quaternary ammonium salt of formula (1-2), polyethylene glycol-2000 monomethyl ether is changed to polyethylene glycol-2000 monoallyl ether, toluene isocyanate trimer is changed to diphenylmethane diisocyanate trimer, toluene diisocyanate is changed to diphenylmethane diisocyanate, and ethylene glycol dimethacrylate is changed to trimethylolpropane triacrylate, to prepare the multifunctional interpenetrating network polymer-4 emulsion.
Wherein the structure of the hydroxyl-terminated polyether quaternary ammonium salt of the formula (1-2) is shown as follows:
the relative density is adjusted to be 0.38 g/cm3The diameter of each bubble is 80-200 mu m, the opening rate is 70%, and the moisture permeability under the common condition is 4700 g/cm224h of a commercially available 10 x 2 x 0.2 cm polyurethane flexible foam sheet is placed in ethanol, ultrasonically cleaned for 30 minutes, taken out and dried, placed in the multifunctional interpenetrating network polymer-1 emulsion for dipping and squeezing, taken out after the emulsion is saturated and absorbed, and placed in a drying oven for drying for 6 hours at the temperature of 60-65 ℃ to prepare the modified polyurethane flexible foam sheet. Measured before modificationThe saturated water absorption of the polyurethane flexible foam sheet is 2.38 times, the saturated water absorption of the modified polyurethane flexible foam sheet is 78.55 times, and the moisture permeability is 2370g/cm2·24h。
The above description is the preferred embodiment of the present invention, and it is within the scope of the appended claims to cover all modifications of the invention which may occur to those skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. The application of the multifunctional interpenetrating network polymer emulsion in the modification of the polyurethane soft foam plastic is characterized in that the cleaned and dried polyurethane soft foam plastic is uniformly soaked in the multifunctional interpenetrating network polymer emulsion to absorb the multifunctional interpenetrating network polymer emulsion; or the multifunctional interpenetrating network polymer emulsion is evenly sprayed on the polyurethane soft foam plastic; then placing the mixture into an oven, and drying the mixture for 2 to 72 hours under the condition of controlling the temperature to be 20 to 80 ℃ to prepare the modified polyurethane flexible foam plastic;
wherein the relative density of the polyurethane soft foam is 0.16-1.6 g/cm3The diameter of each bubble is 10-1000 mu m, the opening rate is 40-90%, and the moisture permeability under the normal temperature condition is 200-20000 g/cm224h of commercial polyurethane flexible foam;
the multifunctional interpenetrating network polymer refers to a polyurethane-polyacrylate multifunctional interpenetrating network polymer with side chains grafted with quaternary ammonium cation polyether chains, polyvinylpyrrolidone chains and oxyl polyethylene glycol chains.
2. The use of the multifunctional interpenetrating network polymer emulsion of claim 1 in the modification of polyurethane flexible foam, wherein the multifunctional interpenetrating network polymer emulsion is prepared by sequential polymerization method, wherein hydroxyl polymer, polymer polyol, chain extender, polyisocyanate and catalyst, N, are added into the polymerization kettle2Under protection, controlling the temperature to be 50-90 ℃ to carry out addition polymerization for 2-10 hours, adding a diluent to reduce the viscosity, and continuing the addition polymerization for 1-2 hours until the content of-NCO in the materials in the polymerization kettle is detectedUntil the temperature cannot be detected, reducing the temperature of the materials in the polymerization kettle to room temperature to prepare a multifunctional polyurethane solution; secondly, adding water, an olefin monomer, a cross-linking agent and an initiator into the multifunctional polyurethane solution, stirring, controlling the temperature to be 20-90 ℃ and carrying out chain polymerization for 2-10 hours, and reducing the temperature of materials in a polymerization kettle to room temperature after emulsion polymerization is completed to prepare the multifunctional interpenetrating network polymer emulsion;
wherein the mass ratio of the water-based hydroxyl-terminated polymer to the polymer polyol to the polyisocyanate to the chain extender to the catalyst to the diluent is 20-200/30-600/30-600/2-20/0.05-5/30-300;
the diluent refers to an olefin monomer;
the mass ratio of the multifunctional polyurethane solution to the water to the olefin monomer to the cross-linking agent to the initiator is 20-200/100-2000/30-300/2-200/0.05-5.
3. The use of the multifunctional interpenetrating network polymer emulsion of claim 2 in the modification of polyurethane flexible foam plastic, wherein said hydroxyl terminated polymer is one or more of hydroxyl terminated polyether quaternary ammonium salt, hydroxyl terminated polyvinylpyrrolidone or polyethylene glycol monoalkyl ether;
the hydroxyl-terminated polyether quaternary ammonium salt is a single-ended hydroxyl-terminated polyether quaternary ammonium salt with the mass average molecular weight of 300-6000, and has a structure shown in a formula (1):
wherein R in the general formula (1)1、R2And R3Are respectively selected from substituted or unsubstituted C1~C18One of the hydrocarbon radicals, X-Refers to Cl-Or Br-N is a natural number of 1-200;
the hydroxyl-terminated polyvinylpyrrolidone refers to single-ended hydroxyl-terminated polyvinylpyrrolidone with the mass average molecular weight of 600-6000;
the mono-alkoxy polyethylene glycol refers to the mass average molecular weight of 600-6000 hydroxyl-terminated polyethylene glycol monoalkyl ether, wherein the alkyl refers to C1~C18One kind of hydrocarbyl.
4. The application of the multifunctional interpenetrating network polymer emulsion in the modification of the polyurethane flexible foam plastic according to claim 2, wherein the polymer polyol refers to one or more of polyether polyol, polyolefin polyol, polyester polyol, polysiloxane polyol and vegetable oil-based polyol with the mass average molecular weight of 150-6000.
5. The use of the multifunctional interpenetrating network polymer emulsion of claim 2 wherein said chain extender is one of diethylene glycol, triethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 12-dodecanediol, glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane or triethanolamine.
6. The use of the multifunctional interpenetrating network polymer emulsion of claim 2, wherein the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, tetramethylxylylene diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or trimethylhexane diisocyanate, toluene diisocyanate trimer, diphenylmethane diisocyanate trimer, 1, 6-hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, and pentamethylene diisocyanate trimer.
7. The use of the multifunctional interpenetrating network polymer emulsion of claim 2 in the modification of polyurethane flexible foam plastic, wherein said catalyst is a combination of an organotin catalyst and an organic amine catalyst;
wherein the organic tin catalyst refers to one of dibutyltin dilaurate, stannous octoate, stannous oxalate, dibutyltin dimaleate, dibutyltin dilauryl sulfide or dibutyltin diacetate;
the organic amine catalyst refers to one of triethylamine, p-dimethylaminopyridine, dimethylethanolamine, N-dimethylformamide, triethylene diamine, dialkyl piperazine, alkyl imidazole, 1, 8-diazabicyclo [5.4.0] undec-7-ene, triethylene diamine carboxylate, dialkyl piperazine carboxylate or alkyl imidazole carboxylate;
the mass ratio of the organic tin catalyst to the organic amine catalyst is 1: 0-1.5.
8. The use of the multifunctional interpenetrating network polymer emulsion of claim 2 wherein the olefin monomer is hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, perfluorobutyl acrylate, perfluorooctyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, perfluorobutyl methacrylate, perfluorooctyl methacrylate, isobornyl methacrylate, styrene, 4-vinylpyridine, acrylonitrile, acrylic acid, N-dimethylacrylamide, N-diethylacrylamide, N-diisopropylacrylamide, N, one or more of N-dimethyl-2-methacrylamide, N-diethyl-2-methacrylamide and N, N-diisopropyl-2-methacrylamide.
9. The use of the multifunctional interpenetrating network polymer emulsion of claim 2, wherein said cross-linking agent is selected from the group consisting of divinyl benzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, 1, 10-hexanediol diacrylate, 1, 10-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, polyethylene glycol diacrylate, Pentaerythritol tetra-methyl acrylate, triallyl isocyanurate, N-methylene bisacrylamide, N-methylene bismethacrylamide, N-dimethyldiallylammonium chloride, N-methyl-N-benzyldiallylammonium chloride, N-ethyl-N-benzyldiallylammonium chloride or N, N-diethyldiallylammonium chloride.
10. The use of the multifunctional interpenetrating network polymer emulsion of claim 2 in the modification of polyurethane flexible foam plastic, wherein said initiator is one or more of hydrogen peroxide, hydrogen peroxide/ferrous sulfate, ammonium persulfate/ferrous sulfate, potassium persulfate, sodium persulfate/sodium sulfite, azodiisopropylamidine hydrochloride, azodiisobutyl amidine hydrochloride, azodimethyl-N-2-hydroxybutylpropamide, azodicyano valeric acid, azodiisobutyronitrile, azodiisoheptonitrile, dimethyl azodiisobutyrate, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, or cyclohexanone peroxide.
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