CN112094494A - Super-barrier thermoplastic polyurethane elastomer and preparation method thereof - Google Patents

Super-barrier thermoplastic polyurethane elastomer and preparation method thereof Download PDF

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CN112094494A
CN112094494A CN202010885977.1A CN202010885977A CN112094494A CN 112094494 A CN112094494 A CN 112094494A CN 202010885977 A CN202010885977 A CN 202010885977A CN 112094494 A CN112094494 A CN 112094494A
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thermoplastic polyurethane
polyurethane elastomer
parts
solution
barrier
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CN112094494B (en
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何建雄
杨博
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Dongguan Jixin Polymer Science & Technology Co ltd
Dongguan Xionglin New Materials Technology Co Ltd
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Dongguan Jixin Polymer Science & Technology Co ltd
Dongguan Xionglin New Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

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Abstract

The invention relates to an ultra-barrier thermoplastic polyurethane elastomer and a preparation method thereof, wherein the ultra-barrier thermoplastic polyurethane elastomer comprises a thermoplastic polyurethane elastomer and modified nano-silica, and the modified nano-silica is nano-silica modified by a surfactant and/or a silane coupling agent. The invention creatively adds the nano silicon dioxide as an additive into the thermoplastic polyurethane elastomer, so that the barrier property of the thermoplastic polyurethane elastomer is obviously improved on the basis of ensuring excellent mechanical property. The surface active agent can be adsorbed on the surface of the silicon dioxide to coat and form a space barrier layer, so that the particles are not easy to agglomerate, the particle size of the nano silicon dioxide is controlled, and the mechanical property and the high barrier property of the polyurethane are better maintained; the silane coupling agent can change hydrophilic nano silicon dioxide into lipophilicity, so that the hydrophilic nano silicon dioxide is better dispersed in a polyurethane material, and the mechanical property and high barrier property of the polyurethane are better maintained.

Description

Super-barrier thermoplastic polyurethane elastomer and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane materials, particularly relates to a thermoplastic polyurethane elastomer and a preparation method thereof, and particularly relates to a super-barrier thermoplastic polyurethane elastomer and a preparation method thereof.
Background
The barrier material is one of the fastest-developing functional materials at present, and is mainly used for packaging foods and medicines, and for example, grease foods are required to have high oxygen resistance and oil resistance; the dried food is required to have high moisture resistance; aromatic foods are required to have high aroma-retaining properties; in addition, the interior material is required to have high barrier property as well as high tensile strength, tear resistance, impact strength, and the like.
Polyurethane is a general name of macromolecular compounds containing repeated urethane groups on main chains, has excellent characteristics of wear resistance, oil resistance, tearing resistance, chemical corrosion resistance and the like, and is widely applied to various fields. Polymers are inherently permeable due to the multiplicity of polyurethane moving units and the creep properties of the polymer, unlike ceramics, glass and metals, but good barrier properties are desirable when polyurethane is used as a packaging or container material.
In recent years, the demand of high-barrier plastic packaging materials is continuously increased, the market prospect is quite wide, the research prospect of the high-barrier materials is wide at present when food packaging materials with quality guarantee and shelf life prolonging are more and more emphasized, and the common high-barrier materials at present comprise polyvinylidene chloride, ethylene-vinyl alcohol copolymer, polyester, polyamide and the like.
CN208263623U discloses a high barrier transparent film and a yin-yang bag, the high barrier transparent film comprises an outer surface layer and a heat sealing layer, a high barrier layer is arranged between the outer surface layer and the heat sealing layer, the high barrier layer comprises at least one polyvinylidene chloride film layer and at least one nylon film layer which are compounded layer by layer in the thickness direction. The high-barrier-property transparent film is characterized in that a polyvinylidene chloride (PVDC) film layer and a nylon film layer are compounded to serve as a high barrier layer, the PVDC film layer has good moisture resistance and comprehensive barrier property, the nylon film layer has the characteristic of low oxygen permeability, and the excellent barrier property and the moisture resistance can be exerted by combining the PVDC film layer and the nylon film layer, so that the barrier property of the transparent film layer is equivalent to that of a non-transparent film on the back of a yin-yang bag, the integral barrier property of the yin-yang bag is improved, and the application range of the yin-yang bag is widened.
CN109397778A discloses a high-barrier multilayer co-extrusion functional packaging film with an anti-ultraviolet effect, which sequentially comprises a first polyamide layer, a first bonding layer, a first polyolefin layer, a second bonding layer, a second polyamide layer, a high barrier layer, a third polyamide layer, a third bonding layer and a second polyolefin layer from top to bottom; the high barrier layer is made of EVOH (ethylene vinyl alcohol), has excellent ultraviolet resistance effect and outstanding performances such as high barrier, high humidity resistance and puncture resistance, is suitable for the fields of food packaging, electronic packaging, medical packaging and the like, and effectively protects contents in the packaging.
At present, how to enable the polyurethane material to have better barrier property is a key difficulty, and the polyurethane material is also limited to be widely applied to the fields of food packaging, electronic packaging, medicine packaging and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a thermoplastic polyurethane elastomer and a preparation method thereof, and particularly provides a super-barrier thermoplastic polyurethane elastomer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a super-barrier thermoplastic polyurethane elastomer, which comprises a thermoplastic polyurethane elastomer and modified nano-silica, wherein the modified nano-silica is nano-silica modified by a surfactant and/or a silane coupling agent.
The invention creatively adds the nano-silica as an additive into the thermoplastic polyurethane elastomer, so that the barrier property of the thermoplastic polyurethane elastomer is obviously improved, and the spherical nano-silica can improve the barrier property of the thermoplastic polyurethane elastomer by prolonging the permeation path of polyurethane, or improving the crystallization property of the polyurethane elastomer, or increasing the density of an amorphous region of the polyurethane. The modifier used in the invention comprises a surfactant and/or a silane coupling agent, wherein the surfactant can be adsorbed on the surface of the silicon dioxide, the hydrophilic group faces outwards, the hydrophobic group faces inwards, and a space barrier layer is formed by coating, so that the particles are not easy to agglomerate, the particle size of the nano silicon dioxide is controlled, and the mechanical property and the high barrier property of the polyurethane material can be better maintained; the silane coupling agent can change hydrophilic nano silicon dioxide into lipophilicity, so that the hydrophilic nano silicon dioxide is better dispersed in the polyurethane material, and the mechanical property and the high barrier property of the polyurethane material can be better maintained.
Preferably, the surfactant comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol or polyacrylic acid, preferably polyethylene glycol; the combination of at least two of the foregoing combinations, such as a combination of polyethylene glycol and polyvinyl alcohol, a combination of polyvinyl alcohol and polyacrylic acid, a combination of polyethylene glycol and polyacrylic acid, and the like, may be selected in any combination manner, and thus, details are not repeated herein.
Preferably, the silane coupling agent comprises any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane or 3- (methacryloyloxy) propyltrimethoxysilane, preferably 3- (methacryloyloxy) propyltrimethoxysilane; the combination of at least two of the above-mentioned compounds, such as the combination of vinyltriethoxysilane and vinyltrimethoxysilane, the combination of 3- (methacryloyloxy) propyltrimethoxysilane and vinyltris (β -methoxyethoxy) silane, etc., can be selected in any combination manner, and will not be described in detail herein.
Preferably, the mass percentage of the modified nano-silica in the thermoplastic polyurethane elastomer is 1-10%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, etc., and other points within the range can be selected, which are not described herein again, and are preferably 6-10%.
The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is specifically selected to be 1-10% because the addition amount is further reduced, the barrier property is not obviously improved, the barrier property is reduced on the contrary when the barrier property is further increased, and the mechanical property is negatively influenced, wherein 6-10% is the range with the best effect.
Preferably, the modified nano-silica is prepared by a chemical deposition method, and the preparation raw materials comprise sodium silicate, a salting-out agent and a modifying agent, wherein the modifying agent is a surfactant and/or a silane coupling agent.
Here, the addition of a salting-out agent destabilizes the silica sol and promotes the precipitation of silica precipitates in the feed liquid directly from the silica containing crystal water.
Preferably, the preparation raw materials comprise, by weight, 10-50 parts of sodium silicate, 1-3 parts of salting-out agent and 1-6 parts of modifying agent, wherein the modifying agent is 1-3 parts of surfactant and/or 1-3 parts of silane coupling agent.
The weight ratio of the sodium silicate, the salting-out agent and the modifier needs to meet the conditions, wherein the purity of the product is influenced by excessive addition of the salting-out agent, and insufficient precipitation is easy to occur by too little addition; the particle size of the prepared nano silicon dioxide is too large due to too much or too little addition amount of the surfactant, and the high barrier property and excellent mechanical property of the prepared nano silicon dioxide cannot be ensured when the surfactant is added into polyurethane; wherein, the too small addition amount of the silane coupling agent can cause the particle size of the prepared nano silicon dioxide to be too large, the addition amount is further increased, and the particle size is not changed greatly.
The weight portion of the sodium silicate can be 10 parts, 20 parts, 30 parts, 40 parts or 50 parts, and other point values in the range can be selected, and are not repeated.
The salting-out agent can be 1 part, 2 parts, 3 parts and the like by weight, and other point values in the range can be selected, so that the repeated description is omitted.
The weight portion of the modifier can be 1 portion, 2 portions, 3 portions and the like, and other point values in the range can be selected, so that the description is omitted.
The weight portion of the surfactant can be 1 part, 2 parts, 3 parts and the like, and other point values in the range can be selected, so that the details are not repeated.
The silane coupling agent can be 1 part, 2 parts, 3 parts and the like by weight, and other values in the range can be selected, so that the repeated description is omitted.
Preferably, the raw materials for preparing the thermoplastic polyurethane elastomer comprise diisocyanate, caprolactone, glycolide, an initiator, a catalyst and a chain extender.
The thermoplastic polyurethane uses diisocyanate, caprolactone and glycolide as raw materials, and due to the fact that the degradation rate of polycaprolactone is low, and the degradation rate of polyglycolide is high, the combination of caprolactone and glycolide not only maintains the degradation capability of polycaprolactone, but also can improve the mechanical property of polycaprolactone.
Preferably, the preparation raw materials of the thermoplastic polyurethane comprise, by weight, 15-75 parts of diisocyanate, 10-50 parts of caprolactone, 1 part of glycolide, 1-5 parts of an initiator, 1-15 parts of a catalyst and 10-50 parts of a chain extender.
The number of the diisocyanate is 15, 20, 30, 40, 55, 65 or 75, and other specific values in the range can be selected, and are not repeated herein.
The parts of the caprolactone can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts and the like, and other specific point values in the range can be selected, so that the descriptions are omitted.
The initiator can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts and the like, and other specific point values in the range can be selected, so that the repeated description is omitted.
The parts of the catalyst can be 1 part, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts or 15 parts, and other specific point values in the range can be selected, and are not repeated.
The parts of the chain extender can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts and the like, and other specific point values in the range can be selected, so that the description is omitted.
Preferably, the diisocyanate comprises any one or combination of at least two of L-lysine ethyl ester diisocyanate, diphenylmethane-4, 4-diisocyanate or isophorone diisocyanate, preferably L-lysine ethyl ester diisocyanate; the combination of at least two of the above-mentioned compounds, for example, the combination of L-lysine ethyl ester diisocyanate and diphenylmethane-4, 4-diisocyanate, the combination of diphenylmethane-4, 4-diisocyanate and isophorone diisocyanate, etc., may be selected in any combination manner, and thus, the details are not repeated herein.
The type of the diisocyanate is preferably L-lysine ethyl ester diisocyanate because the ethyl ester side group in the molecular chain makes the diisocyanate have hydrolyzability, and meanwhile, the hydrolysis product has no toxicity and good biocompatibility.
Preferably, the initiator comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof; the combination of at least two of the above-mentioned compounds, such as the combination of ethylene glycol and ethylenediamine, the combination of hexanediol and diethylene glycol, etc., can be selected in any other combination manner, and thus, the details are not repeated herein.
Preferably, the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin dilaurate or a combination of at least two of the foregoing; the combination of at least two of the foregoing combinations, for example, a combination of stannous octoate and dibutyltin dioctoate, a combination of dibutyltin dioctoate and dibutyltin dilaurate, a combination of stannous octoate and dibutyltin dilaurate, and the like, and any other combination modes are not described in detail herein.
Preferably, the chain extender comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof; the combination of at least two of the foregoing, for example, a combination of ethylene glycol and ethylenediamine, a combination of 1, 3-propanediol and 1, 4-butanediol, a combination of 1, 4-butanediol, hexanediol and diethylene glycol, and the like, and any other combination method is not described in detail. A combination of 1, 4-butanediol, hexanediol and diethylene glycol is preferred.
In another aspect, the present invention provides a method for preparing the above-mentioned super-barrier thermoplastic polyurethane elastomer, wherein the method comprises the following steps: respectively preparing a thermoplastic polyurethane elastomer and nano silicon dioxide modified by a surfactant and/or a silane coupling agent, mixing and extruding to obtain the super-barrier thermoplastic polyurethane elastomer.
In the present invention, the preparation method of the thermoplastic polyurethane elastomer comprises the following steps:
(1) mixing caprolactone, glycolide, an initiator and a catalyst, and reacting under the protection of protective gas to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with diisocyanate, carrying out primary reaction under the protection of protective gas, and then adding a chain extender and a catalyst to carry out secondary reaction to obtain the biodegradable thermoplastic polyurethane.
Preferably, the reaction temperature in step (1) is 120-.
Preferably, after the reaction in the step (1) is completed, the product is added into n-hexane for precipitation, and the precipitate is dried.
Preferably, the temperature of the first reaction in step (2) is 70-90 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, and the like, and the time is 1-3h, for example, 1h, 2h or 3h, and other specific values in the range can be selected, and are not repeated herein.
Preferably, the temperature of the secondary reaction in the step (2) is 85-100 ℃, for example, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, and the like, and the time is 8-12h, for example, 8h, 9h, 10h, 11h or 12h, and other specific values in the range can be selected, which is not described herein again.
Preferably, after the secondary reaction in the step (2) is completed, adding the product into n-hexane for precipitation, and drying the precipitate.
In the invention, the preparation method of the modified nano-silica comprises the following steps:
mixing a sodium silicate solution, a salting-out agent solution, and a modifier solution, stirring the mixture to react, and controlling the pH of the reaction system to 8 to 10 (for example, pH 8, 9, 10) with a hydrochloric acid solution; and settling and aging the reaction product, centrifuging, drying, crushing and sieving to obtain the modified nano silicon dioxide.
The invention adopts a chemical deposition method to prepare the nano silicon dioxide, maintains the pH value within the range of 8-10, can ensure that colloidal particles have both electrostatic effect and steric hindrance effect, and the electrostatic-steric hindrance effect can ensure that colloid is in a stable dispersion state, so that the particle size of the nano silicon dioxide is smaller, the dispersibility in polyurethane materials is better, and the improvement on the barrier property is more obvious.
Preferably, the solvent of the sodium silicate solution is an ethanol aqueous solution.
Preferably, the concentration of the ethanol aqueous solution is 10-50%, for example, 10%, 20%, 30%, 40%, or 50%, etc., and other specific values within the range can be selected, which are not described in detail herein, and are preferably 10-20%.
The concentration of the ethanol water solution is specially selected to be 10-50%, the particle size of the nano silicon dioxide prepared in the range is smaller, and 10-20% is a range with better effect.
Preferably, the mass fraction of the sodium silicate solution is 10-15%, for example, 10%, 11%, 12%, 13%, 14% or 15%, and other specific values within the range can be selected, and are not described in detail herein, and preferably 13-14%.
The mass fraction of the sodium silicate is too much or too little, so that the particle size of the prepared nano silicon dioxide is too large, and the high barrier property and excellent mechanical property of the nano silicon dioxide cannot be ensured when the sodium silicate is added into polyurethane.
Preferably, the salting-out agent solution is a sodium chloride solution.
Preferably, the solvent of the sodium chloride solution is water, the mass fraction of the solvent is 15-25%, for example, 15%, 17%, 18%, 20%, 22% or 25%, and other specific values within the range can be selected, and are not repeated herein.
Preferably, the modifier solution is a surfactant aqueous solution and/or a silane coupling agent alcoholic solution.
Preferably, the mass fraction of the surfactant aqueous solution is 15-25%, for example, 15%, 17%, 18%, 20%, 22%, or 25%, and other specific values within the range can be selected, and are not described in detail herein.
Preferably, the mass fraction of the alcoholic solution of the silane coupling agent is 15-25%, for example 15%, 17%, 18%, 20%, 22% or 25%, etc., and other specific values within the range can be selected, which is not described herein again.
Preferably, the stirring rate is 3000-8000r/min, such as 3000r/min, 4000r/min, 5000r/min, 6000r/min, 7000r/min or 8000r/min, etc., and other specific values within the range can be selected, which are not described in detail herein, and preferably 5000-6000 r/min.
The stirring speed is specially selected to be 3000-.
Preferably, the reaction time is 10-30min, for example, 10min, 20min or 30min, and other specific values in the range can be selected, and are not described herein again, the temperature is 20-30 ℃, for example, 20 ℃, 22 ℃, 25 ℃, 28 ℃ or 30 ℃, and other specific values in the range can be selected, and are not described herein again.
Preferably, the aging time is not less than 24h, such as 24h, 30h, 36h or 48h, and other specific values in the range can be selected, which is not described herein again.
In the present invention, the mixing temperature is 120-.
Preferably, the mixing time is 30min to 5h, for example, 30min, 1h, 2h, 3h, 4h or 5h, and other specific point values within the range can be selected, and are not repeated herein.
As a preferred technical scheme, the preparation method of the super-barrier thermoplastic polyurethane elastomer comprises the following steps:
(1) preparing modified nano silicon dioxide: mixing a sodium silicate solution, a salting-out agent solution and a modifier solution, stirring for reaction, and controlling the pH of a reaction system to be 8-10 by using a hydrochloric acid solution; settling and aging the reaction product, centrifuging, drying, crushing and sieving to obtain the modified nano silicon dioxide;
(2) mixing caprolactone, glycolide, an initiator and a catalyst, reacting for 18-30h at the temperature of 120-130 ℃ under the protection of protective gas, adding a product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(3) mixing the double-end hydroxyl prepolymer obtained in the step (2) with diisocyanate, carrying out primary reaction for 1-3h at 70-90 ℃ under the protection of protective gas, then adding a chain extender and a catalyst to carry out secondary reaction for 8-12h at 85-100 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain thermoplastic polyurethane;
(4) and (3) mixing the modified nano silicon dioxide prepared in the step (1) with the thermoplastic polyurethane prepared in the step (3), mixing for 30min-5h at the temperature of 120-150 ℃, and extruding to obtain the super-barrier thermoplastic polyurethane elastomer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modifier used in the invention comprises a surfactant and/or a silane coupling agent, wherein the surfactant can be adsorbed on the surface of the silicon dioxide, hydrophilic groups face outwards, hydrophobic groups face inwards, and the surface of the silicon dioxide is coated to form a space barrier layer, so that the particles are not easy to agglomerate, the particle size of the nano silicon dioxide is controlled, and the polyurethane material can be better maintainedThe mechanical property and high barrier property of the material; wherein the silane coupling agent can change hydrophilic nano silicon dioxide into lipophilicity, so that the hydrophilic nano silicon dioxide is better dispersed in the polyurethane material, and further the mechanical property and the high barrier property of the polyurethane material can be better maintained, the tensile strength is 36.12-42.85MPa, the elongation at break is 507.64-578.96%, and the oxygen transmission coefficient is not higher than 140.73 x 10-9cm3·cm/cm2s.Pa, having a water vapor transmission coefficient of not more than 1.88X 10-15g·cm/cm2·s·Pa。
(2) The invention creatively takes diisocyanate, caprolactone and glycolide as raw materials to prepare the thermoplastic polyurethane elastomer, because the degradation rate of polycaprolactone is slower, and the degradation rate of polyglycolide is faster, the combination of caprolactone and glycolide not only maintains the degradation capability of polycaprolactone, but also can improve the mechanical property of polycaprolactone, so the polyurethane material also has excellent biodegradability.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
The reagents referred to in the following examples include:
caprolactone: purchasing Aladdin, adding calcium hydride before use, stirring for 12h, and distilling under reduced pressure;
glycolide: purchased from Zhengzhou Akmm chemical Co., Ltd, and recrystallized twice with ethyl acetate before use;
diethylene glycol: purchased from Nanjing reagent, analyzed and purified, added with metal sodium before use, stirred for 12 hours and then distilled under reduced pressure;
1, 4-butanediol: purchased from Nanjing reagent, analyzed and purified, added with metal sodium before use, stirred for 12 hours and then distilled under reduced pressure;
stannous octoate: purchased from Aladdin, distilled under reduced pressure before use;
dibutyltin dilaurate: purchased from Aladdin for direct use;
tetrahydrofuran: purchasing Aladdin, stirring and refluxing for 12h by using calcium hydride under the protection of nitrogen, and distilling at normal pressure to collect 70 ℃ fractions;
n-hexane: purchased from Guangzhou chemical reagent factory, adding calcium hydride before use, stirring for 12h, distilling at normal pressure and collecting 68 ℃ fraction;
l-lysine ethyl ester diisocyanate: purchased from Aladdin for immediate use.
Example 1
This example prepares a thermoplastic polyurethane elastomer, which is prepared as follows:
(1) mixing 40 parts of caprolactone, 1 part of glycolide, 3 parts of diethylene glycol and 2 parts of stannous octoate, reacting for 24 hours at 125 ℃ under the protection of nitrogen, adding the product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 50 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 2h at 80 ℃ under the protection of nitrogen, then adding 20 parts of 1, 4-butanediol and 3 parts of dibutyltin dilaurate, carrying out secondary reaction for 10h at 90 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the thermoplastic polyurethane elastomer.
Example 2
This example prepares a thermoplastic polyurethane elastomer, which is prepared as follows:
(1) mixing 20 parts of caprolactone, 1 part of glycolide, 5 parts of diethylene glycol and 5 parts of stannous octoate, reacting for 30 hours at 120 ℃ under the protection of nitrogen, adding a product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 20 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 3h at 70 ℃ under the protection of nitrogen, then adding 20 parts of 1, 4-butanediol and 5 parts of dibutyltin dilaurate, carrying out secondary reaction for 12h at 85 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the thermoplastic polyurethane elastomer.
Example 3
This example prepares a thermoplastic polyurethane elastomer, which is prepared as follows:
(1) mixing 40 parts of caprolactone, 1 part of glycolide, 5 parts of diethylene glycol and 7 parts of stannous octoate, reacting for 18 hours at 130 ℃ under the protection of nitrogen, adding the product into n-hexane for precipitation, and drying the precipitate to obtain a double-end hydroxyl prepolymer;
(2) and (2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with 70 parts of L-lysine ethyl ester diisocyanate, carrying out primary reaction for 1h at 90 ℃ under the protection of nitrogen, then adding 40 parts of 1, 4-butanediol and 7 parts of dibutyltin dilaurate to carry out secondary reaction for 8h at 95 ℃, adding the product into n-hexane for precipitation, and drying the precipitate to obtain the thermoplastic polyurethane elastomer.
Example 4
This example prepares a modified nanosilicon dioxide, which is prepared by the following method:
(1) mixing a 14% sodium silicate solution (containing 12 parts of sodium silicate and a 20% ethanol aqueous solution as a solvent), a 20% sodium chloride solution (containing 1 part of sodium chloride and water as a solvent), a 20% polyethylene glycol solution (containing 1 part of polyethylene glycol and water as a solvent), and a 20% 3- (methacryloyloxy) propyl trimethoxysilane solution (containing 1 part of 3- (methacryloyloxy) propyl trimethoxysilane and a 10% ethanol aqueous solution as a solvent), stirring and reacting at 25 ℃ at 6000r/min for 10min, and controlling the pH of a reaction system to be 9 by using a 20% hydrochloric acid solution;
(2) and settling the reaction product, aging for 24h, centrifuging, drying for 24h at 90 ℃, crushing, and sieving by a 200-mesh sieve to obtain the modified nano-silicon dioxide.
Example 5
This example prepares a modified nanosilicon dioxide, which is prepared by the following method:
(1) mixing 13% sodium silicate solution (containing 25 parts of sodium silicate and 15% ethanol aqueous solution as solvent), 15% sodium chloride solution (containing 2 parts of sodium chloride and water as solvent), 25% polyethylene glycol solution (containing 3 parts of polyethylene glycol and water as solvent), and 15% 3- (methacryloyloxy) propyl trimethoxy silane solution (containing 2 parts of 3- (methacryloyloxy) propyl trimethoxy silane and 10% ethanol aqueous solution as solvent), stirring at 30 ℃ for 30min at 4000r/min, and controlling the pH of the reaction system to be 8 by using 20% hydrochloric acid solution;
(2) and settling the reaction product, aging for 24h, centrifuging, drying for 24h at 90 ℃, crushing, and sieving by a 200-mesh sieve to obtain the modified nano-silicon dioxide.
Example 6
This example prepared a modified nano-silica, which was prepared by a method different from that of example 4 only in that no polyethylene glycol solution was used in step (1), a 20% 3- (methacryloyloxy) propyltrimethoxysilane solution (containing 2 parts of 3- (methacryloyloxy) propyltrimethoxysilane and 10% aqueous ethanol) was used, and other conditions were maintained, and a single modified nano-silica was prepared.
Example 7
This example prepared a modified nano-silica, which was prepared by a method different from that of example 4 only in that the solution containing 20% polyethylene glycol (containing 2 parts of polyethylene glycol and water as a solvent) and not containing 3- (methacryloyloxy) propyltrimethoxysilane was used in step (1), and other conditions were maintained, and a single modified nano-silica was prepared.
Example 8
This example prepares a modified nanosilica, which is prepared by a method different from that of example 4 only in that a 20% sodium chloride solution (containing 5 parts of sodium chloride, the solvent being water) is prepared in step (1), and other conditions are maintained.
Example 9
This example prepared a modified nanosilica, which was prepared by a method different from that of example 4 only in that a 20% sodium chloride solution (containing 0.3 parts of sodium chloride and water as a solvent) was used in step (1), and other conditions were maintained.
Example 10
This example prepared a modified nanosilica, which was prepared by a method different from that of example 4 only in that 20% polyethylene glycol solution (containing 4 parts of polyethylene glycol and water as a solvent), 20% 3- (methacryloyloxy) propyltrimethoxysilane solution (containing 4 parts of 3- (methacryloyloxy) propyltrimethoxysilane and 10% aqueous ethanol solution as a solvent) were used in step (1), and other conditions were maintained.
Example 11
This example prepared a modified nanosilica, which was prepared by a method different from that of example 4 only in that 20% polyethylene glycol solution (containing 0.2 parts of polyethylene glycol and water as a solvent), 20% 3- (methacryloyloxy) propyltrimethoxysilane solution (containing 0.2 parts of 3- (methacryloyloxy) propyltrimethoxysilane and 10% aqueous ethanol as a solvent) were used in step (1), and other conditions were maintained.
Example 12
This example prepares a modified nano-silica, and the preparation method is different from that of example 4 only in that the pH of the reaction system is controlled to 10 in step (1), and other conditions are kept unchanged.
Example 13
This example prepared a modified nanosilica, which was prepared by a method different from that of example 4 only in that the solvent of the sodium silicate solution in step (1) was a 30% ethanol aqueous solution, and other conditions were maintained.
Example 14
This example prepared a modified nanosilica, which preparation method differed from example 4 only in that the mass fraction of the sodium silicate solution in step (1) was 12%, and other conditions were maintained.
Example 15
This example prepared a modified nanosilica, which preparation method differed from example 4 only in that the mass fraction of the sodium silicate solution in step (1) was 15%, and other conditions were maintained.
Example 16
This example prepared a modified nanosilica, which preparation method differed from example 4 only in that the stirring rate in step (1) was 2000r/min, and other conditions were maintained.
Application example 1
The application example prepares the super-barrier thermoplastic polyurethane elastomer, and the preparation method comprises the following steps:
and mixing the modified nano-silica prepared in the embodiment 4 with the thermoplastic polyurethane prepared in the embodiment 1, then mixing for 1h at 130 ℃, and extruding to obtain the super-barrier thermoplastic polyurethane elastomer. The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is 8%.
Application examples 2 to 12
The application example prepares the super-barrier thermoplastic polyurethane elastomer, and the preparation method comprises the following steps:
the modified nano-silica prepared in the examples 6 to 16 and the thermoplastic polyurethane prepared in the example 1 are mixed, mixed for 1 hour at 130 ℃, and extruded to obtain the super-barrier thermoplastic polyurethane elastomer. The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is 8%.
Application example 13
The application example prepares the super-barrier thermoplastic polyurethane elastomer, and the preparation method comprises the following steps:
and mixing the modified nano-silica prepared in the embodiment 4 with the thermoplastic polyurethane prepared in the embodiment 1, then mixing for 1h at 130 ℃, and extruding to obtain the super-barrier thermoplastic polyurethane elastomer. The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is 5%.
Application example 14
The application example prepares the super-barrier thermoplastic polyurethane elastomer, and the preparation method comprises the following steps:
and mixing the modified nano-silica prepared in the embodiment 4 with the thermoplastic polyurethane prepared in the embodiment 1, then mixing for 1h at 130 ℃, and extruding to obtain the super-barrier thermoplastic polyurethane elastomer. The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is 12%.
Comparative application example 1
The comparative application example prepares a polyurethane elastomer, and the preparation method comprises the following steps:
mixing unmodified nano silicon dioxide with the thermoplastic polyurethane prepared in the embodiment 1, then mixing for 1h at 130 ℃, and extruding to obtain the super-barrier thermoplastic polyurethane elastomer. The mass percentage of the modified nano silicon dioxide in the thermoplastic polyurethane elastomer is 8%.
Comparative application example 2
This comparative application example prepared a polyurethane elastomer without adding modified nano silica, and the preparation method was based on example 1 and kneaded at 130 ℃ for 1h, extruded.
Identification test:
(1) the polyurethane material obtained in example 1 was analyzed by infrared chromatography, and the results are shown in Table 1:
TABLE 1
Figure BDA0002655594020000161
Figure BDA0002655594020000171
As can be seen from the above table, the thermoplastic polyurethanes according to the invention were successfully synthesized.
(2) The modified nanosilica obtained in example 4 was subjected to infrared chromatographic analysis, the results of which are shown in Table 2:
TABLE 2
Wave number (cm)-1) Attribution
1085 Si-O-Si antisymmetric stretching vibration peak
811 Si-O symmetrical stretching vibration peak
2976 Methylene stretching vibration peak
2887 Methylene stretching vibration peak
1450 Peak of methylene bending vibration
1731 Absorption peak of carbonyl vibration
From the above table, it can be seen that the modified nano-silica was successfully synthesized.
Performance evaluation test:
(1) the mechanical properties of the thermoplastic polyurethane elastomers prepared in GB/T1040-2006 application examples 1-14 and comparative application examples 1-2 were measured, each measurement was repeated 3 times, and the average value was obtained, the results are shown in Table 3:
TABLE 3
Figure BDA0002655594020000172
Figure BDA0002655594020000181
As can be seen from the data in Table 3: the super-barrier thermoplastic polyurethane elastomer has excellent mechanical properties, the tensile strength of the super-barrier thermoplastic polyurethane elastomer is 36.12-42.85MPa, and the elongation at break of the super-barrier thermoplastic polyurethane elastomer is 507.64-578.96%.
(2) Oxygen for the thermoplastic polyurethane elastomers obtained in the corresponding examples 1 to 14 and the comparative examples 1 to 2 by using GB/T1038-2000 and GB/T1037-88Transmittance (cm)3·cm/cm2s.Pa) and a water vapor transmission coefficient (g.cm/cm)2S.pa) were performed, and each set of measurements was repeated 3 times, and averaged, and the results are shown in table 4:
TABLE 4
Figure BDA0002655594020000182
Figure BDA0002655594020000191
From the data in table 4, it can be seen that: the super-barrier thermoplastic polyurethane elastomer has excellent oxygen barrier property and water vapor barrier property, and the oxygen transmission coefficient of the super-barrier thermoplastic polyurethane elastomer is not higher than 140.73 multiplied by 10-9cm3·cm/cm2s.Pa, having a water vapor transmission coefficient of not more than 1.88X 10-15g·cm/cm2·s·Pa。
The applicant states that the present invention is illustrated by the above examples of a super-barrier thermoplastic polyurethane elastomer and a preparation method thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims (10)

1. The super-barrier thermoplastic polyurethane elastomer is characterized by comprising a thermoplastic polyurethane elastomer and modified nano-silica, wherein the modified nano-silica is nano-silica modified by a surfactant and/or a silane coupling agent.
2. The superbarrier thermoplastic polyurethane elastomer of claim 1, wherein the surfactant comprises any one of polyethylene glycol, polyvinyl alcohol, or polyacrylic acid, or a combination of at least two thereof, preferably polyethylene glycol;
preferably, the silane coupling agent comprises any one or a combination of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane or 3- (methacryloyloxy) propyltrimethoxysilane, preferably 3- (methacryloyloxy) propyltrimethoxysilane.
3. The super-barrier thermoplastic polyurethane elastomer as claimed in claim 1 or 2, wherein the modified nano silica is present in the thermoplastic polyurethane elastomer in an amount of 1 to 10% by mass, preferably 6 to 10% by mass.
4. The super-barrier thermoplastic polyurethane elastomer as claimed in any one of claims 1 to 3, wherein the modified nano-silica is prepared by a chemical deposition method, and the modified nano-silica is prepared from sodium silicate, a salting-out agent and a modifier, wherein the modifier is a surfactant and/or a silane coupling agent;
preferably, the preparation raw materials comprise, by weight, 10-50 parts of sodium silicate, 1-3 parts of salting-out agent and 1-6 parts of modifying agent, wherein the modifying agent is 1-3 parts of surfactant and/or 1-3 parts of silane coupling agent.
5. The superbarrier thermoplastic polyurethane elastomer of any one of claims 1 to 4, wherein the thermoplastic polyurethane elastomer is prepared from raw materials comprising diisocyanate, caprolactone, glycolide, an initiator, a catalyst and a chain extender;
preferably, the preparation raw materials of the thermoplastic polyurethane comprise, by weight, 15-75 parts of diisocyanate, 10-50 parts of caprolactone, 1 part of glycolide, 1-5 parts of an initiator, 1-15 parts of a catalyst and 10-50 parts of a chain extender.
6. The super-barrier thermoplastic polyurethane elastomer as claimed in claim 5, wherein the diisocyanate comprises any one or a combination of at least two of L-lysine ethyl ester diisocyanate, diphenylmethane-4, 4-diisocyanate or isophorone diisocyanate, preferably L-lysine ethyl ester diisocyanate;
preferably, the initiator comprises any one of ethylene glycol, ethylenediamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof;
preferably, the catalyst comprises any one of stannous octoate, dibutyltin dioctoate or dibutyltin dilaurate or a combination of at least two of the foregoing;
preferably, the chain extender comprises any one of ethylene glycol, ethylene diamine, 1, 3-propanediol, 1, 4-butanediol, hexanediol, diethylene glycol or 1, 5-pentanediol or a combination of at least two thereof.
7. The method of preparing the superbarrier thermoplastic polyurethane elastomer of any one of claims 1 to 6, wherein the method of preparing comprises: respectively preparing a thermoplastic polyurethane elastomer and nano silicon dioxide modified by a surfactant and/or a silane coupling agent, mixing and extruding to obtain the super-barrier thermoplastic polyurethane elastomer.
8. The method for preparing the super-barrier thermoplastic polyurethane elastomer as claimed in claim 7, wherein the method for preparing the thermoplastic polyurethane elastomer comprises the following steps:
(1) mixing caprolactone, glycolide, an initiator and a catalyst, and reacting under the protection of protective gas to obtain a double-end hydroxyl prepolymer;
(2) mixing the double-end hydroxyl prepolymer obtained in the step (1) with diisocyanate, carrying out primary reaction under the protection of protective gas, and then adding a chain extender and a catalyst to carry out secondary reaction to obtain the biodegradable thermoplastic polyurethane;
preferably, the temperature of the reaction in the step (1) is 120-130 ℃, and the time is 18-30 h;
preferably, after the reaction in the step (1) is finished, adding the product into n-hexane for precipitation, and drying the precipitate;
preferably, the temperature of the first reaction in the step (2) is 70-90 ℃ and the time is 1-3 h;
preferably, the temperature of the secondary reaction in the step (2) is 85-100 ℃, and the time is 8-12 h;
preferably, after the secondary reaction in the step (2) is completed, adding the product into n-hexane for precipitation, and drying the precipitate.
9. The preparation method of the super-barrier thermoplastic polyurethane elastomer as claimed in claim 7, wherein the preparation method of the modified nano-silica comprises the following steps:
mixing a sodium silicate solution, a salting-out agent solution and a modifier solution, stirring for reaction, and controlling the pH of a reaction system to be 8-10 by using a hydrochloric acid solution; settling and aging the reaction product, centrifuging, drying, crushing and sieving to obtain the modified nano silicon dioxide;
preferably, the solvent of the sodium silicate solution is ethanol water solution;
preferably, the concentration of the ethanol aqueous solution is 10-50%, preferably 10-20%;
preferably, the mass fraction of the sodium silicate solution is 10-15%, preferably 13-14%;
preferably, the salting-out agent solution is a sodium chloride solution;
preferably, the solvent of the sodium chloride solution is water, and the mass fraction of the water is 15-25%;
preferably, the modifier solution is a surfactant aqueous solution and/or a silane coupling agent alcoholic solution;
preferably, the mass fraction of the surfactant aqueous solution is 15-25%;
preferably, the mass fraction of the alcoholic solution of the silane coupling agent is 15-25%;
preferably, the stirring speed is 3000-8000r/min, preferably 5000-6000 r/min;
preferably, the reaction time is 10-30min, and the temperature is 20-30 ℃;
preferably, the aging time is not less than 24 h.
10. The preparation method of the super-barrier thermoplastic polyurethane elastomer as claimed in any one of claims 7 to 9, wherein the mixing temperature is 120-150 ℃;
preferably, the mixing time is 30min-5 h.
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