CN112574471B - Hyperbranched polymer modified inorganic nano nucleating agent and preparation method and application thereof - Google Patents
Hyperbranched polymer modified inorganic nano nucleating agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched polymer modified inorganic nano nucleating agent, and a preparation method and application thereof. The hyperbranched polymer modified inorganic nano nucleating agent is prepared by the following method: (1) mixing homocysteine thiolactone hydrochloride, alpha-unsaturated alkyl acyl chloride and an organic base in a preset ratio to perform a first reaction so as to obtain a polymerized monomer; (2) mixing an amino coupling agent and the inorganic nanoparticles, and carrying out a second reaction to obtain amino modified inorganic nanoparticles; (3) and mixing the amino-modified inorganic nanoparticles, the polymerization monomer and a photoinitiator, and carrying out a third reaction under the irradiation of ultraviolet light to obtain the hyperbranched polymer modified inorganic nano nucleating agent. The hyperbranched polymer modified inorganic nano nucleating agent prepared by the invention can be added into resin particles to enhance the mechanical property of resin products.
Description
Technical Field
The invention relates to the field of high-molecular modification processing, in particular to a hyperbranched polymer modified inorganic nano nucleating agent, and a preparation method and application thereof.
Background
The control of the crystallization of polyolefin resins is an important means to improve their properties and to increase their functionalization. Nucleating agents are modifiers that promote the crystallization of polymers and improve their grain structure. The nucleating agent is added into the polyolefin resin, so that the crystallization speed of the polyolefin resin can be accelerated, various mechanical properties and processing properties of the polyolefin resin can be improved, and the thermodynamic properties of the polyolefin resin can be improved. The nano nucleating agent is a novel nucleating agent which is developed rapidly in recent years. The prior art has a certain research foundation for inorganic nano-particle nucleating agents, for example, the inorganic nano-particle nucleating agents are used in Chinese patent applications with application numbers of 201110245797.8, 201110245797.8 and 201810653093.6. The small size effect and the strong interface of the nano particles can play a role in strengthening and toughening the polyolefin resin. However, after the solid inorganic particles are subjected to nanocrystallization, the specific surface area is large, the atomic free energy of the surfaces of the solid inorganic particles is sharply enhanced, the surface activity is increased, the solid inorganic particles are in a thermodynamic unsteady state, and the solid inorganic particles are easily combined with themselves and other atoms to form an aggregate, so that the self-nucleating effect is reduced. Therefore, the surface coating polymer of the inorganic nano-particles can improve the dispersity of the inorganic nano-particles in polypropylene, which is an effective means for improving the nucleation effect.
The existing inorganic nano particle surface polymer coating technology is obtained by polymerizing or aggregating active monomers on the surface of inorganic nano particles based on surface energy. Because the polymerization process is relatively complex, not only the composite nanoparticles with the core-shell structure can be generated in a reaction system, but also ineffective particles such as inorganic nanoparticles with incomplete polymer coating, independent polymer nanoparticles, a plurality of inorganic nanoparticle aggregates coated by polymers and the like can be generated. Therefore, the nucleation capability of the nucleating agent prepared by this method is improved to a limited extent.
How to improve the nucleation effect of the nucleating agent needs to be further improved. Therefore, the restriction that the polymerization monomer only generates polymerization reaction on the surface of the inorganic nanoparticles is a difficulty in controlling high dispersibility and difficult aggregation of the polymer modified nanoparticles.
Disclosure of Invention
The present invention aims at solving at least the above-mentioned technical problems. The inventor creatively thinks in the research process that the polymerization monomer is limited to only carry out polymerization reaction on the surface of the inorganic nano particle to obtain the composite nano particle with the core-shell structure, and the generation of ineffective particles such as the inorganic nano particle with incomplete polymer coating, independent polymer nano particle, a plurality of inorganic nano particle aggregates coated by the polymer and the like is reduced; therefore, the invention provides a hyperbranched polymer modified inorganic nano nucleating agent, and a preparation method and application thereof. Firstly, preparing a dormant polymerization monomer which can not be polymerized under the condition of not being activated by amino; then activating dormant polymerization monomer groups through reaction with the amino-modified inorganic nano particles, and forming a polymer with a hyperbranched structure on the surfaces of the inorganic nano particles through Michael addition polymerization between mercapto-unsaturated alkyl under the action of a photoinitiator and ultraviolet illumination, namely obtaining the hyperbranched modified inorganic nano nucleating agent. The hyperbranched polymer modified inorganic nano nucleating agent can effectively improve the comprehensive performance of the polyolefin resin through blending processing.
Specifically, the invention provides the following technical scheme:
in a first aspect of the present invention, the present invention provides a preparation method of a hyperbranched polymer-modified inorganic nano-nucleating agent, comprising: (1) mixing homocysteine thiolactone hydrochloride, alpha-unsaturated alkyl acyl chloride and an organic base in a preset ratio to perform a first reaction so as to obtain a polymerized monomer; (2) mixing an amino coupling agent and the inorganic nanoparticles, and carrying out a second reaction to obtain amino modified inorganic nanoparticles; (3) and mixing the amino-modified inorganic nanoparticles, the polymerization monomer and a photoinitiator, and carrying out a third reaction under the irradiation of ultraviolet light to obtain the hyperbranched polymer modified inorganic nano nucleating agent.
The invention provides a preparation method of a hyperbranched polymer modified inorganic nano nucleating agent. Firstly, it prepares a polymerized monomer by reacting homocysteine thiolactone hydrochloride, alpha-unsaturated alkyl acid chloride and an organic base, the polymerized monomer formed is a thiolactone structure, which does not contain a thiol end by itself without being activated by an amino group, and cannot be polymerized under a photosensitizer and ultraviolet light, thus preventing hyperbranched polymer particles containing no inorganic nanoparticles from being generated in the reaction system, and thus the polymerized monomer formed may also be referred to as "dormant polymerized monomer" herein. In addition, the inorganic nanoparticles are modified by an amino coupling agent to obtain amino-modified inorganic nanoparticles. The amino on the surface of the amino-modified inorganic nanoparticle can activate the ring opening of a dormant polymerization monomer to generate a mercapto group and an unsaturated alkyl terminal, so that a polymer with a hyperbranched structure, namely the hyperbranched polymer-modified inorganic nano nucleating agent, can be formed on the surface of the inorganic nanoparticle through Michael addition polymerization between the mercapto group and the unsaturated alkyl under the action of a photoinitiator and ultraviolet illumination. The prepared hyperbranched polymer modified inorganic nano nucleating agent has the advantages of better compatibility with polyolefin resin and higher dispersibility. And the reaction between the mercapto group and the unsaturated alkyl group is more likely to occur on the surface of a single nanoparticle rather than between nanoparticles due to the strong interface effect on the surface of the nanoparticle. Therefore, the hyperbranched polymer is prevented from wrapping aggregates of a plurality of inorganic nanoparticles in a reaction system, so that the nucleation effect of the hyperbranched polymer modified nanoparticles is improved.
Further, the preparation method of the hyperbranched polymer modified inorganic nano nucleating agent provided above may further include the following technical features:
further, the molar mass ratio of the homocysteine thiolactone hydrochloride, the alpha-unsaturated alkyl acyl chloride and the organic base in the step (1) is 1: 1: 1 to 1.2. The organic base is used as an acid-binding agent and can neutralize acid in the reaction process in time. According to a preferred embodiment of the present invention, the organic base is present in an appropriate amount without affecting the progress of the reaction.
Further, the organic base comprises any one selected from triethylamine, pyridine and lutidine. The organic base is preferably triethylamine.
Further, the alpha-unsaturated alkyl acyl chloride is at least one of alkenyl acyl chloride and alkynyl acyl chloride. According to embodiments of the present invention, the α -unsaturated alkyl acid chlorides include, but are not limited to, vinyl acid chloride, methacrylic acid chloride, butenoyl chloride, 4-pentenoyl chloride, hexenoyl chloride, ethynyl acid chloride, and the like. According to a preferred embodiment of the present invention, the α -unsaturated alkyl acid chloride is 4-pentenoyl chloride.
Further, the homocysteine thiolactone hydrochloride, the alpha-unsaturated alkyl acid chloride and the organic base in step (1) are subjected to the first reaction in a medium polar solvent. In the first reaction, the reaction is carried out in a proper solvent, and the solvent is selected according to the principle that dormant monomers can be dissolved, but organic base hydrochloride cannot be dissolved, so that the purification is easy; furthermore, the choice of solvent has no particular influence on the degree of reaction. According to a specific embodiment of the present invention, the medium-polar solvent includes at least one selected from the group consisting of diethyl ether, tetrahydrofuran, and dichloromethane.
Further, the reaction temperature of the first reaction in the step (1) is-20-10 ℃, and the reaction time is 2-6 h. The inventor finds in the process of research that the low reaction temperature can reduce the occurrence of side reactions and improve the yield, and has no influence on the reaction degree when the first reaction is carried out. Therefore, the first reaction is carried out at the temperature of-20-10 ℃, so that the smooth proceeding of the reaction can be ensured, the occurrence of side reactions can be reduced, and the yield is improved. According to the specific embodiment of the invention, the reaction temperature of the first reaction in the step (1) is-10 to 10 ℃. According to the specific embodiment of the invention, the reaction temperature of the first reaction in the step (1) is-5 to 10 ℃. According to the specific embodiment of the invention, the reaction temperature of the first reaction in the step (1) is-5 to 5 ℃. According to the specific embodiment of the invention, the reaction time of the first reaction is 2-4 hours.
Further, the mass ratio of the inorganic nanoparticles to the amino coupling agent in the step (2) is 100-1000: 1. The use amount of the amino coupling agent can influence the particle size and the nucleation effect of the finally obtained hyperbranched polymer modified inorganic nano nucleating agent. In the research process, the inventor finds that when the inorganic nanoparticles are higher or lower than the proportion, the particle size of the obtained hyperbranched polymer modified inorganic nano nucleating agent is smaller, and the nucleating effect is reduced sharply.
In addition, the inorganic nanoparticle species also affect the final nucleation effect in polyolefin resins to some extent, such as: the silicon dioxide promotes the formation of polypropylene alpha crystals and improves the tensile modulus of the polypropylene resin; the light calcium carbonate promotes the formation of polypropylene beta crystal and improves the flexural modulus of the polypropylene resin. Thus, by selecting suitable inorganic nanoparticles, a desirable nucleating agent can be obtained. According to the embodiment of the present invention, the inorganic nanoparticles are inorganic particles such as inorganic oxide, inorganic salt, metal oxide, metal salt, transition metal oxide, transition metal salt, etc. According to the specific embodiment of the present invention, the inorganic nanoparticles include, but are not limited to: silica, calcium carbonate, hydrotalcite, zinc oxide, zirconium oxide, aluminum oxide, titanium oxide, silicate, aluminosilicate inorganic particles.
According to the embodiment of the invention, the particle size of the inorganic nanoparticles is 1-2000 nm. According to the embodiment of the invention, the particle size of the inorganic nanoparticles is 1-1500 nm, 10-1200 nm, 50-1000 nm, 100-800 nm, 100-700 nm, 100-600 nm or 100-500 nm.
Further, the amino coupling agent is a silane coupling agent containing an amino group.
Furthermore, the photoinitiator is a water-soluble photoinitiator, the reaction degree can be influenced to a certain extent by the selection influence of the photoinitiator, and the final particle size of the hyperbranched polymer modified nanoparticles is greatly influenced. According to embodiments of the present invention, the photoinitiator includes, but is not limited to, those available under the trade name: quantacure BTC, Quantacure BPQ, Quantacure ABP, Quantacure QTX, Quantacure BMS, Darocur 2959. According to a preferred embodiment of the present invention, the photoinitiator is Darocur 2959.
Further, the ultraviolet light is electromagnetic radiation with a wavelength of 220-420 nm, especially 250-370nm, and more preferably 365 nm. The ultraviolet light in the present invention can be generated by, for example, a composition containing xenon chloride (XeCl, 308nm), xenon fluoride (XeF, 351nm), krypton fluoride (KrF, 249nm), krypton chloride (KrCl, 222nm), argon fluoride (ArF, 193nm), or Xe2(172nm) laser activating mediumAll devices known to the person skilled in the art, such as LEDs, excimer radiators (excimer radiators), or UV fluorescent tubes. Preferably, an excimer radiator is used, since it can be pulsed to adjust the power from 10% to 100%, thereby better regulating the polymerization process.
Further, the time of the third reaction is 0.2 to 2 hours. Thus, the hyperbranched polymer modified inorganic nano nucleating agent can be quickly and conveniently obtained.
Further, the weight ratio of the amino-modified inorganic nanoparticles to the polymerized monomers is 1: 10 to 100. Generally speaking, the larger the amount of the polymeric monomer, the larger the particle size of the inorganic nano nucleating agent modified by the hyperbranched polymer finally obtained. Under the condition of the proportion, the inorganic nano nucleating agent modified by the hyperbranched polymer with proper particle size can be obtained.
Further, the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.05 to 0.5. Thereby effectively promoting the photoinitiated reaction.
In a second aspect of the invention, the invention provides a hyperbranched polymer-modified inorganic nano-nucleating agent prepared by the method according to any one of the embodiments of the first aspect of the invention.
In a third aspect of the present invention, the present invention provides a hyperbranched polymer-modified inorganic nano-nucleating agent, which has a core of inorganic nanoparticles and an outer surface of a hyperbranched polymer, and has the following structure:
wherein R is alkyl, and A1 is the junction with the inorganic nano-particle. According to embodiments of the invention, R may be an n-alkyl group or an isomeric alkyl group.
In a fourth aspect of the invention, the invention provides a polyolefin resin comprising the hyperbranched polymer-modified inorganic nano-nucleating agent of the second or third aspect of the invention.
Further, the provided polyolefin resin may further include the following technical features:
according to the embodiment of the invention, the content of the hyperbranched polymer modified inorganic nano nucleating agent in the polyolefin resin is 0.01-1%.
According to the embodiment of the invention, the content of the hyperbranched polymer modified inorganic nano nucleating agent in the polyolefin resin is 0.05-0.1%.
The hyperbranched polymer modified inorganic nano nucleating agent can be directly blended in the processing process of polyolefin resin, so that the polyolefin resin can be endowed with more excellent mechanical property and processing property; polyolefin resin article forms include, but are not limited to: films, foams, sheets, and the like; the processing method includes but is not limited to: injection molding, rotational molding, calendering, film blowing, mold pressing, and the like. According to an embodiment of the present invention, the polyolefin resin is used for a film, a foamed material or a sheet.
The beneficial effects obtained by the invention are as follows:
(1) the synthesized dormant polymerization monomer has a thiolactone structure, does not contain a sulfhydryl end under the condition of not being activated by amino, and cannot be polymerized under the irradiation of a photosensitizer and ultraviolet light, so that hyperbranched polymer particles without inorganic nanoparticles are prevented from being generated in a reaction system.
(2) The amino on the surface of the modified inorganic nano particle can activate the ring opening of the dormant polymerization monomer to generate the tail end of the sulfhydryl group and the unsaturated alkyl group, so that the polymer with a hyperbranched structure is formed on the surface of the inorganic nano particle through Michael addition polymerization between the sulfhydryl group and the unsaturated alkyl group under the action of a photoinitiator and ultraviolet illumination. The hyperbranched polymer modified nanoparticle nucleating agent has better compatibility and higher dispersibility with polyolefin resin.
(3) Due to the strong interface effect on the surface of the nanoparticles, the reaction between the thiol group and the unsaturated alkyl group occurs more easily on the surface of a single nanoparticle than between nanoparticles. Therefore, the hyperbranched polymer is prevented from wrapping aggregates of a plurality of inorganic nanoparticles in a reaction system, so that the nucleation effect of the hyperbranched polymer modified nanoparticles is improved.
Drawings
Fig. 1 is a schematic structural diagram of a hyperbranched polymer-modified inorganic nano-nucleating agent provided according to an embodiment of the present invention.
FIG. 2 is a schematic structural diagram of a hyperbranched polymer-modified inorganic nano-nucleating agent provided according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
The invention provides a preparation method of a hyperbranched polymer modified inorganic nano nucleating agent, which comprises the following steps:
(1) mixing homocysteine thiolactone hydrochloride, alpha-unsaturated alkyl acyl chloride and an organic base in a preset ratio, and carrying out a first reaction in a medium-polarity solvent so as to obtain a polymerized monomer;
(2) mixing an amino coupling agent and the inorganic nanoparticles, and carrying out a second reaction to obtain amino modified inorganic nanoparticles;
(3) and mixing the amino-modified inorganic nanoparticles, the polymerization monomer and a photoinitiator, and carrying out a third reaction under the irradiation of ultraviolet light to obtain the hyperbranched polymer modified inorganic nano nucleating agent.
Reacting homocysteine thiolactone hydrochloride with alpha-unsaturated alkyl acyl chloride to prepare a dormant polymerization monomer; the inorganic nano particles activate the dormant monomer, and initiate Michael addition reaction between mercapto-unsaturated alkyl under the action of a photoinitiator and ultraviolet light to form hyperbranched polymer surface modification. The dormant polymerization monomer used in the method is of a thiolactone structure, cannot polymerize, can only react with amino groups on the surface of the inorganic nanoparticles to obtain sulfhydryl terminals, and can polymerize under the conditions of ultraviolet illumination and a photoinitiator, thereby avoiding the defects of easy agglomeration and poor dispersibility of the inorganic nanoparticles caused by uncontrollable common polymerization modification methods.
The sequence of the step (1) and the step (2) is not specially required, the step (1) can be performed first, the step (2) can be performed first, or the step (1) and the step (2) can be performed simultaneously or alternately.
In the step (1), the reaction temperature is-20-10 ℃, the reaction temperature is 2-6 h, and the stirring speed is 50-200 rpm. After the first reaction, the organic basic hydrochloride solid was removed by filtration, and the solvent was distilled off under reduced pressure to obtain a polymerized monomer. In the reaction process, the low reaction temperature can reduce the occurrence of side reactions and improve the yield, but has no influence on the reaction degree; maintaining a certain stirring speed and reaction time can improve the reaction degree, but continuously increasing the stirring speed and prolonging the reaction time has no influence on the reaction degree. Therefore, the reaction temperature is-20-10 ℃, the reaction temperature is 2-6 h, and the stirring speed is 50-200 rpm, so that an ideal reaction effect can be obtained.
In at least some embodiments of the present invention, step (2) may be stirred on a high speed mixer for 10-30 min.
In at least some embodiments of the present invention, the organic base is any one of triethylamine, pyridine, and lutidine. Preferably, the organic base is triethylamine.
The alpha-unsaturated alkyl acyl chloride is alkenyl acyl chloride or alkynyl acyl chloride, and includes but is not limited to: methacryloyl chloride, butenoyl chloride, 4-pentenoyl chloride, hexenoyl chloride, and ethynyl chloride, and the like.
The selection principle of the solvent is that the dormant monomer is dissolved, and triethylamine hydrochloride cannot be dissolved, so that the purification is easy; the choice of solvent has no specific influence on the degree of reaction; the medium-polarity solvent is: any one of diethyl ether, tetrahydrofuran and dichloromethane.
The photoinitiator is a water-soluble photoinitiator, and includes but is not limited to the following trade names: any one of Quantacure BTC, Quantacure BPQ, Quantacure ABP, Quantacure QTX, Quantacure BMS, Darocur 2959; preferably, the photoinitiator is Darocur 2959; the selection of the photoinitiator can influence the reaction degree to a certain extent, and has great influence on the final particle size of the hyperbranched polymer modified nanoparticles.
In at least some embodiments of the present invention, the molar mass ratio of homocysteine thiolactone hydrochloride, vinyl chloride and organic base is 1: 1: 1 to 1.2.
In at least some embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 1000: 1. the use amount of the amino coupling agent influences the particle size of the finally obtained hyperbranched polymer modified inorganic nanoparticle nucleating agent. When the inorganic nano particles are higher or lower than the proportion, the particle size of the obtained hyperbranched polymer modified inorganic nano nucleating agent is smaller, and the nucleating effect is reduced sharply. In at least some embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 800: 1. in at least some embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 700: 1. in at least some embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 600: 1. in other embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 500: 1. in still other embodiments of the present invention, the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100 to 400: 1.
the inorganic nanoparticle species affect the final nucleation effect in the polyolefin resin, such as: the silicon dioxide promotes the formation of polypropylene alpha crystals and improves the tensile modulus of the polypropylene resin; the light calcium carbonate promotes the formation of polypropylene beta crystal and improves the flexural modulus of the polypropylene resin. In at least some embodiments of the present invention, the inorganic nanoparticles are inorganic particles of inorganic oxides, inorganic salts, metal oxides, metal salts, transition metal oxides, transition metal salts, and the like. Including but not limited to: silica, calcium carbonate, hydrotalcite, zinc oxide, zirconium oxide, aluminum oxide, titanium oxide, silicate, aluminosilicate inorganic particles. The particle size of the inorganic nanoparticles can be 1-2000 nm.
In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the polymerized monomers is 1: (10-100). Generally, the larger the amount of the monomer, the larger the particle size of the finally obtained hyperbranched polymer modified nano nucleating agent. In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the polymerized monomers is 1: (10 to 90), 1: (10-80), or 1: (10-60) and the like.
In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.05 to 0.5. In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.1 to 0.5. In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.2 to 0.5. In at least some embodiments of the present invention, the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.2 to 0.4. According to the embodiment of the invention, the ultraviolet light is electromagnetic radiation with a wavelength of 220-420 nm, especially 250-370nm, and more preferably 365 nm. The ultraviolet light in the present invention can be generated by, for example, a composition containing xenon chloride (XeCl, 308nm), xenon fluoride (XeF, 351nm), krypton fluoride (KrF, 249nm), krypton chloride (KrCl, 222nm), argon fluoride (ArF, 193nm), or Xe2(172nm) as a laser-activated medium, such as an LED, an excimer radiator (excimer radiator), or a UV fluorescent tube. Preferably, an excimer radiator is used, since it can be pulsed to adjust the power from 10% to 100%, thereby better regulating the polymerization process.
In at least some embodiments of the present invention, provided hyperbranched polymer-modified inorganic nano-nucleating agents are shown in fig. 1. In at least some embodiments of the present invention, a hyperbranched polymer-modified inorganic nano-nucleating agent is provided as shown in fig. 2. Wherein R shown in fig. 1 and 2 is a normal alkyl group or an isomeric alkyl group. For example, R can be methyl, ethyl, propyl, and the like.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Mixing homocysteine thiolactone hydrochloride, butenoyl chloride and an organic base according to a ratio of 1: 1: 1, adding the mixture into a 100L reaction vessel, adding 60L tetrahydrofuran for dissolving, and stirring for reacting for 6 h. The reaction temperature was 0 ℃ and the stirring speed was 200 rpm. After the reaction is finished, triethylamine hydrochloride precipitate is removed by filtration, and the solvent is removed by reduced pressure distillation to obtain the dormant polymerization monomer.
Preparing 10% of amino silane coupling agent by mass, and mixing silica nano-particles and amino silane coupling agent solution according to the ratio of 100: 1, uniformly mixing the mixture on a high-speed mixer, and stirring for 30min to obtain the amino modified silicon dioxide particles.
Amino-modified silica particles, dormant polymerization monomer, photoinitiator Darocur 2959 were as follows 1: 10: adding 0.1 mass ratio of the mixture into a 100L reaction vessel, adding 60L of methanol, stirring and dispersing, reacting for 1h under the illumination of ultraviolet light (365nm), filtering, collecting and precipitating to obtain the hyperbranched polymer modified nano nucleating agent.
The hyperbranched polymer modified nano nucleating agent and the polypropylene are mixed according to the weight ratio of 0.1: 100, melt-extruding and granulating by a double-screw extruder at the temperature of 210 ℃ and the screw rotating speed of 100rpm, and injection-molding a tensile test standard sample strip.
Example 2
The experimental procedure was essentially the same as in example 1, except that: methacryloyl chloride is used for replacing butenoyl chloride, and light calcium carbonate is used for replacing silicon dioxide. The reaction temperature of the dormant polymerization monomer was 10 ℃, the reaction time was 2 hours, and the stirring speed was 50 rpm. In addition, the weight ratio of the light calcium carbonate to the amino coupling agent is 1000: 1.
example 3
The experimental procedure was essentially the same as in example 1, except that: butynoyl chloride is used for replacing butenoyl chloride, and hydrotalcite is used for replacing silicon dioxide. The reaction temperature of the dormant polymerization monomer was-10 ℃, the reaction time was 4 hours, and the stirring speed was 100 rpm. In addition, the weight ratio of the hydrotalcite to the amino coupling agent is 500: 1.
example 4
The experimental procedure was essentially the same as in example 1, except that: darocur 2959 was replaced with the photoinitiator Quantacure QTX. The reaction time of ultraviolet irradiation is adjusted to 0.5 h. In addition, the mass ratio of the amino-modified silicon dioxide particles to the dormant polymerization monomers to the Quantacure QTX is adjusted to be 1: 10: 0.05.
example 5
The experimental procedure was essentially the same as in example 1, except that: darocur 2959 was replaced with the photoinitiator quantacuure BMS. The reaction time of ultraviolet irradiation is adjusted to 2 hours. In addition, the mass ratio of the amino-modified silica particles to the dormant polymerization monomers to the Quantacure BMS is adjusted to 1: 100: 0.5.
comparative example 1
And (3) obtaining a tensile test standard sample strip by injection molding of polypropylene (the melt index is 2-8 g/10min, and the commercially available Daqing petrochemical T30G, the pacific petrochemical T30S, the Quanzhou petrochemical L5D98, the Quanzhou petrochemical H3030 and similar melt index polypropylene brands).
Comparative example 2
This comparative example converts homocysteine thiolactone hydrochloride into the active monomer by adding ethylenediamine during the polymerization. The active monomer can react with the inorganic nano particles under ultraviolet irradiation, can be polymerized by itself, and can also crosslink a plurality of inorganic nano particles. Preparing 10% of amino silane coupling agent by mass, and mixing silica nano-particles and amino silane coupling agent solution according to the ratio of 100: 1, and stirring for 30min to obtain the amino modified silicon dioxide particles.
Amino-modified silica particles, homocysteine thiolactone hydrochloride, ethylenediamine, photoinitiator Darocur 2959 according to 1: 10: 10: adding 0.1 mass ratio of the mixture into a 100L reaction vessel, adding 60L of methanol, stirring and dispersing, reacting for 1h under the illumination of ultraviolet light (365nm), filtering, collecting and precipitating to obtain the hyperbranched polymer modified nano nucleating agent.
Comparative example 3
The experimental procedure was essentially the same as in example 1, except that: the weight ratio of the silica nanoparticles to the amino coupling agent was adjusted to 10: 1.
comparative example 4
The experimental procedure was essentially the same as in example 1, except that: the reaction temperature of homocysteine thiolactone hydrochloride, butenoyl chloride and organic base in tetrahydrofuran was 80 ℃.
The hyperbranched polymer modified nano nucleating agent prepared in each example and the comparative example and the polypropylene are respectively mixed according to the weight ratio of 0.1: 100, melt-extruding and granulating by a double-screw extruder at 210 ℃ and a screw rotating speed of 100rpm, injection-molding a tensile test standard sample strip, and carrying out mechanical property test, wherein the results are shown in table 1.
Table 1 shows the results of mechanical property tests of examples and comparative examples (base resin H3030)
As can be seen from Table 1, the inventive hyperbranched polymer modified inorganic nano nucleating agent improves the Young's modulus of polypropylene by blending, melting and extruding. Compared with the pure polypropylene comparative example 1, the hyperbranched polymer modified inorganic nano nucleating agent prepared by the invention has excellent nucleating effect in polypropylene matrix resin, and improves the mechanical property of polypropylene plastic products. The tensile test bars prepared according to the invention have a higher Young's modulus than comparative example 2 with the reactive monomer. This illustrates: the hyperbranched polymer formed by polymerizing the dormant monomer can effectively control the polymerization degree, improve the dispersion degree of the nano nucleating agent in polypropylene and improve the mechanical property of polypropylene plastic products.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a hyperbranched polymer modified inorganic nano nucleating agent is characterized by comprising the following steps:
(1) mixing homocysteine thiolactone hydrochloride, alpha-unsaturated alkyl acyl chloride and organic base in a preset proportion, and carrying out a first reaction in a medium-polarity solvent at the reaction temperature of-20-10 ℃ for 2-6 h so as to obtain a polymerization monomer;
the predetermined proportion is that the mol mass ratio of the homocysteine thiolactone hydrochloride to the alpha-unsaturated alkyl acyl chloride to the organic base is 1: 1: 1 to 1.2;
the organic base comprises any one of triethylamine, pyridine and lutidine;
the alpha-unsaturated alkyl acyl chloride is at least one of alkenyl acyl chloride and alkynyl acyl chloride;
(2) mixing an amino coupling agent and the inorganic nanoparticles, and carrying out a second reaction to obtain amino modified inorganic nanoparticles;
the mass ratio of the inorganic nanoparticles to the amino coupling agent is 100-1000: 1;
the inorganic nano-particles comprise at least one of inorganic oxide, metal salt, transition metal oxide and transition metal salt;
(3) mixing the amino modified inorganic nano particles, the polymerization monomer and a photoinitiator, and carrying out a third reaction under the irradiation of ultraviolet light for 0.2-2h so as to obtain a hyperbranched polymer modified inorganic nano nucleating agent;
the photoinitiator is a water-soluble photoinitiator; the photoinitiator comprises any one selected from Quantacure BTC, Quantacure BPQ, Quantacure ABP, Quantacure QTX, Quantacure BMS and Darocur 2959;
the wavelength of the ultraviolet light is 250-420 nm.
2. The process according to claim 1, wherein the organic base is triethylamine;
the α -unsaturated alkyl acid chloride includes at least one selected from the group consisting of vinyl acid chloride, methacrylic acid chloride, butenoyl chloride, 4-pentenoyl chloride, hexenoyl chloride and ethynyl acid chloride.
3. The method of claim 1, wherein: the medium polar solvent includes at least one selected from the group consisting of diethyl ether, tetrahydrofuran and dichloromethane.
4. The method according to claim 1, wherein the inorganic nanoparticles in the step (2) comprise at least one selected from the group consisting of silica, calcium carbonate, hydrotalcite, zinc oxide, zirconium oxide, aluminum oxide, titanium oxide, silicate, and aluminosilicate;
the particle size of the inorganic nano particles is 1-2000 nm;
the amino coupling agent is a silane coupling agent containing amino.
5. The process according to claim 1, wherein the photoinitiator is preferably Darocur 2959;
the wavelength of the ultraviolet light is 250-370 nm.
6. The method of claim 1, wherein: the weight ratio of the amino-modified inorganic nanoparticles to the polymerized monomers is 1: 10 to 100 parts;
the weight ratio of the amino-modified inorganic nanoparticles to the photoinitiator is 1: 0.05 to 0.5.
7. A hyperbranched polymer modified inorganic nano nucleating agent is characterized in that: the hyperbranched polymer modified inorganic nano nucleating agent is obtained by the preparation method of any one of claims 1 to 6.
8. A polyolefin resin characterized by: the polyolefin resin comprises the hyperbranched polymer-modified inorganic nano-nucleating agent of claim 7;
the content of the hyperbranched polymer modified inorganic nano nucleating agent in the polyolefin resin is 0.01-1%.
9. The polyolefin resin according to claim 8, characterized in that: the content of the hyperbranched polymer modified inorganic nano nucleating agent in the polyolefin resin is 0.05-0.1%.
10. The polyolefin resin according to claim 8 or 9, characterized in that: the polyolefin resin is used for a film, a foamed material or a sheet.
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| JP6783931B2 (en) * | 2016-10-26 | 2020-11-11 | アルコン インク． | Amphiphile branched chain polydiorganosiloxane macromer |
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| CN103261098A (en) * | 2010-12-22 | 2013-08-21 | 3M创新有限公司 | Surface-modified zirconia nanoparticles |
| CN110615915A (en) * | 2018-06-20 | 2019-12-27 | 华东理工大学 | Composite polypropylene nucleating agent and preparation method and application thereof |
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