CN107573693B - Liquid silicone resin foam material and preparation method thereof - Google Patents
Liquid silicone resin foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a liquid silicone resin foam material, which comprises the following components: (A) vinyl M (D) Q liquid silicone resin 100 parts by mass; (B) 0.1-120 parts by mass of liquid organopolysiloxane; (C) 0-60 parts of micro-nano inorganic particles by mass; (D) 1-30 parts by mass of a crosslinking agent; (E) 1-60 ppm (calculated by Pt mass) of a platinum catalyst; (F) 0-2 parts of an inhibitor. The invention also discloses a preparation method of the liquid silicone resin foam material. The liquid silicone resin foam material obtained by the invention can be prepared into a liquid silicone resin foam material with higher mechanical strength and good appearance no matter a compression molding method or an injection and casting molding method is used.
Description
Technical Field
The invention relates to a liquid organosilicon foam material and a preparation method thereof, in particular to a liquid silicone resin foam material of vinyl M (D) Q silicone resin and a preparation method thereof, belonging to the technical field of organic materials and preparation thereof.
Background
The liquid organosilicon foam material has the advantages of low specific gravity, good flexibility, excellent biocompatibility, weather resistance, ozone resistance, heat resistance and rebound resilience, has good buffering, vibration reduction, heat insulation and sound insulation effects, is easy to form into various shapes, is a novel foam material, and is applied to electronic appliances, building doors and windows, vehicle transportation, sailing ships, aircrafts, precision instruments, aerospace and special equipment.
The inventor discovers that high-dosage (more than 25 parts by mass) nano inorganic particles have poor flowability and are difficult to foam to obtain proper foaming ratio due to the influence of nano particles on the flowability when researching the liquid silicone rubber foam material; the nano inorganic particle reinforced liquid silicone rubber with the dosage less than 25 parts by mass has good fluidity and high foaming ratio, and the obtained foam material has low mechanical property and tensile strength of only 0.2MPa (the density is about 0.5 g/cm)3). Although the solid MQ silicon resin has a certain reinforcing effect on liquid addition silicone rubber, a complex and tedious method is required to be adopted during use: MQ silicone resin is first dissolved with an organic solvent, dispersed in silicone rubber, and then the solvent is removed, and there is a problem of brittleness.
The inventor researches and discovers that a novel organic silicon elastic material, namely M (D) Q vinyl liquid silicone resin material has higher mechanical strength and good rebound resilience without nano particle reinforcement, and a novel liquid silicone resin foam material with adjustable cellular structure can be obtained by adopting organic polysiloxane with hydroxyl functional groups as a foaming component and further controlling the foaming fluidity of glue solution through inorganic nano particles. The test results show that the novel liquid silicone resin foam material has higher strength and mechanical property and good flexibility, and is particularly suitable for the situations of filling, buffering, isolating, damping and the like. Because inorganic nanoparticles can be omitted or omitted, the novel liquid silicone foams have a lower moisture absorption and are particularly suitable for use in moisture-sensitive applications.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid silicone resin foam which is cross-linked and foamed at room temperature (or at a temperature not too high) and under a necessary pressure condition to give a uniform cell structure of a desired shape and has a higher hardness and load-bearing capacity.
As a result of intensive studies to achieve the above object, the inventors have found that a silicone resin containing a liquid vinyl MQ is obtainedLiquid organopolysiloxane, micro-nano particles with the particle size not more than 2 microns (wherein the specific surface area (BET method) of the inorganic nanoparticles is 5-400 m)2The active hydrogen polysiloxane is crosslinked and foamed at room temperature (or at a not too high temperature), and a liquid silicone resin foam material with higher strength and mechanical property, good flexibility and strong bearing capacity can be obtained.
Accordingly, the present invention provides a liquid silicone resin foam, the composition comprising:
the vinyl M (D) Q liquid silicone resin comprises vinyl MQ silicone resin and vinyl MDQ silicone resin, the MQ value is 0.4-1.5, the vinyl content is 0.3-5%, and the viscosity is not more than 50000 mPa.
The liquid silicone resin foam material is characterized in that the organopolysiloxane of component (B) has a degree of polymerization of not more than 2000 and contains at least 2 functional groups bonded to silicon atoms, the functional groups being alkenyl groups or hydroxyl groups.
The liquid silicone resin foam material is characterized in that the micro-nano inorganic particles of the component (C) are selected from at least one of calcium carbonate, aluminum oxide, titanium dioxide, montmorillonite, argil, silicon dioxide, clay, zinc oxide, ferric oxide, diatomite, kaolin and the like, the size of the micro-nano inorganic particles is not more than 2 micrometers, and the specific surface area (BET method) of the nano inorganic particles is 5-400 m2Between/g.
The liquid silicone resin foam material is characterized in that the component (D) is hydrogen-containing polysiloxane, a single molecule of which contains not less than two hydrogen atoms which are connected with silicon atoms, and the content of the hydrogen atoms connected with the silicon atoms is not less than 0.5 percent.
The liquid silicone resin foam material is characterized in that the platinum catalyst of the component (E) is chloroplatinic acid (hydrate) and a platinum complex generated by the reaction of chloroplatinic acid and olefin, alcohol and alkyne; the olefins include propylene, cyclopropene, cyclohexene, hexene and derivatives thereof, vinylsilanes, vinylsiloxanes, vinylcyclosiloxanes, polyvinylcyclosiloxane telomers, unsaturated ethers, vinylpyridine, cyclodienes; the alcohol includes ethanol, isopropanol, and octanol. The alkyne includes acetylene, phenylacetylene, trimethylsilylacetylene, and the like.
The liquid silicone resin foam material is characterized in that the inhibitor of the component (F) is selected from alkynol, polyvinyl siloxane, polyvinyl cyclosiloxane, reactants of alkynol and silane, and polyvinyl cyclosiloxane telomer.
The preparation method of the liquid silicone resin foam material is characterized by mainly comprising the following steps of:
a. mixing and dispersing micro-nano inorganic particles in liquid organopolysiloxane or liquid vinyl M (D) Q silicone resin;
b. mixing liquid vinyl M (D) Q silicone resin, liquid organopolysiloxane and the micro-nano inorganic particle dispersion liquid, and then adding a cross-linking agent, a catalyst, an inhibitor and the like for rapid mixing and uniform dispersion;
c. and quickly pouring the mixed solution into a container, and foaming under the action of proper temperature and time to obtain the liquid silicone resin foam material.
The liquid silicone resin foam material can be obtained according to the invention, and the liquid silicone resin foam material with higher mechanical strength and good appearance can be obtained no matter a compression molding method or an injection and casting molding method is used.
The present invention will be described in further detail below in order to make the technical solutions of the present invention more apparent to those skilled in the art.
Component (A)
The liquid vinyl M (D) Q silicon resin comprises vinyl MQ silicon resin and vinyl MDQ silicon resin, the MQ value is 0.4-1.5, the vinyl content is 0.3-5%, and the viscosity is not more than 50000 mPa.
The liquid vinyl MQ silicon resin is prepared by monofunctional chain link (R)3SiO0.5Code number M) and tetrafunctional units (-SiO)2-, code Q), aliveThe functional group Vi is a liquid polyorganosiloxane having a highly branched three-dimensional (nonlinear) structure comprising a Si-O bond as a skeleton and having a vinyl group. The MQ silicon resin is mainly synthesized by a water glass method and an ethyl orthosilicate method. During the preparation process of the MQ silicon resin, the MQ silicon resin containing different groups such as alkyl, phenyl, vinyl and the like can be prepared by introducing comonomers with different functional group side groups, so that the MQ silicon resin is endowed with specific properties. When the vinyl group is introduced, the curing property can be improved, the adhesion to the base material can be adjusted, and the effect of improving the tearing strength is particularly obvious.
The vinyl modified MDQ silicone resin (or MVDQ silicone resin) is prepared from a monofunctional unit (M) [ Vi (CH)3)2SiO0.5-]A bifunctional unit (D) [ - (CH)3)2SiO-]And tetrafunctional units (Q) [ -SiO [ ]2-]The polysiloxane compound with the structural composition has better flexibility and elongation property compared with the vinyl MQ silicone resin due to the introduction of the bifunctional unit MVDQ silicone resin. MVDQ silicone resins are typically prepared using acid catalyzed hydrolytic polycondensation, base catalyzed hydrolytic polycondensation, and metal salt catalyzed polycondensation. The acid-catalyzed hydrolysis polycondensation method has the advantages of simple process, easily controllable M/Q value (monofunctional chain number/tetrafunctional chain number), narrow molecular molar mass distribution and the like, and is a commonly adopted method for synthesizing the silicon resin at present.
In the synthesis of the liquid MQ silicon resin, bifunctional chain organic silicon materials such as diphenyl dimethoxysilane, hydroxyl-terminated polydimethylsiloxane and vinyl-terminated polydimethylsiloxane, and trifunctional chain organic silicon materials such as phenyl trimethoxysilane, methyl triethoxysilane, vinyl trimethoxysilane and allyl triethoxysilane can be selected as raw materials to synthesize organic silicon resins which can flow at room temperature and have various characteristics and do not contain solvents.
The liquid vinyl M (D) Q silicone resin has properties between those of common inorganic and organic high molecular compounds, has high temperature resistance, hydrophobicity, low temperature resistance, film forming property, flexibility, water resistance, adhesive property, chemical resistance and other properties which are difficult to achieve by common resins, and also has excellent electrical insulation property, mechanical property, heat resistance, flexibility, film forming property and adhesive property, and has high industrial application value, so that the liquid vinyl M (D) Q silicone resin is widely applied to the fields of reinforcing fillers, tackifiers, pressure-sensitive adhesives, surface treatment agents, personal care product additives and the like of liquid silicone rubber. The M (D) Q silicone resin with the surface introduced with the vinyl has better reinforcing effect on the liquid silicone rubber, so the M (D) Q silicone resin has good development prospect and application value in the field of reinforcing of packaging materials.
The liquid vinyl M (D) Q silicone resin of component (A) can adopt a single molecular chain structure, or a mixture of two or more liquid MQ or MDQ silicone resins with different molecular chain structures or different viscosity-average polymerization degrees.
The MQ value of the liquid vinyl MQ silicon resin is between 0.4 and 1.5, preferably between 0.8 and 1.2; the content of vinyl is 0.3-5%, preferably 0.5-3%; the viscosity is not more than 50000 mPas, and the preferable range is 2000-10000 mPas.
Component (B)
The liquid organopolysiloxane of component (B) is specifically characterized by: polyorganosiloxane having a polymerization degree of not more than 2000 and containing at least 2 functional groups directly bonded to silicon atoms per molecule, wherein the functional groups are hydroxyl groups or alkenyl groups. The organopolysiloxane is a low molecular weight polysiloxane polymer matrix material, and the structural formula of which the end group is a monofunctional group is shown as a formula (I).
(in the formula, R1Represent identical or different monovalent hydrocarbon radicals, R2Represents a functional group of a hydroxyl group or an alkenyl group. )
In the formula (I), R1Represent identical or different monovalent hydrocarbon groups, generally 1 to 6 carbon atoms. R1The monovalent hydrocarbon group may be mono-or poly-substituted, and the substituent may be halogen or cyano. R1Examples of (b) include alkyl types of butyl, hexyl, methyl, ethyl, propyl; cycloalkyl type of cyclohexyl; aryl of phenyl, methylphenylMolding; types of monovalent substituted hydrocarbon groups include chloromethyl, trifluoropropyl, or cyanoethyl.
Monovalent hydrocarbon radicals R of organopolysiloxanes1Among them, methyl, ethyl, phenyl or trifluoropropyl is preferable, and the ratio of methyl groups in the total number of R is preferably 80 to 99.99mo 1%, more preferably 95 to 99.99mo 1%. The end group of the organopolysiloxane is dimethylvinylsiloxane, dimethylhydroxystanxane group, trivinylsiloxane group, or the like which can participate in the crosslinking reaction.
The organopolysiloxane of component (B) can be prepared by ring-opening polymerization, vinyl or hydroxyl capping reaction of cyclic low molecular weight organopolysiloxane (such as trimer or tetramer of organosiloxane) in alkaline or acidic catalyst and high temperature condition, or by hydrolysis-condensation polymerization of one or more kinds of organohalosilanes.
The organopolysiloxane of component (B) may have a single molecular chain structure, or may have a combination of two or more organopolysiloxanes having different molecular chain structures or different degrees of viscosity-average polymerization, such as hydroxy-terminated polydimethylsiloxane (B1) having a single number of segments n of 3 to 16, or hydroxy-terminated polydimethylsiloxane (B2) having a single number of segments n of 100 to 1000, or vinyl-terminated polydimethylsiloxane (B3) having a single number of segments B1 and n of 100 to 1000, or a combination of B2 and B3.
The liquid organopolysiloxane contains at least 2 functional groups such as alkenyl groups, hydroxyl groups, alkenyl groups such as vinyl groups, allyl groups, etc. directly bonded to silicon atoms per molecule. Alkenyl content ranges from 0.04 mol% to 1.0mo 1%, preferably 0.1 mol% to 0.3mo 1%; the content of the hydroxyl is 0.04-10%, preferably 0.08-8%.
The viscosity average degree of polymerization of the organopolysiloxane of component (B) is 2000 or less, preferably 3 to 1000, more preferably 14 to 500. The organopolysiloxane of component (B) has suitable flowability, good processability, and suitable mechanical strength as long as the viscosity average polymerization degree is within this range.
The amount of the organopolysiloxane of component (B) is preferably 0 to 120 parts by mass per 100 parts by mass of component (A), more preferably 10 to 100 parts by mass, and still more preferably 30 to 70 parts by mass. As long as the amount of the organopolysiloxane of component (B) added is within this range, the processability and physical mechanical properties of the liquid silicone foam can be brought to an acceptable level.
Component (C)
The component (C) inorganic micro-nano particles are used for ensuring that the liquid silicone resin foam material with proper rheological property is obtained. The micro-nano inorganic particles of the component (C) are selected from at least one of calcium carbonate, aluminum oxide, titanium dioxide, montmorillonite, argil, silicon dioxide, clay, zinc oxide, ferric oxide, diatomite, kaolin and the like, and the average particle size of the micro-nano inorganic particles is not more than 2 microns; wherein the nanoparticles have a specific surface area (BET method) of 5 to 400m2Between/g.
In order to ensure proper rheological property, the specific surface area of the inorganic nano particles is 5-400 m2Between/g, preferably 10 to 300m2A concentration of 50 to 240m2(ii) in terms of/g. Examples of the inorganic nanoparticles include fumed silica (dry silica, fumed silica) and precipitated silica (wet silica, precipitated silica), brilliant white, nano kaolin, nano titanium dioxide, nano alumina, hard clay, soft clay and the like, and fumed silica (dry silica), precipitated silica are preferred. The inorganic micro-nano particles can be made of a single material or a combination of two or more different materials.
The addition amount of the micro-nano inorganic particles is preferably 0 to 60 parts by mass per 100 parts by mass of the organic polymer of the component (A), preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass. As long as the amount of the inorganic nanoparticles is within this range, the processability and physical mechanical properties of the liquid silicone foam can be brought to an acceptable level.
In order to disperse the inorganic micro-nano particles in the organic polymer of the component (A, B), a dispersing agent which can react with the surface of the inorganic nano particles, such as trimethylsilanol, diphenylsilanediol, hexamethylsilazane, hexamethylcyclotrisilazane, dimethyldiethoxysilane, or poly dimethylpolysiloxane (hydroxy silicone oil or alkoxy silicone oil) with hydroxyl and alkoxy as end groups, can be added, and alkyl triethoxysilane, alkyl trimethoxysilane and the like can also be added, wherein the alkyl group comprises methyl, ethyl, propyl, butyl, pentyl, and hexyl, octyl, dodecyl, hexadecyl and the like. The amount of the dispersant to be added is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the nanoparticles. The surface of the inorganic nanoparticles may also be previously subjected to hydrophobic treatment with organosiloxanes, organopolysilazanes, hexamethylsilazane, alkoxysilanes (e.g., dimethyldiethoxysilane), chlorosilanes (e.g., dimethyldichlorosilane), and the like.
The organic siloxane polymer of the components (A), (B) and the inorganic nanoparticles of the component (C) may be mixed together with the above-mentioned preferred dispersing agent using a mill or a kneader, a planetary mixer, a mechanical stirrer or the like, and then the resulting mixture is subjected to (vacuum) heat treatment in a kneader or a high-temperature dry box to obtain a polymeric nanoparticle composite base. The purpose of the (vacuum) heat treatment is to remove volatile components from the liquid silicone resin and the liquid organopolysiloxane and to accelerate the reaction between the inorganic nanoparticle powder and the dispersant molecules. The (vacuum) heat treatment is generally carried out by heating the above mixture at a temperature of 100 to 250 ℃, preferably 150 to 220 ℃ for 1 to 6 hours. The inorganic nanoparticles, which are subjected to hydrophobic treatment in advance, may be mixed with the organosiloxane polymer and dispersed without being subjected to (vacuum) heat treatment.
Component (D)
The cross-linking agent of the component (D), namely the active hydrogen polyorganosiloxane (hydrogen-containing silicone oil), contains not less than two hydrogen atoms which are connected with silicon atoms in a single molecule, and the content of the hydrogen atoms connected with the silicon atoms is not less than 0.5 percent.
The structural formula of the active hydrogen polyorganosiloxane is shown as formula II:
HcR3-cSi-(SiHRO)a-(SiR2O)b-SiR3-cHc (II)
(wherein R represents identical or different monovalent hydrocarbon groups, a and b are degrees of polymerization of different units, c is the number of terminal functional groups, and c is 0 or a positive integer less than 3.)
In the formula (II), R represents identical or different monovalent hydrocarbon groups, and usually has 1 to 6 carbon atoms. The univalent hydrocarbon group represented by R can be mono-substituted or multi-substituted, and the substituent can be halogen or cyano. Examples of R include alkyl types of butyl, hexyl, methyl, ethyl, propyl. As shown in formula II, the active hydrogen can be located on a side group or end group of the crosslinker molecule, or both.
The hydrogen content of the active hydrogen polyorganosiloxane (in terms of hydrogen atoms directly bonded to silicon atoms) is preferably 0.5 to 1.6%, more preferably 0.6 to 1.5%.
The active hydrogen polyorganosiloxane can adopt a single molecular chain structure or a mixture of two or more organopolysiloxanes with different molecular chain structures or different viscosity-average polymerization degrees, and preferably adopts a method that trimethyl polyhydromethyl siloxane with 1.6 percent of hydrogen content is used alone or a method that trimethyl end-capped polyhydromethyl siloxane with 1.6 percent of hydrogen content and 0.5 to 1.2 percent of hydrogen content are used together.
The preparation of the active hydrogen polyorganosiloxane can adopt a telomerization method of high hydrogen polysiloxane (hydrogen content is more than 1.5 percent), octamethylcyclotetrasiloxane and hexamethyldisiloxane (MM) under the catalysis of concentrated sulfuric acid, for example, the reaction is carried out for 4 hours at 60-65 ℃, and low-boiling-point substances are removed by reduced pressure distillation, thus obtaining the required active hydrogen polyorganosiloxane with low hydrogen content (<1.5 percent).
The amount of the component (D) to be added is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the organic polymer of the component (A). As long as the amount of component (E) is within this range, the processability and physical mechanical properties of the liquid silicone foam can be brought to an acceptable level.
Component (E)
The catalyst of the component (E) is a platinum catalyst with catalytic activity on hydrosilylation and dehydrogenation condensation reactions, and is characterized in that the platinum catalyst is chloroplatinic acid (hydrate) and a platinum complex compound generated by the reaction of chloroplatinic acid and olefin, alcohol and alkyne; the olefin includes propylene, cyclopropene, cyclohexene, hexene and its derivatives, vinylsilanes, vinylsiloxanes, vinylcyclosiloxanes, unsaturated ethers, ethylenePhenylpyridine, cyclodiolefins; the alcohol includes ethanol, isopropanol, and octanol. The alkyne includes acetylene, phenylacetylene, trimethylsilylacetylene, and the like. The vinyl siloxane includes tetramethyldivinyldisiloxane, 1, 3-divinyl-1, 3 diphenyl-dimethyldisiloxane, 1-hydroxy-3-vinyl-tetramethyldisiloxane. Specifically, platinum catalysts such as complexes of platinum metal with olefinic compounds such as Pt (0) complex (PPh)3)2Pt-(CH2＝CH2) Reaction products of chloroplatinic acid with organic alcohols, e.g. chloroplatinic acid (H)2PtCl6·H2O) in isopropanol (Speier catalyst), in octanol (Clo platinic acid), in ethanol (Clo platinic acid), in acetone (Clo platinic acid) systems, in anisole (Clo platinic acid), in platinum-alkynyl complexes such as bis (alkynyl) bis (triphenylphosphine) platinum complex, in bis (alkynyl) (cyclodialkenyl) platinum complex, in Karstedt's catalyst ([ (CH)2＝CHSiMe2)2O]2Pt)——H2PtCl6With tetramethyldivinylsiloxane (DVDM) and NaHCO3Reaction product of (1), Willing's catalyst-H2PtCl6The acid product was washed with water after reaction with tetramethyldivinylsiloxane. The olefin compound is selected from, but not limited to, tetramethyldivinyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, 1, 3-divinyl-1, 3 diphenyl-dimethyldisiloxane, 1-hydroxy-3-vinyl-tetramethyldisiloxane, propylene, cyclopropene, cyclohexene, hexene and its derivatives, vinyltrimethoxysilane, vinyltriethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, unsaturated ethers, vinylpyridine, and the like.
Component (E) is preferably a platinum-methyldiethylenedisiloxane Complex (CH)2＝CHSiMe2)2Pt, platinum-tetramethyltetravinylcyclotetrasiloxane complex, (PPh)3)2Pt(CH2＝CH2) And chloroplatinic acid (H)2PtCl6·H2O) in isopropanol (Speier catalyst).
The purity or concentration of component (E) is not subject to any significant restrictions, but the noble metal content can be 1000ppm or 5000ppm, or even more 18%, provided that the amount added, in terms of Pt by mass, is within a defined concentration range such that the desired foam can be formed, i.e. both initiated and cured in time; the mode of addition of the component (E) is not particularly limited, and it may be added directly or after dilution to a low concentration component.
The amount of the component (E) is preferably 1 to 60ppm (ppm is abbreviated as "ppm in English" in terms of Pt by mass) in the total of the components (A) to (B), and the processability and physicomechanical properties of the liquid silicone foam can be brought to an acceptable level as long as the amount of the component (E) is within this range. The addition amount of the component (E) is preferably in the range of 3 to 40ppm, more preferably 5 to 25ppm (in terms of Pt mass). Since the method based on the mass of Pt in the active ingredient is adopted, even if the supplier of the component (E) provides different purities or concentrations or the custom of the user is different, the same amount of the effective ingredient is added, which ensures the same forming effect.
Component (F)
The inhibitor of component (F) is selected from at least one of alkynol, polyvinyl siloxane, polyvinyl cyclosiloxane, phenylacetylene, reactants of alkynol and silane as a foaming curing regulator. Specifically, the silicone oil is selected from propiolic alcohol, 1-butynol, methylbutynol, 3-dimethyl-pentynol, 1-ethynyl-cyclohexanol, phenylbutynol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn-3-ol, divinyltetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, and tetramethyltetravinylcyclotetrasiloxane telomer-siloxane. Examples of the reaction product of the alkynol and the silane include methyltrichlorosilane vinyltrichlorosilane, tris- (3-methyl-1-butyn-3-oxy) methylsilane, tris- (3-methyl-1-butyn-3-oxy) vinylsilane, which is a reaction product of phenyltrichlorosilane with 3-methyl-1-butyn-3-ol or 1-ethynyl-cyclohexanol, and the like. Tetramethyltetravinylcyclotetrasiloxane telomers, e.g. R- (MeViSiO-)nR, wherein n is 8-16, and examples of the terminal group R include trimethylsiloxy, trivinylsiloxy, vinyldimethylsiloxy and the like.
Component (F) is preferably a polyvinyl siloxane, polyvinyl cyclosiloxane, alkynol, or the like.
The amount of the component (F) to be added is preferably 0 to 2 parts by mass, more preferably 0.03 to 0.8 part by mass, and still more preferably 0.08 to 0.4 part by mass, per 100 parts by mass of the organic polymer of the component (A). As long as the amount of component (E) is within this range, the processability and physical mechanical properties of the liquid silicone foam can be brought to an acceptable level.
Other components-
The present invention may further contain a thermal conductivity-imparting agent such as magnesium oxide, zinc oxide, or aluminum oxide; conductivity-imparting agents such as acetylene black and conductive carbon black; non-reinforcing fillers of micron/submicron size such as diatomaceous earth, kaolin, soft china clay, light calcium carbonate, talc; softeners such as liquid paraffin, machine oil, paraffin oil, etc., for improving processability.
Preparation method
The preparation method of the liquid silicone resin foam material is characterized by mainly comprising the following steps of:
a. mixing and dispersing micro-nano inorganic particles
Mixing liquid vinyl M (D) Q silicone resin or organopolysiloxane with polymerization degree not higher than 2000 with micro-nano inorganic particles with particle size not greater than 2 micron and specific surface area (BET method) not less than 10m by using rubber mixing mill, internal mixer, kneader, mechanical stirrer, planetary stirrer, etc2The inorganic nanoparticle reinforcing agent/g, necessary dispersing agent and weak reinforcing filler such as white brilliant, diatomaceous earth, etc. are mixed together, and then the obtained nano inorganic particle mixture is subjected to heat treatment by means of an internal mixer, a kneader, a forced air dryer, etc., and discharged and cooled, thereby obtaining the organic polymer nanoparticle reinforcing base material. The purpose of the heat treatment is to remove volatile components and accelerate the reaction between the inorganic nanoparticles and the dispersant. The temperature or heating time for the heat treatment of the liquid vinyl M (D) Q silicone resin or low molecular weight organopolysiloxane is not particularly limited, and for example, the above mixture can be heated at a temperature of 100 ℃ to 250 ℃, preferably 150 ℃ to 220 ℃ for 1 to 6 hours for the heat treatment. For the inorganic nanoparticles which have been subjected to a hydrophobic treatment in advance, inAfter mixing and dispersing with the organosiloxane polymer or the liquid vinyl M (D) Q silicone resin, the (vacuum) heat treatment can be omitted.
b. Mixing of the components
Quickly mixing and uniformly dispersing liquid vinyl M (D) Q silicone resin, liquid organopolysiloxane, nano inorganic particle dispersion liquid, a crosslinking agent, a catalyst, an inhibitor and the like by adopting a mechanical stirrer, a planetary stirrer or a reaction extrusion mixer (RIM).
c. Cross-linked foaming of compositions
And quickly pouring the mixed solution into a container, and foaming under the action of proper temperature and time to obtain the liquid silicone resin foam material. After the foam structure was stabilized, a liquid silicone foam was obtained.
The foaming mode of the foam is not particularly limited, and the foam can be extruded, cast or molded, can obtain a fine, uniform and elastic cell structure, and has stable foaming and forming effects and good repeatability.
The manner of addition of the liquid organopolysiloxane is not particularly limited. The liquid organopolysiloxane can be completely mixed with the micro-nano inorganic particles and then mixed with liquid vinyl M (D) Q silicone resin; or mixing part of the mixture with micro-nano inorganic particles, and then mixing and dispersing the mixture with liquid vinyl M (D) Q silicone resin and the rest liquid organopolysiloxane; and the micro-nano inorganic particle mixture can be mixed and dispersed with liquid vinyl M (D) Q silicon resin, and the like.
The mixing method of the inorganic micro-nano particles is not particularly limited. The inorganic micro-nano particles can be mixed with liquid organopolysiloxane or liquid vinyl M (D) silicone resin to obtain an inorganic micro-nano particle mixture. The mixture can be obtained by mixing a predetermined amount of the above components with a twin-roll plasticator, a rubber mixer, a kneader or a banbury mixer, a rubber (plastic) internal mixer or a pressure type kneader, a screw extruder, or the like. The manner of rapid mixing of the materials is not particularly limited, and any method such as a mechanical stirrer, a planetary stirrer, a high-speed mixer or a reactive extrusion mixer may be used as long as uniform and rapid mixing can be achieved.
The crosslinking or curing method of the liquid silicone resin foam of the present invention is not particularly limited, and casting, pressing (molding), injection molding or transfer (injection molding), extrusion molding, and the like can be used, and casting, pressing, injection molding, and the like are preferably used. The temperature conditions for molding the liquid silicone resin foam are not particularly limited, and may be room temperature or a not too high temperature (e.g., not more than 60 ℃), preferably room temperature or room temperature. The pressure conditions for molding the liquid silicone resin foam are not particularly limited, and the foam may be freely foamed without pressure or foamed under pressure, and preferably, the foam is freely foamed into a predetermined shape and then closed and pressurized to maintain a desired shape, and the desired pressure is set so that the cavity retains the desired shape and the foamed composition is filled and molded.
Detailed Description
The present invention will be specifically described below by way of a series of examples and comparative examples, but the present invention is not limited in any way by the following examples. In the following examples, "parts" means "parts by mass".
Example 1
100 parts by mass of alpha, omega-dihydroxypolydimethylsiloxane (colorless transparent fluid, viscosity 2000 mPas, volatile 1.0%, manufactured by Shanghai resin works Co., Ltd.) 40 parts by mass of a mixture having a BET specific surface area of 125m2(5 parts by mass) of hydrophobic precipitated silica having silanol groups at both ends and a viscosity of 29mm (manufactured by Jilin Tonghuan Shuanglong chemical Co., Ltd.)2Adding/s (23 ℃) dimethyl polysiloxane into a 5L vacuum kneader, mixing at room temperature, kneading for 2h at 130 ℃ in vacuum, discharging and cooling to room temperature to obtain the liquid polysiloxane nanoparticle base material.
100 parts by mass of liquid vinyl MDQ silicone resin (with a vinyl content of 3%, an MQ value of 0.8, a viscosity of 5000 mPa. s, manufactured by Shanghai-Eibo chemical Co., Ltd.), 100 parts by mass of liquid polysiloxane nanoparticle base material (containing about 71 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and about 29 parts by mass of nano-silica particles), 20 parts by mass of liquid hydrogen-containing silicone oil (with a hydrogen content of 1.56%, manufactured by Zhejiang-Zhou orange-build Silicone Co., Ltd.), 3.3 parts by mass of hydroxyl silicone oil (Zhongjiang-Zhi-Jian orange-build Silicone Co., Ltd.), and a mixture209-3 produced by Hao Chen photochemical research institute, 15-20 mPa.s in viscosity, 7-9% in hydroxyl content and 14-15 in polymerization degree, 0.16 part by mass of tetramethyltetravinylcyclotetrasiloxane (produced by Hao Chen photochemical research institute, the purity of which is not less than 99%) and 0.75 part by mass of VM-23 platinum catalyst (mainly comprising [ (CH-Cf)2＝CHSiMe2)2O]2Pt and [ (CH)2＝CHSiMe2)O]Pt[CH2＝CHSiMe2OSiMe2OH]3000ppm of Pt complex catalyst, manufactured by Zhejiang thoroughfare Jian orange organosilicon Co., Ltd.) wherein the Pt catalyst is 13ppm by mass of Pt, and the Pt catalyst is mixed in a beaker at room temperature for 30 seconds at the rotating speed of 500-1000 rpm by a mechanical stirrer and is uniformly mixed.
And quickly pouring the uniformly mixed materials into a container, fixing the container by using bolts at room temperature for a certain time, and foaming to obtain the liquid silicone resin foam material which is fully cured and has good foaming performance.
The hardness of a foaming sample of the liquid silicone rubber foam material is tested according to GB/T531-1999, the density of the foam is measured according to GB/T533-2008, a foam sheet with the thickness of 1 mm-2 mm is obtained through sheet cutting processing, the size of the foam hole is observed visually, and the foaming effect is comprehensively evaluated through the aspects of hand resilience, the foaming effect, hardness, elasticity/brittleness and the like.
Example 2
100 parts by mass of alpha, omega-bisvinyl polydimethylsiloxane (0.31% of vinyl content, 500mPa & s of viscosity, manufactured by Zhejiang thoroughfare Jian orange organosilicon Co., Ltd.) and 40 parts by mass of BET specific surface area of 197.5m2(5 parts by mass) of fumed silica (Shenyang chemical Co., Ltd.) having silanol groups at both ends and having a viscosity of 29mm2Adding 5 mass parts of hexamethyldisilazane (purity of more than 98 percent produced by Anhui Union Siliconization factories) into a 5L vacuum kneader, mixing at room temperature, kneading at 130 ℃ for 2h in vacuum, discharging and cooling to room temperature to obtain the liquid polysiloxane nanoparticle base material.
100 mass parts of liquid vinyl MDQ silicone resin (the vinyl content is 3 percent, the MQ value is 0.8, the viscosity is 5000 mPa.s, manufactured by Shanghai Eishibo chemical Co., Ltd.), 50 mass parts of the above-mentioned divinyl polydimethylsiloxane nano-silica mixture (containing about 36 mass parts of alpha, omega-divinyl polydimethylsiloxane and about 14 mass parts of nano-silica particles), 50 mass parts of alpha, omega-divinyl polydimethylsiloxane (the vinyl content is 0.1 percent, the viscosity is 10000 mPa.s, manufactured by Zhejiang Quzhou Jian Orangent organosilicon Co., Ltd.), 15.5 mass parts of liquid hydrogen-containing silicone oil (the hydrogen content is 1.56 percent, manufactured by Zhejiang Quzhou Jian Cheng organosilicon Co., Ltd.), 10 mass parts of hydroxyl silicone oil (209-3, the viscosity is 15-20 mPa.s, the hydroxyl content is 7-9 percent), 0.1 mass part of tetramethyl tetravinyl cyclotetrasiloxane (manufactured by Zhonghao Guanyu chemical research institute, purity not less than 99%) and 0.75 part by mass of VM-23 platinum catalyst (Pt mass fraction of 3000ppm, Zhejiang thoroughfare Jian Organo Silicone Co., Ltd.) wherein the Pt catalyst is 12ppm by mass of Pt, and the Pt catalyst is mixed in a beaker at room temperature for 30 seconds at a rotating speed of 500-1000 rpm by a mechanical stirrer and is uniformly mixed.
And quickly pouring the uniformly mixed materials into a container, and foaming at room temperature for a certain time to obtain the liquid silicone resin foam material which is fully cured and has good foaming performance.
Example 3
100 parts by mass of liquid vinyl MQ silicon resin (1% of vinyl content, MQ value of 0.8, viscosity of 5000 mPas, manufactured by Zhejiang Runshe organosilicon New Material Co., Ltd.), 2.7 parts by mass of hydroxy silicone oil (209-3, viscosity of 15-20 mPas, hydroxy content of 7-9% by mass, produced by Zhonghao Chenghua Photochemcial research institute), 7.3 parts by mass of liquid hydrogen-containing silicone oil (1.56% of hydrogen content, produced by Zhejiang Zhengzhou Jiancheng organosilicon Co., Ltd.), 0.083 part by mass of tetramethyl tetravinylcyclotetrasiloxane (produced by Zhonghao Cheng Photochemcial research institute, purity of not less than 99%) and 0.39 parts by mass of VM-23 platinum catalyst (3000 ppm by Pt mass fraction, produced by Zhejiang Jian organosilicon Co., Ltd.) wherein the Pt catalyst is 11.7ppm by mass, because component (C) is not used, the dispersion step of nanoparticles is not needed, the above components are directly mixed in a beaker at room temperature of 500-1000 rpm for 30 seconds, mixing evenly, pouring into a container quickly, and foaming at room temperature for a certain time to obtain the liquid silicone resin foam material which is fully cured and has good foaming performance.
Example 4
100 parts by mass of liquid vinyl MDQ silicon resin (the vinyl content is 3 percent, the MQ value is 0.8, the viscosity is 5000 mPa.s, and the product is manufactured by Shanghai Eibo chemical Co., Ltd.), 5 parts by mass of hydroxyl silicone oil (209-3 produced by Zhonghao Chen photochemical research institute, the viscosity is 15-20 mPa.s, the hydroxyl content is 7-9 percent, the degree of polymerization is 14.5), 9.5 parts by mass of liquid hydrogen-containing silicone oil (the hydrogen content is 1.56 percent, produced by Zhejiang orange-producing organosilicon Co., Ltd.), 0.25 part by mass of platinum catalyst (VM-23, the Pt mass fraction is 3000ppm, Zhejiang orange-producing organosilicon Co., Ltd.) wherein the Pt catalyst is 7.5ppm by mass, because the component (C) is not used, the dispersion step of nano particles is not needed, the components are directly mixed in a beaker at the rotating speed of 500-1000 rpm for 30 seconds at room temperature, the mixture is poured into a container, and the container is rapidly fixed by a bolt at, i.e. foamable to give a liquid silicone foam that is well cured and gives good rise.
Comparative example 1
100 parts by mass of alpha, omega-dihydroxypolydimethylsiloxane (colorless transparent fluid, viscosity 2000 mPas, volatile 1.0%, manufactured by Shanghai resin works Co., Ltd.) 55 parts by mass of a mixture having a BET specific surface area of 125m2(hydrophobic precipitated silica) 3 parts by mass of a hydrophobic precipitated silica having silanol groups at both ends and a viscosity of 29mm (manufactured by Jilin Tonghi Shuanglong chemical Co., Ltd.)2Adding/s (23 ℃) dimethyl polysiloxane into a 5L vacuum kneader, mixing at room temperature, kneading for 2h at 130 ℃ in vacuum, discharging and cooling to room temperature to obtain the liquid polysiloxane nanoparticle base material.
Mixing 100 parts by mass of the dihydroxy polydimethylsiloxane nano silica mixture (containing about 64.5 parts by mass of alpha, omega-dihydroxy polydimethylsiloxane and about 35.5 parts by mass of nano silica particles), 18.8 parts by mass of alpha, omega-bis-vinyl polydimethylsiloxane (having a vinyl content of 0.23%, a viscosity of 2000mPa s, manufactured by Zhejiang thoroughfare orange silicone Co., Ltd.), 12 parts by mass of liquid hydrogen-containing silicone oil (having a hydrogen content of 1.56%, manufactured by Zhejiang thoroughfare orange silicone Co., Ltd.), 0.105 part by mass of tetramethyl tetravinylcyclotetrasiloxane (manufactured by Zhonghao Cheng Photochemic research institute, a purity of not less than 99%) and 0.275 part by mass of VM-23 platinum catalyst (having a Pt mass fraction of 3000ppm, manufactured by Jianjiang thoroughfare orange silicone Co., Ltd.) at room temperature and a rotation speed of 500 to 1000rpm for 30 seconds by a mechanical stirrer at Pt mass of 9.9ppm, and (4) uniformly mixing.
And quickly pouring the uniformly mixed materials into a container, and foaming at room temperature for a certain time to obtain the liquid silicone rubber foam material which is fully cured, has good foaming effect and is low in foaming rate.
Comparative example 2
100 parts by mass of alpha, omega-dihydroxypolydimethylsiloxane (colorless transparent fluid, viscosity 2000 mPas, volatile 1.0%, manufactured by Shanghai resin works Co., Ltd.), 20 parts by mass of BET specific surface area of 125m2The hydrophobic precipitated silica/g white carbon black (manufactured by Jilin Tonghua Shuanglong chemical industry Co., Ltd., dried at 110 ℃ for 3 hours), 30 parts by mass of solid vinyl MQ silicon resin (the vinyl content is 2.2%, the MQ value is 0.6, manufactured by Shanghai Eibo Shibo chemical industry Co., Ltd.), 60 parts by mass of toluene (analytically pure), 5 parts by mass of hydroxyl silicone oil (209-3 manufactured by Zhonghao Cheng photochemical research institute, the viscosity is 15-20 mPa.s, the hydroxyl content is 7-9%, the polymerization degree is 14-15), 9.5 parts by mass of liquid hydrogen-containing silicone oil (the hydrogen content is 1.56%, manufactured by Zhejiang Quzhou Jianzhou orange organosilicon Co., Ltd.), 0.25 parts by mass of VM-23 platinum catalyst (the Pt mass fraction is 3000ppm, and is manufactured by Zhejiang Quzhou Jianzhou orange organosilicon Co., Ltd.), wherein the Pt catalyst is 5 ppm. Because the solid vinyl MQ silicon resin is difficult to dissolve in alpha and omega-dihydroxy polydimethylsiloxane at normal temperature, the effect of melting and dispersing the alpha and omega-dihydroxy polydimethylsiloxane at the elevated temperature is poor, the method for dissolving the solid MQ silicon resin in toluene, mixing and dispersing the solid MQ silicon resin and the alpha and omega-dihydroxy polydimethylsiloxane and discharging the toluene in vacuum is adopted to obtain the dispersion liquid of the alpha, omega-dihydroxy polydimethylsiloxane and the (solid) MQ silicon resin, hydrophobic white carbon black and other components are added into a beaker at room temperature by a mechanical stirrer, the mixture is mixed for 30 seconds at the rotating speed of 500-1000 rpm, the mixture is uniformly mixed and quickly poured into a container, and the mixture can be foamed to obtain the silicon liquid which is fully cured and has better initiation but slight brittleness after a certain time at room temperatureA rubber foam material.
The results relating to examples 1 to 4 and comparative examples 1 and 2 are shown in table 1 below.
TABLE 1
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (5)
1. A liquid silicone resin foam material, characterized by: the composition is prepared from the following components:
the vinyl M (D) Q liquid silicone resin comprises vinyl MQ silicone resin and vinyl MDQ silicone resin, the MQ value is 0.4-1.5, the vinyl content is 0.3-5%, and the viscosity is 2000-10000 mPa & s;
the polymerization degree of the liquid organopolysiloxane is not higher than 2000, and the liquid organopolysiloxane contains at least 2 functional groups connected with silicon atoms, wherein the functional groups are hydroxyl groups and alkenyl groups;
the nanometer inorganic particle rulerThe size is not more than 2 microns, and the specific surface area of a BET method is 5-400 m2Between/g.
2. The liquid silicone foam of claim 1, wherein:
(C) the nano inorganic particles of the component are selected from at least one of calcium carbonate, aluminum oxide, titanium dioxide, montmorillonite, pottery clay, silicon dioxide, clay, zinc oxide, ferric oxide, diatomite and kaolin.
3. A liquid silicone foam material as claimed in claim 1, wherein:
(D) the cross-linking agent of the component is hydrogen-containing polysiloxane, a single molecule contains not less than two hydrogen atoms which are connected with silicon atoms, and the content of the hydrogen atoms connected with the silicon atoms is not less than 0.5 percent.
4. A liquid silicone foam material as claimed in claim 1, wherein:
(E) the platinum catalyst of the component is a platinum complex generated by the reaction of hydrated chloroplatinic acid and hydrated chloroplatinic acid with olefin, alcohol and alkyne, wherein the olefin comprises propylene, cyclopropene, cyclohexene, hexene and derivatives thereof, vinyl silane, vinyl siloxane, vinyl cyclosiloxane, polyvinyl cyclosiloxane telomer, unsaturated ether, vinyl pyridine and cyclodiolefine; the alcohol comprises ethanol, isopropanol and octanol; the alkyne includes acetylene, phenylacetylene and trimethylsilyl acetylene.
5. A liquid silicone foam material as claimed in claim 1, wherein:
(F) the inhibitor of the component is selected from at least one of alkynol, polyvinyl siloxane, polyvinyl cyclosiloxane, reactants of alkynol and silane, and polyvinyl cyclosiloxane telomer.
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| CN111592764B (en) * | 2020-05-29 | 2021-08-31 | 浙江新安化工集团股份有限公司 | Silicone resin reinforced organosilicon elastomer aqueous dispersion liquid and preparation method and application thereof |
| CN111691193A (en) * | 2020-06-30 | 2020-09-22 | 福建宝利特科技股份有限公司 | Foaming organic silicon synthetic leather and preparation method thereof |
| CN112662185B (en) * | 2020-12-07 | 2022-06-07 | 合盛硅业(嘉兴)有限公司 | Method for preparing liquid silicone rubber-based adhesive by using hexamethyldisilazane |
| CN114854366B (en) * | 2022-05-11 | 2023-12-12 | 南京科矽新材料科技有限公司 | Anti-poisoning organic silicon die bond adhesive for LED |
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