CN103319719B - Method for preparing intelligent stress responding type silicon-boron polymer microgel - Google Patents
Method for preparing intelligent stress responding type silicon-boron polymer microgel Download PDFInfo
- Publication number
- CN103319719B CN103319719B CN201210072585.9A CN201210072585A CN103319719B CN 103319719 B CN103319719 B CN 103319719B CN 201210072585 A CN201210072585 A CN 201210072585A CN 103319719 B CN103319719 B CN 103319719B
- Authority
- CN
- China
- Prior art keywords
- type silicon
- stress response
- response type
- silicon boron
- boron polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/56—Boron-containing linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
The invention discloses a method for preparing intelligent stress responding type silicon-boron polymer microgel, comprising the following steps of: stirring a prepolymerization reaction solution at 70-130 DEG C to react for 1-6h, continuously stirring after adding a bifunctional chain extender to react at 30-90 DEG C for 2-6h, and finally stirring after adding a functional modifier to react at 30-120 DEG C for 4-8h, to obtain the intelligent stress responding type silicon-boron polymer microgel. The prepolymerization reaction solution comprises: 75.0-96.5 wt. % low molecular weight polydiorganosiloxane, and 3.50-25.0 wt. % of boron-containing compound. The method for preparing the intelligent stress responding type silicon-boron polymer microgel has advantages of low reaction temperature and easy operation, has no need to introduce a catalyst, and is in favor of large scale production.
Description
Technical field
The present invention relates to Polymer Synthesizing field, more particularly, relate to and a kind ofly flood or coat flexible sheet material, the intelligent stress response type silicon boron polymer microgel of defense of resistance to impact yarn fabric and preparation method.
Background technology
Surge guard material is the specific function material that a class has wide application prospect, because its good EAC, makes it be widely used in athletic protective, the police protective clothes of the packing of product and army etc.A kind of desirable defense of resistance to impact fabric should have obvious stress response.When not being subject to external impacts, should be soft and comfortable.When it is subject to external impacts, material is given the interim rigidity of fabric and in impact process, is absorbed large energy, plays excellent protection function.
The siloxanes that boron is cross-linked has special dilatancy energy, presents unique stress response.GB-A-890007, US-A-2431898, GB-A-1387040 individually disclose dilatancy silicone composition, but do not relate to the application of field of textiles.Patent WO-A-03/022085, the CN101400516A of DOW CORNING company find that the crosslinked organopolysiloxane of boron can be used as energy-absorbing material because of its dilatancy the earliest, and are successfully applied to armored fabric system.And then the said firm discloses again the flexible sheet material of a kind of dilatancy silicone composition dipping in patent WO-2007/102020, WO-00/69293.2011, DOW CORNING company disclosed a kind of preparation method of dilatancy silicone emulsion and is applied to armored fabric manufacture in patent CN 102037088A.In protective clothes research field, Japanese Patent JP-A-4-257439 and JP-A-4-257440 disclose separately with heat-resistant paint coating or dipping weave or nonwoven fabric.Heat-resistant paint described in it is made up of polyborosiloxane, silicone resin, mineral filler, glass powder or staple fibre inorganic materials.
To have about dilatancy silicon boron cross-linking system as energy-absorbing material what announced, be applied in the patent of field of textiles, still there are some technical problems urgently to be resolved hurrily.1., under the condition of not extra catalyst, silicon boron cross-linked polymer synthesis temperature is too high, such as 150-250 DEG C.2., although to a certain degree temperature of reaction can be being reduced adding of catalyzer, improve cost, and disadvantageous effect is being brought to the safety performance of product.3. reaction system disclosed in above-mentioned patent, because in system, silicon boron polymer chain extension and crosslinking reaction occur simultaneously, higher scale operation and the subsequent handling of giving of product viscosity brings very big inconvenience.4., although the dilatancy silicone emulsion announced in patent CN 102037088A has certain technical superiority, use tensio-active agent in a large number, and complicated operation.
Summary of the invention
The technical problem to be solved in the present invention is, for defect of the prior art, provide a kind of temperature of reaction low, simple to operate, do not need introduce catalyzer and be conducive to the preparation method of the intelligent stress response type silicon boron polymer microgel of scale operation.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method providing a kind of intelligent stress response type silicon boron polymer microgel, comprise the steps: prepolymerization reaction liquid stirring reaction 1-6 hour under 70-130 DEG C of condition, then add bifunctional chainextender and continue stirring reaction 2-6 hour, temperature of reaction is 30-90 DEG C, finally add functional modification agent stirring reaction 4-8 hour under 30-120 DEG C of condition, obtain described intelligent stress response type silicon boron polymer microgel; Described prepolymerization reaction liquid comprises:
Lower molecular weight polydiorganosiloxane, its quality accounts for the 75.0-96.5% of described prepolymerization reaction liquid quality;
Boron-containing compound, its quality accounts for the 3.50-25.0% of described prepolymerization reaction liquid quality.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, the molecular weight ranges of described lower molecular weight polydiorganosiloxane is 80-6000 dalton; Under 25 DEG C of conditions, range of viscosities is 10-2000mpa.s.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described lower molecular weight polydiorganosiloxane is two hydroxy-end capped polydimethylsiloxanes.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described two hydroxy-end capped polydimethylsiloxane and the product of boron-containing compound pre-polymerization liquid gained contain silanol stopped or are connected formed linear polymer by-OBO-.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described boron-containing compound is the one in boron oxide, boric acid, boric acid precursor and boric acid ester;
Described boric acid is the one in ortho-boric acid, metaboric acid or tetraboric acid, described boric acid precursor comprises trimethoxyboroxine, described boric acid ester is boric acid front three phenyl ester, triethyl borate, tricyclohexyl borate, boric acid three Bian ester, boric acid triallyl, boric acid three (dodecyl) ester, boric acid three (octadecyl) ester, boric acid three tert-butyl ester, phenyl-ethylene boric acid ester, cyclohexyl ethylidene boric acid ester, cyclohexyl phenylene boric acid ester, glyceryl borate, three-trimethyl silyl boric acid ester, tetraboric acid two ammonium, ammonium pentaborate, eight boric acid two ammoniums, borax, potassium pentaborate, hypoboric acid magnesium, single lime borate, one in three barium borates and zinc metaborate.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described bifunctional chainextender is oxalic acid, hexanodioic acid, quadrol or vulcabond; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, the quality of the described bifunctional chainextender added is the 0-15% of described prepolymerization reaction liquid quality.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described functional modification agent is titanic acid ester, zirconate, zirconium phosphoric acid ester, silicon ester, alcoholization titanium, zirconium alkoxides or hafnium alkoxides; Described titanic acid ester is the one in titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate and sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, the quality of the described functional modification agent added is the 0-10% of described prepolymerization reaction liquid quality.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel is in building-up process, and the stirring velocity of described stirring reaction is 100-1500rpm.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel is in building-up process, and the stirring velocity of described stirring reaction is 300-800rpm.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, the particle size range of described intelligent stress response type silicon boron polymer microgel is 0.3-10 μm.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, the particle size range of described intelligent stress response type silicon boron polymer microgel is 0.6-1.5 μm.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel directly adds the treatment solution use that solvent cut is flexible sheet material, or under 40-80 DEG C of condition, be dried to colloid, then add the treatment solution use that solvent is mixed with flexible sheet material.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described solvent is alcohols, ester or supercutical fluid; Described alcohols comprises Virahol, butanols, isopropylcarbinol, n-propyl alcohol, amylalcohol or ether alcohol, and described ester comprises butylacetate or ester alcohol; Described supercutical fluid comprises supercritical co.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described in the treatment solution of described flexible sheet material, the concentration of intelligent stress response type silicon boron polymer microgel is 10-95wt%.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described in the treatment solution of described flexible sheet material, the concentration of intelligent stress response type silicon boron polymer microgel is 40-90wt%.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described flexible sheet material is fabric, and described fabric is formed by polymeric amide, polyester, aromatic poly amide, cotton, wool, acrylic fibre or cellulosic fibre.
In the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention, described flexible sheet material is foams, and described foams comprise open-celled foams, and described open-celled foams comprises polyurethane foam or cellulose foam.
The preparation method of intelligent stress response type silicon boron polymer microgel of the present invention has following beneficial effect: the chain extension of silicon boron polymer and crosslinking reaction separately carry out by the preparation method of intelligent stress response type silicon boron polymer microgel of the present invention.First lower molecular weight polydiorganosiloxane and boron-containing compound is utilized to prepare linear silicon boron polymer, then introduce bifunctional chainextender and increase silicon boron polymer molecular weight further, finally utilize functional modification agent to make it tangle in system, precipitate formation microgel; The method temperature of reaction is lower, technique and simple to operate, do not need introduce catalyzer, be conducive to scale operation, simultaneously, silicon boron polymer microgel is added functional modification agent and is obtained by crosslinking reaction, there is higher molecular weight, be conducive to improving its energy absorption efficiency as energy-absorbing material, the silicon boron polymer microgel that the present invention obtains can be applied to the police protective clothing of intelligent protection fabric, wrapping material and army, has excellent energy absorption efficiency.
In addition, the silicon boron polymer microgel viscosity that the present invention obtains is relatively low, facilitates subsequent technique.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
A preparation method for intelligent stress response type silicon boron polymer microgel, comprises the steps:
By prepolymerization reaction liquid stirring reaction 1-6 hour under 70-130 DEG C of condition; Prepolymerization reaction liquid comprises lower molecular weight polydiorganosiloxane and boron-containing compound, and both reactions above generate linear silicon boron polymer;
Then add bifunctional chainextender and continue stirring reaction 2-6 hour, temperature of reaction is 30-90 DEG C; Now, after adding bifunctional chainextender, in reaction solution, there is chain extending reaction, the molecular chain diffusion of linear silicon boron polymer is extended;
Finally add functional modification agent stirring reaction 4-8 hour under 30-120 DEG C of condition, there is crosslinking reaction in reaction solution after adding functional modification agent here, the linear silicon boron polymer through chain extending reaction tangles, precipitation obtains intelligent stress response type silicon boron polymer microgel.Be understandable that, functional modification agent is here exactly linking agent in fact.
In addition, in prepolymerization reaction liquid, each component and content thereof are:
Lower molecular weight polydiorganosiloxane, its quality accounts for the 75.0-96.5% of described prepolymerization reaction liquid quality;
Boron-containing compound, its quality accounts for the 3.50-25.0% of described prepolymerization reaction liquid quality.
In the present invention, the molecular weight ranges of lower molecular weight polydiorganosiloxane is 80-6000 dalton; Under 25 DEG C of conditions, range of viscosities is 10-2000mpa.s.
In the present invention, lower molecular weight polydiorganosiloxane is a kind of is preferred embodiment two hydroxy-end capped polydimethylsiloxanes, now, two hydroxy-end capped polydimethylsiloxane with in the product of boron-containing compound pre-polymerization liquid gained containing silanol stopped or be connected formed linear polymer by-OBO-.
Preferably, boron-containing compound is the one in boron oxide, boric acid, boric acid precursor and boric acid ester;
In the present invention, boric acid is the one in ortho-boric acid, metaboric acid or tetraboric acid, and wherein, ortho-boric acid is the boric acid do not dewatered, and its molecular formula is H
3bO
3, metaboric acid is by obtaining ortho-boric acid Dehydration in dry air stream or in 80-140 DEG C of air, and its molecular formula is HBO
2.Boric acid precursor is the compound that hydrolysis generates boric acid, be trimethoxyboroxine in the present embodiment, but also boric acid precursor of the present invention is not limited to the present embodiment.In addition, boric acid ester is the one in boric acid front three phenyl ester, triethyl borate, tricyclohexyl borate, boric acid three Bian ester, boric acid triallyl, boric acid three (dodecyl) ester, boric acid three (octadecyl) ester, boric acid three tert-butyl ester, phenyl-ethylene boric acid ester, cyclohexyl ethylidene boric acid ester, cyclohexyl phenylene boric acid ester, glyceryl borate, three-trimethyl silyl boric acid ester, tetraboric acid two ammonium, ammonium pentaborate, eight boric acid two ammoniums, borax, potassium pentaborate, hypoboric acid magnesium, single lime borate, three barium borates and zinc metaborate.Be understandable that, boric acid ester can be the boric acid ester of simple boric acid ester or partial hydrolysis.
Preferably, bifunctional chainextender is oxalic acid, hexanodioic acid, quadrol or vulcabond; Wherein, vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.In the present invention, the quality of the bifunctional chainextender added is the 0-15% of prepolymerization reaction liquid quality.
Preferably, functional modification agent is titanic acid ester, zirconate, zirconium phosphoric acid ester, silicon ester, alcoholization titanium, zirconium alkoxides or hafnium alkoxides; Titanic acid ester is the one in titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate and sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, wherein functional modification agent can also be titanium phosphoric acid ester, and sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester is exactly a kind of titanium phosphoric acid ester.In the present invention, the quality of the functional modification agent added is the 0-10% of prepolymerization reaction liquid quality.
Preferably, intelligent stress response type silicon boron polymer microgel is in building-up process, and the stirring velocity of stirring reaction is 100-1500rpm, and generally speaking, the stirring velocity of stirring reaction can be chosen within the scope of 300-800rpm.
The treatment solution that the intelligent stress response type silicon boron polymer microgel be obtained by reacting needs to be converted into flexible sheet material just can come into operation, it directly can be added the treatment solution use that solvent cut is flexible sheet material, or under 40-80 DEG C of condition, be dried to colloid, then add the treatment solution use that solvent is mixed with flexible sheet material.Preferably, this solvent is alcohols, ester or supercutical fluid; Wherein, alcohols comprises Virahol, butanols, isopropylcarbinol, n-propyl alcohol, amylalcohol or ether alcohol, and ester comprises butylacetate or ester alcohol; Supercutical fluid comprises supercritical co, is understandable that, solvent is not limited to mention several embodiment above.
Preferably, intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of flexible sheet material, and in the treatment solution of flexible sheet material, the concentration of intelligent stress response type silicon boron polymer microgel is 10-95wt%.Generally speaking, the minimum meeting of this concentration is configured to 40-50wt%, and most conference is configured to 90wt%.
Preferably, the particle size range of the intelligent stress response type silicon boron polymer microgel obtained is 0.3-10 μm; Generally speaking, the particle diameter of intelligent stress response type silicon boron polymer microgel that the present invention obtains can within the scope of 0.6-1.5 μm.
Preferably, flexible sheet material can be fabric, and it can be that this fabric is formed by polymeric amide, polyester, aromatic poly amide, cotton, wool, acrylic fibre or cellulosic fibre by weaving, weaving or the fabric of non-woven generation.
Preferably, flexible sheet material can also be foams, and foams comprise open-celled foams, and open-celled foams comprises polyurethane foam or cellulose foam.
The following describes and utilize method of the present invention to the embodiment preparing intelligent stress response type silicon boron polymer microgel at different conditions.
Embodiment 1
Be 4000 by the molecular weight accounting for prepolymerization reaction liquid weight 75wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 1600mpa.s and the cyclohexyl ethylidene boric acid ester that accounts for prepolymerization reaction liquid weight 25wt% are mixed into prepolymerization reaction liquid stirring reaction 4 hours under 110 DEG C of conditions, then in reaction solution, add the bifunctional chainextender hexamethylene diisocyanate being equivalent to prepolymerization reaction liquid quality 5% continue stirring reaction 2 hours, temperature of reaction is 40 DEG C, finally add be equivalent to prepolymerization reaction liquid quality 3% functional modification agent tetrabutyl titanate stirring reaction 8 hours under 70 DEG C of conditions, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 300rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 165mpa.s, microgel particle diameter testing method is as follows: microgel dispersions 0.25mL adds in 5mL Virahol, and dispersed with stirring is even, obtains the microgel dispersion that transmittance is higher.Dispersion liquid, at 25 DEG C, adopts BROOK HAVEN particle-size analyzer test particle diameter.Gained intelligence stress response type silicon boron polymer microgel particle diameter is 2.0 μm, and the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 40wt%.
Embodiment 2
Be 2000 by the molecular weight accounting for prepolymerization reaction liquid weight 85wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 1200mpa.s and the trimethoxyboroxine that accounts for prepolymerization reaction liquid weight 15wt% are mixed into prepolymerization reaction liquid stirring reaction 4 hours under 90 DEG C of conditions, then in reaction solution, add the bifunctional chainextender tolylene diisocyanate being equivalent to prepolymerization reaction liquid quality 2.5% continue stirring reaction 4 hours, temperature of reaction is 70 DEG C, finally add the functional modification agent titanium isopropylate stirring reaction 8 hours under 90 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 4.5%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 500rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 135mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 0.8 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 25wt% to the test of microgel particle diameter.
Embodiment 3
By account for pre-polymerization liquid reaction weight 90wt% molecular weight be 1000, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 600mpa.s and three-trimethyl silyl boric acid ester of accounting for pre-polymerization liquid weight 10wt% are mixed into prepolymerization reaction liquid stirring reaction 5 hours under 100 DEG C of conditions, then in reaction solution, add the bifunctional chainextender diphenylmethanediisocyanate being equivalent to prepolymerization reaction liquid quality 5.0% continue stirring reaction 4 hours, temperature of reaction is 60 DEG C, finally add functional modification agent sec.-propyl three (dioctylphyrophosphoric acid ester) the titanic acid ester stirring reaction 6 hours under 90 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 3.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 800rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 245mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 3.8 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 50wt% to the test of microgel particle diameter.
Embodiment 4
Be 6000 by the molecular weight accounting for prepolymerization reaction liquid weight 80wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 2000mpa.s and the boric acid front three phenyl ester that accounts for pre-polymerization liquid weight 20wt% are mixed into prepolymerization reaction liquid stirring reaction 3 hours under 90 DEG C of conditions, then in reaction solution, add the bifunctional chainextender isophorone diisocyanate being equivalent to prepolymerization reaction liquid quality 10.0% continue stirring reaction 6 hours, temperature of reaction is 60 DEG C, finally add the functional modification agent tetrabutyl titanate stirring reaction 8 hours under 90 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 10.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 1500rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 175mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 8.8 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 90wt% to the test of microgel particle diameter.
Embodiment 5
Be 1000 by the molecular weight accounting for prepolymerization reaction liquid weight 75wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 600mpa.s and the boric acid front three phenyl ester that accounts for pre-polymerization liquid weight 25wt% are mixed into prepolymerization reaction liquid stirring reaction 4 hours under 70 DEG C of conditions, then in reaction solution, add the bifunctional chainextender isophorone diisocyanate being equivalent to prepolymerization reaction liquid quality 1.0% continue stirring reaction 4 hours, temperature of reaction is 40 DEG C, finally add the functional modification agent tetrabutyl titanate stirring reaction 8 hours under 50 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 2.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 100rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 85mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 1.8 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 36wt% to the test of microgel particle diameter.
Embodiment 6
Be 6000 by the molecular weight accounting for prepolymerization reaction liquid weight 96.5wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 200mpa.s and the boric acid front three phenyl ester that accounts for pre-polymerization liquid weight 3.50wt% are mixed into prepolymerization reaction liquid stirring reaction 6 hours under 130 DEG C of conditions, then in reaction solution, add the bifunctional chainextender isophorone diisocyanate being equivalent to prepolymerization reaction liquid quality 15% continue stirring reaction 4 hours, temperature of reaction is 30 DEG C, finally add the functional modification agent tetrabutyl titanate stirring reaction 4 hours under 30 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 2.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 800rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 195mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 10 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 95wt% to the test of microgel particle diameter.
Embodiment 7
By account for pre-polymerization liquid reaction weight 90wt% molecular weight be 80, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 10mpa.s and three-trimethyl silyl boric acid ester of accounting for pre-polymerization liquid weight 10wt% are mixed into prepolymerization reaction liquid stirring reaction 1 hour under 110 DEG C of conditions, then in reaction solution, add the bifunctional chainextender diphenylmethanediisocyanate being equivalent to prepolymerization reaction liquid quality 0.0% continue stirring reaction 4 hours, temperature of reaction is 90 DEG C, finally add functional modification agent sec.-propyl three (dioctylphyrophosphoric acid ester) the titanic acid ester stirring reaction 6 hours under 120 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 0.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 400rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 120mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 0.3 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 10wt% to the test of microgel particle diameter.
Embodiment 8
Be 1600 by the molecular weight accounting for prepolymerization reaction liquid weight 75wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 1000mpa.s and the trimethoxyboroxine that accounts for prepolymerization reaction liquid weight 25wt% are mixed into prepolymerization reaction liquid stirring reaction 4 hours under 80 DEG C of conditions, then in reaction solution, add the bifunctional chainextender tolylene diisocyanate being equivalent to prepolymerization reaction liquid quality 2.5% continue stirring reaction 4 hours, temperature of reaction is 70 DEG C, finally add the functional modification agent titanium isopropylate stirring reaction 8 hours under 90 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 4.5%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 500rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 135mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 0.6 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 25wt% to the test of microgel particle diameter.
Embodiment 9
Be 1000 by the molecular weight accounting for prepolymerization reaction liquid weight 75wt%, under 25 DEG C of conditions, viscosity is that the polydimethylsiloxane of 600mpa.s and the boric acid front three phenyl ester that accounts for pre-polymerization liquid weight 25wt% are mixed into prepolymerization reaction liquid stirring reaction 4 hours under 90 DEG C of conditions, then in reaction solution, add the bifunctional chainextender isophorone diisocyanate being equivalent to prepolymerization reaction liquid quality 1.0% continue stirring reaction 5 hours, temperature of reaction is 60 DEG C, finally add the functional modification agent tetrabutyl titanate stirring reaction 8 hours under 50 DEG C of conditions being equivalent to prepolymerization reaction liquid quality 2.0%, obtain described intelligent stress response type silicon boron polymer microgel (in experiment, stirring velocity is 400rpm), 25 DEG C, 170S
-1the silicon boron polymer microgel dispersions viscosity of lower gained is 80mpa.s, as described in Example 1, gained intelligence stress response type silicon boron polymer microgel particle diameter 1.5 μm, the concentration after making the treatment solution of flexible sheet material in the treatment solution of flexible sheet material is 32wt% to the test of microgel particle diameter.
Although the present invention is described by specific embodiment, it will be appreciated by those skilled in the art that, without departing from the present invention, various conversion can also be carried out and be equal to substituting to the present invention.In addition, for particular condition or material, various amendment can be made to the present invention, and not depart from the scope of the present invention.Therefore, the present invention is not limited to disclosed specific embodiment, and should comprise the whole embodiments fallen within the scope of the claims in the present invention.
Claims (19)
1. the preparation method of an intelligent stress response type silicon boron polymer microgel, it is characterized in that, comprise the steps: prepolymerization reaction liquid stirring reaction 1-6 hour under 70-130 DEG C of condition, then add bifunctional chainextender and continue stirring reaction 2-6 hour, temperature of reaction is 30-90 DEG C, finally add functional modification agent stirring reaction 4-8 hour under 30-120 DEG C of condition, obtain described intelligent stress response type silicon boron polymer microgel; Described prepolymerization reaction liquid comprises:
Lower molecular weight polydiorganosiloxane, its quality accounts for the 75.0-96.5% of described prepolymerization reaction liquid quality;
Boron-containing compound, its quality accounts for the 3.50-25.0% of described prepolymerization reaction liquid quality.
2. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, the molecular weight ranges of described lower molecular weight polydiorganosiloxane is 80-6000 dalton; Under 25 DEG C of conditions, range of viscosities is 10-2000mpa.s.
3. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, is characterized in that, described lower molecular weight polydiorganosiloxane is two hydroxy-end capped polydimethylsiloxanes.
4. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 3, it is characterized in that, described two hydroxy-end capped polydimethylsiloxane and the product of boron-containing compound pre-polymerization liquid gained contain silanol stopped or are connected formed linear polymer by-OBO-.
5. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, described boron-containing compound is the one in boron oxide, boric acid, boric acid precursor and boric acid ester;
Described boric acid is the one in ortho-boric acid, metaboric acid or tetraboric acid, described boric acid precursor comprises trimethoxyboroxine, described boric acid ester is boric acid front three phenyl ester, triethyl borate, tricyclohexyl borate, boric acid three Bian ester, boric acid triallyl, boric acid three (dodecyl) ester, boric acid three (octadecyl) ester, boric acid three tert-butyl ester, phenyl-ethylene boric acid ester, cyclohexyl ethylidene boric acid ester, cyclohexyl phenylene boric acid ester, glyceryl borate, three-trimethyl silyl boric acid ester, tetraboric acid two ammonium, ammonium pentaborate, eight boric acid two ammoniums, borax, potassium pentaborate, hypoboric acid magnesium, single lime borate, one in three barium borates and zinc metaborate.
6. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, described bifunctional chainextender is oxalic acid, hexanodioic acid, quadrol or vulcabond; Described vulcabond is tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate or isophorone diisocyanate.
7. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, the quality of the described bifunctional chainextender added is the 1.0-15% of described prepolymerization reaction liquid quality.
8. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, described functional modification agent is titanic acid ester, zirconate, zirconium phosphoric acid ester, silicon ester, alcoholization titanium, zirconium alkoxides or hafnium alkoxides; Described titanic acid ester is the one in titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate and sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester.
9. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, it is characterized in that, the quality of the described functional modification agent added is the 2.0-10% of described prepolymerization reaction liquid quality.
10. the preparation method of intelligent stress response type silicon boron polymer microgel according to claim 1, is characterized in that, described intelligent stress response type silicon boron polymer microgel is in building-up process, and the stirring velocity of described stirring reaction is 100-1500rpm.
The preparation method of 11. intelligent stress response type silicon boron polymer microgels according to claim 10, is characterized in that, described intelligent stress response type silicon boron polymer microgel is in building-up process, and the stirring velocity of described stirring reaction is 300-800rpm.
The preparation method of 12. intelligent stress response type silicon boron polymer microgels according to claim 1, is characterized in that, the particle size range of described intelligent stress response type silicon boron polymer microgel is 0.3-10 μm.
The preparation method of 13. intelligent stress response type silicon boron polymer microgels according to claim 12, is characterized in that, the particle size range of described intelligent stress response type silicon boron polymer microgel is 0.6-1.5 μm.
The preparation method of 14. intelligent stress response type silicon boron polymer microgels according to claim 1 ~ 13 any one, it is characterized in that, described intelligent stress response type silicon boron polymer microgel directly adds the treatment solution use that solvent cut is flexible sheet material, or under 40-80 DEG C of condition, be dried to colloid, then add the treatment solution use that solvent is mixed with flexible sheet material.
The preparation method of 15. intelligent stress response type silicon boron polymer microgels according to claim 14, it is characterized in that, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described solvent is alcohols, ester or supercutical fluid; Described alcohols comprises Virahol, butanols, isopropylcarbinol, n-propyl alcohol, amylalcohol or ether alcohol, and described ester comprises butylacetate or ester alcohol; Described supercutical fluid comprises supercritical co.
The preparation method of 16. intelligent stress response type silicon boron polymer microgels according to claim 14 any one, it is characterized in that, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described in the treatment solution of described flexible sheet material, the concentration of intelligent stress response type silicon boron polymer microgel is 10-95wt%.
The preparation method of 17. intelligent stress response type silicon boron polymer microgels according to claim 16, it is characterized in that, described intelligent stress response type silicon boron polymer microgel is when being formulated as the treatment solution of described flexible sheet material, and described in the treatment solution of described flexible sheet material, the concentration of intelligent stress response type silicon boron polymer microgel is 40-90wt%.
The preparation method of 18. intelligent stress response type silicon boron polymer microgels according to claim 14 any one, it is characterized in that, described flexible sheet material is fabric, and described fabric is formed by polymeric amide, polyester, aromatic poly amide, cotton, wool, acrylic fibre or cellulosic fibre.
The preparation method of 19. intelligent stress response type silicon boron polymer microgels according to claim 14 any one, it is characterized in that, described flexible sheet material is foams, and described foams comprise open-celled foams, and described open-celled foams comprises polyurethane foam or cellulose foam.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210072585.9A CN103319719B (en) | 2012-03-19 | 2012-03-19 | Method for preparing intelligent stress responding type silicon-boron polymer microgel |
| PCT/CN2012/081379 WO2013139114A1 (en) | 2012-03-19 | 2012-09-14 | Method for preparing intelligent stress response type silicon-boron polymer micro-gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210072585.9A CN103319719B (en) | 2012-03-19 | 2012-03-19 | Method for preparing intelligent stress responding type silicon-boron polymer microgel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103319719A CN103319719A (en) | 2013-09-25 |
| CN103319719B true CN103319719B (en) | 2015-07-22 |
Family
ID=49188794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210072585.9A Expired - Fee Related CN103319719B (en) | 2012-03-19 | 2012-03-19 | Method for preparing intelligent stress responding type silicon-boron polymer microgel |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103319719B (en) |
| WO (1) | WO2013139114A1 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113591B (en) * | 2013-03-05 | 2015-02-18 | 中国科学院长春应用化学研究所 | Intelligent stress response material and preparation method of intelligent stress response material |
| WO2017064044A1 (en) * | 2015-10-16 | 2017-04-20 | Basf Se | Process for producing isocyanate-based xerogels and aerogels with mineral acids |
| CN105385164A (en) * | 2015-12-30 | 2016-03-09 | 中物功能材料研究院有限公司 | Smart impact-resisting material and preparation method thereof |
| CN105566914A (en) * | 2015-12-30 | 2016-05-11 | 中物功能材料研究院有限公司 | Intelligent energy absorbing material and preparation method thereof |
| CN105646872A (en) * | 2016-02-26 | 2016-06-08 | 翁秋梅 | Dynamic polymer material |
| CN107446135B (en) * | 2016-06-01 | 2020-04-10 | 翁秋梅 | Dynamic polymer with dynamic cross-linked structure |
| CN107805308B (en) * | 2016-09-09 | 2022-04-15 | 翁秋梅 | Dynamic polymer with hybrid cross-linked network and application thereof |
| CN106496450B (en) * | 2016-09-30 | 2018-11-27 | 深圳航天科技创新研究院 | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof |
| CN106519242B (en) * | 2016-11-23 | 2018-03-30 | 常州工程职业技术学院 | A kind of ultraviolet light solidifies the titanium doped application containing Borosiloxane and preparation method thereof and in 3D printing material |
| CN108342072A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application with hybrid cross-linked structure |
| CN108341951B (en) * | 2017-01-25 | 2023-06-20 | 厦门天策材料科技有限公司 | Dynamic polymer with hybrid cross-linked structure and application thereof |
| CN108342062A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of hydridization dynamic aggregation object composition and its application |
| CN108341954A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of dynamic aggregation object and its application with hybrid cross-linked structure |
| CN107158752B (en) * | 2017-05-25 | 2019-04-12 | 中原工学院 | The preparation method of light wood material is released in a kind of responsive to temperature type keratin base suction |
| CN107501945A (en) * | 2017-09-04 | 2017-12-22 | 句容躬行创客管理咨询有限公司 | A kind of stress response intellectual material and preparation method thereof |
| CN108070044B (en) * | 2018-02-05 | 2021-01-08 | 中国科学院长春应用化学研究所 | Gel material and preparation method thereof |
| CN109438666B (en) * | 2018-10-31 | 2021-09-28 | 湖南铁研博发科技有限公司 | Low-temperature-resistant and impact-resistant material and preparation method and application thereof |
| CN111906862B (en) * | 2020-08-17 | 2021-05-25 | 广西经纬木业有限公司 | High-strength environment-friendly plywood and manufacturing method thereof |
| CN113621237A (en) * | 2021-08-10 | 2021-11-09 | 吉林省华裕汽车零部件有限公司 | Organosilicon microgel impact-resistant additive and preparation method and application thereof |
| CN115416124A (en) * | 2022-08-29 | 2022-12-02 | 华南师范大学 | Composite material and preparation method and application thereof |
| CN115305023A (en) * | 2022-08-30 | 2022-11-08 | 中国科学院长春应用化学研究所 | Transparent or semitransparent adhesive film material, preparation method and application thereof |
| CN115710425A (en) * | 2022-11-10 | 2023-02-24 | 云南迈特力医疗技术有限公司 | Energy-absorbing material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400516A (en) * | 2006-03-08 | 2009-04-01 | 陶氏康宁公司 | Impregnated flexible sheet material |
| CN102037088A (en) * | 2008-04-14 | 2011-04-27 | 陶氏康宁公司 | Emulsions of dilatant organopolysiloxanes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3987132B2 (en) * | 1995-11-24 | 2007-10-03 | 東レ・ダウコーニング株式会社 | Method for extrusion molding of silicone rubber moldings |
| KR20110003367A (en) * | 2008-04-14 | 2011-01-11 | 다우 코닝 코포레이션 | Emulsions of boron crosslinked organopolysiloxanes |
| CN101638847B (en) * | 2009-07-24 | 2012-10-24 | 东莞市德能化工有限公司 | Formaldehyde-free durable crease-proof finishing agent used for cellulosic fiber fabric |
| US8785507B2 (en) * | 2010-03-09 | 2014-07-22 | University Of Virginia Patent Foundation | Viscoelastic silicon rubber compositions |
-
2012
- 2012-03-19 CN CN201210072585.9A patent/CN103319719B/en not_active Expired - Fee Related
- 2012-09-14 WO PCT/CN2012/081379 patent/WO2013139114A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400516A (en) * | 2006-03-08 | 2009-04-01 | 陶氏康宁公司 | Impregnated flexible sheet material |
| CN102037088A (en) * | 2008-04-14 | 2011-04-27 | 陶氏康宁公司 | Emulsions of dilatant organopolysiloxanes |
Non-Patent Citations (1)
| Title |
|---|
| 聚硼硅氧烷的制备及应用研究进展;吴艳金等;《高分子通报》;20120228(第2期);94-98 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013139114A1 (en) | 2013-09-26 |
| CN103319719A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103319719B (en) | Method for preparing intelligent stress responding type silicon-boron polymer microgel | |
| Li et al. | Ecofriendly flame-retardant cotton fabrics: preparation, flame retardancy, thermal degradation properties, and mechanism | |
| US8673448B2 (en) | Articles containing precisely branched functional polymeric phase change materials | |
| EP2362830B1 (en) | Microcapsules and other containment structures for articles incorporating functional polymeric phase change materials | |
| CN105646944B (en) | A kind of preparation method of organically-modified molybdenum disulfide nano sheet | |
| Sun et al. | A novel P/N-based flame retardant synthesized by one-step method toward cotton materials and its flame-retardant mechanism | |
| EP2300224A1 (en) | Articles containing functional polymeric phase change materials and methods of manufacturing the same | |
| Sun et al. | Preparation, characterization and testing of flame retardant cotton cellulose material: flame retardancy, thermal stability and flame-retardant mechanism | |
| CN109504090B (en) | Cold-flow-inhibiting flame-retardant impact-hardening gel and preparation method and application thereof | |
| CN109912799B (en) | Phosphorus-containing organic silicon flame retardant and preparation and application thereof | |
| CN103304999B (en) | The silsesquioxane composition of cyanate ester resin/containing metal aluminium or titanium | |
| CN111253575A (en) | Preparation method and application of high-refractive-index phenyl methyl amino silicone resin | |
| Liang et al. | Fabrication of highly efficient flame-retardant and fluorine-free superhydrophobic cotton fabric by constructing multielement-containing POSS@ ZIF-67@ PDMS micro–nano hierarchical coatings | |
| Li et al. | Biomass-based coating from chitosan for cotton fabric with excellent flame retardancy and improved durability | |
| Jin et al. | Developing flame-retardant, antibacterial cotton fabric by incorporating a linear polysiloxane-based coating | |
| CN105506962A (en) | Capacity increasing method for nano particle modified carbon fiber sizing agent | |
| CN107698731A (en) | The high rigidity acroleic acid polyurethane emulsion that a kind of POSS/B is modified | |
| CN105696100B (en) | A kind of green charcoal source copolymerization flame-proof polylactic acid fiber and preparation method thereof | |
| CN106496450B (en) | A kind of stress response type polymethyl methacrylate modified silicon boron polymer microgel and preparation method thereof | |
| CN105218812B (en) | A kind of insoluble halogen-free flame retardants of cross-linking type and its preparation method and application | |
| Shi et al. | An eco-friendly B/P/N flame retardant for its fabrication of high-effective and durable flame-retardant cotton fabric | |
| CN105906791A (en) | Preparation method of flame-retardant PET (polyethylene terephthalate) material | |
| Bakar et al. | Sol-Gel Finishing for Protective Fabrics | |
| CN111041610B (en) | Melamine/cellulose flame-retardant material and preparation method thereof | |
| Ali et al. | Nanoparticles: A potential alternative to classical fire retardants for textile substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 |