WO2013139114A1

WO2013139114A1 - Method for preparing intelligent stress response type silicon-boron polymer micro-gel

Info

Publication number: WO2013139114A1
Application number: PCT/CN2012/081379
Authority: WO
Inventors: 忻浩忠; 徐昆; 胡红
Original assignee: 香港纺织及成衣研发中心有限公司
Priority date: 2012-03-19
Filing date: 2012-09-14
Publication date: 2013-09-26
Also published as: CN103319719A; CN103319719B

Abstract

Disclosed is a method for preparing intelligent stress response type silicon-boron polymer micro-gel, comprising the following steps of: performing agitation reaction on pre-polyreaction liquid under 70-130°C for 1-6 hours; adding a di-functional chain extender to continue the agitation reaction for 2-6 hours with a reaction temperature being 30-90°C; and finally adding a functional modifying agent to perform the agitation reaction under 30-120°C for 4-8 hours, so as to obtain the intelligent stress response type silicon-boron polymer micro-gel. The pre-polyreaction liquid comprises: low molecular weight polyorganosiloxane occupying 75.0-96.5% of the mass of the pre-polyreaction liquid by weight; and a boron containing compound occupying 3.50-25.0% of the mass of the pre-polyreaction liquid by weight. The method for preparing intelligent stress response type silicon-boron polymer micro-gel of the present invention has a low reaction temperature and a simple operation, does not need a catalyser to be introduced, and facilitates large-scale production.

Description

Method for preparing intelligent stress response type silicon boron polymer microgel

Technical field

The invention relates to the field of polymer synthesis, and more particularly to an intelligent stress-responsive type silicon boron polymer microgel which can be impregnated or coated on a flexible sheet and an impact resistant textile fabric and a preparation method thereof.

Background technique

Impact protection materials are a special type of functional materials with wide application prospects. Because of their good energy absorption characteristics, they are widely used in sports protection, product packaging, and military and police protective clothing. An ideal impact resistant fabric should have significant stress response. It should be soft and comfortable when not subjected to external impact. When it is impacted by an external force, the material imparts temporary rigidity to the fabric and absorbs a large amount of energy during the impact, providing excellent protection.

Boron-crosslinked siloxanes have exceptional dilatancy properties and exhibit unique stress responsiveness. GB-A-890007, US-A-2431898, GB-A-1387040 disclose dilatant silicone compositions, respectively, but do not relate to applications in the textile field. DOW CORNING The company's patents WO-A-03/022085 and CN101400516A first discovered that boron crosslinked organopolysiloxanes can be used as energy absorbing materials due to their dilatant properties, and have been successfully applied to protective fabric systems. Further, a flexible sheet material impregnated with a dilatant silicone composition is disclosed in the patents WO-2007/102020, WO-00/69293. 2011, DOW CORNING company in patent CN A method for preparing a dilatant silicone emulsion is disclosed in 102037088 A and is applied to the manufacture of protective fabrics. In the field of protective clothing research, Japanese Patent No. JP-A-4-257439 and JP-A-4-257440 each disclose a woven or nonwoven fabric coated or impregnated with a heat resistant paint. The heat resistant paint thereof is composed of a polyborosiloxane, a silicone resin, an inorganic filler, a glass powder or a short fiber inorganic material.

In the patents already published for the expansion of the silicon-boron cross-linking system as an energy absorbing material and applied to the textile field, there are still some technical problems to be solved. 1. The synthesis temperature of the silicon-boron crosslinked polymer is too high, for example, 150-250 ° C without the addition of a catalyst. 2. The addition of the catalyst can lower the reaction temperature to some extent, but increases the cost and adversely affects the safety performance of the product. 3. The reaction system disclosed in the above patent, because the silicon boron polymer chain extension and crosslinking reaction occur simultaneously in the system, the high viscosity of the product brings great inconvenience to large-scale production and subsequent processes. 4. Although the dilatant silicone emulsion disclosed in the patent CN 102037088A has certain technical advantages, a large amount of surfactant is used and the operation is complicated.

Summary of the invention

The technical problem to be solved by the present invention is to provide a smart stress-responsive type silicon-boron polymer microgel having a low reaction temperature, simple operation, no need to introduce a catalyst, and is advantageous for mass production, in view of the defects in the prior art. Preparation.

The technical solution adopted by the present invention to solve the technical problem thereof is to provide a method for preparing an intelligent stress-responsive silicon-boron polymer microgel, comprising the following steps: stirring the pre-polymerization reaction solution at 70-130 ° C; -6 hours, then add the bifunctional chain extender and continue to stir the reaction for 2-6 hours, the reaction temperature is 30-90 ° C, and finally add the functional modifier to stir the reaction at 30-120 ° C for 4-8 hours, that is, The smart stress-responsive type silicon boron polymer microgel; the prepolymerization reaction liquid comprises:

a low molecular weight polydiorganosiloxane having a mass of 75.0 to 96.5% by mass of the prepolymerized reaction solution;

The boron-containing compound has a mass of 3.50-25.0% of the mass of the prepolymerized reaction solution.

In the method for preparing the smart stress-responsive silicone-boron polymer microgel according to the present invention, the molecular weight of the low molecular weight polydiorganosiloxane ranges from 80 to 6000. Dalton; viscosity ranged from 10 to 2000 mpa.s at 25 °C.

In the method for preparing a smart stress-responsive silicone-boron polymer microgel according to the present invention, the low molecular weight polydiorganosiloxane is a dihydroxy-terminated polydimethylsiloxane.

In the method for preparing the smart stress-responsive silicon-boron polymer microgel according to the present invention, the product obtained by the dihydroxy-terminated polydimethylsiloxane and the boron-containing compound pre-polymer contains silanol-terminated Or a linear polymer consisting of -OBO- linkages.

In the method for preparing a smart stress-responsive silicon-boron polymer microgel according to the present invention, the boron-containing compound is one of boron oxide, boric acid, boric acid precursor and boric acid ester;

The boric acid is one of orthoboric acid, metaboric acid or tetraboric acid; the boric acid precursor comprises trimethoxyboroxane; the boric acid ester is tricresyl borate, triethyl borate, boric acid tricyclic Hexyl ester, tridecyl borate, triallyl borate, tris(dodecyl) borate, tris(octadecyl)borate, tri-tert-butyl borate, phenylethylidene borate, ring Hexylethylidene borate, cyclohexylphenylene borate, glycerol borate, tris-trimethylsilyl borate, diammonium tetraborate, ammonium pentaborate, diammonium octaborate, borax, One of potassium pentaborate, magnesium diborate, calcium monoborate, bismuth triborate and zinc metaborate.

In the method for preparing the smart stress-responsive silicone-boron polymer microgel of the present invention, the bifunctional chain extender is oxalic acid, adipic acid, ethylenediamine or diisocyanate; the diisocyanate It is toluene diisocyanate, diphenylmethane diisocyanate, hexamethyl diisocyanate or isophorone diisocyanate.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the mass of the bifunctional chain extender added is 0-15% of the mass of the prepolymerization liquid.

In the preparation method of the smart stress-responsive silicon-boron polymer microgel according to the present invention, the functional modifier is titanate, zirconate, zirconium phosphate, silicate, titanium alkoxide, alcoholization Zirconium or cerium alkoxide; the titanate is one of tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, and isopropyl tris(dioctyl pyrophosphate) titanate .

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the mass of the functionalized modifier added is 0-10% of the mass of the prepolymerization liquid.

In the method for preparing the smart stress-responsive silicon-boron polymer microgel according to the present invention, the stirring speed of the stirring reaction is 100- in the synthesis process of the smart stress-responsive silicon-boron polymer microgel. 1500 Rpm.

In the method for preparing the smart stress-responsive silicon-boron polymer microgel according to the present invention, the stirring speed of the stirring reaction is 300- in the synthetic stress-responsive silicon-boron polymer microgel. 800 Rpm.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the smart stress-responsive type silicon boron polymer microgel has a particle diameter ranging from 0.3 to 10 μm.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the smart stress-responsive type silicon boron polymer microgel has a particle diameter ranging from 0.6 to 1.5 μm.

In the method for preparing the smart stress-responsive silicon-boron polymer microgel according to the present invention, the smart stress-responsive silicon-boron polymer microgel is directly added to a solvent for dilution into a treatment liquid of a flexible sheet, or It is dried to a colloid at 40-80 ° C, and then added with a solvent to prepare a treatment liquid for a flexible sheet.

In the method for preparing the smart stress-responsive silicone-boron polymer microgel according to the present invention, the smart stress-responsive silicone-boron polymer microgel is formulated as the treatment liquid of the flexible sheet, The solvent is an alcohol, ester or supercritical fluid; the alcohol comprises isopropanol, butanol, isobutanol, n-propanol, pentanol or ether alcohol, the ester comprising butyl acetate or ester alcohol; Supercritical fluids include supercritical carbon dioxide.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the smart stress-responsive type silicon boron polymer microgel is prepared as the treatment liquid of the flexible sheet. The concentration of the smart stress-responsive type silicon boron polymer microgel in the treatment liquid of the flexible sheet is from 10 to 95% by weight.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the smart stress-responsive type silicon boron polymer microgel is prepared as the treatment liquid of the flexible sheet. The concentration of the smart stress-responsive type silicon boron polymer microgel in the treatment liquid of the flexible sheet is 40 to 90% by weight.

In the preparation method of the smart stress-responsive type silicon boron polymer microgel according to the present invention, the flexible sheet is a fabric composed of polyamide, polyester, aramid, cotton, wool, Acrylic fiber or cellulose fiber is formed.

In the method for preparing the smart stress-responsive silicone-boron polymer microgel of the present invention, the flexible sheet is a foam, the foam comprises an open-cell foam, and the open-cell foam comprises polyurethane. Foam or cellulose foam.

The preparation method of the intelligent stress-responsive silicon-boron polymer microgel of the invention has the following beneficial effects: the preparation method of the intelligent stress-responsive silicon-boron polymer microgel of the invention extends and cross-links the silicon-boron polymer The reaction was carried out separately. First, a linear silicon-boron polymer is prepared by using a low molecular weight polydiorganosiloxane and a boron-containing compound, and then a bifunctional chain extender is introduced to further increase the molecular weight of the silicon-boron polymer, and finally the functionalized modifier is used to entangle the system. Precipitation to form microgel; the method has low reaction temperature, simple process and operation, no need to introduce catalyst, and is favorable for large-scale production. Meanwhile, the silicon-boron polymer microgel is added with a functional modifier through a crosslinking reaction. The obtained high molecular weight is beneficial to improving the energy absorption efficiency of the energy absorbing material. The silicon boron polymer microgel obtained by the invention can be applied to intelligent protective fabrics, packaging materials and protective clothing for military and police. Excellent energy absorption efficiency.

In addition, the silicon-boron polymer microgel obtained by the present invention has a relatively low viscosity and is convenient for subsequent processes.

detailed description

In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

A method for preparing an intelligent stress-responsive silicon-boron polymer microgel comprises the following steps:

The prepolymerization reaction solution is stirred at 70-130 ° C for 1-6 hours; the prepolymerization reaction solution comprises a low molecular weight polydiorganosiloxane and a boron containing compound, and the above two react to form a linear silicon boron polymer;

Then, the bifunctional chain extender is added to continue the stirring reaction for 2-6 hours, and the reaction temperature is 30-90 ° C; at this time, after the addition of the bifunctional chain extender, a chain extension reaction occurs in the reaction liquid to make the linear silicon boron polymer molecule Chain diffusion is extended;

Finally, the functionalized modifier is added to stir the reaction at 30-120 ° C for 4-8 hours. After the addition of the functional modifier, a cross-linking reaction occurs in the reaction solution, and the linear silicon-boron polymer is entangled by the chain extension reaction. The smart stress-responsive silicon-boron polymer microgel is obtained by precipitation and precipitation. It can be understood that the functional modifier here is actually a crosslinking agent.

In addition, the components and their contents in the prepolymerization reaction solution are:

In the present invention, the molecular weight of the low molecular weight polydiorganosiloxane ranges from 80 to 6000. Dalton; viscosity ranged from 10 to 2000 mpa.s at 25 °C.

In the present invention, a preferred embodiment of the low molecular weight polydiorganosiloxane is a bishydroxy terminated polydimethylsiloxane, in which case a bishydroxy terminated polydimethylsiloxane and a boron containing compound The product obtained from the prepolymer contains a silanol terminated or linear polymer consisting of -OBO-linking.

Preferably, the boron-containing compound is one of boron oxide, boric acid, boric acid precursor and boric acid ester;

In the present invention, the boric acid is one of orthoboric acid, metaboric acid or tetraboric acid, wherein the orthoboric acid is an undehydrated boric acid having a molecular formula of H3BO3, and the metaboric acid is obtained by flowing orthoboric acid in a dry air stream or at 80-140. °C is dehydrated in air and its molecular formula is HBO2. The boric acid precursor is a compound which hydrolyzes to form boric acid, and is trimethoxyboroxane in the present embodiment, but the boric acid precursor of the present invention is not limited to this embodiment. Further, the borate ester is tricresyl borate, triethyl borate, tricyclohexyl borate, tridecyl borate, triallyl borate, tris(dodecyl) borate, trisoctadecyl borate Ester, tri-tert-butyl borate, phenylethylidene borate, cyclohexylethylene borate, cyclohexylphenylene borate, glycerol borate, tris-trimethylsilyl boron One of an acid ester, diammonium tetraborate, ammonium pentaborate, diammonium octaborate, borax, potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate and zinc metaborate. It will be appreciated that the borate ester can be a simple borate ester or a partially hydrolyzed borate ester.

Preferably, the bifunctional chain extender is oxalic acid, adipic acid, ethylene diamine or diisocyanate; wherein the diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethyl diisocyanate or isophorone Diisocyanate. In the present invention, the mass of the added bifunctional chain extender is 0-15 of the mass of the prepolymerization solution. %.

Preferably, the functional modifier is titanate, zirconate, zirconium phosphate, silicate, titanium alkoxide, zirconate alkoxide or cerium alkoxide; titanate is tetraisopropyl titanate, tetrabutyl titanate One of tetraisobutyl titanate and isopropyl tris(dioctyl pyrophosphate) titanate, wherein the functional modifier may also be titanium phosphate, isopropyl tris(dioctyl coke) Phosphate) Titanate is a titanium phosphate. In the present invention, the mass of the functionalized modifier added is 0-10 of the mass of the prepolymerized solution. %.

Preferably, the intelligent stress-responsive silicone-boron polymer microgel has a stirring speed of 100-1500 during the synthesis process. Rpm, in general, the stirring speed of the stirring reaction is selected in the range of 300-800 rpm.

The intelligent stress-responsive type silicon-boron polymer microgel obtained by the reaction needs to be converted into a processing liquid of a flexible sheet before it can be put into use, and can be directly added to a solvent for diluting the solvent into a flexible sheet, or at 40- It is dried to a colloid at 80 ° C, and then added with a solvent to prepare a treatment liquid for a flexible sheet. Preferably, the solvent is an alcohol, an ester or a supercritical fluid; wherein the alcohol comprises isopropanol, butanol, isobutanol, n-propanol, pentanol or ether alcohol, and the ester comprises butyl acetate or ester alcohol The supercritical fluid includes supercritical carbon dioxide, and it is understood that the solvent is not limited to the several embodiments mentioned above.

Preferably, the intelligent stress-responsive silicone-boron polymer microgel has a concentration of the intelligent stress-responsive silicone-boron polymer microgel in the treatment liquid of the flexible sheet when the preparation is a processing liquid of the flexible sheet, and the concentration is 10-95 wt. %. In general, the minimum concentration will be configured as 40-50 Wt%, the maximum configuration is 90 wt%.

Preferably, the obtained intelligent stress-responsive silicone-boron polymer microgel has a particle size ranging from 0.3 to 10 Μm; In general, the particle size of the smart stress-responsive silicone-boron polymer microgel obtained by the present invention may range from 0.6 to 1.5 μm.

Preferably, the flexible sheet may be a fabric, which may be a fabric produced by weaving, weaving or non-woven, formed from polyamide, polyester, aramid, cotton, wool, acrylic or cellulose fibers. .

Preferably, the flexible sheet may also be a foam, the foam comprising an open cell foam, and the open cell foam comprising a polyurethane foam or a cellulosic foam.

An example of preparing an intelligent stress-responsive silicone-boron polymer microgel under different conditions using the method of the present invention is described below.

Example 1

The molecular weight of 75 wt% of the prepolymerization reaction solution is 4000, and the viscosity is 1600 at 25 ° C. Mpa.s of polydimethylsiloxane and the weight of the prepolymerization reaction solution 25 The wt% cyclohexylethylene borate is mixed into a prepolymerization reaction solution and stirred at 110 ° C for 4 hours, and then the reaction liquid is added to the mass of the prepolymerization reaction solution 5 % of the difunctional chain extender hexamethyl diisocyanate was stirred for 2 hours, the reaction temperature was 40 ° C, and finally the equivalent of the mass of the prepolymerized solution was added. The functionalized modifier tetraisobutyl titanate was stirred and reacted at 70 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive type silicon boron polymer microgel (the stirring speed in the experiment was 300 rpm); 25°C, 170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 165 mpa.s; the microgel particle size test method is as follows: microgel dispersion 0.25 mL is added to 5 In the isopropyl alcohol, the mixture was uniformly dispersed by stirring to obtain a microgel dispersion having a high light transmittance. Dispersion at 25 ° C with BROOK HAVEN The particle size analyzer measures the particle size. The obtained smart stress-responsive type silicon-boron polymer microgel had a particle diameter of 2.0 μm, and the concentration of the treatment liquid of the flexible sheet was 40% by weight in the treatment liquid of the flexible sheet.

Example 2

The molecular weight of the prepolymerized reaction solution is 85 wt%, the viscosity is 1200, and the viscosity is 1200 at 25 ° C. Mpa.s of polydimethylsiloxane and the weight of the prepolymerization reaction liquid 15 The wt% trimethoxyboroxane is mixed into a prepolymerization reaction solution and stirred at 90 ° C for 4 hours, and then the reaction liquid is added to the equivalent mass of the prepolymerization solution 2.5. The bifunctional chain extender toluene diisocyanate was stirred for 4 hours, the reaction temperature was 70 ° C, and finally the equivalent of the prepolymerization solution was 4.5. The functionalized modifier tetraisopropyl titanate was stirred and reacted at 90 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive type silicon boron polymer microgel (the stirring speed in the experiment was 500 rpm); 25°C, 170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 135 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 0.8 μm, and the treatment liquid of the flexible sheet is prepared into a treatment liquid of the flexible sheet. The concentration in the range was 25 wt%.

Example 3

The molecular weight of the prepolymerized solution is 90 wt%, the molecular weight is 1000, and the viscosity is 600 at 25 ° C. Mpa.s polydimethylsiloxane and prepolymer concentration 10 The wt% tris-trimethylsilyl borate is mixed into a prepolymerization reaction solution and stirred at 100 ° C for 5 hours, and then the reaction liquid is added to the mass of the prepolymerization solution 5.0. % difunctional chain extender diphenylmethane diisocyanate was stirred for 4 hours, the reaction temperature was 60 ° C, and finally added to the equivalent of prepolymerization solution mass 3.0 % of the functional modifier isopropyl tris(dioctyl pyrophosphate) titanate was stirred and reacted at 90 ° C for 6 hours to obtain the intelligent stress-responsive silicone boron polymer microgel (experiment) The internal mixing speed is 800 Rpm); the viscosity of the silicon-boron polymer microgel dispersion obtained at 170 °C at 25 ° C is 245 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 3.8 μm, and the treatment liquid of the flexible sheet is prepared into a treatment liquid of the flexible sheet. The concentration in the medium is 50% by weight.

Example 4

The molecular weight of the prepolymerized reaction solution is 80 wt%, the molecular weight is 6000, and the viscosity at 2000 °C is 2000. The polydimethylsiloxane of mpa.s and the tricresyl borate of 20 wt% of the prepolymer are mixed to form a prepolymerization reaction solution, and the reaction mixture is stirred at 90 ° C for 3 hours, and then the equivalent reaction is added to the reaction liquid. Polyreaction solution mass 10.0 % difunctional chain extender isophorone diisocyanate is stirred for 6 hours, the reaction temperature is 60 ° C, and finally the equivalent of prepolymerization solution mass 10.0 The functionalized modifier tetrabutyl titanate was stirred and reacted at 90 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive silicone boron polymer microgel (the stirring speed in the experiment was 1500 rpm); °C,170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 175 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 8.8 μm, and the treatment liquid of the flexible sheet is made into a treatment liquid of the flexible sheet. The concentration in the solution was 90% by weight.

Example 5

The molecular weight of 75 wt% of the prepolymerization reaction solution is 1000, and the viscosity is 600 at 25 ° C. The polydimethylsiloxane of mpa.s and the tricresyl borate of 25 wt% of the prepolymer are mixed to form a prepolymerization reaction solution, and the reaction mixture is stirred at 70 ° C for 4 hours, and then the equivalent reaction is added to the reaction liquid. Polyreaction solution quality 1.0 % difunctional chain extender isophorone diisocyanate was stirred for 4 hours, the reaction temperature was 40 ° C, and finally the equivalent of prepolymerization solution mass 2.0 The functionalized modifier tetrabutyl titanate was stirred and reacted at 50 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive type silicon boron polymer microgel (the stirring speed in the experiment was 100 rpm); °C,170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 85 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 1.8 μm, and is used as a treatment liquid for a flexible sheet after the treatment liquid of the flexible sheet. The concentration in the range was 36% by weight.

Example 6

The molecular weight of the prepolymerized reaction solution is 96.5 wt%, the molecular weight is 6000, and the viscosity at 200 ° C is 200. Mpa.s polydimethylsiloxane and pre-polymer weight 3.50 The wt% tricresyl borate is mixed into a prepolymerization reaction solution and stirred at 130 ° C for 6 hours, and then the equivalent amount of the prepolymerization reaction liquid is added to the reaction liquid. % difunctional chain extender isophorone diisocyanate is stirred for 4 hours, the reaction temperature is 30 ° C, and finally the equivalent of prepolymerization solution mass 2.0 The functionalized modifier tetrabutyl titanate was stirred and reacted at 30 ° C for 4 hours to obtain the above-mentioned intelligent stress-responsive silicone boron polymer microgel (the stirring speed in the experiment was 800 rpm); °C,170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 195. Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 10 μm, and is made into a treatment liquid of a flexible sheet in a treatment liquid of a flexible sheet. The concentration is 95% by weight.

Example 7

The molecular weight of the prepolymerized solution is 90 wt%, the molecular weight is 80, and the viscosity is 10 at 25 ° C. Mpa.s polydimethylsiloxane and prepolymer concentration 10 The wt% tris-trimethylsilyl borate is mixed into a prepolymerization reaction solution and stirred at 110 ° C for 1 hour, and then the reaction liquid is added to the mass of the prepolymerization solution. % difunctional chain extender diphenylmethane diisocyanate is stirred for 4 hours, the reaction temperature is 90 ° C, and finally the equivalent of the prepolymerization liquid mass is 0.0 % of the functional modifier isopropyl tris(dioctyl pyrophosphate) titanate was stirred at 120 ° C for 6 hours to obtain the intelligent stress-responsive silicon-boron polymer microgel (experiment) The internal stirring speed is 400 Rpm); the viscosity of the silicon-boron polymer microgel dispersion obtained at 170 °C at 25 ° C is 120 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 0.3 μm, and the treatment liquid of the flexible sheet is processed into a flexible sheet. The concentration in the medium is 10% by weight.

Example 8

The molecular weight of 75 wt% of the prepolymerization reaction solution is 1600, and the viscosity is 1000 at 25 ° C. Mpa.s of polydimethylsiloxane and the weight of the prepolymerization reaction solution 25 The wt% trimethoxyboroxane is mixed into a prepolymerization reaction solution and stirred at 80 ° C for 4 hours, and then the reaction liquid is added to the mass of the prepolymerization solution 2.5. The bifunctional chain extender toluene diisocyanate was stirred for 4 hours, the reaction temperature was 70 ° C, and finally the equivalent of the prepolymerization solution was 4.5. The functionalized modifier tetraisopropyl titanate was stirred and reacted at 90 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive type silicon boron polymer microgel (the stirring speed in the experiment was 500 rpm); 25°C, 170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 135 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel has a particle size of 0.6 μm, and is used as a treatment liquid for a flexible sheet after treatment liquid of a flexible sheet. The concentration in the range was 25 wt%.

Example 9

The molecular weight of 75 wt% of the prepolymerization reaction solution is 1000, and the viscosity is 600 at 25 ° C. The polydimethylsiloxane of mpa.s and the tricresyl borate of 25 wt% of the prepolymer are mixed to form a prepolymerization reaction solution, and the reaction mixture is stirred at 90 ° C for 4 hours, and then the equivalent reaction is added to the reaction liquid. Polyreaction solution quality 1.0 % of the bifunctional chain extender isophorone diisocyanate is stirred for 5 hours, the reaction temperature is 60 ° C, and finally the equivalent of the prepolymerization solution is 2.0. The functionalized modifier tetrabutyl titanate was stirred and reacted at 50 ° C for 8 hours to obtain the above-mentioned intelligent stress-responsive type silicon boron polymer microgel (the stirring speed in the experiment was 400 rpm); °C,170 The viscosity of the silicon-boron polymer microgel dispersion obtained under S-1 is 80 Mpa.s; microgel particle size test as described in Example 1, the obtained smart stress-responsive type silicon-boron polymer microgel particle size 1.5 μm, the treatment liquid of the flexible sheet was made into the treatment liquid of the flexible sheet The concentration in the medium was 32% by weight.

While the invention has been described by way of specific embodiments, the embodiments of the invention In addition, various modifications may be made to the invention without departing from the scope of the invention. Therefore, the invention is not limited to the specific embodiments disclosed, but all the embodiments falling within the scope of the appended claims.

Claims

A method for preparing an intelligent stress-responsive silicon-boron polymer microgel, comprising the steps of: stirring a prepolymerization reaction solution at 70-130 ° C for 1-6 hours, and then adding a bifunctional chain extension; The agent continues to stir the reaction for 2-6 hours, the reaction temperature is 30-90 ° C, and finally the functionalized modifier is added to stir the reaction at 30-120 ° C for 4-8 hours to obtain the smart stress-responsive silicon-boron polymer. a microgel; the prepolymerization reaction solution comprises:

a low molecular weight polydiorganosiloxane having a mass of 75.0 to 96.5% by mass of the prepolymerized reaction solution;

The boron-containing compound has a mass of 3.50-25.0% of the mass of the prepolymerized reaction solution.
The method for preparing a smart stress-responsive silicone-boron polymer microgel according to claim 1, wherein the low molecular weight polydiorganosiloxane has a molecular weight ranging from 80 to 6000. Dalton; viscosity ranged from 10 to 2000 mpa.s at 25 °C.
The method for preparing a smart stress-responsive silicone-boron polymer microgel according to claim 1, wherein the low molecular weight polydiorganosiloxane is a dihydroxy-terminated polydimethylsiloxane.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 3, wherein the product obtained by the dihydroxy-terminated polydimethylsiloxane and the boron-containing compound pre-polymer contains A linear polymer consisting of silanol terminated or by -OBO-linking.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the boron-containing compound is one of boron oxide, boric acid, boric acid precursor and boric acid ester;

The boric acid is one of orthoboric acid, metaboric acid or tetraboric acid; the boric acid precursor comprises trimethoxyboroxane; the boric acid ester is tricresyl borate, triethyl borate, boric acid tricyclic Hexyl ester, tridecyl borate, triallyl borate, tris(dodecyl) borate, tris(octadecyl)borate, tri-tert-butyl borate, phenylethylidene borate, ring Hexylethylidene borate, cyclohexylphenylene borate, glycerol borate, tris-trimethylsilyl borate, diammonium tetraborate, ammonium pentaborate, diammonium octaborate, borax, One of potassium pentaborate, magnesium diborate, calcium monoborate, bismuth triborate and zinc metaborate.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the bifunctional chain extender is oxalic acid, adipic acid, ethylenediamine or diisocyanate; The diisocyanate is toluene diisocyanate, diphenylmethane diisocyanate, hexamethyl diisocyanate or isophorone diisocyanate.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the mass of the bifunctional chain extender added is 0-15 of the mass of the prepolymerized solution. %.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the functionalizing modifier is titanate, zirconate, zirconium phosphate, silicate, a titanium alkoxide, a zirconium alkoxide or a cerium alkoxide; the titanate is tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate and isopropyl tris(dioctyl pyrophosphate) titanate One of them.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the mass of the functionalized modifier added is 0-10 of the mass of the prepolymerized solution. %.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the smart stress-responsive silicone-boron polymer microgel is stirred during the synthesis process. Speed is 100-1500 Rpm.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 10, wherein the smart stress-responsive silicon-boron polymer microgel is stirred during the synthesis process Speed is 300-800 Rpm.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 1, wherein the smart stress-responsive silicon-boron polymer microgel has a particle size ranging from 0.3 to 10. Mm.
The method for preparing a smart stress-responsive silicone-boron polymer microgel according to claim 12, wherein the smart stress-responsive silicone-boron polymer microgel has a particle size ranging from 0.6 to 1.5 μm.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to any one of claims 1 to 13, wherein the smart stress-responsive silicon-boron polymer microgel is directly added to a solvent to be diluted into a flexible one. The treatment liquid of the sheet is used, or dried at 40-80 ° C to form a colloid, and a solvent is added to prepare a treatment liquid for the flexible sheet.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 14, wherein the smart stress-responsive silicone-boron polymer microgel is formulated into the flexible sheet. In the case of a liquid, the solvent is an alcohol, an ester or a supercritical fluid; the alcohol includes isopropanol, butanol, isobutanol, n-propanol, pentanol or ether alcohol, and the ester includes butyl acetate or An ester alcohol; the supercritical fluid comprising supercritical carbon dioxide.
The method for preparing a smart stress response type silicon boron polymer microgel according to any one of claims 14 to 4, wherein the smart stress response type silicon boron polymer microgel is formulated into the flexible sheet. In the treatment liquid of the material, the concentration of the smart stress-responsive type silicon boron polymer microgel in the treatment liquid of the flexible sheet is from 10 to 95% by weight.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to claim 16, wherein the smart stress-responsive silicone-boron polymer microgel is formulated into the flexible sheet. In the case of liquid, the concentration of the smart stress-responsive type silicon boron polymer microgel in the treatment liquid of the flexible sheet is 40 to 90% by weight.
The method for preparing a smart stress-responsive silicone-boron polymer microgel according to any one of claims 14 to 4, wherein the flexible sheet is a fabric, and the fabric is made of polyamide, polyester, and aromatic. Formed from polyamide, cotton, wool, acrylic or cellulose fibers.
The method for preparing a smart stress-responsive silicon-boron polymer microgel according to any one of claims 14 to 4, wherein the flexible sheet is a foam, and the foam comprises an open-cell foam. The open cell foam comprises a polyurethane foam or a cellulosic foam.