CN104327236A - Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof - Google Patents
Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104327236A CN104327236A CN201410573372.3A CN201410573372A CN104327236A CN 104327236 A CN104327236 A CN 104327236A CN 201410573372 A CN201410573372 A CN 201410573372A CN 104327236 A CN104327236 A CN 104327236A
- Authority
- CN
- China
- Prior art keywords
- sio
- composite material
- oil
- nano
- nano composite
- 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.)
- Pending
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a vegetable oil based polyurethane/silicon dioxide nano composite material and a preparation method thereof. The material is the composite material which takes vegetable oil based polyurethane prepared by reaction between vegetable oil based polyalcohol and isophorone diisocyanate as a main body and modified or unmodified nano SiO2 as packing, wherein the modified or unmodified nano SiO2 accounts for 5-13% by mass of the composite material. According to the vegetable oil based polyurethane/silicon dioxide nano composite material disclosed by the invention, the tensile strength and the Young modulus can be remarkably improved and the thermal stability of the material can be enhanced.
Description
Technical field
The invention belongs to polyurethane material technical field, relate to a kind of urethane/silicon dioxide nano composite material and preparation method thereof, specifically, relate to a kind of silane coupler modified nano silicon and strengthen vegetable oil based polyurethane resin and preparation method thereof.
Background technology
Urethane (PU) resin is the important synthetic resins of a class, is made up of polyisocyanates and polyol reaction.As a class multi-purpose polymer material, PU resin can be applied to the numerous areas such as communications and transportation (vehicle, boats and ships, aircraft, road, bridge), building, machinery, electronics, furniture, food-processing, clothes, weaving, synthetic leather, printing, mining and metallurgy, petrochemical complex, water conservancy, national defence, physical culture, medical treatment with multiple product forms such as coating, sizing agent, porous plastics, elastomerics, fiber, synthetic leather, water-proof material, pavement material, matrix material and bio-medical materials.Because PU has the physicals of many excellences, constantly come into one's own as excellent wear resisting property, resistance to fatigue, chemical resistance and impact, excellent kindliness and fabulous damping and amortization, biocompatibility etc., just becoming the material of the important widespread use of a class.Along with each Application Areas requires to improve constantly to material over-all properties, the performance of conventional P U material can not meet the requirement of practical application, and therefore many research work are intended to the over-all properties improving PU material.
Along with environment protection and exhausted two hang-ups of petroleum resources are more and more taken seriously, studying with renewable resources is the focus that raw material prepares that eco-friendly polymkeric substance more and more becomes concern.Plant main body of oil is tri-glyceride, and wherein 3 acyl groups derive from the lipid acid that carbon atom is 14 ~ 22 usually.Most plants lipid acid is unsaturated fatty acids, and their position of double bond is usually at 9 or 10 carbon, and linoleic acid plus linolenic acid has 12 or 13 double bonds in addition, and linolenic acid also has double bond on 15 or 16 carbon.The textural difference of most plants oil is only the conjugated degree of degree of unsaturation and unsaturated link(age), and their chemical property is close, and particularly conventional oleum lini, soybean oil, Semen Maydis oil, vegetable seed wet goods chemical modification mechanism are basically identical.Some crude vegetal contains special functional group, as in Viscotrol C, the ricinolic acid of hydroxyl exceedes 90% of fatty acid total amount, can be directly used in preparation PU material.The vegetable oil-based polyols of wide material sources, a kind of extremely important environment-friendly materials, there is biodegradable and biocompatibility, therefore prepare PU material with vegetable oil-based polyols and not only there is unique performance, and there is important environmental protection and economic double benefit.
In recent years, polymer/inorganic thing nano composite material one of study hotspot developing into polymer materials, and nano silicon (SiO
2) be the maximum nano material of current industrialization output, in preparation nano composite material, have boundless application prospect, functional materials exploitation to property has important practical significance.Industrially, Nano-meter SiO_2
2usually be referred to as " ultra-fine white carbon black ", it is a kind of unformed white powder, nontoxic, tasteless, pollution-free, particle diameter is little, specific surface area is large, chemical purity is high, dispersing property is good, there is superior thermostability, reinforcing, thixotropy and excellent optics and mechanical property, be widely used in the fields such as pottery, rubber, plastics, coating, pigment and support of the catalyst.But due to Nano-meter SiO_2
2between intrinsic model ylid bloom action power and great specific surface area make it very easily reunite, be difficult to dispersed in polymeric matrix, thus effectively can not improve the over-all properties of polymkeric substance, so effective dispersing nanometer SiO
2it is one of gordian technique of the polymer nanocomposites preparing excellent combination property.Nano-meter SiO_2 simultaneously
2when preparing polymer nanocomposites, addition needs to optimize, and when addition is lower, improves polymer performance not obvious; When addition is too high, prepares in polymer nanocomposites process and be difficult to dispersed Nano-meter SiO_2
2and eliminate the defects such as bubble, reduce the performance of polymkeric substance on the contrary, but also can high cost be caused.
Summary of the invention
The object of the invention is on the basis of existing technology, a kind of plant oil based PU/SiO is provided
2nano composite material.
Another object of the present invention is to provide a kind of above-mentioned plant oil based PU/SiO
2the preparation method of nano composite material.
Object of the present invention can be reached by following measures:
A kind of vegetable oil based polyurethane/silicon dioxide nano composite material, it is react obtained vegetable oil based polyurethane, with modification or unmodified Nano-meter SiO_2 based on vegetable oil-based polyols and isophorone diisocyanate
2for the matrix material of filler, wherein modification or unmodified Nano-meter SiO_2
2mass content is in the composite 5 ~ 13%.
Further, modification or unmodified Nano-meter SiO_2
2mass content is in the composite 6 ~ 12%, further preferably 10 ~ 12%.
Experiment confirms, the enhancement of nano silicon, in specified range, particularly within the scope of the interpolation of 5 ~ 13%, effectively can be eliminated in preparation process and produces bubble and play remarkable enhancement to polymeric matrix.Nano-meter SiO_2 is worked as in vegetable oil based polyurethane
2when addition is lower, improve polymer performance not obvious, such as, at castor oil-base PU/SiO
2in nano composite material, lower than the Nano-meter SiO_2 of 5%
2addition to the raising of the Young's modulus of polymkeric substance lower than 0.1MPa, and the SiO of modification
2nanometer can make more than the raising 0.8MPa of Young's modulus when the addition of 6%, the SiO after silane coupling agent surface modification is described
2dispersed better in polymeric matrix, play more obvious enhancement.If the addition of nano silicon is too high, as higher than 13% time, experiment discovery prepare in polymer nanocomposites process be difficult to dispersed Nano-meter SiO_2
2and eliminate the defects such as bubble, reduce the mechanical property of polymkeric substance on the contrary, and bring the unfavorable effect of high cost lower performance.
Filler in the present invention preferably adopts modified Nano SiO
2, this modified Nano SiO
2refer to and carry out through silane coupling agent the Nano-meter SiO_2 that surface modification crosses
2.The wherein preferred γ of silane coupling agent-(2,3-glycidoxy) propyl trimethoxy silicane (KH560) and/or γ-(methacryloxy) propyl trimethoxy silicane (KH570).Therefore nano silicon of the present invention comprises unmodified silicon-dioxide (SiO
2), the nano silicon (KH560-SiO of KH560 surface modification
2) and the nano silicon (KH570-SiO of KH570 surface modification
2).
Further, modified Nano SiO
2surface modifying method be: by Nano-meter SiO_2
2in a solvent after ultrasonic disperse, add the silane coupling agent mixed solution be hydrolyzed in the aqueous acetic acid of pH value 3 ~ 4 in advance, back flow reaction after Homogeneous phase mixing, after reaction, suction filtration, washing, drying, grind and get final product.Wherein solvent is toluene or water; Containing silane coupling agent, isopropyl alcohol and water in described silane coupling agent mixed solution, its quality amount ratio is 20:70 ~ 75:5 ~ 10.
Vegetable oil-based polyols in the present invention can be selected from one or more in Viscotrol C, the soybean oil base polyol obtained through phosphoric acid open loop by epoxy soybean oil, Semen Maydis oil polylol, Rap Oil-based polyvalent alcohol, peanut oil polylol, palm oil-base polyvalent alcohol, sunflower seed oil polylol or Oleum Gossypii semen polylol, the soybean oil base polyol preferably adopting Viscotrol C or obtained through phosphoric acid open loop by epoxy soybean oil.
Following method can be adopted by epoxy soybean oil to prepare through the soybean oil base polyol that phosphoric acid open loop obtains in the present invention: to take soybean oil as raw material, epoxy soybean oil is obtained through epoxidation reaction, again by after Ring Opening Reagent phosphoric acid and solvent tertiary butanol and water mixing, slowly add epoxy soybean oil, vigorous stirring back flow reaction, after reaction, cooling, neutralizes with strong aqua, be washed to neutral rear underpressure distillation, obtain soybean oil base polyol.
The invention provides a kind of preparation method of above-mentioned vegetable oil based polyurethane/silicon dioxide nano composite material: by modification or unmodified Nano-meter SiO_2
2in a solvent after ultrasonic disperse, add vegetable oil-based polyols and fully stir, then except desolventizing, after cooling, add isophorone diisocyanate, at 80 ~ 120 DEG C, carry out one or many after mixing all and solidify and get final product.
In preparation method, solvent preferably adopts acetone, and after adding vegetable oil-based polyols, the well-beaten time is preferably 10 ~ 15 hours, and the hydroxyl of vegetable oil-based polyols and isophorone diisocyanate and the mol ratio of isocyano are preferably 1:1.1.Further, solidification process can be solidify 1 ~ 3 hour at 85 ~ 95 DEG C successively and solidify 20 ~ 26 hours at 105 ~ 115 DEG C; Solidification process carries out in a mold.
Further, below respectively with SiO
2, modified Nano SiO
2, soybean oil base polyol is raw material, provides a kind of plant oil based PU/SiO
2the preparation method of nano composite material, it specifically comprises the steps:
Step 1.SiO
2surface modification: by SiO
2ultrasonic disperse 1h (power 100W) under room temperature in solvent toluene, add the KH560 mixed solution (KH560/ isopropanol/water=20/72/8) be hydrolyzed in the aqueous acetic acid of pH=3 ~ 4 in advance, Homogeneous phase mixing, reflux at 110 DEG C 4h, suction filtration, by toluene wash three times, after acetone washing, by filter cake vacuum-drying 12h at 120 DEG C, after grinding, namely obtain KH560-SiO
2; Adopt KH570 to SiO
2during surface modification, first by SiO
2ultrasonic disperse 1h (power 100W) under room temperature in aqueous solvent, then KH570 hydrolyzed solution (KH570/ isopropanol/water=20/72/8) is joined SiO
2dispersion liquid in, reflux 4h, suction filtration, is washed to neutrality, then with after washing with acetone, by filter cake vacuum-drying 12h at 120 DEG C, namely obtains KH570-SiO after grinding
2.
Step 2. soybean oil base polyol: take soybean oil as raw material, obtain epoxy soybean oil through epoxidation reaction, then using phosphoric acid as Ring Opening Reagent, be solvent with the trimethyl carbinol, be mixed in flask, water bath with thermostatic control is heated, epoxy soybean oil dropwise adds in mixed solution, vigorous stirring, back flow reaction 6h.After reaction terminates, be cooled to room temperature, drip strong aqua neutralization, be washed to neutral rear underpressure distillation, obtain soybean oil base polyol.
Step 3. weighs the SiO of prescription quality mark
2, KH560-SiO
2or KH570-SiO
2, add solvent acetone, ultrasonic disperse 1h, add Viscotrol C or soybean oil base polyol again, after mechanical stirring 12h, at 80 DEG C, remove solvent acetone, after cooling, add isophorone diisocyanate, the hydroxyl of vegetable oil-based polyols and isophorone diisocyanate and the mol ratio of isocyano are 1:1.1, stir, be cast in mould, solidify at 90 DEG C/2h and 110 DEG C/24h, the cool to room temperature demoulding after solidification, namely obtains plant oil based PU/SiO
2nano composite material.
Beneficial effect of the present invention:
Plant oil based PU/SiO of the present invention
2nano composite material can significantly improve tensile strength and the Young's modulus of material, the thermal stability of strongthener.Experiment confirms, at plant oil based PU/SiO
2in nano composite material, when adding the SiO of 12wt%
2and KH560-SiO
2time, castor oil-base PU/SiO
2the tensile strength of nano composite material improves 222% and 230% respectively, and Young's modulus all improves 182%; At soybean oil based PU/SiO
2nano composite material, when adding the SiO of 12wt%
2time, tensile strength and Young's modulus improve 22% and 43% respectively.KH570-SiO
2can effectively improve plant oil based PU/SiO
2the thermostability of nano composite material.
Accompanying drawing explanation
Fig. 1. castor oil-base PU/SiO
2the tensile strength figure of nano composite material.
Fig. 2. soybean oil based PU/SiO
2the tensile strength figure of nano composite material.
Embodiment
The present invention will be further described by the following examples, but protection scope of the present invention is not limited to these embodiments.
Embodiment 1.
(1) SiO
2surface modification
KH560-SiO
2: by the SiO of 12g
2(by Aladdin reagent, company limited provides, SiO
2median size be ~ 50nm) ultrasonic disperse 1h (power 100W) under room temperature in 240ml solvent toluene, add the KH560 mixed solution (KH560/ isopropanol/water=20/72/8) that 100ml is hydrolyzed in advance in the aqueous acetic acid of pH=3 ~ 4, Homogeneous phase mixing, reflux at 110 DEG C 4h, suction filtration, by toluene wash three times, after acetone washing, by filter cake vacuum-drying 12h at 120 DEG C, after grinding, namely obtain KH560-SiO
2.
KH570-SiO
2: by the SiO of 18g
2ultrasonic disperse 1h (power 100W) under room temperature in 360ml aqueous solvent, add the KH570 mixed solution (KH570/ isopropanol/water=20/72/8) that 150ml is hydrolyzed in advance in the aqueous acetic acid of pH=3 ~ 4, Homogeneous phase mixing, reflux 4h, suction filtration, is washed to neutrality, then with after washing with acetone, by filter cake vacuum-drying 12h at 120 DEG C, after grinding, namely obtain KH570-SiO
2.
(2) preparation of soybean oil polyol
Taking 150g soybean oil (commercially available) joins in the four-hole boiling flask of 1000mL, is heated to 70 DEG C.(glacial acetic acid 35g, hydrogen peroxide 165g, drip the 10d vitriol oil to start to drip epoxidizing agent, and at 40 DEG C, mix and be placed on dark place and leave standstill 12h), drip off in 2h, stirring velocity controls at 1200 revs/min, guarantee that oil phase fully disperses, after isothermal reaction 5.5h, stratification, point sub-cloud waste liquid, oil reservoir dilute alkaline soln washes crude product to pH=5 ~ 6, then is washed till pH=7 with saturated aqueous common salt and distilled water successively.Then at 98 DEG C, carry out underpressure distillation namely obtain epoxy soybean oil, its oxirane value is 6.3%.
Be that Ring Opening Reagent carries out ring-opening reaction with phosphoric acid: employing epoxy soybean oil is raw material, using phosphoric acid as Ring Opening Reagent, get the trimethyl carbinol (150g), phosphoric acid (6g), water (90g) is mixed in 1000ml flask, water bath with thermostatic control is heated, 300g epoxy soybean oil dropwise adds in mixed solution, vigorous stirring, when temperature rises to boiling point 82 DEG C, maintain temperature of reaction, back flow reaction 6h.After reaction terminates, be cooled to room temperature, drip strong aqua neutralization, be washed to neutral rear underpressure distillation, obtain viscous brown liquid soybean oil base polyol, its hydroxyl value is 211mg KOH/g, called after Soy-polyol.
(3) (6% refers to SiO to weigh 6wt%
2account for the massfraction of total mass) the SiO without silane coupling agent surface modification
2add solvent acetone, ultrasonic disperse 1h, add Viscotrol C (CO again, hydroxyl value is 160mg KOH/g), after mechanical stirring 12h, acetone is desolventized at 80 DEG C, after cooling, isophorone diisocyanate (hydroxyl of Viscotrol C and isophorone diisocyanate and the mol ratio of isocyano are 1:1.1) (being provided by German Crendva Speziaichemie company) is provided, stirs, be cast in mould, solidify at 90 DEG C/2h and 110 DEG C/24h, the cool to room temperature demoulding after solidification, namely obtains castor oil-base PU/SiO
2nano composite material I.Comparative example is not plus nano filler, and obtain polyurethane based on castor oil resin CO-PU, at 23 DEG C, draw speed is under 50mm/min condition, and the tensile strength and the Young's modulus that record comparative example CO-PU are respectively 2.3MPa and 1.7MPa (see table 1).And add 6wt%SiO
2the nano composite material I obtained, tensile strength and Young's modulus rise to 3.9MPa and 1.8MPa (as shown in Figure 1) respectively.The thermogravimetic analysis (TGA) of comparative example and nano composite material I adopts Pyris 1 type thermal gravimetric analyzer (Perkin-Elmer company of the U.S.) to measure; protect in a nitrogen atmosphere; its flow velocity is 20mL/min; Range of measuring temp is 25 ~ 600 DEG C; temperature rise rate is 20 DEG C/min, TGA and DTG the results are shown in Table shown in 3.Nano composite material I compares comparative example CO-PU, and thermostability slightly reduces.As shown in table 3, due to inorganic nano SiO
2add, nano composite material I level of residue at 600 DEG C brings up to 8.4% from 3.4%.
Embodiment 2.
Castor oil-base PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just SiO
2amount is increased to 12wt%, obtains castor oil-base PU/SiO
2nano composite material II, mechanical property is in table 1, tensile strength and the Young's modulus of nano composite material II are respectively 7.4MPa and 4.8MPa, and compared with comparative example CO-PU, tensile strength and Young's modulus improve for 222%, 182% (as shown in Figure 1) respectively.TGA and the DTG result of nano composite material II is as shown in table 3, and nano composite material II level of residue at 600 DEG C is 12.7%.
Embodiment 3.
Castor oil-base PU/SiO is prepared with method identical in embodiment 1
2nano composite material, is just replaced by the KH560-SiO added through silane coupling agent KH560 surface modification treatment
2, add-on is 6wt%, obtains castor oil-base PU/SiO
2nano composite material III, mechanical property is in table 1, and tensile strength and the Young's modulus of nano composite material III significantly improve, and rises to 5.5MPa and 3.0MPa (as shown in Figure 1) respectively.TGA and the DTG result of nano composite material III is as shown in table 3, and nano composite material III level of residue at 600 DEG C is 7.6%.
Embodiment 4.
Castor oil-base PU/SiO is prepared with method identical in embodiment 1
2nano composite material, is just replaced by the KH560-SiO added through silane coupling agent KH560 surface modification treatment
2, add-on is 12wt%, obtains castor oil-base PU/SiO
2nano composite material IV, mechanical property is in table 1, the tensile strength of nano composite material III and Young's modulus are respectively 7.6MPa and 4.8MPa (as shown in Figure 1), and compared with the blank CO-PU of comparative example, tensile strength and Young's modulus improve 230%, 182% respectively.TGA and the DTG result of nano composite material IV is as shown in table 3, and nano composite material IV level of residue at 600 DEG C is 13.1%.
Embodiment 5
Castor oil-base PU/SiO is prepared with method identical in embodiment 1
2nano composite material, is just replaced by the KH570-SiO added through silane coupling agent KH570 surface modification treatment
2, add-on is 6wt%, obtains castor oil-base PU/SiO
2nano composite material V, mechanical property is in table 1, and tensile strength and the Young's modulus of nano composite material V significantly improve, and rises to 3.4MPa and 2.5MPa (as shown in Figure 1) respectively.TGA and the DTG result of nano composite material V is as shown in table 3, and nano composite material V level of residue at 600 DEG C is 7.0%.
Embodiment 6
Castor oil-base PU/SiO is prepared with method identical in embodiment 1
2nano composite material, is just replaced by the KH570-SiO added through silane coupling agent KH570 surface modification treatment
2, add-on is 12wt%, obtains castor oil-base PU/SiO
2nano composite material VI, mechanical property is in table 1, tensile strength and the Young's modulus of nano composite material VI are respectively 4.3MPa and 3.2MPa, and compared with the blank CO-PU of comparative example, tensile strength and Young's modulus improve for 87%, 88% (as shown in Figure 1) respectively.TGA and the DTG result of nano composite material VI is as shown in table 3, adds the SiO through KH570 surface modification
2after, IDT and T
maxall slightly improve, the thermostability of nano composite material VI is improved, and nano composite material VI level of residue at 600 DEG C is 10.6% simultaneously.
Embodiment 7.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is the SiO without silane coupling agent surface modification
2, SiO
2addition is 6wt%, obtains soybean oil based PU/SiO
2nano composite material VII, mechanical property is as shown in table 2, and comparative example is not plus nano filler, and obtain soybean oil based urethane resin Soy-PU, tensile strength and Young's modulus are respectively 27.1MPa and 505.1MPa.Tensile strength and the Young's modulus of nano composite material VII increase, and are respectively 31.4MPa and 615.5MPa (as shown in Figure 2).TGA and DTG of nano composite material VII the results are shown in Table shown in 4.Compare comparative example Soy-PU, IDT of nano composite material VII slightly reduces, T
maxincrease, nano composite material VII level of residue at 600 DEG C brings up to 10.4% (see table 4) from 6.0% simultaneously.
Embodiment 8.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is the SiO without silane coupling agent surface modification
2, SiO
2addition is 12wt%, obtains soybean oil based PU/SiO
2nano composite material VIII, mechanical property is as shown in table 2.Tensile strength and the Young's modulus of nano composite material VIII are improved, and are respectively 33.0MPa and 720.6MPa, and compared with the blank Soy-PU of comparative example, tensile strength and Young's modulus improve for 22%, 43% (as shown in Figure 2) respectively.TGA and the DTG result of nano composite material VIII is as shown in table 4, and IDT improves about 10 DEG C, the T of the soft or hard section of PU
maxall increase, add 12wt% Nano-meter SiO_2
2after, the thermostability of nano composite material VIII is significantly improved, and nano composite material VIII level of residue at 600 DEG C is 16.3% simultaneously.
Embodiment 9.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is KH560-SiO
2, KH560-SiO
2addition is 6wt%, obtains soybean oil based PU/SiO
2nano composite material Ⅸ, mechanical property is as shown in table 2.Tensile strength and the Young's modulus of nano composite material Ⅸ increase, and are respectively 28.4MPa and 615.9MPa (as shown in Figure 2).TGA and the DTG result of nano composite material Ⅸ is as shown in table 4, and IDT improves about 10 DEG C, the T of the soft or hard section of PU
maxall increase, add 6wt% nanometer KH560-SiO
2after, the thermostability of nano composite material Ⅸ is significantly improved, and nano composite material Ⅸ level of residue at 600 DEG C is 10.7% simultaneously.
Embodiment 10.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is KH560-SiO
2, KH560-SiO
2addition is 12wt%, obtains soybean oil based PU/SiO
2nano composite material Ⅹ, mechanical property is as shown in table 2.Tensile strength and the Young's modulus of nano composite material Ⅹ increase, and are respectively 28.3MPa and 602.7MPa (as shown in Figure 2).TGA and the DTG result of nano composite material Ⅹ is as shown in table 4, and IDT slightly improves, T
2maximprove ~ 11 DEG C, thermostability is improved, and nano composite material Ⅹ level of residue at 600 DEG C is 15.5% simultaneously.
Embodiment 11.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is KH570-SiO
2, KH570-SiO
2addition is 6wt%, obtains soybean oil based PU/SiO
2nano composite material Ⅺ, mechanical property is as shown in table 2.Tensile strength and the Young's modulus of nano composite material Ⅺ increase, and are respectively 29.1MPa and 551.0MPa (as shown in Figure 2).TGA and the DTG result of nano composite material Ⅺ is as shown in table 4, and IDT slightly reduces, the T of the soft or hard section of PU
maxall increase, nano composite material Ⅺ level of residue at 600 DEG C is 10.8% simultaneously.
Embodiment 12.
Soybean oil based PU/SiO is prepared with method identical in embodiment 1
2nano composite material, just changing polyvalent alcohol is soybean oil base polyol Soy-polyol, and Nano filling is KH570-SiO
2, KH570-SiO
2addition is 12wt%, obtains soybean oil based PU/SiO
2nano composite material Ⅻ, mechanical property is as shown in table 2.Tensile strength and the Young's modulus of nano composite material Ⅻ increase, and are respectively 31.0MPa and 649.4MPa (as shown in Figure 2).TGA and the DTG result of nano composite material Ⅻ is as shown in table 4, and IDT improves about 10 DEG C, the T of the soft or hard section of PU
maxbe significantly increased, add 12wt% nanometer KH570-SiO
2after, the thermostability of nano composite material Ⅸ is significantly improved, and nano composite material Ⅻ level of residue at 600 DEG C is 14.3% simultaneously.
Table 1. castor oil-base PU/SiO
2the mechanical property of nano composite material
The soybean oil based PU/SiO of table 2.
2the mechanical property of nano composite material
Table 3. castor oil-base PU/SiO
2tGA and the DTG result of nano composite material
a)temperature during IDT:TGA analyzes during thermal weight loss 5%;
b)t
max: by the temperature corresponding to the peak value obtained after TGA curve differential calculus.
The soybean oil based PU/SiO of table 4.
2tGA and the DTG result of nano composite material
Claims (10)
1. vegetable oil based polyurethane/silicon dioxide nano composite material, is characterized in that it is react obtained vegetable oil based polyurethane, with modification or unmodified Nano-meter SiO_2 based on vegetable oil-based polyols and isophorone diisocyanate
2for the matrix material of filler, wherein modification or unmodified Nano-meter SiO_2
2mass content is in the composite 5 ~ 13%.
2. vegetable oil based polyurethane/silicon dioxide nano composite material according to claim 1, is characterized in that modification or unmodified Nano-meter SiO_2
2mass content is in the composite 6 ~ 12%.
3. vegetable oil based polyurethane/silicon dioxide nano composite material according to claim 1, is characterized in that one or more that described vegetable oil-based polyols is selected from Viscotrol C, the soybean oil base polyol obtained through phosphoric acid open loop by epoxy soybean oil, Semen Maydis oil polylol, Rap Oil-based polyvalent alcohol, peanut oil polylol, palm oil-base polyvalent alcohol, sunflower seed oil polylol or Oleum Gossypii semen polylol; Described modified Nano SiO
2for the nano silicon of γ-(2,3-glycidoxy) propyl trimethoxy silicane surface modification is or/and the nano silicon of γ-(methacryloxy) propyl trimethoxy silicane surface modification.
4. vegetable oil based polyurethane/silicon dioxide nano composite material according to claim 1, is characterized in that the preparation method of this material is: by modification or unmodified Nano-meter SiO_2
2in a solvent after ultrasonic disperse, add vegetable oil-based polyols and fully stir, then except desolventizing, after cooling, add isophorone diisocyanate, at 80 ~ 120 DEG C, carry out one or many after mixing all and solidify and get final product.
5. a preparation method for vegetable oil based polyurethane/silicon dioxide nano composite material described in Claims 1 to 4, is characterized in that modification or unmodified Nano-meter SiO_2
2in a solvent after ultrasonic disperse, add vegetable oil-based polyols and fully stir, then except desolventizing, after cooling, add isophorone diisocyanate, at 80 ~ 120 DEG C, carry out one or many solidification after mixing all, namely obtain plant oil based PU/SiO
2nano composite material; Wherein said vegetable oil-based polyols is selected from one or more in Viscotrol C, the soybean oil base polyol obtained through phosphoric acid open loop by epoxy soybean oil, Semen Maydis oil polylol, Rap Oil-based polyvalent alcohol, peanut oil polylol, palm oil-base polyvalent alcohol, sunflower seed oil polylol or Oleum Gossypii semen polylol; Described modified Nano SiO
2for the nano silicon of γ-(2,3-glycidoxy) propyl trimethoxy silicane surface modification is or/and the nano silicon of γ-(methacryloxy) propyl trimethoxy silicane surface modification.
6. preparation method according to claim 5, it is characterized in that described solvent is acetone, after adding vegetable oil-based polyols, the well-beaten time is 10 ~ 15 hours, and the hydroxyl of vegetable oil-based polyols and isophorone diisocyanate and the mol ratio of isocyano are 1:1.1.
7. preparation method according to claim 5, is characterized in that solidification process is solidify 1 ~ 3 hour at 85 ~ 95 DEG C successively and solidify 20 ~ 26 hours at 105 ~ 115 DEG C; Solidification process carries out in a mold.
8. preparation method according to claim 5, it is characterized in that the preparation method of described soybean oil base polyol is: take soybean oil as raw material, epoxy soybean oil is obtained through epoxidation reaction, again by after Ring Opening Reagent phosphoric acid and solvent tertiary butanol and water mixing, slowly add epoxy soybean oil, vigorous stirring back flow reaction, cooling after reaction, with strong aqua neutralization, be washed to neutral rear underpressure distillation, obtain soybean oil base polyol.
9. preparation method according to claim 5, is characterized in that described modified Nano SiO
2surface modifying method be: by Nano-meter SiO_2
2in a solvent after ultrasonic disperse, add the silane coupling agent mixed solution be hydrolyzed in the aqueous acetic acid of pH value 3 ~ 4 in advance, back flow reaction after Homogeneous phase mixing, after reaction, suction filtration, washing, drying, grind and get final product.
10. preparation method according to claim 9, is characterized in that described solvent is toluene or water; Containing silane coupling agent, isopropyl alcohol and water in described silane coupling agent mixed solution, its quality amount ratio is 20:70 ~ 75:5 ~ 10; Described silane coupling agent is γ-(2,3-glycidoxy) propyl trimethoxy silicane or γ-(methacryloxy) propyl trimethoxy silicane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410573372.3A CN104327236A (en) | 2014-10-23 | 2014-10-23 | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410573372.3A CN104327236A (en) | 2014-10-23 | 2014-10-23 | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104327236A true CN104327236A (en) | 2015-02-04 |
Family
ID=52402048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410573372.3A Pending CN104327236A (en) | 2014-10-23 | 2014-10-23 | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327236A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365408A (en) * | 2017-09-06 | 2017-11-21 | 厦门厦广安工贸有限公司 | Castor oil based polyurethanes resin and its making |
| CN109265977A (en) * | 2018-09-07 | 2019-01-25 | 江苏叙然信息科技有限公司 | A kind of athletic ground surface material and preparation process |
| CN111180641A (en) * | 2018-11-09 | 2020-05-19 | 湖北江升新材料有限公司 | Diaphragm with self-crosslinking function and preparation method thereof |
| CN112126214A (en) * | 2019-06-25 | 2020-12-25 | 杭州巨星科技股份有限公司 | Nano composite polyurethane composite material applied to shock absorption layer of tool handle, tool handle and manufacturing method of tool handle |
| CN112679972A (en) * | 2020-12-24 | 2021-04-20 | 江苏馨而美木业有限公司 | Preparation method of environment-friendly flame-retardant corrosion-resistant nano composite fiber base material |
| CN116675822A (en) * | 2023-06-14 | 2023-09-01 | 河北金谷再生资源开发有限公司 | Preparation method of phosphorylated modified vegetable oil polyol |
-
2014
- 2014-10-23 CN CN201410573372.3A patent/CN104327236A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365408A (en) * | 2017-09-06 | 2017-11-21 | 厦门厦广安工贸有限公司 | Castor oil based polyurethanes resin and its making |
| CN109265977A (en) * | 2018-09-07 | 2019-01-25 | 江苏叙然信息科技有限公司 | A kind of athletic ground surface material and preparation process |
| CN111180641A (en) * | 2018-11-09 | 2020-05-19 | 湖北江升新材料有限公司 | Diaphragm with self-crosslinking function and preparation method thereof |
| CN112126214A (en) * | 2019-06-25 | 2020-12-25 | 杭州巨星科技股份有限公司 | Nano composite polyurethane composite material applied to shock absorption layer of tool handle, tool handle and manufacturing method of tool handle |
| CN112679972A (en) * | 2020-12-24 | 2021-04-20 | 江苏馨而美木业有限公司 | Preparation method of environment-friendly flame-retardant corrosion-resistant nano composite fiber base material |
| CN116675822A (en) * | 2023-06-14 | 2023-09-01 | 河北金谷再生资源开发有限公司 | Preparation method of phosphorylated modified vegetable oil polyol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104327236A (en) | Vegetable oil based polyurethane/silicon dioxide nano composite material and preparation method thereof | |
| CN106520040B (en) | A kind of modified graphene oxide, MGO-SiO2Nano-hybrid material and MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film | |
| CN106751906B (en) | Preparation method with controllable multiple dimensioned pore structure silicon rubber foam | |
| CN104277699A (en) | High-strength modified waterborne polyurethane coating | |
| CN102532951B (en) | Method for toughening epoxy resin by adopting modified wollastonite | |
| CN104341568B (en) | A kind of preparation method of nano silicon dioxide polyethers (ester) polyol dispersions of modified polyurethane | |
| CN105524300A (en) | Modified nano-silica and preparation method thereof | |
| CN103113712A (en) | Preparation method and application of modified nano-silicon dioxide toughened epoxy resin | |
| CN109796802A (en) | A kind of preparation method and applications of the hollow carbosphere of carbon coating titanium dioxide | |
| CN108034305A (en) | A kind of iron oxide pigment mill base and preparation method thereof | |
| CN106398508A (en) | Electromagnetic shielding coating for electronic element and preparation method thereof | |
| CN108912417A (en) | One kind constructing SiO2The method of the 3-dimensional multi-layered reinforced structure material of/lignin/NR | |
| CN105315817A (en) | Water-based acrylic resin paint and preparing method thereof | |
| CN104277579A (en) | Waterproof low-odor environment-friendly printing ink and preparation method thereof | |
| CN104985111A (en) | Corundum slag-gangue lost foam casting coating and preparation method thereof | |
| CN110172180A (en) | Inorfil/silica nano material and its preparation method and application | |
| CN104312265B (en) | Molten color inhibition plastic printing ink of a kind of environment-friendly type alcohol and preparation method thereof | |
| CN109251585A (en) | A kind of dry company's degree, anti-stick dirty performance and the strong water-based ink of heat resistance and preparation method thereof | |
| CN103102763B (en) | A kind of environment-friendly water-based glass lacquer and preparation method thereof | |
| CN104592764A (en) | Safe and environment-friendly plastic reversible silica gel and preparation method thereof | |
| CN101367997B (en) | Process for producing epoxy resin MC nylon composite material | |
| CN110499048A (en) | A kind of bi-component modified inorganic floor coatings | |
| CN106380656A (en) | Car roof bracket | |
| CN106554477B (en) | A kind of polyurethane elastomer that acid and alkali-resistance is wear-resisting and preparation method | |
| CN106317780A (en) | Method for preparing wollastonite toughened epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150204 |