CN104448183A - Plant oil-based polyurethane composite material and preparation method thereof - Google Patents
Plant oil-based polyurethane composite material and preparation method thereof Download PDFInfo
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a plant oil-based polyurethane composite material and a preparation method thereof and belongs to the technical field of high polymer materials. The synthesized composite material comprises the following components: plant oil-based polyhydric alcohols, an organic tin catalyst, polyisocyanates and a short chain extender, wherein the modified nano reinforced material is polysilsesquioxane. According to the polyurethane composite material disclosed by the invention, the reproducible epoxidized plant oil serves as an initial raw material, and a modification effect is achieved by physically dispersing the polysilsesquioxane in a polyurethane matrix. The plant oil-based polyurethane composite material has the advantages that the initial raw material is green and environment-friendly, and multiple problems such as energy crisis and environmental pollution can be relieved; physical modification is performed by adopting the polysilsesquioxane with a regular structure, and the method is easy and convenient to implement; and moreover, the modified material has the advantages of high mechanical strength and high heat stability, and the application range of the materials can be further widened.
Description
Technical field
The present invention relates to a kind of vegetable oil based polyurethane matrix material and preparation method thereof, belong to and utilize reproducible vegetables oil to prepare novel high polymer material technical field for raw material.
Background technology
Urethane, due to its versatility, is widely used in fields such as coating, sizing agent, elastomerics, sealing materials.But the synthesis of conventional urethane is raw material based on petroleum chemicals completely, in its production process, be inevitably subject to petroleum resources exhaustion and threaten and the impact of crude oil fluctuation, and bring many serious problems such as environmental pollution and Greenhouse effect.Comparatively speaking, vegetables oil belongs to natural fats and oils, it is cheap and easy to get, the renewable characteristic such as by force of environmental protection makes it to be subject to increasing concern, the particularly development of epoxidation technology and epoxy soybean oil industry, brings unprecedented innovation opportunity for synthesizing target product of the present invention.The proposition of the schemes such as especially atmospheric oxidation, ozonize-reduction, epoxy-hydroxylation, hydroformylation, transesterify, successfully realizes introducing in plant oil structure hydroxyl, synthesis vegetable oil-based polyols, and for polyurethane industrial provide abundant, the raw material of environmental protection.
A large amount of results of study shows that the performance of traditional plant oil base urethane depends on the hydroxyl value of polyvalent alcohol, the chain length of vegetables oil and structure, simultaneously due to the deficiency (facile hydrolysis) of plant oil structure itself, the mechanicalness of this kind of urethane, thermal characteristics and weathering resistance are poor.Therefore, investigators are just making great efforts to carry out study on the modification to it.Wherein, organic-inorganic nano material is easy to processibility and the good mechanicalness of inorganic materials and thermostability due to what have organic materials concurrently, receives increasing concern.Particularly this kind of nanoparticle containing Si-O-Si skeleton structure of polysilsesquioxane (POSS), is easy to functionalized owing to possessing good thermostability simultaneously, can be incorporated in organic matrix well and improves polymer performance.Therefore, utilize POSS modification traditional plant oil tomb urethane, for the performance improving such material, expand its scope of application significant.
Summary of the invention
The object of the invention there are provided a kind of vegetable oil based polyurethane matrix material and preparation method thereof.It is good that compound polyurethane material obtained in this way has environmental protection recyclability, and the features such as thermostability and mechanical property excellence, provide new way for improving vegetable oil based polyurethane performance.
Technical scheme of the present invention:
A kind of vegetable oil based polyurethane matrix material, comprises the component of following percentage composition:
(a) vegetable oil-based polyols;
(b) organic tin catalyzer, consumption is 1% ~ 10% of vegetable oil-based polyols quality;
(c) polyisocyanates, consumption is 0.8 ~ 1.0 times of vegetable oil-based polyols quality;
D () short chain chainextender, consumption is according to chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds, and namely controlling hydroxyl molar weight and isocyanic ester molar weight ratio in material is 1 ︰ 1 ~ 1 ︰ 1.5;
F () nanoreinforcement material is fluorine-containing polysilsesquioxane (POSS), weight percentage, is 0.1% ~ 1.2% of composite material component total mass.
Described polyvalent alcohol is soybean oil polyol, and hydroxyl value is 155 mg KOH/g.
Described short chain chainextender is alcohols chainextender BDO.
Described organic tin catalyzer is one in dibutyl tin laurate, stannous octoate or its combination.
Described polyisocyanates is that aliphatic isocyanates comprises 1,6-di-isocyanate HDI, isophorone diisocyanate IPDI; Or aromatic isocyanate comprises one in tolylene diisocyanate TDI, ditolyl methane-4,4 '-vulcabond MDI, poly methylene poly phenyl poly isocyanate PAPI or its combination.
Described nanoreinforcement material is homemade fluorine-containing polysilsesquioxane POSS, and its structure has fluoropropyl and phenyl Liang Lei functional group.
Described compound polyurethane material is by solution method preparation, and solvent used is tetrahydrofuran (THF), and to control solid content be 30% ~ 40%.
And the preparation method of this vegetable oil based polyurethane matrix material, comprises the following steps:
According to described vegetable oil based polyurethane nanocomposite constituents and consumption formula, take each component respectively and comprise vegetable oil-based polyols, the fluorine-containing polysilsesquioxane of organic tin catalyzer, solvent, nanoreinforcement material (POSS) and polyisocyanates, N
2lower 60 ~ 80 DEG C of reaction 1 ~ 3h of protection, synthesis of polyurethane performed polymer;
According to chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds the chainextender of required quality, 60 ~ 80 DEG C of reactions 30 min, subsequent ultrasonic 30 min; Product is applied on polyfluortetraethylene plate, and room temperature is 60 ~ 90 DEG C of solidification 4 ~ 8h after solvent evaporates, obtain described vegetable oil based polyurethane matrix material.
Beneficial effect of the present invention: compound polyurethane material of the present invention substitutes traditional polyether glycol with soybean oil base polyol, not only meet the requirement of society to " Green Chemistry " and " Sustainable development ", simultaneously along with the development of epoxidized vegetable and ring-opening process, synthesize such polyvalent alcohol cheapness easily execute, greatly reduce production cost for the preparation of urethane.Additionally by solution mixed method mutually, by fluorine-containing polysilsesquioxane (POSS) physical dispersion in vegetable oil based polyurethane organic matrix, according to the electronegativity effect that fluorine atom (F) is powerful, improve the dispersiveness of nanoparticle.In view of the calorifics of POSS excellence, mechanical stability and nanometer enhancement thereof, thus obtain the environment-protecting polyurethane matrix material with very good mechanical properties, thermostability, meet material low cost, high performance development trend.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly, below in conjunction with specific embodiment, the present invention is described in detail.But specific embodiment below, only for explaining the present invention, is not used in restriction the present invention.
Have an environment-protecting polyurethane method for synthesizing composite material for very good mechanical properties, thermostability, this vegetable oil based polyurethane matrix material, comprises following composition:
(a) vegetable oil-based polyols;
(b) organic tin catalyzer, consumption is 1% ~ 10% of vegetable oil-based polyols quality;
(c) polyisocyanates, consumption is 0.8 ~ 1.0 times of vegetable oil-based polyols quality;
D () short chain chainextender, consumption is according to chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds, and namely controlling hydroxyl molar weight and isocyanic ester molar weight ratio in material is 1 ︰ 1 ~ 1 ︰ 1.5;
F () nanoreinforcement material is fluorine-containing polysilsesquioxane (POSS), weight percentage, is 0.1% ~ 1.2% of component total mass;
Particularly, the polyol starting material that above-mentioned vegetable oil-based polyols synthesizes as urethane, select the epoxy soybean oil product of methyl alcohol open loop, in view of this synthesis technique abundant raw material source, synthetic schemes alcohol are easy, easily execute, change the polyvalent alcohol that synthesis condition can prepare hydroxyl ranges 150 ~ 200 KOH/g, the hydroxyl value just prepared with early stage in the present embodiment is that 155 mg KOH/g soybean oil polyol are for raw material simultaneously.
Above-mentioned organic tin catalyzer is the one in stannous octoate or dibutyl tin laurate, organic tin catalyzer has higher catalytic activity in urethane resin synthesis, widely use, but because the toxicity of stannous octoate and corrodibility are starkly lower than dibutyl tin laurate, the sub-tin of catalyzer preferably octanoic acid of the present invention.
Above-mentioned isocyanic ester is 1,6-di-isocyanate (HDI), isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), ditolyl methane-4, at least one in 4 '-vulcabond (MDI), poly methylene poly phenyl poly isocyanate (PAPI) etc., the preferred isophorone diisocyanate of the present invention (IPDI), not only be that its toxicity is lower, and synthetic products have excellent resistance to optical stability and chemical proofing.
Above-mentioned short chain chainextender is alcohols chainextender BDO, and in urethane building-up process, the add-on of chainextender directly affects the ratio of soft, hard section, thus affects product performance, and in the present invention, the consumption of chainextender preferably presses chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds.
Above-mentioned used nanoreinforcement material is homemade fluorine-containing polysilsesquioxane (OF-POSS), because nanoparticle has larger specific surface area and specific surface energy, very easily reunite, therefore the polysilsesquioxane that the present invention is preferably fluorine-containing, weight percentage is 0.1% ~ 1.2 %, and rely on fluorine atom and the intersegmental polar-polar effect of rigid polyurethane, improve that it is dispersed, in the present invention, the synthetic method of fluorine-containing polysilsesquioxane is as follows:
1. flucride siloxane is hydrolyzed POSS tri-sodium alkoxide generating incomplete condensation in the basic conditions, detailed process is as follows: 3,3, (25.00 g) for 3-trifluoro propyl Trimethoxy silane, tetrahydrofuran (THF) (125 mL), (2.00 g), (2.70 g) stirring and refluxing 5 h at 70 DEG C, continue reaction 15 h to deionized water to sodium hydroxide under room temperature, rotation steams solvent, and product vacuum is dry;
2. POSS tri-sodium alkoxide with carry out " holding angle-block " containing the trichlorosilane of benzene and react, the required OF-POSS product of synthesis, detailed process is as follows: above-mentioned steps 1 product 10.00 g(8.80mmol), dry triethylamine 8.80mmol, after 250 mL purified tetrahydrofurans mixing, pass into high pure nitrogen, vigorous stirring in the ice bath of 0 DEG C.In reaction system, dropwise add 9.68 mmol phenyl-trichloro-silicanes, continue reaction 20 h under room temperature after reacting 4 h, filter out solid sodium chloride, steam solvent, 60 DEG C of vacuum-drying 12 h.Add 150 mL methyl alcohol in above-mentioned solid product and stir 30 min, filter out throw out and use methanol wash three times, 40 DEG C of vacuum-drying 24 h, obtain required fluorine-containing polysilsesquioxane.
Correspondingly, the embodiment of the present invention additionally provides the preparation method of above-mentioned vegetable oil based polyurethane matrix material, comprises the steps:
1. taking formula constituent, Reactive Synthesis base polyurethane prepolymer for use as: according to filling a prescription above, taking each component respectively, N
2the lower pyroreaction of protection, synthesis of polyurethane performed polymer;
2. add chainextender, reaction after fixing: the chainextender adding required quality in the performed polymer synthesized by step 1, hot setting after reaction, obtains described vegetable oil based polyurethane matrix material.。
Particularly, in above-mentioned steps 1, by described vegetable oil based polyurethane composite-material formula, take each component respectively and comprise vegetable oil-based polyols, the fluorine-containing polysilsesquioxane of organic tin catalyzer, solvent, nanoreinforcement material (POSS) and polyisocyanates, N
2lower 60 ~ 80 DEG C of reaction 1 ~ 3 h of protection, synthesis performed polymer, preferred 80 DEG C of reaction 2 h in the present invention.
In above-mentioned steps 2, according to chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds the chainextender of required quality, 60 ~ 80 DEG C of reactions 30 min, subsequent ultrasonic 30 min, and product is applied on polyfluortetraethylene plate, room temperature after solvent evaporates 60 ~ 90 DEG C set time 4 ~ 8 h, the vegetable oil based polyurethane matrix material in example of the present invention can be obtained.In the present invention preferably 80 DEG C reaction 6 h.
Now in conjunction with specific examples, a kind of vegetable oil based polyurethane matrix material of the embodiment of the present invention and preparation method thereof is further described.
Embodiment 1
A kind of vegetable oil based polyurethane matrix material, comprises following component:
Soybean oil base polyol (hydroxyl value is 155mg KOH/g) 2 g;
Stannous octoate: 0.20 g, 10% of vegetable oil-based polyols quality;
Isophorone diisocyanate (IPDI) 1.90g, 0.95 times of vegetable oil polyol quality;
BDO 0.30 g, chain extension ratio
n oH︰
n nCO=1 ︰ 1.27;
Fluorine-containing polysilsesquioxane (POSS) 0.0060 g, weight percentage is 0.14 %;
Solvents tetrahydrofurane 10 mL, solid content 33 %;
The preparation method of this compound polyurethane material is as follows:
1. according to formula, take each component respectively, comprise vegetable oil-based polyols, the fluorine-containing polysilsesquioxane of organic tin catalyzer, solvent, nanoreinforcement material (POSS) and polyisocyanates, N
2protect lower 80 DEG C of reaction 2 h reaction, synthesis of polyurethane performed polymer;
2. in the base polyurethane prepolymer for use as synthesized by step 1, add the chainextender 1 of required quality, 4-butyleneglycol, 80 DEG C of reaction 30 min, subsequent ultrasonic 30 min, and product is applied on polyfluortetraethylene plate, room temperature after solvent evaporates 80 DEG C set time 6 h, i.e. obtained vegetable oil based polyurethane matrix material.
Embodiment 2:
A kind of vegetable oil based polyurethane matrix material, comprises following component:
Soybean oil based polylol (hydroxyl value is 155mg KOH/g) 2 g;
Stannous octoate 0.20 g, 10% of vegetable oil-based polyols quality;
Isophorone diisocyanate (IPDI) 1.90g, 0.95 times of vegetable oil polyol quality;
BDO 0.30 g, chain extension ratio
n oH︰
n nCO=1 ︰ 1.27;
Fluorine-containing polysilsesquioxane (POSS) 0.0240 g, weight percentage is 0.54%;
Solvents tetrahydrofurane 10 mL, solid content 33%;
The preparation method of this compound polyurethane material as described in example 1 above, for saving length, does not repeat them here.
Embodiment 3
A kind of vegetable oil based polyurethane matrix material, comprises following component:
Soybean oil based polylol (hydroxyl value is 155mg KOH/g) 2 g;
Stannous octoate 0.20 g, 10% of vegetable oil-based polyols quality;
Isophorone diisocyanate (IPDI) 1.90g, 0.95 times of vegetable oil polyol quality;
BDO 0.30 g, chain extension ratio
n oH:
n nCO=1:1.27;
Fluorine-containing polysilsesquioxane (POSS) 0.0530 g, weight percentage is 1.2%;
Solvents tetrahydrofurane 10 mL, solid content 33%;
The preparation method of this compound polyurethane material as described in example 1 above, for saving length, does not repeat them here.
Embodiment 4
A kind of vegetable oil based polyurethane matrix material, comprises following component:
Soybean oil based polylol (hydroxyl value is 155mg KOH/g) 2 g;
Stannous octoate 0.20 g, 10% of vegetable oil-based polyols quality;
Isophorone diisocyanate (IPDI) 1.90g, 0.95 times of vegetable oil polyol quality;
BDO 0.30 g, chain extension ratio
n oH︰
n nCO=1 ︰ 1.27;
Fluorine-containing polysilsesquioxane (POSS) 0.0815 g, weight percentage is 1.84%;
Solvents tetrahydrofurane 10 mL, solid content 34%;
The preparation method of this compound polyurethane material as described in example 1 above, for saving length, does not repeat them here.
Performance test
Vegetable oil based polyurethane matrix material above-described embodiment 1 to embodiment 4 prepared carries out thermal property and measuring mechanical property, and measurement result is as following table 1.
Table 1
Data from embodiment 1 to the embodiment 4 in table 1 and comparative example: (do not add POSS compared with common vegetable oil based polyurethane, do blank), compound polyurethane material prepared by the embodiment of the present invention is owing to the addition of the fluorine-containing polysilsesquioxane of modification (POSS), the tensile strength of material is apparently higher than the former, and along with the increase of POSS content, the tensile strength of compound polyurethane material increases, and shows in this content range, adds the mechanical property that POSS is conducive to improving material; And the temperature of initial decomposition of material is in the POSS content range that embodiment adopts, as shown in data in embodiment 3, about 50 DEG C can be improved, great at the application value in high temperature resistant field for such vegetable oil based polyurethane material of expansion.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments within principle of the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a vegetable oil based polyurethane matrix material, is characterized in that: the component comprising following percentage composition:
(a) vegetable oil-based polyols;
(b) organic tin catalyzer, consumption is 1% ~ 10% of vegetable oil-based polyols quality;
(c) polyisocyanates, consumption is 0.8 ~ 1.0 times of vegetable oil-based polyols quality;
D () short chain chainextender, consumption is according to chain extension ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds, and namely controlling hydroxyl molar weight and isocyanic ester molar weight ratio in material is 1 ︰ 1 ~ 1 ︰ 1.5;
F () nanoreinforcement material is fluorine-containing polysilsesquioxane POSS, weight percentage, is 0.1% ~ 1.2% of composite material component total mass.
2. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described polyvalent alcohol is soybean oil polyol, and hydroxyl value is 155 mg KOH/g.
3. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described short chain chainextender is alcohols chainextender BDO.
4. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described organic tin catalyzer is one in dibutyl tin laurate, stannous octoate or its combination.
5. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described polyisocyanates is that aliphatic isocyanates comprises 1,6-di-isocyanate HDI, isophorone diisocyanate IPDI; Or aromatic isocyanate comprises one in tolylene diisocyanate TDI, ditolyl methane-4,4 '-vulcabond MDI, poly methylene poly phenyl poly isocyanate PAPI or its combination.
6. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described nanoreinforcement material is homemade fluorine-containing polysilsesquioxane POSS, and its structure has fluoropropyl and phenyl Liang Lei functional group.
7. vegetable oil based polyurethane matrix material according to claim 1, is characterized in that: described compound polyurethane material is by solution method preparation, and solvent used is tetrahydrofuran (THF), and to control solid content be 30% ~ 40%.
8. a preparation method for vegetable oil based polyurethane matrix material described in claim 1-7, is characterized in that: comprise the following steps:
According to the vegetable oil based polyurethane nanocomposite constituents described in claim 1 ~ 7 and consumption formula, take each component respectively and comprise vegetable oil-based polyols, the fluorine-containing polysilsesquioxane POSS of organic tin catalyzer, solvent, nanoreinforcement material and polyisocyanates, N
2lower 60 ~ 80 DEG C of reaction 1 ~ 3h of protection, synthesis of polyurethane performed polymer;
According to expansion link ratio
n oH︰
n nCO=1 ︰ 1 ~ 1 ︰ 1.5 adds the chainextender of required quality, 60 ~ 80 DEG C of reactions 30 min, subsequent ultrasonic 30 min; Product is applied on polyfluortetraethylene plate, and room temperature is 60 ~ 90 DEG C of solidification 4 ~ 8h after solvent evaporates, obtain described vegetable oil based polyurethane matrix material.
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| CN115651151A (en) * | 2022-10-25 | 2023-01-31 | 上海普信高分子材料有限公司 | Preparation method of polysilsesquioxane modified polyurethane flame retardant |
| WO2023030317A1 (en) * | 2021-08-30 | 2023-03-09 | 山东一诺威新材料有限公司 | Low-viscosity reactive flame-retardant polyether polyol, and preparation method therefor and application thereof |
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