CN105860501A - Heat-resistant and water-resistant polyurethane composite material - Google Patents

Heat-resistant and water-resistant polyurethane composite material Download PDF

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Publication number
CN105860501A
CN105860501A CN201610249145.4A CN201610249145A CN105860501A CN 105860501 A CN105860501 A CN 105860501A CN 201610249145 A CN201610249145 A CN 201610249145A CN 105860501 A CN105860501 A CN 105860501A
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parts
chain extender
water
heat
resistant
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龚文祥
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Chuzhou Huanqiu Polyurethane Technology Co Ltd
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Chuzhou Huanqiu Polyurethane Technology Co Ltd
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Abstract

The invention discloses a heat-resistant and water-resistant polyurethane composite material, which comprises the following raw materials including polycarbonate diol, terminal hydroxyl liquid silicon rubber, terminal hydroxyl liquid nitrile rubber, 1, 4-hexamethylene diisocyanate, nano calcium carbonate, cetyl trimethyl ammonium bromide modified montmorillonoid, starch, zinc oxide, molybdenum trioxide, epoxy resin, diocatanoate dibutyltin, 1, 4-bi(2-hydroxyl ethoxy) benzene, 4, 4'-diamino-diphenyl sulfone, silicon-containing chain extendors, polyhedral oligomerization octa(aminophenyl) polyhedral silsesquioxane, calcium stearate, high boiling solvents lignin, nanometer carbon fiber and polystyrene. The heat-resistant and water-resistant polyurethane composite material provided by the invention has the advantages of high intensity, excellent heat-resistant performance and good water-resistant performance, and can meet the use requirements in various fields.

Description

A kind of heat-resisting water-fast compound polyurethane material
Technical field
The present invention relates to polyurethanes technology field, particularly relate to a kind of heat-resisting water-fast compound polyurethane material.
Background technology
Polyurethane is the general designation on main chain containing the macromolecular compound repeating carbamate groups, has excellent The characteristics such as different wear-resisting, oil resistant, tear-resistant, resistance to chemical attack, its purposes is very wide, can substitute for rubber, Plastics, nylon etc., for airport, hotel, building materials, automobile factory, colliery factory, cement plant, condo, The fields such as villa, landscaping, colored stone art, park.But its thermostability of common polyurethane material and resistance to Aqueous is not fine, during using, easily hydrolyzes, and yellowing, hardening etc. existing easily occurs simultaneously As, greatly limit polyurethane material application in practice.
Summary of the invention
The technical problem existed based on background technology, the present invention proposes a kind of heat-resisting water-fast polyurethane composite Material, its intensity is high, Good Heat-resistance, and water-tolerant can meet the use requirement of multiple fields.
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 30-50 part, terminal hydroxy liquid silicone rubber 20-35 part, hydroxyl terminated butyl nitrile (HTBN) rubber 10-25 part, 1,4-cyclohexane diisocyanate 30-50 part, nano-calcium carbonate 5-12 part, cetyl trimethylammonium bromide change Property montmorillonite 3-12 part, starch 20-35 part, zinc oxide 4-15 part, molybdenum trioxide 2-10 part, epoxy resin 5-20 Part, two octanoic acid dibutyl tin 0.01-0.12 parts, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 1-3.5 part, 4,4 '- DADPS 2-5 part, siliceous chain extender 2-10 part, polyhedral oligomeric eight aminophenyl silsesquioxane 3-8 Part, calcium stearate 1-2.5 part, high-boiling alcohol lignin 2-5 part, carbon nano-fiber 3-12 part, polystyrene 10-25 Part；
Wherein, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl first Base dimethoxysilane is that the ratio of 1:2-3 adds in reaction vessel in molar ratio, reacts at 125-135 DEG C 2.5-3.5h, reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
Preferably, in its raw material, PCDL, terminal hydroxy liquid silicone rubber, terminal hydroxy liquid fourth Nitrile rubber, the weight ratio of 1,4-cyclohexane diisocyanate are 35-47:26-34:13-22:36-48.
Preferably, its raw material includes by weight: PCDL 40-45 part, terminal hydroxy liquid silicon rubber Glue 30-33 part, hydroxyl terminated butyl nitrile (HTBN) rubber 16-20 part, 1,4-cyclohexane diisocyanate 42-45 part, receive Rice calcium carbonate 9-12 part, cetyl trimethylammonium bromide modified montmorillonoid 5.5-9 part, starch 26-30 part, Zinc oxide 7-10 part, molybdenum trioxide 5.5-7 part, epoxy resin 7-13 part, two octanoic acid dibutyl tin 0.06-0.1 Part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 2.1-2.6 part, DDS 3-3.6 part, siliceous Chain extender 6-7.2 part, polyhedral oligomeric eight aminophenyl silsesquioxane 5.5-6.3 part, calcium stearate 1.4-2 Part, high-boiling alcohol lignin 3.2-4 part, carbon nano-fiber 7-10 part, polystyrene 17-21 part.
Preferably, its raw material includes by weight: PCDL 42 parts, terminal hydroxy liquid silicone rubber 31 parts, hydroxyl terminated butyl nitrile (HTBN) rubber 18 parts, 1,4-cyclohexane diisocyanate 43 parts, nano-calcium carbonate 10 Part, cetyl trimethylammonium bromide modified montmorillonoid 8 parts, starch 28 parts, zinc oxide 8.5 parts, three oxidations Molybdenum 6 parts, epoxy resin 11 parts, two octanoic acid dibutyl tin 0.08 part, 1,4-bis-(2-hydroxyl-oxethyl) benzene 2.4 Part, DDS 3.3 parts, siliceous chain extender 6.5 parts, polyhedral oligomeric eight aminophenyl silicon Sesquioxyalkane 6 parts, calcium stearate 1.8 parts, high-boiling alcohol lignin 3.7 parts, carbon nano-fiber 8.5 parts, polyphenyl Ethylene 20 parts.
Preferably, the mean diameter of described nano-calcium carbonate is 10-35nm, and specific surface area is 85-135m2/g。
Preferably, the epoxide number of described epoxy resin is 0.35-0.46.
Preferably, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl Methyl dimethoxysilane is that the ratio of 1:2-2.6 adds in reaction vessel, at 128-133 DEG C in molar ratio Reaction 2.9-3.2h, reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
Preferably, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl Methyl dimethoxysilane is that the ratio of 1:2 adds in reaction vessel in molar ratio, reacts 3h at 130 DEG C, Reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
Heat-resisting water-fast compound polyurethane material of the present invention can be prepared according to conventional compound polyurethane material Technique is prepared from.
In the present invention, with PCDL, terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber Be urethane monomer with Isosorbide-5-Nitrae-cyclohexane diisocyanate, by control each monomer ratio so as to get poly- Urethane have excellent mechanical property, hydrolytic resistance, thermostability, oxidative resistance, weatherability, tolerance to cold and Wearability；In the preparation process of siliceous chain extender, have selected hexafluoro bisphenol-a and 3-aminopropyltriethoxy dimethoxy Base silane is raw material, the condition reacted by control, makes the hydroxyl in hexafluoro bisphenol-a and 3-aminopropyltriethoxy two The hydroxyl that methoxy silane hydrolysis produces there occurs reaction, has obtained the chain extender containing amino, fluorine and silicon, has added Enter in system, with Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene, DDS, polyhedral oligomeric eight After aminophenyl silsesquioxane coordinates, by silicon, fluorine and benzene ring structure introducing system, improve further The thermostability of composite and resistance to water；In zinc oxide, molybdenum trioxide addition system, with nano-calcium carbonate, Cetyl trimethylammonium bromide modified montmorillonoid, starch coordinate as filler, have collaborative in addition system Effect, significantly improves the mechanical strength of composite, resistance to water and light stability；Polystyrene adds body In system, having the effect of free radical that the degraded of seizure system produces, thus protect polyurethane, retardation is poly- The degraded of urethane, coordinates with calcium stearate, high-boiling alcohol lignin and carbon nano-fiber, improves composite Thermostability and resistance to ag(e)ing.
Detailed description of the invention
Below, by specific embodiment, technical scheme is described in detail.
Embodiment 1
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 50 parts, 20 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 25 parts, 1,4-ring Hexane diisocyanate 30 parts, nano-calcium carbonate 12 parts, cetyl trimethylammonium bromide modified montmorillonoid 3 parts, Starch 35 parts, zinc oxide 4 parts, molybdenum trioxide 10 parts, epoxy resin 5 parts, two octanoic acid dibutyl tins 0.12 part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 1 part, DDS 5 parts, siliceous chain extender 2 parts, many The oligomeric eight aminophenyl silsesquioxane of face body 8 parts, calcium stearate 1 part, high-boiling alcohol lignin 5 parts, nano-sized carbon Fiber 3 parts, polystyrene 25 parts；
Wherein, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl first Base dimethoxysilane is that the ratio of 1:2 adds in reaction vessel in molar ratio, reacts 2.5h at 135 DEG C, Reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
Embodiment 2
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 30 parts, 35 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 10 parts, 1,4-ring Hexane diisocyanate 50 parts, nano-calcium carbonate 5 parts, cetyl trimethylammonium bromide modified montmorillonoid 12 parts, Starch 20 parts, zinc oxide 15 parts, molybdenum trioxide 2 parts, epoxy resin 20 parts, two octanoic acid dibutyl tins 0.01 part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 3.5 parts, DDS 2 parts, siliceous chain extender 10 parts, Polyhedral oligomeric eight aminophenyl silsesquioxane 3 parts, calcium stearate 2.5 parts, high-boiling alcohol lignin 2 parts, receive Rice 12 parts of carbon fiber, polystyrene 10 parts；
Wherein, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl first Base dimethoxysilane is that the ratio of 1:3 adds in reaction vessel in molar ratio, reacts 3.5h at 125 DEG C, Reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
Embodiment 3
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 45 parts, 30 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 20 parts, 1,4-ring Hexane diisocyanate 42 parts, nano-calcium carbonate 12 parts, cetyl trimethylammonium bromide modified montmorillonoid 5.5 Part, starch 30 parts, zinc oxide 7 parts, molybdenum trioxide 7 parts, epoxy resin 7 parts, two octanoic acid dibutyl tins 0.1 Part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 2.1 parts, DDS 3.6 parts, siliceous chain extender 6 parts, polyhedral oligomeric eight aminophenyl silsesquioxane 6.3 parts, calcium stearate 1.4 parts, high-boiling alcohol lignin 4 parts, carbon nano-fiber 7 parts, polystyrene 21 parts；
Wherein, the mean diameter of described nano-calcium carbonate is 35nm, and specific surface area is 85m2/g；
The epoxide number of described epoxy resin is 0.35；
Described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyltriethoxy diformazan TMOS is that the ratio of 1:2 adds in reaction vessel in molar ratio, reacts 2.9h, reaction knot at 133 DEG C Shu Houjing decompression distillation, cooling obtain described siliceous chain extender.
Embodiment 4
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 40 parts, 33 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 16 parts, 1,4-ring Hexane diisocyanate 45 parts, nano-calcium carbonate 9 parts, cetyl trimethylammonium bromide modified montmorillonoid 9 parts, Starch 26 parts, zinc oxide 10 parts, molybdenum trioxide 5.5 parts, epoxy resin 13 parts, two octanoic acid dibutyl tins 0.06 Part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 2.6 parts, DDS 3 parts, siliceous chain extender 7.2 Part, polyhedral oligomeric eight aminophenyl silsesquioxane 5.5 parts, calcium stearate 2 parts, high-boiling alcohol lignin 3.2 Part, carbon nano-fiber 10 parts, polystyrene 17 parts；
Wherein, the mean diameter of described nano-calcium carbonate is 10nm, and specific surface area is 135m2/g；
The epoxide number of described epoxy resin is 0.46；
Described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyltriethoxy diformazan TMOS is that the ratio of 1:2.6 adds in reaction vessel in molar ratio, reacts 3.2h, reaction at 128 DEG C Described siliceous chain extender is obtained through decompression distillation, cooling after end.
Embodiment 5
The heat-resisting water-fast compound polyurethane material of one that the present invention proposes, its raw material includes by weight: poly-carbon Acid esters dihydroxylic alcohols 42 parts, 31 parts of terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber 18 parts, 1,4-ring Hexane diisocyanate 43 parts, nano-calcium carbonate 10 parts, cetyl trimethylammonium bromide modified montmorillonoid 8 parts, Starch 28 parts, zinc oxide 8.5 parts, molybdenum trioxide 6 parts, epoxy resin 11 parts, two octanoic acid dibutyl tins 0.08 Part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 2.4 parts, DDS 3.3 parts, siliceous chain extender 6.5 parts, polyhedral oligomeric eight aminophenyl silsesquioxane 6 parts, calcium stearate 1.8 parts, high-boiling alcohol lignin 3.7 parts, carbon nano-fiber 8.5 parts, polystyrene 20 parts；
Wherein, the mean diameter of described nano-calcium carbonate is 20nm, and specific surface area is 120m2/g；
The epoxide number of described epoxy resin is 0.42；
Described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyltriethoxy diformazan TMOS is that the ratio of 1:2 adds in reaction vessel in molar ratio, reacts 3h at 130 DEG C, and reaction terminates Described siliceous chain extender is obtained by decompression distillation, cooling.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention not office Being limited to this, any those familiar with the art is in the technical scope that the invention discloses, according to this The technical scheme of invention and inventive concept thereof in addition equivalent or change, all should contain the protection in the present invention Within the scope of.

Claims (8)

1. a heat-resisting water-fast compound polyurethane material, it is characterised in that its raw material includes by weight: poly- Carbonic ester dihydroxylic alcohols 30-50 part, terminal hydroxy liquid silicone rubber 20-35 part, hydroxyl terminated butyl nitrile (HTBN) rubber 10-25 Part, 1,4-cyclohexane diisocyanate 30-50 part, nano-calcium carbonate 5-12 part, cetyl trimethyl bromination Ammonium modified montmorillonoid 3-12 part, starch 20-35 part, zinc oxide 4-15 part, molybdenum trioxide 2-10 part, asphalt mixtures modified by epoxy resin Fat 5-20 part, two octanoic acid dibutyl tin 0.01-0.12 parts, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 1-3.5 part, 4, 4 '-DADPS 2-5 part, siliceous chain extender 2-10 part, polyhedral oligomeric eight aminophenyl silicon sesquialter oxygen Alkane 3-8 part, calcium stearate 1-2.5 part, high-boiling alcohol lignin 2-5 part, carbon nano-fiber 3-12 part, polyphenyl second Alkene 10-25 part；
Wherein, described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyl first Base dimethoxysilane is that the ratio of 1:2-3 adds in reaction vessel in molar ratio, reacts at 125-135 DEG C 2.5-3.5h, reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
The most heat-resisting water-fast compound polyurethane material, it is characterised in that in its raw material, PCDL, terminal hydroxy liquid silicone rubber, hydroxyl terminated butyl nitrile (HTBN) rubber, 1,4-hexamethylene two are different The weight ratio of cyanate is 35-47:26-34:13-22:36-48.
Heat-resisting water-fast compound polyurethane material the most according to claim 1 or claim 2, it is characterised in that its raw material Include by weight: PCDL 40-45 part, terminal hydroxy liquid silicone rubber 30-33 part, terminal hydroxy group LNBR 16-20 part, 1,4-cyclohexane diisocyanate 42-45 part, nano-calcium carbonate 9-12 part, Cetyl trimethylammonium bromide modified montmorillonoid 5.5-9 part, starch 26-30 part, zinc oxide 7-10 part, three Molybdenum oxide 5.5-7 part, epoxy resin 7-13 part, two octanoic acid dibutyl tin 0.06-0.1 part, 1,4-bis-(2-hydroxyls Base oxethyl) benzene 2.1-2.6 part, DDS 3-3.6 part, siliceous chain extender 6-7.2 part, Polyhedral oligomeric eight aminophenyl silsesquioxane 5.5-6.3 part, calcium stearate 1.4-2 part, high boiling alcohol are wooden Element 3.2-4 part, carbon nano-fiber 7-10 part, polystyrene 17-21 part.
4. according to water-fast compound polyurethane material heat-resisting according to any one of claim 1-3, it is characterised in that Its raw material includes by weight: PCDL 42 parts, 31 parts of terminal hydroxy liquid silicone rubber, terminal hydroxy group LNBR 18 parts, 1,4-cyclohexane diisocyanate 43 parts, nano-calcium carbonate 10 parts, cetyl Trimethylammonium bromide modified montmorillonoid 8 parts, starch 28 parts, zinc oxide 8.5 parts, molybdenum trioxide 6 parts, asphalt mixtures modified by epoxy resin 11 parts of fat, two octanoic acid dibutyl tins 0.08 part, Isosorbide-5-Nitrae-two (2-hydroxyl-oxethyl) benzene 2.4 parts, 4,4 '-two ADP sulfone 3.3 parts, siliceous chain extender 6.5 parts, polyhedral oligomeric eight aminophenyl silsesquioxane 6 parts, Calcium stearate 1.8 parts, high-boiling alcohol lignin 3.7 parts, carbon nano-fiber 8.5 parts, polystyrene 20 parts.
5. according to water-fast compound polyurethane material heat-resisting according to any one of claim 1-4, it is characterised in that The mean diameter of described nano-calcium carbonate is 10-35nm, and specific surface area is 85-135m2/g。
6. according to water-fast compound polyurethane material heat-resisting according to any one of claim 1-5, it is characterised in that The epoxide number of described epoxy resin is 0.35-0.46.
7. according to water-fast compound polyurethane material heat-resisting according to any one of claim 1-6, it is characterised in that Described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyltriethoxy dimethoxy Silane is that the ratio of 1:2-2.6 adds in reaction vessel in molar ratio, reacts 2.9-3.2h at 128-133 DEG C, Reaction obtains described siliceous chain extender through decompression distillation, cooling after terminating.
8. according to water-fast compound polyurethane material heat-resisting according to any one of claim 1-7, it is characterised in that Described siliceous chain extender is prepared according to following technique: by hexafluoro bisphenol-a and 3-aminopropyltriethoxy dimethoxy Silane is that the ratio of 1:2 adds in reaction vessel in molar ratio, reacts 3h, react warp after terminating at 130 DEG C Decompression distillation, cooling obtain described siliceous chain extender.
CN201610249145.4A 2016-04-19 2016-04-19 Heat-resistant and water-resistant polyurethane composite material Pending CN105860501A (en)

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Application publication date: 20160817