CN107353630A - A kind of compound polyurethane material of modification - Google Patents

A kind of compound polyurethane material of modification Download PDF

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Publication number
CN107353630A
CN107353630A CN201710728285.4A CN201710728285A CN107353630A CN 107353630 A CN107353630 A CN 107353630A CN 201710728285 A CN201710728285 A CN 201710728285A CN 107353630 A CN107353630 A CN 107353630A
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nano
polyurethane
cnt
titanium dioxide
silica
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张正辉
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Sea Of Jiangsu New Materials Co Ltd
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Sea Of Jiangsu New Materials Co Ltd
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Abstract

The present invention is to provide a kind of compound polyurethane material of modification, the material is prepared by TPUE with modified carbon nano-tube@silicon dioxide and titanium dioxides nano material using solution process is compound, wherein, modified carbon nano-tube@silicon dioxide and titanium dioxide nano materials are that CNT@silicon dioxide and titanium dioxide nano materials are made with γ glycidyl ether oxygen propyl trimethoxy silicanes, and CNT@silicon dioxide and titanium dioxide nano materials are to be made by tetraethyl orthosilicate, butyl titanate in acidifying carbon nano tube surface hydrolysis growth in situ.The polyurethane nano composite material of the present invention has excellent mechanical property and heat resistance, fracture strength has reached 36~53 MPa, elongation at break has reached 700%~1200%, and in mass loss 10%, corresponding temperature has reached 317~350 DEG C, has widened the application of polyurethane.

Description

A kind of compound polyurethane material of modification
Technical field
The present invention relates to a kind of modified polyurethane composite and preparation method thereof, is mainly used in improving thermoplastic polyurethane Mechanical property and thermal stability.
Background technology
Thermoplastic polyurethane（TPU）It is that one kind can be added with unique made from polyisocyanates and polyol reaction Hot plasticization, the high polymer being soluble in certain solvent.Thermoplastic polyurethane（TPU）With high rigidity, high resiliency, good Oil resistivity and excellent cryogenic property, be widely used.But the shortcomings that some are obvious be present, it greatly limit its application Scope.Intensity is not high, and heat resistance is poor, and easily softening is decomposed at high temperature, its mechanical performance is drastically declined, generally, Can not be long-term use of when temperature is more than 80 DEG C, and Short-range Temperature is no more than 120 DEG C.
CNT（CNTs）With high intensity, toughness and modulus of elasticity, mainly divide multi-walled carbon nanotube or single wall CNT.Single-walled carbon nanotube is made up of individual layer cylindrical type graphite linings, and diameter distribution is small, defect is few, is had higher Homogeneity；Multi-walled carbon nanotube has sandwich construction, layer by layer between readily become Trapping Centers and capture various defects, because And the defects of duck eye is generally discontented with the tube wall of multi-walled pipes.Using CNTs as composite material reinforcement body, can show good light Degree, elasticity, anti-fatigue performance etc., this is advantageous to the development of composite.In addition, CNT have excellent mechanical property, Electric property, heat endurance and non-linear optical property, it is to prepare the preferable filler of functional composite material at present.Silica and Titanium dioxide has the premium properties such as good chemical stability, heat endurance, nontoxic, and preparation method is simple ripe and cheap It is easy to get, is widely used in modified polyurethane elastomer.Nano silicon size is small, specific surface area is big, energy high temperature resistant, silica Mechanical strength, elongation percentage, anti-wear performance and the ageing-resistant performance of thermoplastic polyurethane can be improved.Titanium dioxide is not only obvious Improve the mechanical property of polyurethane, the heat resistance of elastomer is also improved, moreover, adding the elasticity after titanium dioxide Body also has rotproofness and antibiotic property.
In recent years, it is more and more to the study on the modification of polyurethane, but multiple material is combined with each other, then go to be modified again Polyurethane is seldom seen, therefore is explored a variety of common modified polyurethanes of inorganic material and seemed highly important important.In addition, It is coupling agent modified with γ-glycidyl ether oxygen propyl trimethoxy silicane to the nano material of preparation, make the nano material of preparation Chemical bond is formed between polyurethane, is not simple physical blending, composite property is improved and played an important roll.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of compound polyurethane material of modification, the composite can be very well Ground improves the mechanical property and heat resistance of TPUE, while modifying agent can be sent out with the urethano in polyurethane Raw effect, promote it is organic with it is inorganic between crosslinking, the dispersiveness of raising inorganic material in the composite.
Technical scheme：A kind of compound polyurethane material of modification of the present invention is by TPUE and carbon modified Nanotube@silica-titania nano materials（Modified MWCNTs@SiO2-TiO2Nano material）Using the compound system of solution process It is standby to form, wherein, modified carbon nano-tube@silica-titania nano materials are to use γ-glycidyl ether oxygen propyl front three CNT@silica-titania nano materials are made TMOS, and CNT@silica-titanias are received Rice material is that modified polyurethane is made in acidifying carbon nano tube surface hydrolysis growth in situ by tetraethyl orthosilicate, butyl titanate Composite（TPU/MWCNTs@ SiO2-TiO2Nano composite material）.@is the meaning of sum.
The weight/mass percentage composition of thermoplastic polyurethane is the wt.% of 95 wt.%~99.9 in the material, the quality of CNT Percentage composition is the wt.% of 0.03 wt.%~4, and the weight/mass percentage composition of silica is the wt.% of 0.01 wt.%~1, titanium dioxide The weight/mass percentage composition of titanium is the wt.% of 0.01 wt.%~1.
Beneficial effect：The present invention improves the mechanical property and heat resistance of TPUE.By by CNTs With SiO2、TiO2Nano material is prepared into composite, and is added in TPUE, makes modified thermoplastic Property polyurethane nano composite material has CNTs, SiO2And TiO2The special performance of three kinds of materials, thermoplastic poly can be improved well The mechanical property and heat resistance of urethane elastomer, while modifying agent can have an effect with the urethano in polyurethane, promote It is organic with it is inorganic between crosslinking, improve inorganic material dispersiveness in the composite.
Polyurethane nano composite material prepared by the present invention has excellent mechanical property and heat resistance, fracture strength 36~53 MPa are reached, elongation at break has reached 700%~1200%, and corresponding temperature reaches in mass loss 10% 317~350 DEG C, the application of polyurethane is widened.
Embodiment
Weight/mass percentage composition in the material is：
Thermoplastic polyurethane：95wt.%~99.9wt.%,
The weight/mass percentage composition of CNT is the wt.% of 0.03 wt.%~4,
The weight/mass percentage composition of silica is the wt.% of 0.01 wt.%~1,
The weight/mass percentage composition of titanium dioxide is the wt.% of 0.01 wt.%~1.
At 25 DEG C, by 0.5 g multi-walled carbon nanotubes（MWCNTs）It is added in core acidifier, core acidifier is hanged It is vacant in containing 2.5 mL（The wt.% of mass fraction 65）In 100 mL closed reactors of nitric acid, 160 DEG C are then heated to, acid Change 4 h.Reaction end is cooled to room temperature, removes salpeter solution, is washed with deionized to neutrality, and 60 DEG C of vacuum drying ovens are dried After obtain be acidified CNT.Then take 0.1 g acidifying CNTs to be added in reactor, and add 5 mL ethanol and 5 ML water, the h of ultrasonic disperse 1.PH to 9.0~10.0 is adjusted with the ammoniacal liquor that mass fraction is the wt.% of 25 wt.%~28, is dripped with constant pressure The 60 mL ethanol containing 1 mL tetraethyl orthosilicates and 1 mL tetrabutyl titanates are added dropwise into reaction system in 1 h for liquid funnel Mixed solution, react 8 h.Filtering, is washed three times with 50 mL ethanol, is then washed three times with 50 mL deionized waters, at 60 DEG C 24 h are dried in vacuum drying oven, obtain CNT@silica-titania nano materials（MWCNTs@SiO2-TiO2Nanometer material Material）；
At 25 DEG C, 0.1 g MWCNTs@SiO are taken2-TiO2Nano material adds 20 mL ethanol solutions, then plus 1 mL γ- (oxygen of 2,3- epoxies third) propyl trimethoxy silicane（KH-560）, 4 h are heated to reflux after the h of ultrasonic disperse 1, are cooled to room temperature, Filtering, is washed three times with 50 mL deionized waters, and 24 h are dried in 60 DEG C of vacuum drying ovens, obtain modified carbon nano-tube@titanium dioxides Silicon-titanium dioxide nano material（Modified MWCNTs@SiO2-TiO2Nano material）.
Embodiment 1：
At 25 DEG C, the modification MWCNTs@SiO of the above-mentioned preparations of 0.0025 g are taken2-TiO2Nano material, it is added in reactor, Then 25 mL DMF solutions, 2.5 g Polyether-type thermoplastic polyurethane elastomers are added（ TPU）, the h of ultrasonic disperse 1.It is warming up to 70 DEG C, stir 4 h, finally by the compound polyurethane material of preparation at 80 DEG C removed under reduced pressure DMF solvent, obtain polyurethane nano Composite（TPU/MWCNTs@ SiO2-TiO2Nano composite material）.
Polyurethane nano composite material is cut into the mm of 75 mm × 4 5A type dumbbell battens, by GB/T 1040.2- 2006 are tested the tensile property of sample with electronic universal tester, and rate of extension is 50 mm/min.The preparation gathers Urethane nano composite material fracture strength has reached 36 MPa, and 3% is improved than pure Polyether-type thermoplastic polyurethane elastomer, breaks Split elongation and reached 700% and improve 25% than pure Polyether-type thermoplastic polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, Corresponding temperature has reached 317 DEG C than pure Polyether-type thermoplastic polyurethane elastomer raising 1.6% during mass loss 10%.
Embodiment 2：
At 25 DEG C, the above-mentioned modified MWCNTs@SiO of 0.0125 g are taken2-TiO2Nano material, it is added in reactor, so After add 50 mL DMF solutions, 2.5 g polyester-type TPUEs（TPU）, the h of ultrasonic disperse 1.It is warming up to 75 DEG C, stir 5 h, finally by the compound polyurethane material of preparation at 85 DEG C removed under reduced pressure solvent, obtain TPU/MWCNTs@ SiO2-TiO2Nano composite material.
Polyurethane nano composite material is cut into the mm of 75 mm × 4 5A type dumbbell battens, by GB/T 1040.2- 2006 are tested the tensile property of sample with electronic universal tester, and rate of extension is 50 mm/min.The preparation gathers Urethane nano composite material fracture strength has reached 37 MPa and has improved 5.7% than pure Polyether-type thermoplastic polyurethane elastomer, fracture Elongation has reached 869% and has improved 40% than pure Polyether-type thermoplastic polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, quality Lose corresponding temperature when 10% and improve 2.5% than pure Polyether-type thermoplastic polyurethane elastomer for 320 DEG C.
Embodiment 3：
At 25 DEG C, the above-mentioned modified SWCNTs@SiO of 0.025 g are taken2-TiO2Nano material, it is added in reactor, then Add 60 mL DMF solutions, 2.5 g Polyether-type thermoplastic polyurethane elastomers（TPU）, the h of ultrasonic disperse 2.80 DEG C are warming up to, Stir 5.5 h, finally by the compound polyurethane material of preparation at 90 DEG C removed under reduced pressure solvent, obtain TPU/SWCNTs@SiO2- TiO2Nano composite material.
Polyurethane nano composite material is cut into the mm of 75 mm × 4 5A type dumbbell battens, by GB/T 1040.2- 2006 are tested the tensile property of sample with electronic universal tester, and rate of extension is 50 mm/min.The preparation is answered Close nano material fracture strength and reach 40 MPa than pure Polyether-type thermoplastic polyurethane elastomer raising 14%, elongation at break Reach 943% and improve 52% than pure Polyether-type thermoplastic polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, mass loss 10% When corresponding temperature be 329 DEG C than pure Polyether-type thermoplastic polyurethane elastomer improve 5.7%.
Embodiment 4：
At 25 DEG C, the above-mentioned modified SWCNTs@SiO of 0.05 g are taken2-TiO2Nano material, it is added in reactor, then Add 65 mL DMF solutions, 2.5 g polyester-type TPUEs（TPU）, the h of ultrasonic disperse 2.85 DEG C are warming up to, Stir 6 h, finally by the compound polyurethane material of preparation at 95 DEG C removed under reduced pressure solvent, obtain TPU/SWCNTs@SiO2- TiO2Nano composite material.
Polyurethane nano composite material is cut into the mm of 75 mm × 4 5A type dumbbell battens, by GB/T 1040.2- 2006 are tested the tensile property of sample with electronic universal tester, and rate of extension is 50 mm/min.The preparation gathers Urethane nano composite material fracture strength reaches 53 MPa and improves 51% than pure Polyether-type thermoplastic polyurethane elastomer, and fracture is stretched Long rate reaches 1194% and improves 93% than pure Polyether-type thermoplastic polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, quality damage Lose corresponding temperature when 10% and improve 11.5% than pure Polyether-type thermoplastic polyurethane elastomer for 348 DEG C.
Embodiment 5：
At 25 DEG C, the above-mentioned modified CNTs@SiO of 0.125 g are taken2-TiO2Nano material, it is added in reactor, Ran Houjia Enter 75 mL DMF solutions, 2.5 g Polyether-type thermoplastic polyurethane elastomers（TPU）, the h of ultrasonic disperse 2.90 DEG C are warming up to, is stirred Mix 7 h, finally by the compound polyurethane material of preparation at 100 DEG C removed under reduced pressure solvent, obtain TPU/CNTs@SiO2-TiO2Receive Nano composite material.
Polyurethane nano composite material is cut into the mm of 75 mm × 4 5A type dumbbell battens, by GB/T 1040.2- 2006 are tested the tensile property of sample with electronic universal tester, and rate of extension is 50 mm/min.The preparation gathers Urethane nano composite material fracture strength has reached 38 MPa and has improved 8.5% than pure Polyether-type thermoplastic polyurethane elastomer, fracture Elongation reaches 1126 MPa and improves 82% than pure Polyether-type thermoplastic polyurethane elastomer.Thermogravimetric analysis under nitrogen atmosphere, matter Corresponding temperature is 338 DEG C than pure Polyether-type thermoplastic polyurethane elastomer raising 8.3% during amount loss 10%.

Claims (2)

1. a kind of compound polyurethane material of modification, it is characterised in that the material is received by TPUE and carbon modified Mitron@silica-titanias nano material is prepared using solution process is compound, wherein, modified carbon nano-tube@titanium dioxides Silicon-titanium dioxide nano material is to CNT@silica-two with γ-glycidyl ether oxygen propyl trimethoxy silicane Titanium dioxide nano material is made, and CNT@silica-titania nano materials are by tetraethyl orthosilicate, the fourth of metatitanic acid four Ester is made in acidifying carbon nano tube surface hydrolysis growth in situ.
A kind of 2. compound polyurethane material of modification according to claims 1, it is characterised in that the quality in the material Percentage composition is：
Thermoplastic polyurethane：95wt.%~99.9wt.%,
The weight/mass percentage composition of CNT is the wt.% of 0.03 wt.%~4,
The weight/mass percentage composition of silica is the wt.% of 0.01 wt.%~1,
The weight/mass percentage composition of titanium dioxide is the wt.% of 0.01 wt.%~1.
CN201710728285.4A 2017-08-23 2017-08-23 A kind of compound polyurethane material of modification Pending CN107353630A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108047498A (en) * 2017-12-05 2018-05-18 马鞍山市东方仪表有限公司 A kind of processing technology of filler for automobile instrument macromolecular component
CN114702739A (en) * 2022-01-28 2022-07-05 江西峰竺新材料科技有限公司 Light scattering plastic master batch, preparation method and application thereof in light scattering agricultural film
CN114956771A (en) * 2022-04-29 2022-08-30 山西中矿威特矿山技术开发有限公司 Inorganic composite type mining grouting reinforcement material
CN115073809A (en) * 2022-06-19 2022-09-20 南通恒光大聚氨酯材料有限公司 Preparation method of polyurethane sponge anti-heartburn agent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106751741A (en) * 2016-12-08 2017-05-31 东南大学 A kind of preparation method of polyurethane nano composite material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106751741A (en) * 2016-12-08 2017-05-31 东南大学 A kind of preparation method of polyurethane nano composite material

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108047498A (en) * 2017-12-05 2018-05-18 马鞍山市东方仪表有限公司 A kind of processing technology of filler for automobile instrument macromolecular component
CN114702739A (en) * 2022-01-28 2022-07-05 江西峰竺新材料科技有限公司 Light scattering plastic master batch, preparation method and application thereof in light scattering agricultural film
CN114956771A (en) * 2022-04-29 2022-08-30 山西中矿威特矿山技术开发有限公司 Inorganic composite type mining grouting reinforcement material
CN115073809A (en) * 2022-06-19 2022-09-20 南通恒光大聚氨酯材料有限公司 Preparation method of polyurethane sponge anti-heartburn agent

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