CN103333311B - Fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer and preparation method thereof - Google Patents
Fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer and a preparation method thereof. The fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer comprises non-fluorinated macromolecule polyol, perfluoropolyether diol, fluorinated carbon nano-tubes, a small molecule chain extender and polyisocyanate. The preparation method adopts a bulk polymerization one-step synthesis method, wherein fluorine-containing high polymer grafted carbon nano-tubes are introduced into a thermoplastic fluorine-containing polyurethane elastomer preparation system to obtain the fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer. The preparation method specifically comprises: adding non-fluorinated macromolecule polyol, perfluoropolyether diol, and fluorinated carbon nano-tubes to a reactor, carrying out high speed stirring dehydration, adding polyisocyanate and a small molecule chain extender, carrying out high speed uniform stirring, pouring into a pre-heating mold, carrying out room temperature curing molding, carrying out gradient temperature increase curing for a certain time, and taking to obtain the fluorinated carbon nano-tube/thermoplastic fluorine-containing polyurethane composite elastomer with outstanding comprehensive performances such as surface performance, mechanical property and the like.
Description
Technical field
The present invention relates to a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body and preparation method thereof, belong to technical field of polymer materials.
Background technology
Thermoplastic fluorine-containing polyurethane elastomerics is because containing carbamate (-NH-COO-) and C-F key in its molecular structure simultaneously, not only maintain original good characteristic of polyurethane structural, there is again the features such as the heat-resisting and weathering resistance of remarkable low surface energy, water and oil repellant, chemicals-resistant burn into.Thus fluorochemical urethane has become the study hotspot of urethane industry, is mainly used as bio-medical material.
Because fluorochemical monomer activity is lower, make the molecular weight of final polymkeric substance low, mechanical property is not high, thus limits its application.As Liu Tao etc. adopts loaded down with trivial details mass polymerization two-step approach consuming time (first synthesis of polyurethane performed polymer chain extending reaction again), prepare the thermoplastic fluorine-containing polyurethane elastomerics of high hot toughness.The contact angle of this elastomerics to water is only 72.4 °, and tensile strength lower (maximum value is 14.3 MPa), elongation at break is 634%(Tao Liu, Synthesis and properties of fluorinated thermoplastic polyurethane elastomer. Journal of Fluorine Chemistry, 2010,131,36-41).
Carbon nanotube is by the curling nanometer materials of single or multiple lift graphite flake, is generally acknowledged desirable polyurethane material properties-correcting agent.If the people such as Deng are to find in the research of the carbon nano-tube modified modified polyurethane of ten trifluoro octanols, when carbon nanotube add-on is 0.8%, it can make polyurethane material be increased to 138 ° to the contact angle of water by 80 °, tensile strength is increased to 37.5Mpa(Deng Jinni by 24Mpa, Mechanical and surface properties of polyurethane/fluorinated multi-walled carbon nanotubes composties.
journal of Applied Polymer Science, 2008,108,2023-2028).The preparation cycle overlength (>8 days) of this composite elastic body, and sulfur oxychloride toxic reagent need be used.
As can be seen here, develop a kind of low-carbon environment-friendly energy-conservation, convenient to operation, can large-scale production, there is the over-all properties such as excellent surface and mechanics carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body significant.
Summary of the invention
An object of the present invention: production cycle length, complicated process of preparation, high in cost of production technical problem and a kind of with short production cycle, easy and simple to handle, the environment protecting and power-saving provided are provided for solving above-mentioned thermoplastic fluorine-containing polyurethane elastomers method, are suitable for the carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic preparation of large-scale production.
Object two of the present invention: the carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body having " over-all properties such as excellent surface and mechanics " for solving the not enough and one that is that provide of the elastomeric surface of above-mentioned thermoplastic fluorine-containing polyurethane and mechanical property concurrently.
Technical scheme of the present invention
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 45.4-65.6 part
PFPE dibasic alcohol 4.6-16.3 part
Carbon fluoride nano-tube 0.05 ~ 2.0 part
Small molecule chain extender 1.6-19.2 part
Polyisocyanates 17.7-44.3 part
The molecular weight of described non-fluorine macromolecular polyol is the polybutylene glyool adipate (PBA) of 1000 ~ 3000 g/mol, PTMG (PTMG), polycaprolactone glycol (PCL) or polycarbonate diol (PCDL); Be preferably polybutylene glyool adipate (PBA), PTMG (PTMG) or polycaprolactone glycol (PCL);
Described PFPE glycol molecular weight is 1000 ~ 2000g/mol, and its molecular formula is:
HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 1 ~ 23, and being preferably 2-18, m is 1 ~ 33, is preferably 10-15;
Described small molecule chain extender is 1,4-butyleneglycol, 1,6-cyclohexanediol, 3,3'-bis-chloro-4,4'-diphenylmethanediamiands (MOCA) or 3,5-dimethyl sulfenyl toluene (E-300), be preferably BDO, 1,6-cyclohexanediol or 3, chloro-4, the 4'-diphenylmethanediamiands of 3'-bis-;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 2% ~ 15%;
Described polyisocyanates is 4, 4 ￠-diphenylmethanediisocyanate (MDI), 2, 4-tolylene diisocyanate (TDI), 2, 6-tolylene diisocyanate (TDI), 1, 5-naphthalene diisocyanate (NDI), PPDI (PPDI), dimethyl diphenyl vulcabond (TODI), 1, 6-hexylidene diisocyanate (HDI), isophorone diisocyanate (IPDI) or 4, 4 ￠-two cyclohexyls methane diisocyanate (HMDI), be preferably 4, 4 ￠-diphenylmethanediisocyanate (MDI), 2, 4-tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI) or 4, 4 ￠-two cyclohexyls methane diisocyanate (HMDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1), PFPE dibasic alcohol, non-fluorine macromolecular polyol and carbon fluoride nano-tube are placed in reactor, controlling mixing speed is after 2000 ~ 3000r/min stirs 10 ~ 25min, vacuum hydro-extraction 1 ~ 2h at 100 ~ 130 DEG C of temperature, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 2000 ~ 3000 r/min, polyisocyanates and small molecule chain extender is added successively containing in fluoride mixture to step (1) gained, pour in the mould of preheating after continuing stirring 3 ~ 5min, control temperature is 15 ~ 30 DEG C of curing molding 2 ~ 4h, then control temperature is vacuum solidification 3 ~ 4h at 60 ~ 90 DEG C, last control temperature is 120 ~ 140 DEG C of vacuum solidification 15 ~ 24h, obtains carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
Carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of preparation method's gained of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, it is 90 ~ 145 ° to the contact angle of water, tensile strength is 10.5 ~ 30MPa, and elongation at break is 220 ~ 484%.
Useful achievement of the present invention
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of the present invention, because carbon nanotube itself has excellent mechanical strength and surface property, thus the introducing of Trace Fluoride carbon nano tube significantly can improve the elastomeric surface of thermoplastic fluorine-containing polyurethane and mechanical property.Final carbon fluoride nano-tube of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body is 90 ~ 145 ° to the contact angle of water, and tensile strength is 10.5 ~ 30MPa, and elongation at break is 220 ~ 484%.
The preparation method of a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of the present invention, there is the multi-walled carbon nano-tubes of polymethyl acrylic acid perfluoroalkyl ester for properties-correcting agent with surface grafting, prepare carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body by mass polymerization single stage method.The whole preparation process of this carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body is simple; and energy consumption is low; thus preparation method of the present invention has easy and simple to handle; and whole production process short (the longest only need 36h), therefore have with short production cycle, production cost is low, be suitable for the advantages such as large-scale production.
Further, the preparation method of a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of the present invention, due in its preparation process without the need to using any solvent, environmentally safe, therefore its preparation process has safety, environmental protection, pollution-free, meets the feature of clear production.
Further, the preparation method of a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of the present invention, properties-correcting agent used is the multi-walled carbon nano-tubes that surface grafting has polymethyl acrylic acid perfluoroalkyl ester.According to similar dissolve mutually theory, the fluorine-containing polymer of multi-walled carbon nano-tubes surface grafting, namely polymethyl acrylic acid perfluoroalkyl ester can promote that the dispersed and strong interfaces of carbon fluoride nano-tube in thermoplastic fluorine-containing polyurethane elastomers system combines, thus effectively alleviates because of original carbon nanotubes surface inertness and the technical barrier being difficult to effectively dispersion and strong interfaces combination in macromolecule resin from being wound around self aggregation.
Embodiment
Below by embodiment, the present invention is described in further detail, but do not limit the present invention.
The present invention's carbon fluoride nano-tube used is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its surperficial Oil repellent is 2 ~ 15%, is provided by Xinguang Tech Co., Ltd., Shanghai.
The present invention's non-fluorine macromolecular polyol used is purchased from BASF (China) Shanghai branch office.
The present invention's PFPE dibasic alcohol used, is provided by Su Wei (Shanghai) Co., Ltd..
The present invention's small molecule chain extender used is purchased from Shanghai traditional Chinese medicines group, and polyisocyanates is by Yantai Wan Hua Yantai Wanhua Polyurethane Co., Ltd.
embodiment 1
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 65.6 parts
PFPE dibasic alcohol 9.4 parts
Carbon fluoride nano-tube 0.05 part
Small molecule chain extender 1.9 parts
Polyisocyanates 23.2 parts
Described non-fluorine macromolecular polyol is the polybutylene glyool adipate of molecular weight 1000g/mol;
Described PFPE dibasic alcohol molecular formula is HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 2, m is 15, and its molecular weight is 1000 g/mol;
Described small molecule chain extender is BDO;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 2%;
Described polyisocyanates is 4,4 ￠-diphenylmethanediisocyanate.
The preparation method of above-mentioned a kind of carbon fluoride nano-tube thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1), the non-fluorine macromolecular polyol (i.e. polybutylene glyool adipate) of the PFPE dibasic alcohol of molecular weight 1000g/mol, molecular weight 1000g/mol and carbon fluoride nano-tube are joined in reactor, speed control is after 2000r/min stirs 25min, vacuum hydro-extraction 1.5h at 120 DEG C of temperature, obtains containing fluoride mixture;
(2), continuing to control mixing speed is 2000r/min, polyisocyanates (namely 4 is added successively in the fluorine-containing compound resin of step (1) gained, 4 ￠-diphenylmethanediisocyanate) and small molecule chain extender (namely 1,4-butyleneglycol), pour in the mould of preheating after continuing to stir 5min, then curing molding 4h at control temperature 15 DEG C, then vacuum solidification 4h at 60 DEG C, finally in 120 DEG C of solidification 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, through DSAIOMKZ contact angle tester (German Data physics company), sessile drop method is adopted to detect (Liu Tao, Journal of Fluorine Chemistry, 2010,131,36-41), it is 90 ° to the contact angle of water.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, through GALDABLNI SUN universal testing machine (Italian GALDABLNI company), adopt GB/T528-1998 method to detect, its tensile strength is 28.3 MPa, and elongation at break is 450%.
embodiment 2
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 45.4 parts
PFPE dibasic alcohol 4.6 parts
Carbon fluoride nano-tube 0.2 part
Small molecule chain extender 19.2 parts
Polyisocyanates 44.3 parts
Described non-fluorine macromolecular polyol is the PTMG (PTMEG) of molecular weight 3000 g/mol;
Described PFPE dibasic alcohol molecular formula is HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 2, m is 15, and its molecular weight is 1000 g/mol;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 10%;
Described polyisocyanates is 2,4 toluene diisocyanate (TDI);
Described small molecule chain extender is 1,6-cyclohexanediol.
The preparation method of above-mentioned a kind of carbon fluoride nano-tube thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1) the non-fluorine macromolecular polyol (i.e. PTMG) of the PFPE dibasic alcohol of molecular weight 1000g/mol, molecular weight 3000g/mol and carbon fluoride nano-tube are joined in reactor, controlling mixing speed is after 2500r/min stirs 10min, vacuum hydro-extraction 2h at 100 DEG C of temperature, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 2500r/min, polyisocyanates (namely 2 is added successively in the fluorine-containing compound resin of step (1) gained, 4-tolylene diisocyanate) and small molecule chain extender (namely 1,6-cyclohexanediol), pour in the mould of preheating after continuing to stir 5min, then curing molding 4h at control temperature 15 DEG C, then vacuum solidification 4h at 60 DEG C, finally in 120 DEG C of solidification 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
A kind of carbon fluoride nano-tube thermoplastic fluorine-containing polyurethane composite elastic body of above-mentioned gained, it is 108 ° to the contact angle of water after testing, and tensile strength is 20 MPa, and its elongation at break is 435%.
embodiment 3
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 48.7 parts
PFPE dibasic alcohol 16.3 parts
Carbon fluoride nano-tube 0.5 part
Small molecule chain extender 4.6 parts
Polyisocyanates 29.1 parts
Described non-fluorine macromolecular polyol is the polycaprolactone glycol (PCL) of molecular weight 1000 g/mol;
Described PFPE dibasic alcohol molecular formula is HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 2, m is 15, and its molecular weight is 1000g/mol;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 15%;
Described small molecule chain extender is BDO;
Described polyisocyanates is 4,4 ￠-two cyclohexyls methane diisocyanate (HMDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1), the non-fluorine macromolecular polyol (i.e. polycaprolactone glycol) of the PFPE dibasic alcohol of molecular weight 1000g/mol and molecular weight 1000g/mol and carbon fluoride nano-tube are joined in reactor, controlling mixing speed is after 3000r/min stirs 15min, vacuum hydro-extraction 1h at 130 DEG C, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 3000 r/min, polyisocyanates (namely 4 is added successively in the fluorine-containing compound resin of step (1) gained, 4 ￠-two cyclohexyl methane diisocyanates) and small molecule chain extender (namely 1,4-butyleneglycol), pour in the mould of preheating after continuing to stir 3min, then curing molding 4h at control temperature 15 DEG C, then vacuum solidification 4h at 60 DEG C, finally in 120 DEG C of solidification 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, it is 119 ° to the contact angle of water after testing, and tensile strength is 10.5MPa, and its elongation at break is 220%.
embodiment 4
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 62.5 parts
PFPE dibasic alcohol 12.5 parts
Carbon fluoride nano-tube 2 parts
Small molecule chain extender 9.4 parts
Polyisocyanates 17.7 parts
Described non-fluorine macromolecular polyol is the polycaprolactone glycol (PCL) of molecular weight 2000 g/mol;
Described PFPE dibasic alcohol molecular formula is HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 18, m is 10, and its molecular weight is 2000 g/mol;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 8%;
Described small molecule chain extender is chloro-4, the 4'-diphenylmethanediamiands (MOCA) of 3,3'-bis-;
Described polyisocyanates is isophorone diisocyanate (IPDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1), the non-fluorine macromolecular polyol (i.e. polycaprolactone glycol) of the PFPE dibasic alcohol of molecular weight 2000g/mol and molecular weight 2000g/mol and carbon fluoride nano-tube are joined in reactor, controlling mixing speed is after 3000r/min stirs 15min, vacuum hydro-extraction 1h at 130 DEG C, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 3000r/min, polyisocyanates (i.e. isophorone diisocyanate) and small molecule chain extender (namely 3 is added successively in the fluorine-containing compound resin of step (1) gained, 3'-bis-chloro-4,4'-diphenylmethanediamiand), pour in the mould of preheating after continuing to stir 3min, curing molding 2h at control temperature 30 DEG C again, then vacuum solidification 4h at 90 DEG C, finally in 140 DEG C of solidification 15h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, it is 145 ° to the contact angle of water after testing, and tensile strength is 22MPa, and its elongation at break is 368%.
embodiment 5
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 64.3 parts
PFPE dibasic alcohol 10.7 parts
Carbon fluoride nano-tube 0.5 part
Small molecule chain extender 1.6 parts
Polyisocyanates 22.6 parts
Described non-fluorine macromolecular polyol is the polybutylene glyool adipate (PBA) of molecular weight 1000g/mol;
Described PFPE dibasic alcohol molecular formula is HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 2, m is 15, and its molecular weight is 1000 g/mol;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 15%;
Described small molecule chain extender is BDO;
Described polyisocyanates is 4,4 ￠-diphenylmethanediisocyanate (MDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, specifically comprises the following steps:
(1), the non-fluorine macromolecular polyol (i.e. polybutylene glyool adipate) of the PFPE dibasic alcohol of molecular weight 1000g/mol and molecular weight 1000g/mol and carbon fluoride nano-tube are joined in reactor, controlling mixing speed is after 3000r/min stirs 15min, vacuum hydro-extraction 1.5h at 120 DEG C, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 3000r/min, polyisocyanates (namely 4 is added successively in the fluorine-containing compound resin of step (1) gained, 4 ￠-diphenylmethanediisocyanate) and small molecule chain extender (namely 1,4-butyleneglycol), pour in the mould of preheating after continuing to stir 4min, then curing molding 3h at control temperature 30 DEG C, then vacuum solidification 3h at 90 DEG C, finally in 130 DEG C of solidification 20h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, it is 138 ° to the contact angle of water after testing, and tensile strength is 30MPa, and its elongation at break is 484%.
In sum, a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of the present invention, it is 90 ~ 145 ° to the contact angle of water, and tensile strength is 10.5 ~ 30MPa, and elongation at break is 220 ~ 484%.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (1)
1. a preparation method for carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, described carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 45.4-65.6 part
PFPE dibasic alcohol 4.6-16.3 part
Carbon fluoride nano-tube 0.05 ~ 2.0 part
Small molecule chain extender 1.6-19.2 part
Polyisocyanates 17.7-44.3 part
The molecular weight of described non-fluorine macromolecular polyol is the polybutylene glyool adipate of 1000 ~ 3000g/mol, PTMG, polycaprolactone glycol or polycarbonate diol;
The molecular weight of described PFPE glycol is 1000 ~ 2000 g/mol, and its molecular formula is:
HO-
n(CH
2cH
2o)-CH
2-CF
2o-(CF
2cF
2o)
m-(CF
2o)
n-CF
2-CH
2-(OCH
2cH
2)
n-OH, wherein n is 1 ~ 23, m is 1 ~ 33;
Described small molecule chain extender is BDO, 1,6-cyclohexanediol, 3,3'-bis-chloro-4,4'-diphenylmethanediamiands or 3,5-dimethyl sulfenyl toluene;
Described carbon fluoride nano-tube is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its fluorine-contained surface amount is 2 ~ 15%;
Described polyisocyanates is 4,4 '-diphenylmethanediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthalene diisocyanate, PPDI, dimethyl diphenyl vulcabond, 1,6-hexylidene diisocyanate, isophorone diisocyanate or 4,4 '-two cyclohexyl methane diisocyanate;
It is characterized in that its preparation process specifically comprises the steps:
(1), PFPE dibasic alcohol, non-fluorine macromolecular polyol and carbon fluoride nano-tube are placed in reactor, controlling mixing speed is after 2000 ~ 3000r/min stirs 10 ~ 25min, vacuum hydro-extraction 1 ~ 2h at 100 ~ 130 DEG C of temperature, obtains containing fluoride mixture;
(2), continuing to control mixing speed is under 2000 ~ 3000 r/min, polyisocyanates and small molecule chain extender is added successively containing in fluoride mixture to step (1) gained, pour in the mould of preheating after continuing stirring 3 ~ 5min, control temperature is 15 ~ 30 DEG C of curing molding 2 ~ 4h, then control temperature is vacuum solidification 3 ~ 4h at 60 ~ 90 DEG C, last control temperature is 120 ~ 140 DEG C of vacuum solidification 15 ~ 24h, obtains carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
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| CN104004158B (en) * | 2014-06-13 | 2016-06-08 | 上海理工大学 | The preparation method of a kind of soft segment lateral chain fluorochemical urethane with low fluorine height surface property |
| CN105418874A (en) * | 2015-12-24 | 2016-03-23 | 上海恒安聚氨酯股份有限公司 | 3D-printing thermoplastic polyurethane material and preparation method of same |
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| CN107033323B (en) * | 2017-04-18 | 2019-10-18 | 东莞市吉鑫高分子科技有限公司 | A kind of thermoplastic polyurethane and preparation method thereof with high-biocompatibility |
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| CN1176966C (en) * | 2001-02-28 | 2004-11-24 | 四川大学 | Fluorine containing polyurethane material and preparation method thereof |
| CN101274991B (en) * | 2008-05-15 | 2011-05-04 | 复旦大学 | High molecular hydrophobic film and preparation thereof |
| CN101585902B (en) * | 2009-06-26 | 2011-12-21 | 湖南大学 | Fluorinated polyurethane nanometer composite material and preparation method thereof |
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