CN103333311A - 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
The thermoplastic fluorine-containing polyurethane elastomerics is because containing carbamate simultaneously (NH-COO-) with the C-F key in its molecular structure, the original good characteristic that has not only kept polyurethane structural has characteristics such as the heat-resisting and weathering resistance of remarkable low surface energy, water and oil repellant, chemicals-resistant burn into again.Thereby fluorochemical urethane become the research focus of urethane industry, mainly as bio-medical material.
Because the fluorochemical monomer activity is lower, makes the molecular weight of final polymkeric substance low, mechanical property is not high, thereby limits its application.As employing loaded down with trivial details mass polymerization two-step approachs consuming time (first synthesis of polyurethane performed polymer is chain extending reaction again) such as Liu Tao, prepare the thermoplastic fluorine-containing polyurethane elastomerics of high hot toughness.This elastomerics only is 72.4 ° to the contact angle of water, 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 the nanometer materials of being curled and being formed by the single or multiple lift graphite flake, is the desirable polyurethane material properties-correcting agent of generally acknowledging.As finding in the research of people such as Deng with the carbon nano-tube modified modified polyurethane of ten trifluoro octanols, when the carbon nanotube add-on is 0.8%, it can make polyurethane material that the contact angle of water is increased to 138 ° 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).And need use the sulfur oxychloride toxic reagent preparation cycle overlength (〉 of this composite elastic body 8 days).
This shows, develop a kind of low-carbon environment-friendly energy-conservation, convenient to operation, can large-scale production, carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body with over-all propertieies such as excellent surface and mechanics is significant.
Summary of the invention
One of purpose of the present invention: be a kind of with short production cycle, easy and simple to handle, the environment protecting and power-saving that solves that above-mentioned thermoplastic fluorine-containing polyurethane elastomer production method exists that production cycle length, complicated process of preparation, cost high-technology problem provide, the carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic preparation that is suitable for large-scale production.
Two of purpose of the present invention: for the carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body of not enough a kind of the having concurrently that provides of the elastomeric surface of above-mentioned thermoplastic fluorine-containing polyurethane and mechanical property " over-all propertieies such as excellent surface and mechanics " is provided.
Technical scheme of the present invention
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body calculates by weight, and its raw material composition and content are as follows:
Non-fluorine macromolecular polyol 45.4-65.6 part
PFPE dibasic alcohol 4.6-16.3 part
0.05～2.0 part of carbon fluoride nano-tube
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 poly adipate succinic acid ester glycol (PBA), PTMG (PTMG), polycaprolactone glycol (PCL) or the polycarbonate diol (PCDL) of 1000～3000 g/mol; Be preferably poly adipate succinic acid ester glycol (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, is 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'-two chloro-4,4'-ditan diamines (MOCA) or 3,5-dimethyl sulfenyl toluene (E-300), be preferably 1,4-butyleneglycol, 1,6-cyclohexanediol or 3,3'-two chloro-4,4'-ditan diamines;
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 cyclohexyl methane diisocyanate (HMDI), be preferably 4,4 ￠-diphenylmethanediisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI) or 4,4 ￠-two cyclohexyl methane diisocyanate (HMDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body specifically may further comprise the steps:
(1), PFPE dibasic alcohol, non-fluorine macromolecular polyol and carbon fluoride nano-tube are placed reactor, the control mixing speed is after 2000～3000r/min stirs 10～25min, vacuum hydro-extraction 1～2h under 100～130 ℃ of temperature obtains containing fluoride mixture;
(2), continuing the control mixing speed is under 2000～3000 r/min, contain to step (1) gained and to add polyisocyanates and small molecule chain extender in the fluoride mixture successively, pour in the mould of preheating after continuing to stir 3～5min, the control temperature is 15～30 ℃ of curing molding 2～4h, controlling temperature then is 60～90 ℃ of following vacuum solidification 3～4h, controlling temperature at last is 120～140 ℃ of vacuum solidification 15～24h, namely gets 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, its contact angle to water is 90～145 °, 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 of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body, because carbon nanotube itself has excellent mechanical strength and surface property, thereby the introducing of Trace Fluoride carbon nano tube can significantly 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 of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body, with surface grafting the multi-walled carbon nano-tubes of polymethyl acrylic acid perfluoroalkyl ester being arranged is properties-correcting agent, prepares carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body by the mass polymerization single stage method.The whole process of preparation of this carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body is simple; and energy consumption is low; thereby preparation method of the present invention has easy and simple to handle; and whole process of production short (the longest 36h that only needs), therefore have with short production cycle, production cost is low, be suitable for advantage such as large-scale production.
Further, the preparation method of a kind of carbon fluoride nano-tube of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body is owing to need not to use any solvent in its preparation process, environmentally safe, therefore its preparation process has safety, environmental protection, and is pollution-free, meets clean characteristics of producing.
Further, the preparation method of a kind of carbon fluoride nano-tube of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body, used properties-correcting agent is the multi-walled carbon nano-tubes that surface grafting has the polymethyl acrylic acid perfluoroalkyl ester.According to the similar compatibility principle, the fluorine-containing polymer of multi-walled carbon nano-tubes surface grafting, be that the polymethyl acrylic acid perfluoroalkyl ester can promote even dispersion and the strong interfaces combination of carbon fluoride nano-tube in thermoplastic fluorine-containing polyurethane elastomer production system, self aggregation is difficult to effectively to disperse in macromolecule resin and the technical barrier of strong interfaces combination because of original carbon nano tube surface inertia with from twining thereby effectively alleviated.
Embodiment
Describe in further detail below by the present invention of embodiment, but do not limit the present invention.
The used carbon fluoride nano-tube of the present invention is the multi-walled carbon nano-tubes of surface grafting polymethyl acrylic acid perfluoroalkyl ester, and its surperficial fluorine content is 2 ~ 15%, is provided by Xinguang Tech Co., Ltd., Shanghai.
The used non-fluorine macromolecular polyol of the present invention is available from BASF (China) Shanghai branch office.
The used PFPE dibasic alcohol of the present invention is provided by Su Wei (Shanghai) Co., Ltd..
The used small molecule chain extender of the present invention is available 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, and its raw material composition and content are as follows:
65.6 parts of non-fluorine macromolecular polyols
9.4 parts of PFPE dibasic alcohol
0.05 part of carbon fluoride nano-tube
1.9 parts of small molecule chain extenders
23.2 parts of polyisocyanates
The poly adipate succinic acid ester glycol that described non-fluorine macromolecular polyol is 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 that 2, m is 15, its molecular weight is 1000 g/mol;
Described small molecule chain extender is 1,4-butyleneglycol;
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 may further comprise the steps:
(1), the PFPE dibasic alcohol of molecular weight 1000g/mol, the non-fluorine macromolecular polyol of molecular weight 1000g/mol (being the poly adipate succinic acid ester glycol) and carbon fluoride nano-tube are joined in the reactor, control speed is after 2000r/min stirs 25min, vacuum hydro-extraction 1.5h under 120 ℃ of temperature obtains containing fluoride mixture;
(2), continuing the control mixing speed is 2000r/min, add polyisocyanates (namely 4 in the fluorine-containing compound resin of step (1) gained successively, 4 ￠-diphenylmethanediisocyanate) and small molecule chain extender (namely 1, the 4-butyleneglycol), pour in the mould of preheating after continuing to stir 5min, control 15 ℃ of following curing molding 4h of temperature again, then in 60 ℃ of following vacuum solidification 4h, in 120 ℃ of curing 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body at last.
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), adopt sessile drop method to detect (Liu Tao, Journal of Fluorine Chemistry, 2010,131,36-41), its contact angle to water is 90 °.
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 the 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, and its raw material composition and content are as follows:
45.4 parts of non-fluorine macromolecular polyols
4.6 parts of PFPE dibasic alcohol
0.2 part of carbon fluoride nano-tube
19.2 parts of small molecule chain extenders
44.3 parts of polyisocyanates
The PTMG (PTMEG) that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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 may further comprise the steps:
(1) the PFPE dibasic alcohol of molecular weight 1000g/mol, non-fluorine macromolecular polyol (being PTMG) and the carbon fluoride nano-tube of molecular weight 3000g/mol are joined in the reactor, the control mixing speed is after 2500r/min stirs 10min, vacuum hydro-extraction 2h under 100 ℃ of temperature obtains containing fluoride mixture;
(2), continuing the control mixing speed is under the 2500r/min, add polyisocyanates (namely 2 in the fluorine-containing compound resin of step (1) gained successively, the 4-tolylene diisocyanate) and small molecule chain extender (namely 1, the 6-cyclohexanediol), pour in the mould of preheating after continuing to stir 5min, control 15 ℃ of following curing molding 4h of temperature again, then in 60 ℃ of following vacuum solidification 4h, in 120 ℃ of curing 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body at last.
A kind of carbon fluoride nano-tube thermoplastic fluorine-containing polyurethane composite elastic body of above-mentioned gained, its contact angle to water is 108 ° 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, and its raw material composition and content are as follows:
48.7 parts of non-fluorine macromolecular polyols
16.3 parts of PFPE dibasic alcohol
0.5 part of carbon fluoride nano-tube
4.6 parts of small molecule chain extenders
29.1 parts of polyisocyanates
The polycaprolactone glycol (PCL) that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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 1,4-butyleneglycol;
Described polyisocyanates is 4,4 ￠-two cyclohexyl methane diisocyanate (HMDI).
The preparation method of above-mentioned a kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body specifically may further comprise the steps:
(1), the PFPE dibasic alcohol of molecular weight 1000g/mol and non-fluorine macromolecular polyol (being polycaprolactone glycol) and the carbon fluoride nano-tube of molecular weight 1000g/mol are joined in the reactor, the control mixing speed is after 3000r/min stirs 15min, in 130 ℃ of following vacuum hydro-extraction 1h, obtain containing fluoride mixture;
(2), continuing the control mixing speed is under 3000 r/min, add polyisocyanates (namely 4 in the fluorine-containing compound resin of step (1) gained successively, 4 ￠-two cyclohexyl methane diisocyanate) and small molecule chain extender (namely 1, the 4-butyleneglycol), pour in the mould of preheating after continuing to stir 3min, control 15 ℃ of following curing molding 4h of temperature again, then in 60 ℃ of following vacuum solidification 4h, in 120 ℃ of curing 24h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body at last.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, its contact angle to water is 119 ° 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, and its raw material composition and content are as follows:
62.5 parts of non-fluorine macromolecular polyols
12.5 parts of PFPE dibasic alcohol
2 parts of carbon fluoride nano-tubes
9.4 parts of small molecule chain extenders
17.7 parts of polyisocyanates
The polycaprolactone glycol (PCL) that described non-fluorine macromolecular polyol is 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 that 18, m is 10, 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 3,3'-, two chloro-4,4'-ditan diamines (MOCA);
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 may further comprise the steps:
(1), the PFPE dibasic alcohol of molecular weight 2000g/mol and non-fluorine macromolecular polyol (being polycaprolactone glycol) and the carbon fluoride nano-tube of molecular weight 2000g/mol are joined in the reactor, the control mixing speed is after 3000r/min stirs 15min, in 130 ℃ of following vacuum hydro-extraction 1h, obtain containing fluoride mixture;
(2), continuing the control mixing speed is under the 3000r/min, add polyisocyanates (being isophorone diisocyanate) and small molecule chain extender (namely 3 in the fluorine-containing compound resin of step (1) gained successively, 3'-two chloro-4,4'-ditan diamines), pour in the mould of preheating after continuing to stir 3min, control 30 ℃ of following curing molding 2h of temperature again, then in 90 ℃ of following vacuum solidification 4h, in 140 ℃ of curing 15h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body at last.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, its contact angle to water is 145 ° 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, and its raw material composition and content are as follows:
64.3 parts of non-fluorine macromolecular polyols
10.7 parts of PFPE dibasic alcohol
0.5 part of carbon fluoride nano-tube
1.6 parts of small molecule chain extenders
22.6 parts of polyisocyanates
The poly adipate succinic acid ester glycol (PBA) that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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 1,4-butyleneglycol;
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 may further comprise the steps:
(1), the PFPE dibasic alcohol of molecular weight 1000g/mol and the non-fluorine macromolecular polyol of molecular weight 1000g/mol (being the poly adipate succinic acid ester glycol) and carbon fluoride nano-tube are joined in the reactor, the control mixing speed is after 3000r/min stirs 15min, in 120 ℃ of following vacuum hydro-extraction 1.5h, obtain containing fluoride mixture;
(2), continuing the control mixing speed is under the 3000r/min, add polyisocyanates (namely 4 in the fluorine-containing compound resin of step (1) gained successively, 4 ￠-diphenylmethanediisocyanate) and small molecule chain extender (namely 1, the 4-butyleneglycol), pour in the mould of preheating after continuing to stir 4min, control 30 ℃ of following curing molding 3h of temperature again, then in 90 ℃ of following vacuum solidification 3h, in 130 ℃ of curing 20h, obtain carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body at last.
A kind of carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane the composite elastic body of above-mentioned gained, its contact angle to water is 138 ° after testing, and tensile strength is 30MPa, and its elongation at break is 484%.
In sum, a kind of carbon fluoride nano-tube of the present invention/thermoplastic fluorine-containing polyurethane composite elastic body, its contact angle to water is 90～145 °, and tensile strength is 10.5～30MPa, and elongation at break is 220～484%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (7)
1. carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
Non-fluorine macromolecular polyol 45.4-65.6 part
PFPE dibasic alcohol 4.6-16.3 part
0.05～2.0 part of carbon fluoride nano-tube
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 poly adipate succinic acid ester glycol, PTMG, polycaprolactone glycol or the polycarbonate diol of 1000～3000g/mol;
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 that 1～23, m is 1～33;
Described small molecule chain extender is 1,4-butyleneglycol, 1,6-cyclohexanediol, 3,3'-two chloro-4,4'-ditan diamines 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.
2. a kind of carbon fluoride nano-tube as claimed in claim 1/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
65.6 parts of non-fluorine macromolecular polyols
9.4 parts of PFPE dibasic alcohol
0.05 part of carbon fluoride nano-tube
1.9 parts of small molecule chain extenders
23.2 parts of polyisocyanates
The poly adipate succinic acid ester glycol that described non-fluorine macromolecular polyol is 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 that 2, m is 15, its molecular weight is 1000 g/mol;
Described small molecule chain extender is 1,4-butyleneglycol;
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.
3. a kind of carbon fluoride nano-tube as claimed in claim 1/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
45.4 parts of non-fluorine macromolecular polyols
4.6 parts of PFPE dibasic alcohol
0.2 part of carbon fluoride nano-tube
19.2 parts of small molecule chain extenders
44.3 parts of polyisocyanates
The PTMG that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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;
Described small molecule chain extender is 1,6-cyclohexanediol.
4. a kind of carbon fluoride nano-tube as claimed in claim 1/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
48.7 parts of non-fluorine macromolecular polyols
16.3 parts of PFPE dibasic alcohol
0.5 part of carbon fluoride nano-tube
4.6 parts of small molecule chain extenders
29.1 parts of polyisocyanates
The polycaprolactone glycol that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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 1,4-butyleneglycol;
Described polyisocyanates is 4,4 ￠-two cyclohexyl methane diisocyanate.
5. a kind of carbon fluoride nano-tube as claimed in claim 1/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
62.5 parts of non-fluorine macromolecular polyols
12.5 parts of PFPE dibasic alcohol
2 parts of carbon fluoride nano-tubes
9.4 parts of small molecule chain extenders
17.7 parts of polyisocyanates
The polycaprolactone glycol that described non-fluorine macromolecular polyol is 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 that 18, m is 10, 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 3,3'-, two chloro-4,4'-ditan diamines;
Described polyisocyanates is isophorone diisocyanate.
6. a kind of carbon fluoride nano-tube as claimed in claim 1/thermoplastic fluorine-containing polyurethane composite elastic body is characterized in that calculating by weight, and its raw material composition and content are as follows:
64.3 parts of non-fluorine macromolecular polyols
10.7 parts of PFPE dibasic alcohol
0.5 part of carbon fluoride nano-tube
1.6 parts of small molecule chain extenders
22.6 parts of polyisocyanates
The poly adipate succinic acid ester glycol that described non-fluorine macromolecular polyol is 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 that 2, m is 15, 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 1,4-butyleneglycol;
Described polyisocyanates is 4,4 ￠-diphenylmethanediisocyanate.
7. as the preparation method of the described a kind of carbon fluoride nano-tube of the arbitrary claim of claim 1-6/thermoplastic fluorine-containing polyurethane composite elastic body, it is characterized in that specifically comprising the steps:
(1), PFPE dibasic alcohol, non-fluorine macromolecular polyol and carbon fluoride nano-tube are placed reactor, the control mixing speed is after 2000～3000r/min stirs 10～25min, vacuum hydro-extraction 1～2h under 100～130 ℃ of temperature obtains containing fluoride mixture;
(2), continuing the control mixing speed is under 2000～3000 r/min, contain to step (1) gained and to add polyisocyanates and small molecule chain extender in the fluoride mixture successively, pour in the mould of preheating after continuing to stir 3～5min, the control temperature is 15～30 ℃ of curing molding 2～4h, controlling temperature then is 60～90 ℃ of following vacuum solidification 3～4h, controlling temperature at last is 120～140 ℃ of vacuum solidification 15～24h, namely gets carbon fluoride nano-tube/thermoplastic fluorine-containing polyurethane composite elastic body.
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| CN107033323A (en) * | 2017-04-18 | 2017-08-11 | 东莞市吉鑫高分子科技有限公司 | A kind of thermoplastic polyurethane with high-biocompatibility and preparation method thereof |
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| WO2015075462A1 (en) * | 2013-11-20 | 2015-05-28 | Preservation Paints Limited | Composition |
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