CN103242505B - Thermoplastic fluorinated polyurethane elastomer and preparation method thereof - Google Patents
Thermoplastic fluorinated polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN103242505B CN103242505B CN201310169031.5A CN201310169031A CN103242505B CN 103242505 B CN103242505 B CN 103242505B CN 201310169031 A CN201310169031 A CN 201310169031A CN 103242505 B CN103242505 B CN 103242505B
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Abstract
The invention discloses a thermoplastic fluorinated polyurethane elastomer and a preparation method thereof. The thermoplastic fluorinated polyurethane elastomer is composed of non-fluorinated macromolecular polyols, perfluor polyether glycol, a micromolecular chain extender and polyisocyanates; and the preparation method comprises the following steps of: adding perfluor polyether glycol and non-fluorinated macromolecular polyols into a container; after the obtained fluorinated composite resin is stirred for 10-20 minutes at a speed of 2000-3000 r/min, carrying out vacuum dehydration on the obtained fluorinated composite resin; sequentially adding polyisocyanates and the micromolecular chain extender into the obtained product; continuing to stir the obtained mixture for 3-5 minutes, and pouring the obtained mixture in a preheated die; and after the obtained mixture is subjected to curing forming for 2-4 hours at a controlled temperature of 15-30 DEG C, respectively carrying out vacuum curing on the obtained product for 1-2 hours at a temperature of 50-80 DEG C, carrying out vacuum curing on the obtained product for 1-2 hours at a temperature of 90-110 DEG C, and carrying out vacuum curing on the obtained product for 15-24 hours at a temperature of 120-140 DEG C, thereby obtaining the thermoplastic fluorinated polyurethane elastomer with a low fluoride content and excellent surface and mechanical properties.
Description
Technical field
The present invention is specifically related to a kind of thermoplastic fluorine-containing polyurethane elastomerics and preparation method thereof, belongs to technical field of polymer materials.
Background technology
The good characteristic such as thermoplastic polyurethane (representing with TPU below) elastomerics not only has snappiness, high strength, high abrasion, can process, there is again the advantages such as the anticoagulant property good with human body and biocompatibility, be acknowledged as the polymeric biomaterial of over-all properties optimum, in blood vessel graft, interventional catheter, making assisted circulation of ventriculus cordis system and artificial heart etc., have good application prospect.The micro phase separation structure of TPU uniqueness gives its good anticoagulant property and biocompatibility, but in repeated deformation process, this structure can be destroyed, and result in surface free energy and raises, directly affects anticoagulant property and the biocompatibility of material.
The fluorine element with energy characteristic is introduced in its structure, fluorine-containing TPU elastomerics can be obtained.Not only maintain the substantially excellent mechanical property of TPU elastomeric Microphase Structure characteristic sum, also effectively can reduce the surface free energy of material, give the low surface energy characteristic of its excellence, oxidation-resistance and chemical resistance medium etc., the anticoagulant property of material and biocompatibility are significantly improved.At present, many international major companies such as BASF, the Bayer amount of having high input fund all in succession, develops this kind of type material., because being subject to the restriction such as raw material, fund, only there is minute quantity research in China.
2009, Sichuan University Ye Lin etc. (CN101717485A), it is soft section with non-fluorine macromolecular polyol and (or) fluorochemical polyether glycol, with small molecules glycol for chainextender, go out to have the thermoplastic fluorine-containing polyurethane elastomerics of high tenacity by mass polymerization two step synthesis, its Oil repellent is 11.9 ~ 23.9%, is 64.0 ~ 72.4 ° to the contact angle of water, tensile strength is 6.6 ~ 14.3MPa, and elongation at break is 89.1 ~ 634.3%.Because this preparation method need through two-step reaction (first synthesizing performed polymer chain extending reaction again), thermoplastic fluorine-containing polyurethane elastomerics can be obtained, thus there is length reaction time, complicated process of preparation, high in cost of production is not enough, greatly limits its widespread use.
Summary of the invention
An object of the present invention there is length reaction time, complicated process of preparation, high in cost of production technical problem and provide that a kind of reaction time is short, preparation technology is simple, cost is low, is suitable for the thermoplastic fluorine-containing polyurethane elastomers method of large-scale production to solve above-mentioned thermoplastic fluorine-containing polyurethane elastomers method.
Two of object of the present invention is to provide one to have the thermoplastic fluorine-containing polyurethane elastomer product of " low fluorine high-performance ", namely it still has the over-all propertieies such as more excellent surface and mechanics under more low fluorine content, particularly its tensile strength reaches as high as 26MPa, thus gives the advantage of its low-cost and high-performance.
Technical scheme of the present invention
A kind of thermoplastic fluorine-containing polyurethane elastomerics, 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
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 ~ 3000g/mol, PTMG (PTMG), polycaprolactone glycol (PCL) or polycarbonate diol (PCDL), is preferably PBA, PTMG or PCL;
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 1 ~ 23, and being preferably 2-18, m is 1 ~ 33, and be preferably 10-15, its molecular weight is 1000 ~ 2000g/mol;
Described small molecule chain extender is BDO, 1,6-cyclohexanediol, 3,3'-bis-chloro-4,4'-diphenylmethanediamiands (MOCA) or 3,5-dimethyl sulfenyls toluene (E-300);
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), are preferably MDI, TDI, IPDI or HMDI.
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index 0.97 ~ 0.999 and hard segment content are 25 ~ 50%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, specifically comprise the following steps:
(1), join in container by PFPE dibasic alcohol and non-fluorine macromolecular polyol, controlling mixing speed is
After reacting 10 ~ 20min under 2000 ~ 3000r/min, vacuum hydro-extraction at temperature is 100 ~ 120 DEG C
1.5 ~ 2h, obtains fluorine-containing compound resin;
(2), controlling mixing speed is under 2000 ~ 3000r/min, polyisocyanates and small molecule chain extender is added successively in the fluorine-containing compound resin of 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 1 ~ 2h at 50 ~ 80 DEG C, subsequently vacuum solidification 1 ~ 2h at 90 ~ 110 DEG C, last control temperature is 120 ~ 140 DEG C of vacuum solidification 15 ~ 24h, obtains thermoplastic fluorine-containing polyurethane elastomerics.
A kind of thermoplastic fluorine-containing polyurethane elastomerics of above-mentioned gained, its Oil repellent is 2.7 ~ 11.3%, is 75 ~ 115 ° to the contact angle of water, and tensile strength is 8.5 ~ 26MPa, and elongation at break is 200 ~ 450%.
Useful achievement of the present invention
A kind of thermoplastic fluorine-containing polyurethane elastomerics of the present invention, because it is in preparation process, only need can adjust elastomeric soft durometer flexibly according to the elastomeric isocyanate index of thermoplastic fluorine-containing polyurethane and hard segment content, thus guarantee that gained thermoplastic fluorine-containing polyurethane elastomerics not only maintains the linearity molecular structure of polyurethane elastomer, but also there is the excellent performance such as surface, mechanics.
Further, thermoplastic fluorine-containing polyurethane elastomerics of the present invention, its Oil repellent is lower, is 2.7 ~ 11.3% times at Oil repellent, and it is 75 ~ 115 ° to the contact angle of water, and tensile strength is 8.5 ~ 26MPa, reaches as high as 26MPa, and elongation at break is 200 ~ 450%.Compared with patent (CN101717485A) gained thermoplastic fluorine-containing polyurethane elastomerics, thermoplastic fluorine-containing polyurethane elastomerics prepared by the present invention still has the over-all propertieies such as more excellent surface and mechanics under more low fluorine content, thus has the advantage of low fluorine high performance.
Further, a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers of the present invention, have employed mass polymerization one-step synthesis method thermoplastic fluorine-containing polyurethane elastomerics easy and simple to handle, be mixed to get according to a certain ratio by polyvalent alcohol, isocyanic ester and chainextender three kinds of raw materials simultaneously.Its whole preparation process operation is more convenient compared with mass polymerization two-step approach, and energy consumption is lower, thus preparation method of the present invention have easy and simple to handle, with short production cycle, production cost is low, be suitable for the advantages such as large-scale production.
Further, a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers of the present invention, because the raw material adopted is PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol, polyisocyanates and small molecule chain extender, wherein the former two forms flexible polyurethane section, rear both form segmented polyurethanes, thus have the features such as raw materials used simple, wide material sources.And in preparation process, adjust the elastomeric surperficial Oil repellent of thermoplastic fluorine-containing polyurethane flexibly by the proportioning change of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol.
Embodiment
Below by embodiment, the present invention is described in further detail, but do not limit the present invention.
The present invention's non-fluorine macromolecular polyol used is purchased from BASF (China) Shanghai branch office.
The present invention's PFPE polyol resin 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 provided by Yantai Wanhua Polyurethane Co., Ltd.
embodiment 1
A kind of thermoplastic fluorine-containing polyurethane elastomerics, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 65.6 parts
PFPE dibasic alcohol 9.4 parts
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 1000g/mol;
Described small molecule chain extender is BDO;
Described polyisocyanates is 4,4 ￠-diphenylmethanediisocyanate.
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index 0.97 and hard segment content are 25%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, specifically comprise the following steps:
(1) be, that the PFPE dibasic alcohol of 1000g/mol and non-fluorine macromolecular polyol (namely molecular weight is the polybutylene glyool adipate of 1000g/mol) add in reaction vessel by molecular weight according to 1:7 mass ratio, controlling mixing speed is after 2500r/min stirring reaction 20min, vacuum hydro-extraction 2h at 100 DEG C, obtains fluorine-containing compound resin;
(2), controlling mixing speed is under 2500r/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 3min, curing molding 4h at control temperature 20 DEG C, then vacuum solidification 1h at 50 DEG C, subsequently vacuum solidification 1h at 90 DEG C, finally in 120 DEG C of solidification 24h, thermoplastic fluorine-containing polyurethane elastomerics can be obtained.
A kind of thermoplastic fluorine-containing polyurethane composite elastic body of above-mentioned gained, it is through method (the Surface and Coatings Technology of PHI5500ESCASYSTEM type x-ray photoelectron spectroscopy instrument (Perkin Elmer company of the U.S.) according to bibliographical informations such as Min Jiang, 2005,198 (1-3), 237-241) test, the Oil repellent on its surface is 11.3%.
A kind of thermoplastic fluorine-containing polyurethane composite elastic body of above-mentioned gained, through DSAIOMKZ contact angle tester (German Data physics company), adopt sessile drop method (Liu Tao, Journal of Fluorine Chemistry, 2010,131,36-41) detect, it is 115 ° to the contact angle of water.
A kind of thermoplastic fluorine-containing polyurethane 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 24.6MPa, and elongation at break is 296%.
embodiment 2
A kind of thermoplastic fluorine-containing polyurethane elastomerics, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 45.4 parts
PFPE dibasic alcohol 4.6 parts
Small molecule chain extender 19.2 parts
Polyisocyanates 44.3 parts
Described non-fluorine macromolecular polyol is the PTMG (PTMG) of molecular weight 3000g/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 small molecule chain extender is 1,6-cyclohexanediol;
Described polyisocyanates is 2,4 toluene diisocyanate (TDI).
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index be 0.97 and hard segment content be 50%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, specifically comprise the following steps:
(1), according to 1:10 mass ratio, the PFPE dibasic alcohol of molecular weight 1000g/mol and non-fluorine macromolecular polyol (namely molecular weight is the PTMG of 3000g/mol) are added in reaction vessel, controlling mixing speed is after 2000r/min stirring reaction 20min, vacuum hydro-extraction 2h at 100 DEG C, obtains fluorine-containing compound resin;
(2), controlling mixing speed is under 2000r/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 3min, curing molding 4h at control temperature 20 DEG C, then vacuum solidification 1h at 50 DEG C, subsequently vacuum solidification 1h at 90 DEG C, finally in 120 DEG C of solidification 24h, can obtain thermoplastic fluorine-containing polyurethane elastomerics.
Above-mentioned obtained thermoplastic fluorine-containing polyurethane composite elastic body, its surperficial Oil repellent is 2.7%, is 75 ° to the contact angle of water, and tensile strength is 26MPa, and elongation at break is 450%.
embodiment 3
A kind of thermoplastic fluorine-containing polyurethane elastomerics, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 48.7 parts
PFPE dibasic alcohol 16.3 parts
Small molecule chain extender 4.6 parts
Polyisocyanates 29.1 parts
Described non-fluorine macromolecular polyol is the polycaprolactone glycol (PCL) 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 polyisocyanates is 4,4 ￠-two cyclohexyls methane diisocyanate (HMDI).
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index be 0.999 and hard segment content be 35%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, its building-up process specifically comprises the following steps:
(1), according to 1:3 mass ratio, the PFPE dibasic alcohol of molecular weight 1000g/mol and non-fluorine macromolecular polyol (namely molecular weight is the polycaprolactone glycol of 1000g/mol) are added in reaction vessel, controlling mixing speed is after 2000r/min stirring reaction 20min, vacuum hydro-extraction 2h at 100 DEG C, obtains fluorine-containing compound resin;
(2), controlling mixing speed is under 2000r/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 5min, curing molding 2h at control temperature 30 DEG C, then vacuum solidification 2h at 50 DEG C, subsequently vacuum solidification 1h at 110 DEG C, finally in 120 DEG C of solidification 24h, obtains thermoplastic fluorine-containing polyurethane elastomerics.
After testing, its surperficial Oil repellent is 9.8% to above-mentioned obtained thermoplastic fluorine-containing polyurethane composite elastic body, and be 109 ° to the contact angle of water, tensile strength is 8.5MPa, and elongation at break is 200%.
embodiment 4
A kind of thermoplastic fluorine-containing polyurethane elastomerics, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 62.5 parts
PFPE dibasic alcohol 12.5 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 2000g/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 2000g/mol;
Described small molecule chain extender is chloro-4, the 4'-diphenylmethanediamiands (MOCA) of 3,3'-bis-;
Described polyisocyanates is isophorone diisocyanate (IPDI).
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index be 0.97 and hard segment content be 25%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, specifically comprise the following steps:
(1), according to 1:5 mass ratio, the PFPE dibasic alcohol of molecular weight 2000g/mol and non-fluorine macromolecular polyol (i.e. the polycaprolactone glycol of molecular weight 2000g/mol) are added in reaction vessel, controlling mixing speed is after 3000r/min stirring reaction 10min, vacuum hydro-extraction 1.5h at 120 DEG C, obtains fluorine-containing compound resin;
(2), controlling 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 stirring 5 min, curing molding 4h at control temperature 15 DEG C, then vacuum solidification 2h at 50 DEG C, subsequently at 90 DEG C, solidify 2 h, finally in 140 DEG C of solidification 15h, obtain thermoplastic fluorine-containing polyurethane elastomerics.
After testing, its surperficial Oil repellent is 6.5% to above-mentioned obtained thermoplastic fluorine-containing polyurethane composite elastic body, and be 95.3 ° to the contact angle of water, tensile strength is 22.9MPa, and elongation at break is 314%.
embodiment 5
A kind of thermoplastic fluorine-containing polyurethane elastomerics, calculates by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 64.3 parts
PFPE dibasic alcohol 10.7 parts
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 1000g/mol;
Described small molecule chain extender is 3,5-dimethyl sulfenyl toluene;
Described polyisocyanates is 4,4 ￠-diphenylmethanediisocyanate.
Above-mentioned a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers, namely the compound resin formed using a kind of PFPE dibasic alcohol and non-fluorine macromolecule dihydric alcohol is as flexible polyurethane section, with polyisocyanates and small molecule chain extender for segmented polyurethane, isocyanate index be 0.97 and hard segment content be 25%, go out thermoplastic fluorine-containing polyurethane elastomerics by mass polymerization one-step synthesis method, its building-up process specifically comprises the following steps:
(1), according to 1:6 mass ratio, the PFPE dibasic alcohol of molecular weight 1000g/mol and non-fluorine macromolecular polyol (namely molecular weight is the polybutylene glyool adipate of 1000g/mol) are added in reaction vessel, controlling mixing speed is after 2000r/min stirring reaction 20min, vacuum hydro-extraction 2h at 120 DEG C, obtains fluorine-containing compound resin;
(2), controlling mixing speed is under 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 3,5-dimethyl sulfenyl toluene), pour in the mould of preheating after continuing to stir 5min, curing molding 3h at control temperature 25 DEG C, then vacuum solidification 1h at 80 DEG C, subsequently vacuum solidification 1h at 100 DEG C, finally at 130 DEG C, solidify 18h, obtain thermoplastic fluorine-containing polyurethane elastomerics.
After testing, its surperficial Oil repellent is 6.4% to above-mentioned obtained thermoplastic fluorine-containing polyurethane composite elastic body, and be 93.8 ° to the contact angle of water, tensile strength is 19.3MPa, and elongation at break is 334%.
In sum, a kind of thermoplastic fluorine-containing polyurethane elastomerics of the present invention, its surperficial Oil repellent is 2.7 ~ 11.3%, is 75 ~ 115 ° to the contact angle of water, and tensile strength is 8.5 ~ 26MPa, and elongation at break is 200 ~ 450%.
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 (6)
1. a thermoplastic fluorine-containing polyurethane method for producing elastomers, described thermoplastic fluorine-containing polyurethane elastomerics, 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
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;
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 1 ~ 23, m is 1 ~ 33, and its molecular weight is 1000 ~ 2000g/mol;
Described small molecule chain extender is BDO, 1,6-cyclohexanediol, 3,3'-bis-chloro-4,4'-diphenylmethanediamiands or 3,5-dimethyl sulfenyl toluene;
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'-bis-cyclohexyl methane diisocyanate, is characterized in that its preparation process specifically comprises the steps:
(1), PFPE dibasic alcohol and non-fluorine macromolecular polyol are joined in container, control mixing speed be 2000 ~ 3000r/min stir 10 ~ 20min, then at 100 ~ 120 DEG C vacuum hydro-extraction 1.5 ~ 2h, obtain fluorine-containing compound resin;
(2), according to setting isocyanate index 0.97 ~ 0.999 and hard segment content be 25% ~ 50%, under mixing speed is 2000 ~ 3000r/min, polyisocyanates and small molecule chain extender is added successively in the fluorine-containing compound resin of 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 vacuum solidification 1 ~ 2h at 50 ~ 80 DEG C, subsequently vacuum solidification 1 ~ 2h at 90 ~ 110 DEG C, last in 120 ~ 140 DEG C of vacuum solidification 15 ~ 24 h, obtain thermoplastic fluorine-containing polyurethane elastomerics.
2. a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers as claimed in claim 1, is characterized in that calculating by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 65.6 parts
PFPE dibasic alcohol 9.4 parts
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 1000g/mol;
Described small molecule chain extender is BDO;
Described polyisocyanates is 4,4'-diphenylmethanediisocyanate.
3. a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers as claimed in claim 1, is characterized in that calculating by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 45.4 parts
PFPE dibasic alcohol 4.6 parts
Small molecule chain extender 19.2 parts
Polyisocyanates 44.3 parts
The molecular weight of described non-fluorine macromolecular polyol is the PTMG of 3000g/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 small molecule chain extender is 1,6-cyclohexanediol;
Described polyisocyanates is 2,4 toluene diisocyanate.
4. a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers as claimed in claim 1, is characterized in that calculating by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 48.7 parts
PFPE dibasic alcohol 16.3 parts
Small molecule chain extender 4.6 parts
Polyisocyanates 29.1 parts
Described non-fluorine macromolecular polyol is the polycaprolactone glycol 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 polyisocyanates is 4,4'-bis-cyclohexyl methane diisocyanate.
5. a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers as claimed in claim 1, is characterized in that calculating by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 62.5 parts
PFPE dibasic alcohol 12.5 parts
Small molecule chain extender 9.4 parts
Polyisocyanates 17.7 parts
Described non-fluorine macromolecular polyol is the polycaprolactone glycol of molecular weight 2000g/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 2000g/mol;
Described small molecule chain extender is chloro-4, the 4'-diphenylmethanediamiands of 3,3'-bis-;
Described polyisocyanates is isophorone diisocyanate.
6. a kind of thermoplastic fluorine-containing polyurethane method for producing elastomers as claimed in claim 1, is characterized in that calculating by weight, its raw material composition and content as follows:
Non-fluorine macromolecular polyol 64.3 parts
PFPE dibasic alcohol 10.7 parts
Small molecule chain extender 1.6 parts
Polyisocyanates 22.6 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 1000g/mol;
Described small molecule chain extender is 3,5-dimethyl sulfenyl toluene;
Described polyisocyanates is 4,4'-diphenylmethanediisocyanate.
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| CN103467692A (en) * | 2013-09-23 | 2013-12-25 | 广州机械科学研究院有限公司 | Water and oil proofing heat-resisting thermoplastic polyurethane elastomer and preparation method thereof |
| CN104974322A (en) * | 2015-06-11 | 2015-10-14 | 上海应用技术学院 | Thermoplastic fluorine-containing polyurethane biomaterial and preparation method thereof |
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| CN105085857B (en) * | 2015-09-07 | 2018-08-10 | 东莞市吉鑫高分子科技有限公司 | Waterproof and breathable antimicrobial form thermoplastic polyurethane elastomer and preparation method thereof |
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| CN109897155B (en) * | 2017-12-08 | 2021-07-20 | 上海凯众材料科技股份有限公司 | Preparation method of fluorine-containing polyurethane microporous elastomer |
| US20200093969A1 (en) * | 2018-09-24 | 2020-03-26 | Becton, Dickinson And Company | Self-Lubricating Medical Articles |
| US11613719B2 (en) | 2018-09-24 | 2023-03-28 | Becton, Dickinson And Company | Self-lubricating medical articles |
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| WO2021212317A1 (en) * | 2020-04-21 | 2021-10-28 | Evonik Operations Gmbh | Polyurethane insulating foams and production thereof |
| CN114133519B (en) * | 2020-09-04 | 2023-10-17 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
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| CN116425940A (en) * | 2023-03-13 | 2023-07-14 | 南京大学 | Perfluoropolyether block high polymer and preparation method and application thereof |
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