CN105037678B - A kind of the Heat-resistant Polyurethane Elastomers and preparation method thereof - Google Patents
A kind of the Heat-resistant Polyurethane Elastomers and preparation method thereof Download PDFInfo
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- CN105037678B CN105037678B CN201510363553.8A CN201510363553A CN105037678B CN 105037678 B CN105037678 B CN 105037678B CN 201510363553 A CN201510363553 A CN 201510363553A CN 105037678 B CN105037678 B CN 105037678B
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- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 24
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 17
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 17
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 17
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 14
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 10
- 230000008023 solidification Effects 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- -1 poly- ammonia Ester Chemical class 0.000 claims description 8
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000013557 residual solvent Substances 0.000 claims description 7
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000013016 damping Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000646 scanning calorimetry Methods 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 235000017858 Laurus nobilis Nutrition 0.000 description 2
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 2
- 244000125380 Terminalia tomentosa Species 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
A kind of the Heat-resistant Polyurethane Elastomers, it is composed of the following components by mass percentage: 1,4- cyclohexane diisocyanate 13.60~18.09%, polycaprolactone diols 57.01~61.51%, 1,4- butanediol 5.30~5.50%, dibutyl tin dilaurate 0.06~0.10%, cetyl trimethylammonium bromide 1.98~2.23%, conductive black 1.03~1.30%, nano-sized magnesium hydroxide 6.20~6.48%, dimethyl methyl phosphonate 9.63~9.85%, the sum of each component mass percent are 100%.The Heat-resistant Polyurethane Elastomers of the present invention have preferable wearability and lower temperature resistance, and high-intensitive and high elongation rate, load support capacity is big, oil resistance is excellent, adhesiveness is good, and damping capaicty is strong, and the adjustable extent of hardness is larger；Preparation method is simple, and step is clear, and reaction condition readily satisfies, easily operated.
Description
Technical field
The invention belongs to organic polymer resin synthesis technical fields, and in particular to a kind of the Heat-resistant Polyurethane Elastomers,
The invention further relates to the method for preparing polyurethane elastic body.
Background technique
Existing the Heat-resistant Polyurethane Elastomers have certain thermal stability, but its thermostabilization section is not wide enough, cannot compared with
It is used for a long time under high-temperature.Polyurethane elastomer causes it in air due to lower limit oxygen index (LOI) (18% or so)
In be it is flammable, i.e., anti-flammability is poor.In addition to this, the electrical insulating property of polyurethane elastomer is more excellent, in use
It is easy to produce electrostatic, i.e. antistatic property is poor, and then influences the application of elastomer.
Summary of the invention
The object of the present invention is to provide a kind of the Heat-resistant Polyurethane Elastomers, solve existing polyurethane elastomer anti-flammability
With the problem of antistatic property difference.
It is a further object to provide a kind of preparation methods of the Heat-resistant Polyurethane Elastomers.
The technical scheme adopted by the invention is that a kind of the Heat-resistant Polyurethane Elastomers, by mass percentage by with the following group
It is grouped as: 1,4- cyclohexane diisocyanate 13.60%~18.09%, polycaprolactone diols 57.01%~61.51%, 1,
4- butanediol 5.30%~5.50%, dibutyl tin dilaurate 0.06%~0.10%, cetyl trimethylammonium bromide
1.98%~2.23%, conductive black 1.03%~1.30%, nano-sized magnesium hydroxide 6.20%~6.48%, methylphosphonic acid diformazan
Ester 9.63%~9.85%, the sum of each component mass percent are 100%.
Another technical solution of the present invention is a kind of preparation method of the Heat-resistant Polyurethane Elastomers, specifically
Operating procedure is as follows:
Step 1, weigh respectively by mass percentage 13.60%~18.09%1,4- cyclohexane diisocyanate,
57.01%~61.51% polycaprolactone diols, 5.30%~5.50%1,4- butanediol, 0.06%~0.10% 2 laurel
Sour dibutyl tin, 1.98%~2.23% cetyl trimethylammonium bromide, 1.03%~1.30% conductive black, 6.20%~
6.48% nano-sized magnesium hydroxide, 9.63%~9.85% dimethyl methyl phosphonate, the sum of each component mass percent are 100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 100~110 DEG C stop vacuumizing after then cooling the temperature to 50~60 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 75~85 DEG C, and reaction 2h is obtained
Polyurethane elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, place in baking oven 60~
70 DEG C of solidification 7d, the film after solidification extract residual solvent through vacuum, handle 2.5h hours at 120 DEG C, obtain heat resistant poly ammonia
Ester elastomer.
The features of the present invention also characterized in that
Solidification temperature is 60~70 DEG C in step 7, time 7d.
The invention has the advantages that
1. the Heat-resistant Polyurethane Elastomers of the present invention have preferable wearability and lower temperature resistance, high-intensitive and high drawing
Rate, load support capacity is big, oil resistance is excellent, adhesiveness is good, and damping capaicty is strong, and the adjustable extent of hardness is larger, also has
The superior heat resistance that general polyurethane does not have, antistatic property and anti-flammability have latent in amortizing packaging material field
Use value and development prospect.
2. the preparation method of the Heat-resistant Polyurethane Elastomers of the present invention, using prepolymer method synthesis heat-resistant polyurethane elasticity
Body, and the antistatic property and anti-flammability of elastomer are improved in preparation process by adding other auxiliary agents；Synthesis technology is related to
The preparation method of the blending technology of fire retardant and compound antistatic urethane elastomer；Preparation method is simple, and step is clear,
Reaction condition readily satisfies, easily operated.
Detailed description of the invention
Fig. 1 is the infared spectrum for the Heat-resistant Polyurethane Elastomers that embodiment 1 is prepared；
Fig. 2 is the thermogravimetric analysis figure for the Heat-resistant Polyurethane Elastomers that embodiment 1 is prepared；
Fig. 3 is the differential scanning calorimetric thermogram for the Heat-resistant Polyurethane Elastomers that embodiment 1 is prepared；
Fig. 4 is the thermogravimetric analysis figure for the Heat-resistant Polyurethane Elastomers that embodiment 2 is prepared；
Fig. 5 is the differential scanning calorimetric thermogram for the Heat-resistant Polyurethane Elastomers that embodiment 2 is prepared；
Fig. 6 is the thermogravimetric analysis figure for the Heat-resistant Polyurethane Elastomers that embodiment 3 is prepared；
Fig. 7 is the differential scanning calorimetric thermogram for the Heat-resistant Polyurethane Elastomers that embodiment 3 is prepared.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The Heat-resistant Polyurethane Elastomers of the present invention, it is composed of the following components by mass percentage: two isocyanide of Isosorbide-5-Nitrae-hexamethylene
Acid esters 13.60%~18.09%, polycaprolactone diols 57.01%~61.51%, 1,4- butanediol 5.30%~5.50%,
Dibutyl tin dilaurate 0.06%~0.10%, cetyl trimethylammonium bromide 1.98%~2.23%, conductive black
1.03%~1.30%, nano-sized magnesium hydroxide 6.20%~6.48%, dimethyl methyl phosphonate 9.63%~9.85%, each component
The sum of mass percent is 100%.
The preparation method of above-mentioned the Heat-resistant Polyurethane Elastomers, specific steps are as follows:
Step 1, weigh respectively by mass percentage 13.60%~18.09%1,4- cyclohexane diisocyanate,
57.01%~61.51% polycaprolactone diols, 5.30%~5.50%1,4- butanediol, 0.06%~0.10% 2 laurel
Sour dibutyl tin, 1.98%~2.23% cetyl trimethylammonium bromide, 1.03%~1.30% conductive black, 6.20%~
6.48% nano-sized magnesium hydroxide, 9.63%~9.85% dimethyl methyl phosphonate, the sum of each component mass percent are 100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 100~110 DEG C stop vacuumizing after then cooling the temperature to 50~60 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 75~85 DEG C, and reaction 2h is obtained
Polyurethane elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, place in baking oven 60~
70 DEG C of solidification 7d, the film after solidification extract residual solvent through vacuum, handle 2.5h hours at 120 DEG C, obtain heat resistant poly ammonia
Ester elastomer.
Embodiment 1
Step 1,13.60%1,4- cyclohexane diisocyanate, 61.51% polycaprolactone are weighed respectively by mass percentage
Dihydric alcohol, 5.50%1,4- butanediol, 0.08% dibutyl tin dilaurate, 1.98% cetyl trimethylammonium bromide,
1.13% conductive black, 6.35% nano-sized magnesium hydroxide, 9.85% dimethyl methyl phosphonate, the sum of each component mass percent are
100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 100 DEG C stop vacuumizing after then cooling the temperature to 60 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 75 DEG C, and reaction 2h obtains poly- ammonia
Ester elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, places in baking oven at 65 DEG C
Solidify 7d, the film after solidification extracts residual solvent through vacuum, handles 2.5h hours at 120 DEG C, obtain heat-resistant polyurethane bullet
Property body.
Using the functional group of polyurethane elastomer prepared by Fourier infrared spectrograph detection embodiment 1, its function is determined
Group's type and product, testing result is as shown in Figure 1, show infrared line in 3340cm in Fig. 1-1And 1530cm-1Place occurs
The stretching vibration characteristic absorption peak of apparent N-H, in 1720cm-1Nearby there is the characteristic absorption peak of ester group (C=O),
1110cm-1Nearby there is the stretching vibration peak of C-O-C, is all the typical absorption peak of polyurethane, shows to generate polyurethane bullet
Property body.Heat resistance detection is carried out to polyurethane elastomer prepared by embodiment 1 using thermogravimetric analyzer (TGA)；Use differential
The hot property for the polyurethane elastomer that scanning calorimetry (DSC) prepares embodiment 1 and thermal behavior detect.As a result such as Fig. 2
With shown in Fig. 3, as shown in Figure 2, initial decomposition temperature is about 250 DEG C, and terminating decomposition temperature is about 600 DEG C, in decomposable process,
There is three-stage decomposition, respectively corresponds the residual small molecule dihydric alcohol (BDO) in polyurethane elastomer, the hard section of polyurethane elastomer
Ingredient and soft segment ingredient, from the figure 3, it may be seen that the thermal change that wherein third section is decomposed is maximum, this is because soft segment ingredient is in poly- ammonia
It is main constituents in ester elastomer, content is maximum.By TGA and DSC temperature curve it is found that the polyurethane elastomer synthesized is resistance to
Hot property is good.
Embodiment 2
Step 1,14.26%1,4- cyclohexane diisocyanate, 60.59% polycaprolactone are weighed respectively by mass percentage
Dihydric alcohol, 5.30%1,4- butanediol, 0.10% dibutyl tin dilaurate, 2.23% cetyl trimethylammonium bromide,
1.30% conductive black, 6.48% nano-sized magnesium hydroxide, 9.74% dimethyl methyl phosphonate, the sum of each component mass percent are
100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 105 DEG C stop vacuumizing after then cooling the temperature to 65 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 85 DEG C, and reaction 2h obtains poly- ammonia
Ester elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, places in baking oven at 70 DEG C
Solidify 7d, the film after solidification extracts residual solvent through vacuum, handles 2.5h hours at 120 DEG C, obtain heat-resistant polyurethane bullet
Property body.
Heat resistance detection is carried out to polyurethane elastomer prepared by embodiment 2 using thermogravimetric analyzer (TGA)；Use difference
The hot property and thermal behavior for showing the polyurethane elastomer that scanning calorimetry (DSC) prepares embodiment 2 detect.As a result as schemed
Shown in 4 and 5, as shown in Figure 4, initial decomposition temperature is about 225 DEG C, and terminating decomposition temperature is about 620 DEG C, in decomposable process,
There is three-stage decomposition, respectively corresponds the residual small molecule dihydric alcohol (BDO) in polyurethane elastomer, the hard section of polyurethane elastomer
Ingredient and soft segment ingredient, as shown in Figure 5, the thermal change that wherein third section is decomposed are maximum, this is because soft segment ingredient is in poly- ammonia
It is main constituents in ester elastomer, content is maximum.By TGA and DSC temperature curve it is found that the polyurethane elastomer synthesized is resistance to
Hot property is good.
Embodiment 3
Step 1,18.09%1,4- cyclohexane diisocyanate, 57.40% polycaprolactone are weighed respectively by mass percentage
Dihydric alcohol, 5.40%1,4- butanediol, 0.06% dibutyl tin dilaurate, 2.19% cetyl trimethylammonium bromide,
1.03% conductive black, 6.20% nano-sized magnesium hydroxide, 9.63% dimethyl methyl phosphonate, the sum of each component mass percent are
100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 110 DEG C stop vacuumizing after then cooling the temperature to 50 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 80 DEG C, and reaction 2h obtains poly- ammonia
Ester elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, places in baking oven at 60 DEG C
Solidify 7d, the film after solidification extracts residual solvent through vacuum, handles 2.5h hours at 120 DEG C, obtain heat-resistant polyurethane bullet
Property body.
Heat resistance detection is carried out to polyurethane elastomer prepared by embodiment 3 using thermogravimetric analyzer (TGA)；Use difference
Show that polyurethane elastomer hot property that scanning calorimetry (DSC) prepares embodiment 3 and thermal behavior detect.As a result such as Fig. 6
Shown in 7, it will be appreciated from fig. 6 that initial decomposition temperature is about 230 DEG C, terminating decomposition temperature is about 585 DEG C, in decomposable process, is had
Three-stage is decomposed, and respectively corresponds the residual small molecule dihydric alcohol (BDO) in polyurethane elastomer, the hard section of polyurethane elastomer at
Divide and soft segment ingredient, as shown in Figure 7, the thermal change maximum that wherein third section is decomposed, this is because soft segment ingredient is in polyurethane
It is main constituents in elastomer, content is maximum.By TGA and DSC temperature curve it is found that the polyurethane elastomer synthesized is heat-resisting
It is functional.
Embodiment 4
Step 1,17.94%1,4- cyclohexane diisocyanate, 57.01% polycaprolactone are weighed respectively by mass percentage
Dihydric alcohol, 5.40%1,4- butanediol, 0.10% dibutyl tin dilaurate, 2.08% cetyl trimethylammonium bromide,
1.23% conductive black, 6.45% nano-sized magnesium hydroxide, 9.79% dimethyl methyl phosphonate, the sum of each component mass percent are
100%；
Step 2, polycaprolactone two is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface
First alcohol, vacuum dehydration 2.5h after being heated to 105 DEG C stop vacuumizing after then cooling the temperature to 50 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added to the pretreated polycaprolactone binary of step 2
In alcohol, 10min is stirred under the revolving speed of 2000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 75 DEG C, and reaction 2h obtains poly- ammonia
Ester elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, so
1,4-butanediol and dibutyl tin dilaurate are added after temperature is risen to 70 DEG C afterwards, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, places in baking oven at 70 DEG C
Solidify 7d, the film after solidification extracts residual solvent through vacuum, handles 2.5h hours at 120 DEG C, obtain heat-resistant polyurethane bullet
Property body.
Claims (1)
1. a kind of preparation method of the Heat-resistant Polyurethane Elastomers, which is characterized in that specific steps are as follows:
Step 1, weigh respectively by mass percentage 13.60%~18.09%1,4- cyclohexane diisocyanate, 57.01%~
61.51% polycaprolactone diols, 5.30%~5.50%1,4- butanediol, 0.06%~0.10% di lauric dibutyl
Tin, 1.98%~2.23% cetyl trimethylammonium bromide, 1.03%~1.30% conductive black, 6.20%~6.48% are received
Rice magnesium hydroxide, 9.63%~9.85% dimethyl methyl phosphonate, the sum of each component mass percent are 100%；
Step 2, polycaprolactone diols is added into the three neck round bottom flask for having blender, temperature sensor, vacuum interface,
Vacuum dehydration 2.5h after being heated to 100~110 DEG C stops vacuumizing after then cooling the temperature to 50~60 DEG C；
Step 3, cetyl trimethylammonium bromide, conductive black are added in the pretreated polycaprolactone diols of step 2,
10min is stirred under the revolving speed of 2 000r/min, temperature is adjusted to 20 DEG C, solution A is obtained；
Step 4, Isosorbide-5-Nitrae-cyclohexane diisocyanate is added in solution A, and stirs 30min at 60 DEG C of water-bath；
Step 5, after the reaction solution temperature of step 4 is stablized, slowly heating up and controlling is 75~85 DEG C, and reaction 2h obtains poly- ammonia
Ester elastomer performed polymer, after complete reaction, vacuum outgas 30min is sealed stand-by；
Step 6, it is added in polyurethane elastomer performed polymer after nano-sized magnesium hydroxide and dimethyl methyl phosphonate being mixed, then will
1,4-butanediol and dibutyl tin dilaurate is added after rising to 70 DEG C in temperature, with vigorous stirring chain extension 3min；
Step 7, solution step 6 obtained pours into casting film-forming in Teflon mould, places in baking oven at 60~70 DEG C
Solidify 7d, the film after solidification extracts residual solvent through vacuum, handles 2.5h hours at 120 DEG C, obtain heat-resistant polyurethane bullet
Property body.
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