CN105542114A - Thermoplastic polyurethane elastomer containing cyano in soft segment and preparation method thereof - Google Patents
Thermoplastic polyurethane elastomer containing cyano in soft segment and preparation method thereof Download PDFInfo
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- CN105542114A CN105542114A CN201610065975.1A CN201610065975A CN105542114A CN 105542114 A CN105542114 A CN 105542114A CN 201610065975 A CN201610065975 A CN 201610065975A CN 105542114 A CN105542114 A CN 105542114A
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- DTEBZGKINVACPT-FMIVXFBMSA-N Cc1ccc(/C=C/C(c2ccc(C)cc2)=O)cc1 Chemical compound Cc1ccc(/C=C/C(c2ccc(C)cc2)=O)cc1 DTEBZGKINVACPT-FMIVXFBMSA-N 0.000 description 1
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
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- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- 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
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/27—Compounds containing a nitrogen atom bound to two other nitrogen atoms, e.g. diazoamino-compounds
- C08K5/28—Azides
Abstract
The invention relates to a thermoplastic polyurethane elastomer containing cyano in a soft segment and a preparation method thereof. The preparation method comprises the following steps: polymerizing hydroxyl-terminated polybutadiene acrylonitrile, polyester macromolecular dihydric alcohol and/or polyether macromolecular dihydric alcohol, organic diisocyanate and micromolecule dihydric alcohol to obtain a product, namely, a thermoplastic polyurethane elastomer body containing the cyano in the soft segment; and blending the thermoplastic polyurethane elastomer body containing the cyano in the soft segment , a cross-linking agent containing diazido functional groups and a cross-linking catalyst, and performing a cross-linking reaction to obtain the thermoplastic polyurethane elastomer. The performance of a material can be conveniently adjusted by simply adjusting the consumption of the cross-linking agent, the cross-linked thermoplastic polyurethane elastomer has excellent mechanical performance and relatively low compressive permanent deformation, and can better meet the requirements of high-pressure sealing elements, automobile cushions and other parts requiring high mechanical strength and low compressive permanent deformation.
Description
Technical field
The invention belongs to polyurethane elastomer preparing technical field, relate to Polyurethane Thermoplastic Elastomer and preparation method thereof containing cyano group in a kind of soft section, particularly relate to a kind of click-reaction method that adopts and cross-linking modified Polyurethane Thermoplastic Elastomer and preparation method thereof is carried out to the thermoplastic polyurethane elastomer body containing cyano units in soft section of synthesis.
Background technology
Polyurethane Thermoplastic Elastomer (TPU) a kind of to be made up of soft segment and rigid chain segment, has caoutchouc elasticity at low temperatures, again can the high molecular synthetic material of plasticizing forming during raised temperature.TPU has good processing characteristics, and durometer level is wide, oil resistant, solvent resistant, wear-resisting, is the good selection of engineering materials.
Along with industrial expansion, require that material has very high mechanical strength, good hydrolytic resistance and lower compression set value at some special outdoor field high-pressure sealing rings, vehicle shock pad etc. as field machine.But, TPU belongs to polar macromolecule material, be easy to absorb the moisture in air, carbamate groups in TPU molecular chain, the urea groups ester bond particularly in soft section of polyester type TPU is easy to react with water, cause TPU molecular chain degradation, thus cause mechanical strength to decline and affect compression set; On the other hand, the TPU material of non-modified is due to the linear structure of its molecular chain, and molecular chain can produce a lot of irreversible slip in compression process, thus creates irreversible compressive set, cause Compression Set value bigger than normal, be difficult to the requirement meeting these fields.
Chemically crosslinked to a certain degree improves TPU mechanical property, reduces the important method of Compression Set.
Chinese patent CN102532464 discloses a kind of crosslinked TPU, this kind of TPU adopts the compound with three-functionality-degree that can react with isocyanate groups if glycerol, trihydroxy methyl propane and trolamine etc. are as linking agent in building-up process, make TPU molecular chain by linearly becoming three-dimensional net structure, suppress the sliding deformation that it produces in compression process, the TPU Compression Set value prepared by the method can be reduced to about 20%.But because linking agent adds when synthesizing TPU, the crosslinked TPU adopting this kind of method to prepare can cause post-production difficulty, and the adjustment of degree of crosslinking is more loaded down with trivial details.
Chinese patent CN101466755A add in TPU building-up process there is unsaturated link(age) single methanol or monoamine as chain terminator, TPU is made to contain unsaturated functional group at molecule chain end, later stage adds initiator again and carries out thermal initiation or ultraviolet photo-initiated crosslinking in the TPU course of processing, avoid processing difficulties problem and can the degree of crosslinking of more easily control TPU.But TPU synthesis is normally at high temperature carried out, and unsaturated functional group likely can produce decomposition in the process, and the thermal initiation in later stage and UV-light elicitation procedure can cause the xanthochromia of TPU itself to a certain extent.
Chinese patent CN101198648A has prepared the TPU master batch being rich in isocyanic ester, is then added by master batch in proportion in the TPU base-material course of processing, obtained crosslinked TPU.The method is easy to use, and degree of crosslinking is controlled, but loses activity because isocyanic ester is easy to react with the water in air, and therefore the preservation condition of master batch can be harsher.
Summary of the invention
The object of this invention is to provide Polyurethane Thermoplastic Elastomer and preparation method thereof containing cyano group in a kind of soft section, particularly provide a kind of click-reaction method that adopts to carry out cross-linking modified Polyurethane Thermoplastic Elastomer and preparation method thereof to the thermoplastic polyurethane elastomer body containing cyano units in soft section of synthesis.Polyurethane Thermoplastic Elastomer containing cyano group in a kind of soft section of the present invention and preparation method thereof, degree of crosslinking is controlled, processes easy to use, the good mechanical properties of gained Polyurethane Thermoplastic Elastomer.
Polyurethane Thermoplastic Elastomer containing cyano group in a kind of soft section of the present invention, general structure is as follows:
Wherein, R
1for
R
2for
R
3for
R
4for
Wherein, a=1-10, b=1-10, x=1-10, y=1-10, n=3-15;
Polyurethane Thermoplastic Elastomer containing cyano group in described soft section is soaked Compression Set value after 168 hours and is less than 35% in 80 DEG C of constant temperature water-baths from the beginning.
As preferred technical scheme:
Polyurethane Thermoplastic Elastomer containing cyano group in a kind of soft section as above, durometer level is shore 80A-shore 65D; In general structure
part is removed containing in the Polyurethane Thermoplastic Elastomer of cyano group in described soft section
other soft sections outside soft section, for soft section of polyethylene glycol adipate, poly-hexanodioic acid-1, soft section of 4-butanediol ester, poly-hexanodioic acid-1, soft section of 6-hexylene glycol ester, poly-adipate glycol-1, soft section of 4-butanediol ester, poly-adipate glycol-1, soft section of 6-hexylene glycol ester, poly-hexanodioic acid-1,4-butyleneglycol-1, soft section of 6-hexylene glycol ester, poly-soft section of adipate glycol-propylene glycol ester, poly-soft section of hexanodioic acid glycol ether ester, soft section of polycaprolactone, poly-soft section of carbonic acid 1,6-hexylene glycol ester, soft section of polytetrahydrofuran or soft section of polypropylene glycol.
Present invention also offers the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section, comprise the following steps:
(1) preparation of the thermoplastic polyurethane elastomer body containing cyano group in soft section;
By hydroxyl terminated butadiene acrylonitrile copolymer, polyester macromolecule dibasic alcohol and or polyethers macromolecule dihydric alcohol, organic diisocyanate and small molecules glycol chain extender carry out polyreaction, products therefrom is in described soft section containing the thermoplastic polyurethane elastomer body of cyano group;
(2) preparation of Polyurethane Thermoplastic Elastomer;
By blended to the thermoplastic polyurethane elastomer body containing cyano group in described soft section, linking agent and crosslinking catalyst, and carry out crosslinking reaction, the Polyurethane Thermoplastic Elastomer containing cyano group in namely obtaining described soft section; Described linking agent is the compound containing two azido-functional group, fusing point <200 DEG C.
Containing the method for preparing thermoplastic polyurethane elastomer of cyano group in a kind of soft section as above, described hydroxyl terminated butadiene acrylonitrile copolymer account for polyester macromolecule dibasic alcohol and or the mole number per-cent of polyethers macromolecule dihydric alcohol be 1-50%.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, described small molecules glycol chain extender is ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, BDO, 1,6-hexylene glycol, 1,3-butyleneglycol, 1,5-PD or neopentyl glycol.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, with the total mass of a kind of in hydroxyl terminated butadiene acrylonitrile copolymer, polyester macromolecule dibasic alcohol and polyethers macromolecule dihydric alcohol or its combination, organic diisocyanate and small molecules glycol chain extender for benchmark, the per-cent that hydroxyl terminated butadiene acrylonitrile copolymer, polyester diol and/or polyether Glycols account for total mass is 40-65%, the per-cent that organic diisocyanate accounts for total mass is 30-45%, and the per-cent that small molecules glycol chain extender accounts for total mass is 5-15%; When polyester diol and polyether Glycols are for combination, it is the combination of arbitrary proportion.
Described polyester diol is polyethylene glycol adipate glycol, poly-hexanodioic acid-1,4-butanediol ester glycol, poly-hexanodioic acid-1,6-hexylene glycol esterdiol, poly-adipate glycol-1,4-butanediol ester glycol, poly-adipate glycol-1,6-hexylene glycol esterdiol, poly-hexanodioic acid-1,4-butyleneglycol-1,6-hexylene glycol esterdiol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, polycaprolactone glycol or poly-carbonic acid 1,6-hexylene glycol esterdiol.
Described polyether Glycols is polytetrahydrofuran or polypropylene glycol.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, the temperature of described polyreaction is 150-220 DEG C; Described polyreaction adopts twin screw reactive extrursion method, and screw speed is set as 150-300r/min.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, also polymerizing catalyst is added during described polyreaction, described polymerizing catalyst is one or more in trimethylamine or metal organic acid salt, and described metal organic acid salt is the organic acid salt of bismuth, tin, titanium, iron, antimony, cobalt, aluminium, thorium, zinc, nickel, cerium, molybdenum, vanadium, manganese or zirconium; Polyester diol used during to be polymerized and/or the total mass of polyether Glycols are benchmark, and the addition of described polymerizing catalyst is 1-500ppm; Described polymerizing catalyst directly adds in polyester diol and/or polyether Glycols before the reaction;
Described trimethylamine is triethylamine, triethylenediamine, N-ethylmorpholine or N, N-dimethylethanolamine;
Described metal organic acid salt is new certain herbaceous plants with big flowers acid bismuth, bismuth naphthenate, isocaprylic acid bismuth, stannous octoate, dibutyl tin laurate, titanium isopropylate, tetrabutyl titanate, isocaprylic acid lead, isocaprylic acid zinc, zinc naphthenate, isocaprylic acid potassium, Potassium ethanoate, potassium oleate, antimony acetate, cobalt naphthenate, ferric acetyl acetonade, nickel acetate, molybdenum naphthenate, vanadium iso-octoate, manganese acetate or methyl ethyl diketone zirconium.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, described linking agent is the compound containing two azido-functional group, fusing point <200 DEG C; The described compound containing two azido-functional group is 4,4 '-two-fold nitrogen biphenyl, 4,4 '-biphenyl dibenzyl nitrine, 2, two (the 4 '-nitrine benzal) pimelinketone of 6-, 1,3-two (4 '-nitrine benzal) acetone or 4,4 '-two-fold nitrogen phenyl styryl ketone; To synthesize mole number containing hydroxyl terminated butadiene acrylonitrile copolymer used during the thermoplastic polyurethane elastomer body of cyano group in soft section for benchmark, the addition of described linking agent is 5-50% mole number.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, described crosslinking catalyst is Inorganic Ammonium compound, is ammonium sulfate, monoammonium sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium iodide, brometo de amonio or ammonium chloride; With the linking agent mole number added for benchmark, the addition of described crosslinking catalyst is 50-100% mole number.
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as above, described crosslinking reaction is carried out under temperature 100 ~ 220 DEG C of conditions.Thermoplastic polyurethane elastomer body containing cyano group in soft section of the present invention, linking agent and crosslinking catalyst blended material, to be injection molding or extrude etc. in the course of processing, cyano units in TPU and the azido group in linking agent with under the effect of crosslinking catalyst, there is click chemistry react, thermoplastic polyurethane elastomer body is produced and is cross-linked.
Enumerate except component or raw material except above-mentioned, the present invention also can contain other raw material and chemical assistant, as oxidation inhibitor, lubricant and anti ultraviolet agent etc.Its consumption is advisable with the various performances not affecting Polyurethane Thermoplastic Elastomer of the present invention.
Polyurethane Thermoplastic Elastomer of the present invention, in the injection moulding of TPU with in the course of processing such as extruding, under crosslinking catalyst effect, impel the nitrine structure in linking agent and the cyano units in TPU body to occur to click chemical reaction, make TPU produce crosslinked at soft section of place, the TPU after crosslinked still has excellent mechanical property and lower compression set after the hot-water soak of certain hour.
TPU belongs to polar macromolecule material, be easy to absorb the moisture in air, carbamate groups in TPU molecular chain, the urea groups ester bond particularly in soft section of polyester type TPU is easy to react with water, cause TPU molecular chain degradation, thus cause mechanical strength to decline and affect compression set; On the other hand, the TPU material of non-modified is due to the linear structure of its molecular chain, and molecular chain can produce a lot of irreversible slip in compression process, thus creates irreversible compressive set, causes Compression Set value bigger than normal.Chemically crosslinked improves TPU mechanical property, reduce the important method of Compression Set, but degree of crosslinking must control within certain scope.When degree of crosslinking is too small, because most of molecular chain is still in linear structure, the remarkable improvement of mechanical property and compression set therefore can't be brought; And when degree of crosslinking is excessive, molecular chain is crosslinked serious, the stretching motion of segment is subject to serious suppression, and deformation recovery is slow, also easily causes compression set to rise on the contrary.The present invention is three-dimensional net structure by introducing cyano group structure and introduce the crosslinked linear structure that not only can change TPU herein by click-reaction in soft section, can also effectively suppress to be hydrolyzed and the mechanical property that causes and compression set loss.Simultaneously the present invention can also by the crosslinking degree of the consumption that increases or reduce linking agent control TPU molecular chain easily.
Beneficial effect:
Method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section of the present invention, first the thermoplastic polyurethane elastomer body containing cyano units in soft section is prepared, then with a certain proportion of linking agent 4,4 '-biphenyl dibenzyl nitrine and crosslinking catalyst ammonium chloride Homogeneous phase mixing, in the injection moulding of TPU with in the course of processing such as extruding, under catalyst action, azido-and cyano units occur to click chemical reaction, Polyurethane Thermoplastic Elastomer are produced crosslinked.
Polyurethane Thermoplastic Elastomer containing cyano group in a kind of soft section of the present invention, there is excellent mechanical property and lower compression set, the needs that high-pressure sealing ring, vehicle shock pad and other requirements have high mechanical strength and low compression set parts can be adapted to better.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
By structural formula be
the 0.1mol hydroxyl terminated butadiene acrylonitrile copolymer of a=1, b=10, y=2, poly-hexanodioic acid-BDO ester 10mol mixes, and composition hydroxyl terminated butadiene acrylonitrile copolymer molar content is the pre-composition of 1%.
Then get 65 weight part pre-compositions and 30 weight part diphenyl-methyl methane-4,4 ' vulcabond, 5 weight part BDOs mix, then the mixture of gained is injected into the twin screw extruder of heating.Extruder temperature is 150 DEG C, screw speed 150 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described containing the thermoplastic polyurethane elastomer body of cyano group, 4 of hydroxyl terminated butadiene acrylonitrile copolymer mole number 50%, 4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 50%.Melting point compound <200 DEG C containing two azido-functional group, carry out crosslinking reaction, temperature of reaction is 100 DEG C, i.e. obtained described Polyurethane Thermoplastic Elastomer.Structural formula is:
Wherein, R
1for
r
2,
r
3for,
Wherein, a=1, b=10, y=2, x=1, n=3.
Embodiment 2
By structural formula be
the hydroxyl terminated butadiene acrylonitrile copolymer of a=3, b=6, y=3,5mol, 10mol polytetrahydrofuran, composition hydroxyl terminated butadiene acrylonitrile copolymer content is the pre-composition of 50%.
Then 40 weight part pre-compositions and 45 weight part diphenyl-methyl methane-4,4 ' vulcabond, 15 weight part ethylene glycol mix, and then the mixture of gained are injected into the twin screw extruder of heating.Extruder temperature is 220 DEG C, screw speed 300 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described containing the thermoplastic polyurethane elastomer body of cyano group, 4 of hydroxyl terminated butadiene acrylonitrile copolymer mole number 5%, 4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 100%, melting point compound <200 DEG C containing two azido-functional group, carry out crosslinking reaction, temperature of reaction is 200 DEG C, i.e. obtained described Polyurethane Thermoplastic Elastomer.Structural formula is:
Wherein, R
1for,
R
2for,
r
3for,
Wherein, a=3, b=6, y=3, x=1, n=3.
Embodiment 3
By structural formula be
the 2.5mol hydroxyl terminated butadiene acrylonitrile copolymer of a=10, b=10, y=10,5mol tetrahydrofuran (THF) terminal hydroxy group, 5 poly-hexanodioic acid-BDO ester dibasic alcohol, composition hydroxyl terminated butadiene acrylonitrile copolymer content is the pre-composition of 25%.
Then 50 weight part pre-compositions and 40 weight part diphenyl-methyl methane-4,4 ' vulcabond, 10 weight part BDO mixing, are then injected into the twin screw extruder of heating by the mixture of gained.Extruder temperature is 200 DEG C, screw speed 200 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described containing the thermoplastic polyurethane elastomer body of cyano group, 4 of hydroxyl terminated butadiene acrylonitrile copolymer mole number 25%, 4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 80%, melting point compound <200 DEG C containing two azido-functional group, carry out crosslinking reaction, temperature of reaction is 200 DEG C, i.e. obtained described Polyurethane Thermoplastic Elastomer.Structural formula is:
Wherein, R
1for
r
2for,
R
3for,
Wherein, a=10, b=10, y=10, x=10, n=5.
Embodiment 4
By structural formula be
a=1, b=10, y=2,0.5mol hydroxyl terminated butadiene acrylonitrile copolymer, 10mol gathers the mixing of hexanodioic acid-BDO ester, and composition hydroxyl terminated butadiene acrylonitrile copolymer content is the pre-composition of 5%.
Then get 45 weight part pre-compositions, 45 weight part diphenyl-methyl methane-4,4 ' vulcabond, 10 weight part BDOs, 1PPM triethylamine mixes, and then the mixture of gained is injected into the twin screw extruder of heating.Extruder temperature is 150 DEG C, screw speed 150 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described containing the thermoplastic polyurethane elastomer body of cyano group, 4 of hydroxyl terminated butadiene acrylonitrile copolymer mole number 50%, 4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 50% contains the melting point compound <200 DEG C of two azido-functional group, and carry out crosslinking reaction, temperature of reaction is 100 DEG C of i.e. obtained described Polyurethane Thermoplastic Elastomer, Polyurethane Thermoplastic Elastomer obtained in its structural formula similar embodiment 1, wherein, a=3, b=5, y=8, x=10, n=10.
Embodiment 5
Will
the hydroxyl terminated butadiene acrylonitrile copolymer of a=3, b=6, y=3,3mol, 10mol polytetrahydrofuran, composition hydroxyl terminated butadiene acrylonitrile copolymer content is the pre-composition of 30%.
Then 65 weight part pre-compositions, 30 weight part diphenyl-methyl methane-4,4 ' vulcabond, 5 weight part ethylene glycol, 500PPM triethylamine carries out polyreaction, and products therefrom is the thermoplastic polyurethane elastomer body containing cyano group in described hard section; .Mixing, is then injected into the twin screw extruder of heating by the mixture of gained.Extruder temperature is 220 DEG C, screw speed 300 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described thermoplastic polyurethane elastomer body containing cyano group, hydroxyl terminated butadiene acrylonitrile copolymer mole number 5% 4,4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 100% contains the melting point compound <200 DEG C of two azido-functional group, and carry out crosslinking reaction, temperature of reaction is 200 DEG C, i.e. obtained described Polyurethane Thermoplastic Elastomer, Polyurethane Thermoplastic Elastomer obtained in its structural formula similar embodiment 2, wherein, a=5, b=8, y=5, x=2, n=10.
Embodiment 6
By structural formula be
a=10, b=10, y=10,2.5mol hydroxyl terminated butadiene acrylonitrile copolymer, 3mol tetrahydrofuran (THF) terminal hydroxy group, 7mol gathers hexanodioic acid-BDO ester dibasic alcohol, and composition hydroxyl terminated butadiene acrylonitrile copolymer content is the pre-composition of 25%.
Then by 50 weight part pre-compositions, with 40 weight part diphenyl-methyl methane-4,4 ' vulcabond, 10 weight part BDOs and 500PPM triethylamine mix, and then the mixture of gained are injected into the twin screw extruder of heating.Extruder temperature is 200 DEG C, screw speed 200 revs/min; Reactant obtains the thermoplastic polyurethane elastomer body of cyano group through extruding pelletization.
By described containing the thermoplastic polyurethane elastomer body of cyano group, 4 of hydroxyl terminated butadiene acrylonitrile copolymer mole number 25%, 4 '-biphenyl nitrine, 4, the ammonium chloride of 4 '-biphenyl nitrine mole number 80% contains the melting point compound <200 DEG C of two azido-functional group, and carry out crosslinking reaction, temperature of reaction is 200 DEG C, i.e. obtained described Polyurethane Thermoplastic Elastomer, Polyurethane Thermoplastic Elastomer obtained in its structural formula similar embodiment 3, wherein, a=6, b=10, y=2, x=6, n=8.
Embodiment 7-32 and comparative example 1-3
According to the method for embodiment 1, corresponding compound is used according to table 1, formula in table 2 is prepared Polyurethane Thermoplastic Elastomer, and take out after elastomerics obtained for embodiment is soaked 168 hours in 80 DEG C of constant temperature water-baths from the beginning and test according to ASTMD395 the Compression Set value that its compression set value (100 DEG C/24h) measures, result is as table 2
Table 1 embodiment 7-322 and comparative example 1 use compound
Table 2 embodiment 1-32 and comparative example 1 use content and Compression Set
Claims (10)
1. the Polyurethane Thermoplastic Elastomer containing cyano group in soft section, is characterized in that: the general structure of the Polyurethane Thermoplastic Elastomer containing cyano group in described soft section is as follows:
Wherein, R
1for
R
2for
R
3for
R
4for
Wherein, a=1-10, b=1-10, x=1-10, y=1-10, n=3-15;
Polyurethane Thermoplastic Elastomer containing cyano group in described soft section is soaked Compression Set value after 168 hours and is less than 35% in 80 DEG C of constant temperature water-baths from the beginning.
2. the Polyurethane Thermoplastic Elastomer containing cyano group in a kind of soft section according to claim 1, is characterized in that, the durometer level of the Polyurethane Thermoplastic Elastomer containing cyano group in described soft section is shore 80A-shore 65D; In general structure
part is removed containing in the Polyurethane Thermoplastic Elastomer of cyano group in described soft section
other soft sections outside soft section, for poly-hexanodioic acid-1, soft section of 4-butanediol ester, poly-hexanodioic acid-1, soft section of 6-hexylene glycol ester, poly-adipate glycol-1, soft section of 4-butanediol ester, poly-adipate glycol-1, soft section of 6-hexylene glycol ester, poly-hexanodioic acid-1,4-butyleneglycol-1, soft section of 6-hexylene glycol ester, poly-soft section of adipate glycol-propylene glycol ester, poly-soft section of hexanodioic acid glycol ether ester, soft section of polycaprolactone, poly-soft section of carbonic acid 1,6-hexylene glycol ester, soft section of polytetrahydrofuran or soft section of polypropylene glycol.
3. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation of the thermoplastic polyurethane elastomer body containing cyano group in soft section;
By hydroxyl terminated butadiene acrylonitrile copolymer, polyester macromolecule dibasic alcohol and or polyethers macromolecule dihydric alcohol, organic diisocyanate and small molecules glycol chain extender carry out polyreaction, products therefrom is in described soft section containing the thermoplastic polyurethane elastomer body of cyano group;
(2) preparation of Polyurethane Thermoplastic Elastomer;
By blended to the thermoplastic polyurethane elastomer body containing cyano group in described soft section, linking agent and crosslinking catalyst, and carry out crosslinking reaction, the Polyurethane Thermoplastic Elastomer containing cyano group in namely obtaining described soft section; Described linking agent is the compound containing two azido-functional group, fusing point <200 DEG C.
4. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, described hydroxyl terminated butadiene acrylonitrile copolymer account for polyester macromolecule dibasic alcohol and or the mole number per-cent of polyethers macromolecule dihydric alcohol be 1-50%.
5. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, described small molecules glycol chain extender is ethylene glycol, glycol ether, propylene glycol, dipropylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,3-butyleneglycol, 1,5-PD or neopentyl glycol.
6. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, with hydroxyl terminated butadiene acrylonitrile copolymer, one in polyester macromolecule dibasic alcohol and polyethers macromolecule dihydric alcohol or its combination, the total mass of organic diisocyanate and small molecules glycol chain extender is benchmark, hydroxyl terminated butadiene acrylonitrile copolymer, the per-cent that polyester diol and/or polyether Glycols account for total mass is 40-65%, the per-cent that organic diisocyanate accounts for total mass is 30-45%, the per-cent that small molecules glycol chain extender accounts for total mass is 5-15%, when polyester diol and polyether Glycols are for combination, it is the combination of arbitrary proportion.
7. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, the temperature of described polyreaction is 150-220 DEG C; Described polyreaction adopts twin screw reactive extrursion method, and screw speed is set as 150-300r/min.
8. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, also polymerizing catalyst is added during described polyreaction, described polymerizing catalyst is one or more in trimethylamine or metal organic acid salt, and described metal organic acid salt is the organic acid salt of bismuth, tin, titanium, lead, zinc, potassium, antimony, cobalt, iron, nickel, molybdenum, vanadium, manganese or zirconium; Polyester diol used during to be polymerized and/or the total mass of polyether Glycols are benchmark, and the addition of described polymerizing catalyst is 1-500ppm; Described polymerizing catalyst directly adds in polyester diol and/or polyether Glycols before the reaction;
Described trimethylamine is triethylamine, triethylenediamine, N-ethylmorpholine or N, N-dimethylethanolamine;
Described metal organic acid salt is new certain herbaceous plants with big flowers acid bismuth, bismuth naphthenate, isocaprylic acid bismuth, stannous octoate, dibutyl tin laurate, titanium isopropylate, tetrabutyl titanate, isocaprylic acid lead, isocaprylic acid zinc, zinc naphthenate, isocaprylic acid potassium, Potassium ethanoate, potassium oleate, antimony acetate, cobalt naphthenate, ferric acetyl acetonade, nickel acetate, molybdenum naphthenate, vanadium iso-octoate, manganese acetate or methyl ethyl diketone zirconium.
9. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, the described compound containing two azido-functional group, be 4,4 '-two-fold nitrogen biphenyl, 4,4 '-biphenyl dibenzyl nitrine, 2,6-two (4 '-nitrine benzal) pimelinketone, 1, two (the 4 '-nitrine benzal) acetone or 4 of 3-, 4 '-two-fold nitrogen phenyl styryl ketone; To synthesize mole number containing hydroxyl terminated butadiene acrylonitrile copolymer used during the thermoplastic polyurethane elastomer body of cyano group in soft section for benchmark, the addition of described linking agent is 5-50% mole number.
10. the method for preparing thermoplastic polyurethane elastomer containing cyano group in a kind of soft section according to claim 3, it is characterized in that, described crosslinking catalyst is Inorganic Ammonium compound, is ammonium sulfate, monoammonium sulfate, ammonium phosphate, ammonium hydrogen phosphate, ammonium iodide, brometo de amonio or ammonium chloride; With the linking agent mole number added for benchmark, the addition of described crosslinking catalyst is 50-100% mole number; Described crosslinking reaction is carried out under temperature 100 ~ 220 DEG C of conditions.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076423A (en) * | 2016-06-13 | 2016-11-09 | 江苏飞拓界面工程科技有限公司 | A kind of composition metal organic catalyst and preparation method thereof |
| CN107365407A (en) * | 2017-03-08 | 2017-11-21 | 浙江益弹新材料科技有限公司 | A kind of automobile vehicle window sealing strip |
| CN107501504A (en) * | 2017-03-08 | 2017-12-22 | 浙江益弹新材料科技有限公司 | A kind of TPUE and preparation method thereof |
| CN109280367A (en) * | 2018-09-17 | 2019-01-29 | 佛山朝鸿新材料科技有限公司 | A kind of fire-retardant toughened plastic material and preparation method thereof |
| CN111057208A (en) * | 2019-12-17 | 2020-04-24 | 上海汇得科技股份有限公司 | Polyolefin polyol modified thermoplastic polyurethane elastomer and preparation method thereof |
| CN111057207A (en) * | 2018-10-17 | 2020-04-24 | 上海浦加钻采技术有限公司 | Prepolymer of elastomer material for screw drilling tool and preparation method thereof |
| CN112126034A (en) * | 2019-06-24 | 2020-12-25 | 北京化工大学 | Mixed soft segment type polyurethane damping material and preparation method thereof |
| CN114835878A (en) * | 2022-04-27 | 2022-08-02 | 盛鼎高新材料有限公司 | Low-temperature-resistant high-resilience polyurethane elastomer and preparation method thereof |
| CN115197392A (en) * | 2022-07-01 | 2022-10-18 | 江苏省产品质量监督检验研究院 | Organic peroxide micro-crosslinking modified thermoplastic double-soft-segment polyurethane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919890A (en) * | 2006-08-11 | 2007-02-28 | 中国石油天然气集团公司 | Synthesis method of high-performance multipurpose urethane elastomer |
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN103897200A (en) * | 2014-03-31 | 2014-07-02 | 东南大学 | Method for preparing polyurethane polymer network |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
-
2016
- 2016-01-29 CN CN201610065975.1A patent/CN105542114B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919890A (en) * | 2006-08-11 | 2007-02-28 | 中国石油天然气集团公司 | Synthesis method of high-performance multipurpose urethane elastomer |
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| CN103897200A (en) * | 2014-03-31 | 2014-07-02 | 东南大学 | Method for preparing polyurethane polymer network |
Non-Patent Citations (2)
| Title |
|---|
| 宋立民: "叠氮化钠在有机合成中的应用", 《河北化工》 * |
| 来蔚鹏: "叠氮酸与氨氰环加成反应的理论研究", 《计算机与应用化学》 * |
Cited By (12)
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| CN107365407A (en) * | 2017-03-08 | 2017-11-21 | 浙江益弹新材料科技有限公司 | A kind of automobile vehicle window sealing strip |
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| CN107365407B (en) * | 2017-03-08 | 2018-10-02 | 浙江益弹新材料科技有限公司 | A kind of automobile vehicle window sealing strip |
| CN109280367A (en) * | 2018-09-17 | 2019-01-29 | 佛山朝鸿新材料科技有限公司 | A kind of fire-retardant toughened plastic material and preparation method thereof |
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| CN112126034A (en) * | 2019-06-24 | 2020-12-25 | 北京化工大学 | Mixed soft segment type polyurethane damping material and preparation method thereof |
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