CN104558506A - Polyurethane elastomer containing polyether polyol/nano-SiO2 hybrid material - Google Patents
Polyurethane elastomer containing polyether polyol/nano-SiO2 hybrid material Download PDFInfo
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
The invention belongs to the technical field of polyurethane materials and discloses a polyurethane elastomer containing a polyether polyol/nano-SiO2 hybrid material as well as a preparation method and application of the polyurethane elastomer. The elastomer comprises the following components in parts by weight: 25-80 parts of polyether polyol/nano-SiO2 hybrid materials, 9-64 parts of diisocyanate, 100 parts of polyether polyol, 0-5 parts of chain extenders, 0.1-2 parts of defoaming agents and 3-18 parts of curing agents. The polyurethane elastomer containing the polyether polyol/nano-SiO2 hybrid material can be used for solving the problem that the nanoparticles are bad to aggregate and disperse and improving the consistency of nano-SiO2 and a polyurethane matrix, so that the thermal properties and the mechanical properties such as the maximum thermal weight loss temperature, the tensile strength, the hardness and the elongation at break of the prepared elastomer are remarkably improved and the polyurethane elastomer containing the polyether polyol/nano-SiO2 hybrid material can be widely applied to the fields of mines, metallurgy, mechanical parts, vehicles and shoe materials.
Description
Technical field
The invention belongs to polyurethane material technical field, particularly one is containing polyether glycol/Nano-meter SiO_2
2polyurethane elastomer of hybrid material and preparation method thereof and application.
Background technology
Nano-meter SiO_2
2industrially be commonly called ultra-fine white carbon black, often by itself and polymkeric substance compound, prepare Nano-meter SiO_2
2/ polymer composites.The distinctive surface effects of nanoparticle, quantum size effect and volume effect etc., make Nano-meter SiO_2
2/ polymer composites shows the excellent properties that traditional polymer does not have.Polyurethane elastomer has good wear resistance, mechanical property and damping property etc., is widely used in mine, metallurgy, mould liner, mechanical fitting etc.But its thermotolerance is poor, inflammable, and water-repellancy is poor, thus limit its application.Nano-meter SiO_2
2/ compound polyurethane material can comprehensive Nano-meter SiO_2
2with the good characteristic of urethane, show the calorifics more more excellent than conventional polyurethanes material, mechanics and optical property etc.
At Nano-meter SiO_2
2in/compound polyurethane material, due to Nano-meter SiO_2
2surface energy large, cause it easily to reunite.In addition, the interface compatibility of inorganic nano material and polymkeric substance is bad, causes Nano-meter SiO_2
2with urethane in conjunction with weak.Above two factors all can cause Nano-meter SiO_2
2the performance of/compound polyurethane material is difficult to improve.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material.
Another object of the present invention is to provide a kind of above-mentioned containing polyether glycol/Nano-meter SiO_2
2the method for preparing polyurethane elastic body of hybrid material.
Still a further object of the present invention is to provide above-mentioned containing polyether glycol/Nano-meter SiO_2
2the application of polyurethane elastomer in the fields such as mine, metallurgy, mechanical fitting, the vehicles, footwear material of hybrid material.
Object of the present invention is realized by following proposal:
A kind of containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, comprises the component of following mass parts: 25 ~ 80 parts of polyether glycol/Nano-meter SiO_2
2hybrid material, 9 ~ 64 parts of vulcabond, 100 parts of polyether glycols, 0 ~ 5 part of chainextender, 0.1 ~ 2 part of defoamer, 3 ~ 18 parts of solidifying agent.
Described polyether glycol/Nano-meter SiO_2
2hybrid material has structure shown in following structural formula:
Wherein, R is
with
in at least one, the structural formula of above-mentioned R is corresponding in turn to polyether Glycols, polyether-tribasic alcohol, polyethers tetravalent alcohol, polyethers pentavalent alcohol, the polyethers hexavalent alcohol that molecular weight is 200 ~ 10000; M=3 ~ 172; N=1 ~ 58; K=1 ~ 43; P=1 ~ 35; Q=1 ~ 29;
R ' is-HN (CH
2)
3-,-NH (CH
2)
2nH (CH
2)
3-or-C
6h
5-NCH
2-.
Above-mentioned polyether glycol/Nano-meter SiO_2
2hybrid material is prepared by the preparation method comprising following steps:
(1) amino silicane coupling agent is added drop-wise in the toluene solution of vulcabond, stirring reaction, then adds polyether glycol, organo-metallic catalyst, reacting by heating, obtain polymer A;
(2) by polymer A, nano silicon dispersion liquid, water and toluene mixing obtained for step (1), reacting by heating, obtains polyether glycol/Nano-meter SiO_2
2hybrid material.
In step (1), the mass ratio of amino silicane coupling agent used, vulcabond, polyether glycol is 10:(6.4 ~ 14): (38 ~ 186).
In step (2), the mass ratio of polymer A used, nano silicon dispersion liquid and water is (11 ~ 56): (10 ~ 30): (1 ~ 4).
In step (2), toluene used is used for providing solution environmental, and its consumption can adjust according to actual needs, preferably uses the amount of toluene and the mass ratio of polymer A to be 100:56 ~ 200:11.
In step (1), the amount of organo-metallic catalyst used is catalytic amount.
Amino silicane coupling agent described in step (1) can be selected from least one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, anilinomethyl trimethoxy silane and anilinomethyl triethoxysilane.Wherein, described amino silicane coupling agent is preferably γ-aminopropyl triethoxysilane.
Vulcabond described in step (1) can be selected from tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), xylylene diisocyanate (XDI), 1, at least one in 4-cyclohexyl diisocyanate (CHDI) and naphthalene-1,5-vulcabond (NDI).Wherein, described vulcabond is preferably tolylene diisocyanate (TDI) or ditan-4,4 '-vulcabond (MDI).
It is the polyoxytrimethylene ethoxylated polyhydric alcohol (PPG) of 200 ~ 10000, at least one in polytetrahydrofuran ethoxylated polyhydric alcohol (PTMEG) and tetrahydrofuran (THF)-propylene oxide polyol that polyether glycol described in step (1) can be selected from molecular weight; Be more preferably polyoxytrimethylene ether trivalent alcohol.
Organo-metallic catalyst described in step (1) is the organo-metallic catalyst that this area is commonly used, and can be selected from least one in stannous octoate, dibutyl tin dilaurate, lead octoate 36 and two acetic acid di-n-butyl tins.Wherein, described organo-metallic catalyst is preferably dibutyltin dilaurate.
Described in step (1), the toluene solution concentration of vulcabond is preferably 11.3 ~ 21.8wt%.
The condition optimization at room temperature mechanic whirl-nett reaction 0.5 ~ 2h of the stirring reaction described in step (1).
The condition optimization of the reacting by heating described in step (1) is stirring reaction 4 ~ 6h at being heated to 50 ~ 80 DEG C.
Nano silicon dispersion liquid described in step (2) is by obtaining nano silicon ultrasonic disperse in toluene.The concentration of preferred described nano silicon dispersion liquid is 8 ~ 12wt%, is more preferably 9wt%.
Reacting by heating described in step (2) refers to 60 ~ 70 DEG C of stirring reactions 6 ~ 8 hours.
Steaming removing toluene or water equal solvent preferably by revolving after reacting by heating in step (1) and step (2), more preferably steaming at 70 DEG C of backspins.
Above-mentioned preparation method preferably carries out under atmosphere of inert gases, and solvent for use is all preferably dry toluene.
Of the present invention containing polyether glycol/Nano-meter SiO_2
2in the polyurethane elastomer of hybrid material, described vulcabond can be selected from tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI), xylylene diisocyanate (XDI), 1, at least one in 4-cyclohexyl diisocyanate (CHDI) and naphthalene-1,5-vulcabond (NDI).Wherein, described vulcabond is preferably tolylene diisocyanate (TDI) or ditan-4,4 '-vulcabond (MDI).
It is the polyoxytrimethylene ethoxylated polyhydric alcohol (PPG) of 200 ~ 10000, at least one in polytetrahydrofuran ethoxylated polyhydric alcohol (PTMEG) and tetrahydrofuran (THF)-propylene oxide polyol that described polyether glycol can be selected from molecular weight; Be more preferably polyoxytrimethylene ether trivalent alcohol.
Described chainextender is preferably at least one in BDO, ethylene glycol, propylene glycol, hexylene glycol, cyclohexanediol, terephthalic acid dihydroxy ethyl ester and TriMethylolPropane(TMP) mono allyl ether; Be more preferably BDO.
Described defoamer is preferably at least one in silicone antifoam agent and mineral oil defoaming agent; Be more preferably silicone antifoam agent.
Described solidifying agent can be selected from dimethythiotoluene diamine (DMTDA, as Ethacure300), 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane (MOCA), diethyl toluene diamine (DETDA, as Ethacure100), 3,5-diamino-4-chlorobenzene acetic acid isopropyl ester (as CuA-60) and 4, at least one in 4 '-methylene-bis (3-chloro-2,6-diethyl aniline) (MCDEA); Be more preferably dimethythiotoluene diamine.
Present invention also offers a kind of above-mentioned containing polyether glycol/Nano-meter SiO_2
2the method for preparing polyurethane elastic body of hybrid material, comprises following steps: by 25 ~ 80 mass parts polyether glycol/Nano-meter SiO_2
2hybrid material, 9 ~ 64 mass parts vulcabond and 100 mass parts polyether glycols mix, reacting by heating, add 0 ~ 5 mass parts chainextender, 0.1 ~ 2 mass parts defoamer, 3 ~ 18 mass parts solidifying agent again, be heating and curing, obtain containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material.
The condition optimization of described reacting by heating is 50 ~ 90 DEG C of stirring reactions 3 ~ 6 hours.
The described condition optimization be heating and curing is for solidifying 10 ~ 20h at 80 ~ 90 DEG C.
Of the present invention containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material is reunited owing to solving nanoparticle and disperses the problems such as bad, improve the consistency of nano silicon and polyurethane matrix in system, the every modification performance of elastomerics prepared all is significantly improved, its thermal property and mechanical property are all significantly improved, maximum heat weightless temperature, tensile strength, hardness, elongation at breaks etc. are significantly increased, can be widely used in mine, metallurgical, mechanical fitting, the vehicles, in the fields such as footwear material, be particularly useful for making sealing-ring, bearing, sieve plate, rubber roll, industry shaking table, gear, solid tyre, packing ring ball-joint, sole, in the field such as rear.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) first the present invention has prepared a kind of polyether glycol/Nano-meter SiO_2
2hybrid material, the nano silicon in this hybrid material wrap up by polyether glycol, thus effectively reduce the reunion between nanoparticle, be conducive to silicon dioxide granule in the polymer dispersed, give full play to the reinforcing effect of nanoparticle.
(2) of the present invention containing polyether glycol/Nano-meter SiO_2
2polyether glycol/Nano-meter SiO_2 in the polyurethane elastomer of hybrid material
2hybrid material is connected on polyurethane molecular chain by chemical bond-linking, thus nano silicon is effectively disperseed on polyurethane molecular chain, solve the problem that nano silicon is easily reunited in urethane further, and improve the consistency of nano silicon and polyurethane matrix.
(3) of the present invention containing polyether glycol/Nano-meter SiO_2
2in the polyurethane elastomer of hybrid material, owing to improve the modified effect of nano silicon, ensure that the dispersiveness of nanoparticle, only to make in material that need introduce a small amount of nano silicon can obtain good modified effect.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
In following examples, each performance test methods is as follows:
TG adopts the resistance to TG209F3-Brooker TENSOR 27 ftir Analysis combination analysis instrument test of speeding of Germany, N
2atmosphere, temperature rise rate 10 DEG C/min.
Elongation at break and tensile strength adopt RG M-3030 microcomputer controlled electronic universal tester (Shenzhen Rui Geer Instrument Ltd.) by GB1040-79 standard testing.
Hardness adopts AS-120A Shore durometer (Guangzhou An Miao Instrument Ltd.) test, and each sample test 5 points, average.
Embodiment 1: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polyoxytrimethylene ether trivalent alcohol N330/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g γ-aminopropyl triethoxysilane dropping funnel is dropwise joined in the mixed solution of 7.9g tolylene diisocyanate and 50g dry toluene; at 20 DEG C, mechanical stirring is after 0.5 hour; add 135g polyoxytrimethylene ether trivalent alcohol N330,0.5g stannous octoate; stirring reaction 6h at 70 DEG C; then at 70 DEG C of rotary evaporations, removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 0.5h, obtains nano silicon dispersion liquid.
C. by 15g polymer A, 11g nano silicon dispersion liquid, 1g distilled water, 100g toluene, 60 DEG C of stirring reactions 6 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polyoxytrimethylene ether trivalent alcohol N330/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polyoxytrimethylene ether trivalent alcohol N330/ nano silicon dioxide hybridization material
By 25g polyoxytrimethylene ether trivalent alcohol N330/ nano silicon dioxide hybridization material and 21g tolylene diisocyanate and 100g polyoxytrimethylene ether dibasic alcohol N220; under nitrogen protection; 70 DEG C of stirring reactions 6 hours; add 0.1g silicone antifoam agent, 9g dimethythiotoluene diamine; 80 DEG C of solidification 20h, the obtained polyurethane elastomer containing polyoxytrimethylene ether trivalent alcohol N330/ nano silicon dioxide hybridization material.
Embodiment 2: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polyoxytrimethylene ether trivalent alcohol JH-3030/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g γ-aminopropyltrimethoxysilane dropping funnel is dropwise added 14g ditan-4; in the mixed solution of 4 '-vulcabond and 50g dry toluene; at 40 DEG C, mechanical stirring is after 1 hour; add 167g polyoxytrimethylene ether trivalent alcohol JH-3030,0.05g dibutyl tin dilaurate, stirring reaction 4h at 75 DEG C, then at 70 DEG C of rotary evaporations; removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 1h, obtains nano silicon dispersion liquid.
C. 56g is polymerized A, 30g nano silicon dispersion liquid, 4g distilled water, 200 mass parts toluene, 70 DEG C of stirring reactions 6 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polyoxytrimethylene ether trivalent alcohol JH-3030/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polyoxytrimethylene ether trivalent alcohol JH-3030/ nano silicon dioxide hybridization material
By 80g polyoxytrimethylene ether trivalent alcohol JH-3030/ nano silicon dioxide hybridization material and 64g ditan-4; 4 '-vulcabond and 100g polypropylene glycol PPG800; under nitrogen protection; 50 DEG C of stirring reactions 4 hours; add 3g ethylene glycol and 0.9g silicone antifoam agent, 9g liquid state 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane; 90 DEG C of solidification 10h, obtain the polyurethane elastomer containing polyoxytrimethylene ether trivalent alcohol JH-3030/ nano silicon dioxide hybridization material.
Embodiment 3: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polyoxytrimethylene ether trivalent alcohol MN-3050/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g N-β (aminoethyl)-γ-aminopropyltrimethoxysilane dropping funnel is dropwise added in the mixed solution of 10g isophorone diisocyanate and 50g dry toluene; at 30 DEG C, mechanical stirring is after 2 hours; add 135g polyoxytrimethylene ether trivalent alcohol MN-3050; 0.3g lead octoate 36, stirring reaction 4h at 80 DEG C, then at 70 DEG C of rotary evaporations; removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 2h, obtains nano silicon dispersion liquid.
C. by 31g polymer A, 22g nano silicon dispersion liquid, 2g distilled water, 150g toluene, 60 DEG C of stirring reactions 8 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polyoxytrimethylene ether trivalent alcohol MN-3050/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polyoxytrimethylene ether trivalent alcohol MN-3050/ nano silicon dioxide hybridization material
By 50g polyoxytrimethylene ether trivalent alcohol MN-3050/ nano silicon dioxide hybridization material, 19g isophorone diisocyanate and 100g polypropylene glycol PPG3000; under nitrogen protection; 90 DEG C of stirring reactions 3 hours; add 3g hexylene glycol and 1.6g silicone antifoam agent, 12g 3; 5-diamino-4-chlorobenzene acetic acid isopropyl ester; 85 DEG C of solidification 15h, obtain the polyurethane elastomer containing polyoxytrimethylene ether trivalent alcohol MN-3050/ nano silicon dioxide hybridization material.
Embodiment 4: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polytetramethylene ether diol PTMEG1000/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g N-β (aminoethyl)-γ-aminopropyl triethoxysilane dropping funnel is dropwise added in the mixed solution of 6.4g hexamethylene diisocyanate and 50g dry toluene; at 20 DEG C, mechanical stirring is after 2 hours; add 38g polytetramethylene ether diol PTMEG1000; 0.4g bis-acetic acid di-n-butyl tin, stirring reaction 5h at 70 DEG C, then at 70 DEG C of rotary evaporations; removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 0.5 ~ 2h, obtains nano silicon dispersion liquid.
C. by 11g polymer A, 24g nano silicon dispersion liquid, 1g distilled water, 100g toluene, 60 DEG C of stirring reactions 6 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polytetramethylene ether diol PTMEG1000/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polytetramethylene ether diol PTMEG1000/ nano silicon dioxide hybridization material
By 30g polytetramethylene ether diol PTMEG1000/ nano silicon dioxide hybridization material and 9g isophorone diisocyanate and 100g polypropylene glycol PPG6000; under nitrogen protection; 80 DEG C of stirring reactions 4 hours; add 2g 1; 4-butyleneglycol, 3g cyclohexanediol, 0.7g silicone antifoam agent and 3g 4; 4 '-methylene-bis (3-chloro-2; 6-Diethyl Aniline); 80 DEG C of solidification 20h, obtain the polyurethane elastomer containing polytetramethylene ether diol PTMEG1000/ nano silicon dioxide hybridization material.
Embodiment 5: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polyoxytrimethylene ether trivalent alcohol 1618A/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g anilinomethyl triethoxysilane dropping funnel is dropwise added in the mixed solution of 6g PPDI and 50g dry toluene; at 25 DEG C, mechanical stirring is after 2 hours; add 186g polyoxytrimethylene ether trivalent alcohol 1618A; 0.5g dibutyl tin dilaurate, stirring reaction 4h at 80 DEG C, then at 70 DEG C of rotary evaporations; removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 2h, obtains nano silicon dispersion liquid.
C. by 22g polymer A, 12g nano silicon dispersion liquid, 1.5g distilled water, 100g toluene, 60 DEG C of stirring reactions 7 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polyoxytrimethylene ether trivalent alcohol 1618A/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polyoxytrimethylene ether trivalent alcohol 1618A/ nano silicon dioxide hybridization material
By 30g polyoxytrimethylene ether trivalent alcohol 1618A/ nano silicon dioxide hybridization material, 32g PPDI, 90g polytetramethylene ether diol PTMEG1000,10g polyoxytrimethylene ether hexavalent alcohol (molecular weight is 10000); under nitrogen protection; 80 DEG C of stirring reactions 5 hours; add 3g terephthalic acid dihydroxy ethyl ester, 2.0g mineral oil defoaming agent, 18g diethyl toluene diamine; 80 DEG C of solidification 20h, obtain the polyurethane elastomer containing polyoxytrimethylene ether trivalent alcohol 1618A/ nano silicon dioxide hybridization material.
Embodiment 6: containing the preparation of the polyurethane elastomer of polyether glycol/nano silicon dioxide hybridization material
(1) preparation of polypropylene glycol PPG200/ nano silicon dioxide hybridization material
A. under nitrogen protection; 10g anilinomethyl trimethoxy silane dropping funnel is dropwise added in the mixed solution of 8.3g xylylene diisocyanate and 50g dry toluene; at 20 DEG C, mechanical stirring is after 2 hours; add 9g mass parts polypropylene glycol PPG200; stirring reaction 4h at 50 DEG C; then at 70 DEG C of rotary evaporations, removing toluene, obtains polymer A.
B. 10g nano silicon is scattered in 100g toluene, ultrasonic 2h, obtains nano silicon dispersion liquid.
C. by 4g polymer A, 10g nano silicon dispersion liquid, 1g distilled water, 100g toluene, 60 DEG C of stirring reactions 6 hours, then at 70 DEG C of rotary evaporations, removing toluene and water, obtain polypropylene glycol PPG200/ nano silicon dioxide hybridization material.
(2) containing the preparation of the polyurethane elastomer of polypropylene glycol PPG200/ nano silicon dioxide hybridization material
By 13g polypropylene glycol PPG200/ nano silicon dioxide hybridization material and 36g tolylene diisocyanate and 100g polyoxytrimethylene ether dibasic alcohol N210; under nitrogen protection; 70 DEG C of stirring reactions 3 hours; add 3g TriMethylolPropane(TMP) mono allyl ether, 1.5g mineral oil defoaming agent, 12g dimethythiotoluene diamine; 80 DEG C of solidification 20h, obtain the polyurethane elastomer containing polypropylene glycol PPG200/ nano silicon dioxide hybridization material.
Comparative example 1: the preparation of pure urethane
By 17.4g tolylene diisocyanate, 100g polyoxytrimethylene ether dibasic alcohol N220 and 0.1g stannous octoate; under nitrogen protection, at 70 DEG C of stirring reactions after 6 hours, add 0.1g silicone antifoam agent, 9g dimethythiotoluene diamine; 80 DEG C of solidification 20h, obtained polyurethane elastomer material.
Comparative example 2: the polyurethane composite elastic body material that undressed nano silicon is obtained
By 1g nano silicon, 17.4g tolylene diisocyanate, 100g polyoxytrimethylene ether dibasic alcohol N220 and 0.5g stannous octoate under nitrogen protection; at 70 DEG C of stirring reactions after 6 hours; add 0.1g silicone antifoam agent, 9g dimethythiotoluene diamine; 80 DEG C of solidification 20h, obtained nano silicon/polyurethane composite elastic body material.
Comparative example 3: the preparation of pure urethane
By 7.5g isophorone diisocyanate and 100g polypropylene glycol PPG6000; under nitrogen protection; 80 DEG C of stirring reactions 4 hours; add 2g 1; 4-butyleneglycol, 3g cyclohexanediol, 0.7g silicone antifoam agent mass parts and 3g 4,4 '-methylene-bis (3-chloro-2,6-diethyl aniline); 80 DEG C of solidification 20h, obtained polyurethane elastomer material.
Comparative example 4: the polyurethane composite elastic body material that undressed nano silicon is obtained
By 1.7g nano silicon, 7.5g isophorone diisocyanate and 100g polypropylene glycol PPG6000; under nitrogen protection; 80 DEG C of stirring reactions 4 hours; add 2g 1; 4-butyleneglycol, 3g cyclohexanediol, 0.7g silicone antifoam agent and 3g 4,4 '-methylene-bis (3-chloro-2,6-diethyl aniline); 80 DEG C of solidification 20h, obtained nano silicon/polyurethane composite elastic body material.
The elastomer material that the polyurethane elastomer containing polyether glycol/nano silicon dioxide hybridization material prepare embodiment 1 ~ 6 and comparative example 1 ~ 4 prepare carries out performance test, the results are shown in Table 1.
The performance index of table 1 polyurethane elastomer
| Maximum heat weightless temperature (DEG C) | Elongation at break (%) | Tensile strength (MPa) | Hardness (HA) | |
| Embodiment 1 | 370.6 | 440 | 14.8 | 74.5 |
| Embodiment 2 | 380.6 | 364 | 20.3 | 84.5 |
| Embodiment 3 | 381.3 | 504 | 17.6 | 78 |
| Embodiment 4 | 367.7 | 510 | 12.8 | 65.5 |
| Embodiment 5 | 373.2 | 461 | 17.5 | 68.5 |
| Embodiment 6 | 377.4 | 382 | 24.6 | 83.5 |
| Comparative example 1 | 360.2 | 410 | 10.9 | 66.5 |
| Comparative example 2 | 365.6 | 391 | 11.6 | 68 |
| Comparative example 3 | 355.2 | 515 | 8.9 | 56.5 |
| Comparative example 4 | 361.0 | 481 | 10.1 | 60 |
From table 1, embodiment 1 is analyzed known compared with comparative example 1,2, compared with the pure urethane (comparative example 1) of not nano-silica-containing, adopt maximum heat weightless temperature, tensile strength and the hardness of the obtained nano silicon/polyurethane composite elastic body (comparative example 2) of undressed nano silicon all slightly to increase, but its elongation at break obviously decline; And the maximum heat weightless temperature of the polyurethane elastomer containing polyether glycol/nano silicon dioxide hybridization material of the present invention, tensile strength and hardness are improved significantly, and the amplitude that increases is higher than comparative example 2, and its elongation at break is also significantly improved.
Embodiment 4 is analyzed known compared with comparative example 3,4, compared with the pure urethane (comparative example 3) of not nano-silica-containing, adopt maximum heat weightless temperature, tensile strength and the hardness of the obtained nano silicon/polyurethane composite elastic body (comparative example 4) of undressed nano silicon all slightly to increase, but obviously declining appear in its elongation at break; And the maximum heat weightless temperature of the polyurethane elastomer containing polyether glycol/nano silicon dioxide hybridization material of the present invention, tensile strength and hardness are all significantly improved, and the amplitude that increases is higher than comparative example 3, and elongation at break is also improved.
Above embodiment explanation, thermal property and the mechanical property of the polyurethane elastomer containing polyether glycol/nano silicon dioxide hybridization material of the present invention all obtain significant raising, can be widely used in the fields such as mine, metallurgy, mechanical fitting, the vehicles, footwear material, be particularly useful for making in sealing-ring, bearing, sieve plate, rubber roll, industrial shaking table, gear, solid tyre, packing ring ball-joint, sole, the field such as rear.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. one kind contains polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that the component comprising following mass parts: 25 ~ 80 parts of polyether glycol/Nano-meter SiO_2
2hybrid material, 9 ~ 64 parts of vulcabond, 100 parts of polyether glycols, 0 ~ 5 part of chainextender, 0.1 ~ 2 part of defoamer, 3 ~ 18 parts of solidifying agent;
Described polyether glycol/Nano-meter SiO_2
2hybrid material has structure shown in following structural formula:
Wherein, R is
in at least one, the structural formula of above-mentioned R is corresponding in turn to polyether Glycols, polyether-tribasic alcohol, polyethers tetravalent alcohol, polyethers pentavalent alcohol, the polyethers hexavalent alcohol that molecular weight is 200 ~ 10000; M=3 ~ 172; N=1 ~ 58; K=1 ~ 43; P=1 ~ 35; Q=1 ~ 29;
R ' is-HN (CH
2)
3-,-NH (CH
2)
2nH (CH
2)
3-or-C
6h
5-NCH
2-.
2. according to claim 1 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: described polyether glycol/Nano-meter SiO_2
2hybrid material is prepared by the preparation method comprising following steps:
(1) amino silicane coupling agent is added drop-wise in the toluene solution of vulcabond, stirring reaction, then adds polyether glycol, organo-metallic catalyst, reacting by heating, obtain polymer A;
(2) by polymer A, nano silicon dispersion liquid, water and toluene mixing obtained for step (1), reacting by heating, obtains polyether glycol/Nano-meter SiO_2
2hybrid material.
3. according to claim 2 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: in step (1), the mass ratio of amino silicane coupling agent used, vulcabond, polyether glycol is 10:(6.4 ~ 14): (38 ~ 186);
In step (2), the mass ratio of polymer A used, nano silicon dispersion liquid and water is (11 ~ 56): (10 ~ 30): (1 ~ 4);
In step (2), the amount of toluene used and the mass ratio of polymer A are 100:56 ~ 200:11.
4. according to claim 2 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: the amino silicane coupling agent described in step (1) is selected from least one in γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl triethoxysilane, anilinomethyl trimethoxy silane and anilinomethyl triethoxysilane;
Described vulcabond is selected from tolylene diisocyanate, ditan-4,4 '-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, PPDI, xylylene diisocyanate, 1, at least one in 4-cyclohexyl diisocyanate and naphthalene-1,5-vulcabond;
It is the polyoxytrimethylene ethoxylated polyhydric alcohol of 200 ~ 10000, at least one in polytetrahydrofuran ethoxylated polyhydric alcohol and tetrahydrofuran (THF)-propylene oxide polyol that described polyether glycol is selected from molecular weight;
Described organo-metallic catalyst is selected from least one in stannous octoate, dibutyl tin dilaurate, lead octoate 36 and two acetic acid di-n-butyl tins.
5. according to claim 2 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: the condition of the stirring reaction described in step (1) is at room temperature mechanic whirl-nett reaction 0.5 ~ 2h; The condition of the reacting by heating described in step (1) is stirring reaction 4 ~ 6h at being heated to 50 ~ 80 DEG C; Reacting by heating described in step (2) refers to 60 ~ 70 DEG C of stirring reactions 6 ~ 8 hours.
6. according to claim 1 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, it is characterized in that: described vulcabond is selected from tolylene diisocyanate, ditan-4,4 '-vulcabond, isophorone diisocyanate, hexamethylene diisocyanate, PPDI, xylylene diisocyanate, 1, at least one in 4-cyclohexyl diisocyanate and naphthalene-1,5-vulcabond; It is the polyoxytrimethylene ethoxylated polyhydric alcohol of 200 ~ 10000, at least one in polytetrahydrofuran ethoxylated polyhydric alcohol and tetrahydrofuran (THF)-propylene oxide polyol that described polyether glycol is selected from molecular weight.
7. according to claim 1 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: described chainextender is at least one in BDO, ethylene glycol, propylene glycol, hexylene glycol, cyclohexanediol, terephthalic acid dihydroxy ethyl ester and TriMethylolPropane(TMP) mono allyl ether;
Described defoamer is at least one in silicone antifoam agent and mineral oil defoaming agent;
Described solidifying agent is selected from dimethythiotoluene diamine, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, diethyl toluene diamine, 3,5-diamino-4-chlorobenzene acetic acid isopropyl esters and 4, at least one in 4 '-methylene-bis (3-chloro-2,6-diethyl aniline).
8. according to claim 1 containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material, is characterized in that: described vulcabond is tolylene diisocyanate or ditan-4,4 '-vulcabond; Described polyether glycol is polyoxytrimethylene ether trivalent alcohol; Described chainextender is BDO; Described defoamer is silicone antifoam agent; Described solidifying agent is dimethythiotoluene diamine.
9. one kind according to any one of claim 1 ~ 8 containing polyether glycol/Nano-meter SiO_2
2the method for preparing polyurethane elastic body of hybrid material, is characterized in that comprising following steps: by 25 ~ 80 mass parts polyether glycol/Nano-meter SiO_2
2hybrid material, 9 ~ 64 mass parts vulcabond and 100 mass parts polyether glycols mix, reacting by heating, add 0 ~ 5 mass parts chainextender, 0.1 ~ 2 mass parts defoamer, 3 ~ 18 mass parts solidifying agent again, be heating and curing, obtain containing polyether glycol/Nano-meter SiO_2
2the polyurethane elastomer of hybrid material.
10. according to any one of claim 1 ~ 8 containing polyether glycol/Nano-meter SiO_2
2the application of polyurethane elastomer in mine, metallurgy, mechanical fitting, the vehicles, footwear material field of hybrid material.
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| CN104962077A (en) * | 2015-06-11 | 2015-10-07 | 南京大学 | Preparation of modified nano-silica filled modified cyanate ester resin |
| CN107849293B (en) * | 2015-08-12 | 2020-08-25 | 3M创新有限公司 | Polyurethane/urea silicon carbide nanocomposite |
| CN107849293A (en) * | 2015-08-12 | 2018-03-27 | 3M创新有限公司 | Polyurethane/urea nanometer silicon carbide composite |
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| CN110396172B (en) * | 2019-08-14 | 2022-04-08 | 上海鑫普新材料有限公司 | Elastomer for rail transit rail lower cushion block and preparation method thereof |
| CN111662428A (en) * | 2020-05-22 | 2020-09-15 | 中国船舶重工集团公司第七二五研究所 | Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof |
| CN111825886A (en) * | 2020-07-13 | 2020-10-27 | 承德石油高等专科学校 | Hardness regulator of TPU powder for SLS printing and preparation method thereof |
| CN114369220A (en) * | 2020-10-15 | 2022-04-19 | 中国科学院化学研究所 | Thermoplastic polyurethane elastomer nano composite material and preparation method thereof |
| CN114369220B (en) * | 2020-10-15 | 2023-12-22 | 中国科学院化学研究所 | Thermoplastic polyurethane elastomer nanocomposite and preparation method thereof |
| CN113754880A (en) * | 2021-08-30 | 2021-12-07 | 山东一诺威新材料有限公司 | Preparation method of inorganic nano composite polyether polyol |
| CN113754880B (en) * | 2021-08-30 | 2024-02-23 | 山东一诺威新材料有限公司 | Preparation method of inorganic nano composite polyether polyol |
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