CN104448208B - Organic silicon/nanometer ZnO composite modified polyurethane elastomer, preparation and application - Google Patents
Organic silicon/nanometer ZnO composite modified polyurethane elastomer, preparation and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
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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
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- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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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
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Abstract
The invention belongs to the field of high-molecular materials, and discloses an organic silicon/nanometer ZnO composite modified polyurethane elastomer, a preparation method of the elastomer and an application of the elastomer. The elastomer comprises, by weight, 25-80 parts of polyether polyol/nanometer ZnO hybrid materials, 6-12 parts of two-end hydroxide dimethyl silicone polymer, 100 parts of polyether polyol, 10-60 parts of diisocyanate, 0.1-0.5 part of organo-metallic catalyst, 0-5 parts of chain extenders, 0.1-2.0 parts of defoaming agents and 3-17 parts of curing agents. Nanometer ZnO and organic silicon collectively modify polyurethane, excellent performances of the nanometer ZnO, the organic silicon and the polyurethane can be combined, so that the material has various performances such as an excellent surface performance, a fine mechanical performance, ultraviolet ageing resistance and heat resistance, and can be widely applied to fields such as sports apparatuses, clothing, industrial equipment and vehicles.
Description
Technical field
The invention belongs to polymeric material field, the composite modified elastic polyurethane of more particularly to a kind of organosilicon/nano-ZnO
Body and preparation method and application.
Background technology
Polyurethane elastomer is a kind of broad-spectrum macromolecular material, with good mechanical performance, wearability, oil resistant
Property, fatigue durability, can be used for solid tyre, packing ring ball-joint, sole gear, rubber roll, bearing etc..But polyurethane non-refractory,
Inflammable, weatherability, surface property and dielectric properties are poor, thus limit its application.
The features such as organosilicon has high-low temperature resistant, weatherability, low-surface-energy, hydrophobicity, electrical insulating property.With organic-silicon-modified
Polyurethane, can make material have the excellent properties of the two concurrently.However, organosilicon would generally reduce the mechanical property of polyurethane.
Nano-ZnO has the superiority such as high chemical stability, stronger ultraviolet absorption ability, relatively low dielectric constant
Can, therefore nano-ZnO is introduced in polymer mechanical property, thermal property, UV resistance and the antistatic that can improve material
Property.But, nano zine oxide is easily reunited in the polymer, poor compatibility, thus limits its modified effect to material.
Therefore, nano-ZnO is disperseed using effective method, in conjunction with organosilicon, polyurethane is carried out it is dual modified, can
The advantage of comprehensive three, prepares the multifunctional material of function admirable.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art with it is not enough, the primary and foremost purpose of the present invention be provide a kind of organosilicon/
The composite modified polyurethane elastomer of nano-ZnO.
Another object of the present invention is the system for providing a kind of composite modified polyurethane elastomer of above-mentioned organosilicon/nano-ZnO
Preparation Method.
Still a further object of the present invention is to provide the composite modified polyurethane elastomer of above-mentioned organosilicon/nano-ZnO in locomotorium
Application in the fields such as tool, clothing, industrial equipment, the vehicles.
The purpose of the present invention is realized by following proposal：
A kind of composite modified polyurethane elastomer of organosilicon/nano-ZnO, the component comprising following mass parts：25～80 parts
Polyether polyol/nano zinc oxide hybridization material, 6～12 parts of double hydroxyl-terminated injecting two methyl siloxanes, 100 parts of polyether polyol,
10～60 parts of diisocyanate, 0.1～0.5 part of organo-metallic catalyst, 0～5 part of chain extender, 0.1～2.0 part of defoamer, 3～
17 parts of firming agent.
Described double hydroxyl-terminated injecting two methyl siloxanes are preferably the hydroxyl alkyl end-blocking that mean molecule quantity is 2000～50000
At least one in polysiloxanes and silicone hydroxyl terminated polysiloxane.
Described polyether polyol may be selected from polypropylene oxide ethoxylated polyhydric alcohol (PPG) that molecular weight is 200～10000, gather
At least one in tetrahydrofuran ethoxylated polyhydric alcohol (PTMEG) and tetrahydrofuran-propylene oxide polyol；More preferably polyoxy
Change propylene ether trihydroxylic alcohol.
Described diisocyanate may be selected from toluene di-isocyanate(TDI) (TDI), diphenyl methane -4,4 '-diisocyanate
(MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), PPDI (PPDI),
XDI (XDI), 1,4- cyclohexane diisocyanates (CHDI) and naphthalene -1,5- diisocyanate (NDI)
In at least one.More preferably toluene di-isocyanate(TDI) (TDI) or diphenyl methane -4,4 '-diisocyanate (MDI).
Described organo-metallic catalyst may be selected from stannous octoate, dibutyl tin dilaurate, lead octoate and two acetic acid two
At least one in normal-butyl stannum, more preferably dibutyltin dilaurate.
Described chain extender may be selected from 1,4- butanediols, ethylene glycol, Propylene Glycol, hexanediol, cyclohexanediol, p-phthalic acid
At least one in two hydroxyl ethyl esters and trimethyolol propane monoallyl ether；More preferably 1,4- butanediols.
Described defoamer can be at least one in organic silicon defoamer and mineral oil defoaming agent；It is more preferably organic
Silicon defoaming agent.
Described firming agent can for dimethythiotoluene diamine (DMTDA, such as Ethacure300), 3,3 '-two chloro- 4,4 '-
Diaminodiphenyl-methane (MOCA), diethyl toluene diamine (DETDA, such as Ethacure100), 3,5- diaminourea -4- chlorobenzenes
Isopropyl acetate (such as CuA-60) and 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diethyl -3- chloroanilines) (MCDEA) in one kind；It is more excellent
Elect dimethythiotoluene diamine (DMTDA, Ethacure300) as.
Described polyether polyol/nano zinc oxide hybridization material has the structure shown in following structural formula：
Wherein, R is In at least one；The knot of above-mentioned R
Structure formula is corresponding in turn to the polyether Glycols that molecular weight is 200～10000, polyether-tribasic alcohol, polyethers tetrahydroxylic alcohol, five yuan of polyethers
Alcohol, polyethers hexahydroxylic alcohols；M=3～172；N=1～58；K=1～43；P=1～35；Q=1～29.
Above-mentioned polyether polyol/nano zinc oxide hybridization material is prepared by the preparation method for comprising the steps of：
(1) by isocyanato silanes coupling agent, polyether polyol, organo-metallic catalyst mixing, stirring reaction is obtained
Polymer A；
(2) by polymer A, nano zinc oxide fluid dispersion, water, toluene mixing obtained in step (1), stirring reaction is obtained
Polyether polyol/nano zinc oxide hybridization material.
In step (1), the mass ratio of isocyanato silanes coupling agent used and polyether polyol is 10:40.5～10:
146。
The amount of organo-metallic catalyst used is catalytic amount.
In step (2), the mass ratio of polymer A, nano zinc oxide fluid dispersion, water and toluene used is (12～50):(10
～30):(1～4):(100～200).
Nano zinc oxide fluid dispersion described in step (2) is by nano zine oxide ultrasonic disperse is obtained in toluene.
It is preferred that the concentration of the nano zinc oxide fluid dispersion is 8～12wt%, more preferably 9wt%.
Isocyanato silanes coupling agent described in step (1) may be selected from 3- NCO propyl trimethoxy silicanes
With at least one in 3- NCO propyl-triethoxysilicanes.
Polyether polyol described in step (1) may be selected from the polypropylene oxide ethoxylated polyhydric alcohol that molecular weight is 200～10000
(PPG), at least one in PolyTHF ethoxylated polyhydric alcohol (PTMEG) and tetrahydrofuran-propylene oxide polyol；It is more excellent
Elect polypropylene oxide ether trihydroxylic alcohol as.
Organo-metallic catalyst described in step (1) may be selected from stannous octoate, dibutyl tin dilaurate, lead octoate and
At least one in two acetic acid di-n-butyl tins, more preferably dibutyltin dilaurate.
Stirring reaction described in step (1) is preferably stirring reaction 4～6 hours at 50～80 DEG C.
Stirring reaction described in step (2) is preferably in 60～70 DEG C of stirring reactions 6～8 hours.
Preferably more preferably existed by rotating removing toluene or water equal solvent after stirring reaction in step (1) and step (2)
Rotate at 70 DEG C.
Above-mentioned preparation method is preferably carried out under atmosphere of inert gases, and solvent for use is both preferably dry toluene.
Present invention also offers a kind of composite modified method for preparing polyurethane elastic body of above-mentioned organosilicon/nano-ZnO, bag
Containing following steps：
Take 25～80 mass parts polyether polyol/nano zinc oxide hybridization material, the poly- diformazan of 6～12 mass parts both-end hydroxyls
Radical siloxane, 100 mass parts polyether polyol and 10～60 mass parts diisocyanate, 0.1～0.5 mass parts organic metal are urged
Agent mixes, stirring reaction, adds 0～5 mass parts chain extender, 0.1～2.0 mass parts defoamer, the solidification of 3～17 mass parts
Agent, is heating and curing, and the composite modified polyurethane elastomer of organosilicon/nano-ZnO is obtained.
Described stirring reaction is preferably in 75～90 DEG C of stirring reactions 3～5 hours.
Described being heating and curing preferably solidify 10～20h at 80～90 DEG C.
Above-mentioned reaction is preferably carried out in the case where nitrogen protective atmosphere encloses.
The composite modified polyurethane elastomer of organosilicon/nano-ZnO that the present invention is prepared can be widely applied to locomotorium
In the fields such as tool, clothing, industrial equipment, the vehicles, track lanes, garment material, solid tyre, pad are particularly useful for making
Circle ball-joint, bushing bearing, sole, rubber roll, gear, sieve plate, shaking table, safe automobile air bag etc..
The present invention is had the following advantages and beneficial effect relative to prior art：
(1) present invention adopts nano zine oxide and the common modified polyurethane of organosilicon, can comprehensive nano zine oxide, organosilicon
With the excellent properties of polyurethane so that material has excellent surface property, good mechanical property and uvioresistant old simultaneously
Change the multiple performances such as performance, thermostability.
(2) the method comprises the steps of firstly, preparing a kind of polyether polyol/nano zinc oxide hybridization material, the hybrid material is by chemistry
Bonded in polyurethane molecular chain, and nano zine oxide therein is wrapped up by polyether polyol, thus is effectively increased
Nano zine oxide and the compatibility of polyurethane matrix, reduce the reunion of nanoparticle, are conducive to zinc oxide particles in polymer
In it is dispersed.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
In following examples, each performance test methods are as follows：
TG is using resistance to 27 ftir Analysis combination analysis instrument of the TG209F3- Brookers TENSOR test of speeding of Germany, N2Atmosphere,
10 DEG C/min of heating rate.
Elongation at break and tensile strength adopt RG M-3030 microcomputer controlled electronic universal testers (Shenzhen Rui Geer instrument
Device company limited) by GB1040-79 standard testings.
Hardness is tested using AS-120A Shore durometers (Guangzhou An Miao Instrument Ltd.), each sample test 5
Point, averages.
Using the BHO-401A ageing ovens of one permanent company of Shanghai, ageing time is 168 hours to ultraviolet ageing.
Embodiment 1
(1) preparation of polypropylene oxide ether trihydroxylic alcohol N330/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl trimethoxy silicane is added into 146g polypropylene oxide ethers
Trihydroxylic alcohol N330,0.5g stannous octoate, stirring reaction 6h at 70 DEG C obtain polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, ultrasonic 0.5h obtains nano zinc oxide fluid dispersion.
C. by 16g polymer As, 11g nano zinc oxide fluid dispersions, 1g distilled water, 100g toluene, in 60 DEG C of stirring reactions 6
Hour, then in 70 DEG C of rotary evaporations, toluene and water are removed, polypropylene oxide ether trihydroxylic alcohol N330/ nano zinc oxide hybridizations are obtained
Material.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 25g polypropylene oxide ether trihydroxylic alcohol N330/ nano zinc oxide hybridization materials, 6g both-end hydroxyl polydimethylsiloxanes
Alkane (silicone hydroxyl block, mean molecule quantity be 15000), 100g polypropylene oxide ether dihydroxylic alcohols N220,21g toluene diisocynates
Ester, 0.4g stannous octoates, under nitrogen protection, in 80 DEG C of stirring reactions 6 hours, add 0.1g organic silicon defoamers, 10g diformazans
Sulfenyl toluenediamine, 80 DEG C of solidification 20h, is obtained the composite modified polyurethane elastomer of organosilicon/nano-ZnO.
Embodiment 2
(1) preparation of polypropylene oxide ether trihydroxylic alcohol JH-3030/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl trimethoxy silicane is added into 146g polypropylene oxide ethers
Trihydroxylic alcohol JH-3030,0.05g dibutyl tin dilaurate, stirring reaction 4h at 75 DEG C obtain polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, ultrasonic 1h obtains nano zinc oxide fluid dispersion.
C. by 50g polymer As, 33g nano zinc oxide fluid dispersions, 4g distilled water, 200g toluene, in 70 DEG C of stirring reactions 6
Hour, then in 70 DEG C of rotary evaporations, toluene and water are removed, the nano oxidized zinca of polypropylene oxide ether trihydroxylic alcohol JH-3030/ is obtained
Change material.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 80g polypropylene oxide ether trihydroxylic alcohol JH-3030/ nano zinc oxide hybridization materials, 12g both-end hydroxyl poly dimethyls
Siloxanes (silicone hydroxyl block, mean molecule quantity be 50000), 100g polypropylene oxide ether dihydroxylic alcohols N210,60g diphenylmethyls
Alkane -4,4 '-diisocyanate, 0.1g dibutyl tin dilaurates, under nitrogen protection, in 75 DEG C of stirring reactions 5 hours, add
3g ethylene glycol and 0.9g organic silicon defoamers, 10g liquid 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methane, 90 DEG C of solidifications
10h, is obtained the composite modified polyurethane elastomer of organosilicon/nano-ZnO.
Embodiment 3
(1) preparation of polypropylene oxide ether trihydroxylic alcohol MN-3050/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl trimethoxy silicane is added into 146g polypropylene oxide ethers
Trihydroxylic alcohol MN-3050,0.3g lead octoate, stirring reaction 4h at 80 DEG C obtain polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, ultrasonic 2h obtains nano zinc oxide fluid dispersion.
C. by 32g polymer As, 22g nano zinc oxide fluid dispersions, 2g distilled water, 150g toluene, in 60 DEG C of stirring reactions 8
Hour, then in 70 DEG C of rotary evaporations, toluene and water are removed, the nano oxidized zinca of polypropylene oxide ether trihydroxylic alcohol MN-3050/ is obtained
Change material.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 50g polypropylene oxide ether trihydroxylic alcohol MN-3050/ nano zinc oxide hybridization materials, 11g both-end hydroxyl poly dimethyls
Siloxanes (silicone hydroxyl block, mean molecule quantity be 10000), 100g polypropylene glycol PPG3000,20g isophorone diisocyanates
Ester, 0.4g lead octoates, under nitrogen protection, in 90 DEG C of stirring reactions 3 hours, add 3g hexanediol and 1.6g organosilicon froth breakings
Agent, 12g 3,5- diaminourea -4- chlorobenzene acetic acid isopropyl esters, 85 DEG C of solidification 15h are obtained the composite modified poly- ammonia of organosilicon/nano-ZnO
Ester elastomer.
Embodiment 4
(1) preparation of polytetramethylene ether diol PTMEG1000/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl-triethoxysilicane is added into 40.5g polytetramethylenes
Bis- acetic acid di-n-butyl tin of ether glycol PTMEG1000,0.4g, stirring reaction 5h at 70 DEG C obtain polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, 0.5～2h of ultrasound obtains nano zinc oxide fluid dispersion.
C. by 12g polymer As, 24g nano zinc oxide fluid dispersions, 1g distilled water, 100g toluene, in 60 DEG C of stirring reactions 6
Hour, then in 70 DEG C of rotary evaporations, toluene and water are removed, the nano oxidized zinca of polytetramethylene ether diol PTMEG1000/ is obtained
Change material.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 30g polytetramethylene ether diol PTMEG1000/ nano zinc oxide hybridization materials, 7g both-end hydroxyl poly dimethyls
Siloxanes (hydroxyl alkyl block, mean molecule quantity be 5000), 100g polypropylene glycol PPG6000,10g isophorone diisocyanates
Ester, bis- acetic acid di-n-butyl tins of 0.3g, under nitrogen protection, in 90 DEG C of stirring reactions 4 hours, add 2g BDOs, 3g
Cyclohexanediol, 0.7g organic silicon defoamers mass parts and 3g 4,4 '-di-2-ethylhexylphosphine oxide (3- chloro-2,6-diethyl anilines), 80 DEG C are solid
Change 20h, the composite modified polyurethane elastomer of organosilicon/nano-ZnO is obtained.
Embodiment 5
(1) preparation of polypropylene oxide ether trihydroxylic alcohol 1618A/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl-triethoxysilicane is added into 202g polypropylene oxide ethers
Trihydroxylic alcohol 1618A, 0.5g dibutyl tin dilaurate, stirring reaction 4h at 80 DEG C obtain polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, ultrasonic 2h obtains nano zinc oxide fluid dispersion.
C. by 22g polymer As, 12g nano zinc oxide fluid dispersions, 1.5g distilled water, 100g toluene, in 60 DEG C of stirring reactions
7 hours, then in 70 DEG C of rotary evaporations, toluene and water are removed, the nano oxidized zinca of polypropylene oxide ether trihydroxylic alcohol 1618A/ is obtained
Change material.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 30g polypropylene oxide ether trihydroxylic alcohol 1618A/ nano zinc oxide hybridization materials, 12g both-end hydroxyl poly dimethyl silicon
Oxygen alkane (hydroxyl alkyl block, mean molecule quantity be 3000), 91g polytetramethylene ether diol PTMEG1000,9g polypropylene oxide ethers
Hexahydroxylic alcohols (molecular weight is 10000), 34g PPDIs and 0.5g dibutyl tin dilaurates, under nitrogen protection,
80 DEG C of stirring reactions 5 hours, add two hydroxyl ethyl ester of 3g p-phthalic acids, 2.0g mineral oil defoaming agents, 17g diethyltoluenes two
Amine, 80 DEG C of solidification 20h, is obtained the composite modified polyurethane elastomer of organosilicon/nano-ZnO.
Embodiment 6
(1) preparation of polypropylene glycol PPG200/ nano zinc oxide hybridization materials
A. under nitrogen protection, 10g 3- NCOs propyl-triethoxysilicane is added into 8.1g polypropylene glycols
PPG200, stirring reaction 4h at 50 DEG C, obtains polymer A.
B. 10g nano zine oxides are scattered in 100g toluene, ultrasonic 2h obtains nano zinc oxide fluid dispersion.
C. it is by 5g polymer As, 10g nano zinc oxide fluid dispersions, 1g distilled water, 100g toluene, little in 60 DEG C of stirring reactions 6
When, then in 70 DEG C of rotary evaporations, toluene and water are removed, polyether polyol/nano zinc oxide hybridization material is obtained.
(2) preparation of the composite modified polyurethane elastomer of organosilicon/nano-ZnO
By 14g polypropylene glycol PPG200/ nano zinc oxide hybridization materials, double hydroxyl-terminated injecting two methyl siloxane (the hydroxyl hydrocarbon of 9g
Base is blocked, mean molecule quantity be 2000), 100g polypropylene oxide ether dihydroxylic alcohols N210,40g toluene di-isocyanate(TDI)s and 0.2g bis-
Butyl tin dilaurate stannum, under nitrogen protection, in 80 DEG C of stirring reactions 4 hours, add 3g trimethyolol propane monoallyl ethers,
1.5g mineral oil defoaming agents, 12g dimethythiotoluene diamines, 80 DEG C of solidification 20h, are obtained organosilicon/nano-ZnO composite modified
Polyurethane elastomer.
Comparative example 1：Pure polyurethane elastomer
By 100g polypropylene oxide ether dihydroxylic alcohols N220,17.4g toluene di-isocyanate(TDI)s, 0.4g stannous octoates, in nitrogen
Under protection, in 80 DEG C of stirring reactions 6 hours, 0.1g organic silicon defoamers, 9g dimethythiotoluene diamines, 80 DEG C of solidifications are added
20h, is obtained pure polyurethane elastomer.
Comparative example 2：Organic silicon modified polyurethane elastomer
By 6g double hydroxyl-terminated injecting two methyl siloxanes (silicone hydroxyl is blocked, mean molecule quantity be 15000), 100g polyoxygenated third
Alkene ether dihydroxylic alcohols N220,17.5g toluene di-isocyanate(TDI), 0.4g stannous octoates, under nitrogen protection, in 80 DEG C of stirring reactions 6
Hour, add 0.1g organic silicon defoamers, 9g dimethythiotoluene diamines, 80 DEG C of solidification 20h organosilicon/nano-ZnO to be obtained multiple
Close modified polyurethane elastomer.
Comparative example 3：Pure polyurethane elastomer
By 100g polypropylene glycol PPG6000,7.5g isophorone diisocyanate, bis- acetic acid di-n-butyl tins of 0.3g,
Under nitrogen protection, in 90 DEG C of stirring reactions 4 hours, 2g BDOs, 3g cyclohexanediols, 0.7g organic silicon defoamers are added
Mass parts and 2g 4,4 '-di-2-ethylhexylphosphine oxide (3- chloro-2,6-diethyl anilines), 80 DEG C of solidification 20h are obtained pure polyurethane elastomer.
Comparative example 4：Organic silicon modified polyurethane elastomer
By 7g double hydroxyl-terminated injecting two methyl siloxanes (hydroxyl alkyl is blocked, mean molecule quantity be 5000), 100g polypropylene glycols
PPG6000,8.1g isophorone diisocyanate, bis- acetic acid di-n-butyl tins of 0.3g, it is under nitrogen protection, anti-in 90 DEG C of stirrings
Answer 4 hours, add 2g BDOs, 3g cyclohexanediols, 0.7g organic silicon defoamers mass parts and 2g 4,4 '-di-2-ethylhexylphosphine oxide
(3- chloro-2,6-diethyl anilines), 80 DEG C of solidification 20h, is obtained the composite modified polyurethane elastomer of organosilicon/nano-ZnO.
The composite modified polyurethane elastomer of organosilicon/nano-ZnO prepared by embodiment 1～6 and comparative example 1～4
The polyurethane elastomer for preparing carries out performance test, the results are shown in Table 1.
The performance indications of 1 polyurethane elastomer of table
From table 1, embodiment 1 is analyzed compared with comparative example 1,2 and is understood, with pure polyurethane elastomer (comparative example 1)
Compare, the maximum heat weightless temperature of organic silicon modified polyurethane elastomer (comparative example 2) is raised, but its elongation at break, stretching
Declining all occur in intensity and hardness, and the maximum thermal weight loss of the composite modified polyurethane elastomer of organosilicon/nano-ZnO of the present invention
Also purer polyurethane is good for temperature highest, mechanical property；Jing after ultraviolet ageing, the organosilicon/nano-ZnO of the present invention is composite modified poly-
The mechanical property change of urethane elastomer is minimum, illustrates which has preferable resistance to UV aging.
Embodiment 4 is analyzed compared with comparative example 3,4 and is understood, compared with pure polyurethane elastomer (comparative example 3), organosilicon
The maximum heat weightless temperature of modified polyurethane elastomer (comparative example 4) is raised, but its elongation at break, tensile strength and hardness are all
Occur declining, and maximum heat weightless temperature highest, the power of the composite modified polyurethane elastomer of organosilicon/nano-ZnO of the present invention
Also purer polyurethane is good to learn performance；Jing after ultraviolet ageing, the composite modified polyurethane elastomer of organosilicon/nano-ZnO of the present invention
Mechanical property change is minimum, illustrates which has preferable resistance to UV aging.
Above example illustrates that the composite modified polyurethane elastomer of organosilicon/nano-ZnO of the present invention has excellent heat
Performance, mechanical property and anti-uv-ray are learned, the neck such as sports apparatus, clothing, industrial equipment, vehicles is can be widely applied to
In domain, track lanes, garment material, solid tyre, packing ring ball-joint, bushing bearing, sole, rubber roll, tooth are particularly useful for making
Wheel, sieve plate, shaking table, safe automobile air bag etc..
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment
Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the composite modified polyurethane elastomer of a kind of organosilicon/nano-ZnO, it is characterised in that by the component comprising following mass parts
Prepare：25～80 parts of polyether polyol/nano zinc oxide hybridization materials, 6～12 parts of double hydroxyl-terminated injecting two methyl siloxanes,
100 parts of polyether polyol, 10～60 parts of diisocyanate, 0.1～0.5 portion of organo-metallic catalyst, 0～5 part of chain extender, 0.1
～2.0 parts of defoamer, 3～17 parts of firming agent；
Described polyether polyol/nano zinc oxide hybridization material has the structure shown in following structural formula：
Wherein, R is In at least one；The knot of above-mentioned R
Structure formula is corresponding in turn to the polyether Glycols that molecular weight is 200～10000, polyether-tribasic alcohol, polyethers tetrahydroxylic alcohol, five yuan of polyethers
Alcohol, polyethers hexahydroxylic alcohols；M=3～172；N=1～58；K=1～43；P=1～35；Q=1～29；
Polyether polyol/the nano zinc oxide hybridization material is prepared by the preparation method for comprising the steps of：
(1) by isocyanato silanes coupling agent, polyether polyol, organo-metallic catalyst mixing, stirring reaction is polymerized
Thing A；
(2) by polymer A, nano zinc oxide fluid dispersion, water, toluene mixing obtained in step (1), stirring reaction obtains polyethers
Polyhydric alcohol/nano zinc oxide hybridization material；
The composite modified polyurethane elastomer of the organosilicon/nano-ZnO is prepared by the method for comprising the steps of：
Take 25～80 mass parts polyether polyol/nano zinc oxide hybridization material, 6～12 mass parts both-end hydroxyl poly dimethyl silicon
Oxygen alkane, 100 mass parts polyether polyol and 10～60 mass parts diisocyanate, 0.1～0.5 mass parts organo-metallic catalyst
Mixing, stirring reaction add 0～5 mass parts chain extender, 0.1～2.0 mass parts defoamer, 3～17 mass parts firming agent,
It is heating and curing, the composite modified polyurethane elastomer of organosilicon/nano-ZnO is obtained.
2. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Step
(1) in, the mass ratio of isocyanato silanes coupling agent used and polyether polyol is 10:40.5～10:146；
In step (2), the mass ratio of polymer A, nano zinc oxide fluid dispersion, water and toluene used is (12～50):(10～
30):(1～4):(100～200).
3. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Step
(2) concentration of nano zinc oxide fluid dispersion described in is 8～12wt%；
Isocyanato silanes coupling agent described in step (1) is selected from 3- NCOs propyl trimethoxy silicane and 3- is different
At least one in cyanic acid ester group propyl-triethoxysilicane；
Polyether polyol described in step (1) selected from the polypropylene oxide ethoxylated polyhydric alcohol that molecular weight is 200～10000, poly- four
At least one in hydrogen furan ethoxylated polyhydric alcohol and tetrahydrofuran-propylene oxide polyol；
Organo-metallic catalyst described in step (1) is selected from stannous octoate, dibutyl tin dilaurate, lead octoate and two acetic acid
At least one in di-n-butyl tin.
4. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Step
(1) stirring reaction described in is stirring reaction 4～6 hours at 50～80 DEG C；Stirring reaction described in step (2) be
60～70 DEG C of stirring reactions 6～8 hours.
5. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Described
Double hydroxyl-terminated injecting two methyl siloxanes are hydroxyl alkyl terminated polysiloxane that mean molecule quantity is 2000～50000 and silicone hydroxyl envelope
At least one in the polysiloxanes of end；
Described polyether polyol is more selected from the polypropylene oxide ethoxylated polyhydric alcohol, PTMG that molecular weight is 200～10000
At least one in first alcohol and tetrahydrofuran-propylene oxide polyol；
Described diisocyanate be selected from toluene di-isocyanate(TDI), diphenyl methane -4,4 '-diisocyanate, isophorone two
Isocyanates, hexamethylene diisocyanate, PPDI, XDI, 1,4- hexamethylene two
At least one in isocyanates and naphthalene -1,5- diisocyanate.
6. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Described
Organo-metallic catalyst in stannous octoate, dibutyl tin dilaurate, lead octoate and the two acetic acid di-n-butyl tins at least
It is a kind of；
Described chain extender is selected from 1,4- butanediols, ethylene glycol, Propylene Glycol, hexanediol, cyclohexanediol, p-phthalic acid dihydroxy second
At least one in ester and trimethyolol propane monoallyl ether；
Described defoamer is at least one in organic silicon defoamer and mineral oil defoaming agent；
Described firming agent is dimethythiotoluene diamine, 3,3 '-two chloro- 4,4 '-diaminodiphenyl-methanes, diethyltoluene
One kind in diamidogen, 3,5- diaminourea -4- chlorobenzene acetic acids isopropyl ester and 4,4 '-di-2-ethylhexylphosphine oxide (2,6- diethyl -3- chloroanilines).
7. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to claim 1, it is characterised in that：Described
Stirring reaction refers in 75～90 DEG C of stirring reactions 3～5 hours；The described finger that is heating and curing solidifies 10～20h at 80～90 DEG C.
8. the composite modified polyurethane elastomer of organosilicon/nano-ZnO according to any one of claim 1～7 is in locomotorium
Application in tool, clothing, industrial equipment, field of vehicles.
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| CN105237729B (en) * | 2015-10-09 | 2019-01-01 | 滁州环球聚氨酯科技有限公司 | A kind of erosion resistant polyurethane material |
| CN105237731B (en) * | 2015-10-09 | 2017-12-12 | 滁州环球聚氨酯科技有限公司 | A kind of heat-resistant antifriction polyurethane material |
| CN105399917B (en) * | 2015-11-03 | 2020-12-15 | 杭州吉华高分子材料股份有限公司 | Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof |
| CN109054634A (en) * | 2018-08-09 | 2018-12-21 | 望江县天长光学仪器有限公司 | A kind of polycarbonate lens coating |
| 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 |
| CN113040475B (en) * | 2021-03-08 | 2022-07-01 | 深圳市鑫卡立方智能科技有限公司 | Clean silica gel wrist strap and production process thereof |
| CN112754958B (en) * | 2021-03-17 | 2022-10-18 | 上海迪摩化学科技有限公司 | V73E modified shielding agent, preparation method and application thereof in skin care products |
| CN114196310A (en) * | 2021-12-22 | 2022-03-18 | 青岛东鹏环保科技有限公司 | Low-temperature-resistant anticorrosive paint and preparation method and application thereof |
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