CN108178827A - Antistatic urethane elastomer and preparation method thereof - Google Patents
Antistatic urethane elastomer and preparation method thereof Download PDFInfo
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- CN108178827A CN108178827A CN201711457827.5A CN201711457827A CN108178827A CN 108178827 A CN108178827 A CN 108178827A CN 201711457827 A CN201711457827 A CN 201711457827A CN 108178827 A CN108178827 A CN 108178827A
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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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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- C08G18/30—Low-molecular-weight compounds
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- 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
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- 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
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- 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
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- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention belongs to synthesis of polymer material fields, and in particular to a kind of antistatic urethane elastomer and preparation method thereof.It is made of following raw material：Polymer polyatomic alcohol, isocyanates, chain extender, antioxidant, modified graphene, catalyst.The addition manner of modified graphene is：Modified graphene is added in chain extender, under ultrasound condition, forms modified graphene chain extension agent dispersing liquid.Hydroxyl that modified graphene surface is contained, carboxyl, amino groups are reacted with NCO, the antistatic urethane elastomer obtained by the method for in-situ polymerization, with relatively low surface resistivity and volume resistivity, higher mechanical property, preferable wear-resisting and thermal stability, can apply and the fields such as polyurethane textile.
Description
Technical field
The invention belongs to synthesis of polymer material fields, and in particular to a kind of antistatic urethane elastomer and its preparation side
Method.
Background technology
Thermoplastic polyurethane elastomer has good electrical insulation capability, surface resistivity ρ s (about 1011~1014
Ω) and volume resistivity ρ v (are about 1013~1015Ω m) very big, i.e. conductivity very little.Polyurethane elastomer is in industrial production
It is widely used in product, therefore there is friction during normal use, carries the works such as contact separation collision
With.Easily gather a large amount of charges during these, and the charge that these are largely gathered, can to the health of electronic equipment, people,
Production and living form huge harm, cause fire or explosion even in the environment of having flammable explosive substance.
At present, the common anlistatig method of polyurethane elastomer is addition antistatic agent, these antistatic agents have quaternary ammonium salt
Type surfactant and compound addition type antistatic agent, wherein quaternary ammonium salt cationic surfactant are made using coating or dipping method
Material surface has antistatic property, easy to operate and do not influence the performance of polyurethane material in itself, but there are during antistatic continue
Between shorter, antistatic coating the defects of being easy to be washed away after washing or friction.Compound addition type antistatic agent be mainly graphite,
Inorganic material such as metal, metal oxide etc., additive amount is larger and easy precipitation, greatly reduces the mechanics of polyurethane elastomer
Performance.Its Patent CN 105566685A are mainly that the method for adding conductive color reaches anlistatig purpose, wherein conductive color
Containing a large amount of conductive black in cream, preparation process is complicated, needs first to prepare conductive color, is then then added to elastic polyurethane
In body, additive amount is larger.It is then to prepare antistatic urethane elastomer using two-step method in patent CN 102906173A, first
Isocyanate-terminated prepolymer is prepared, then adds conductive black, additive amount is at least 0.3%, finally obtains antistatic poly-
Urethane elastomer.In short, realizing anlistatig purpose by adding carbon black, there are following defects for this method, and addition is largely
Carbon black easily reunite, difficulties in dispersion needs to add a large amount of carbon black and gets to expected conductive effect.And largely reunite
Carbon black can reduce the intensity of material, toughness etc. again.
Invention content
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of antistatic urethane elastomers, have relatively low
Surface resistivity and volume resistivity, higher mechanical property, preferable wear-resisting and thermal stability, the present invention also provides its systems
Preparation Method.
Antistatic urethane elastomer of the present invention is made of the raw material of following weight percent：
The addition manner of modified graphene of the present invention is：Modified graphene is added in chain extender, under ultrasound condition,
Form modified graphene-chain extension agent dispersing liquid.
Modified graphene is graphene oxide, silane coupler modified graphene, hydroxylating modified graphene, amination change
The mixture of one or more of property graphene or alkylamine modified graphene.
Polymer polyatomic alcohol be polyethylene glycol adipate glycol, polybutylene glyool adipate, polyadipate oneself two
Alcohol esterdiol, polyadipate ethylene glycol-butyl glycol ester diol, polybutyleneadipate-hexylene glycol esterdiol, poly terephthalic acid
Glycol ester glycol, polyethylene terephthalate-butyl glycol ester diol, gathers to benzene polybutylene terephthalate (PBT) glycol
Dioctyl phthalate hexylene glycol esterdiol, polybutylene terephthalate-hexylene glycol esterdiol, polydiethylene glycol sebacate glycol, the poly- last of the ten Heavenly stems
Diacid hexylene glycol esterdiol, polyethylene glycol sebacate glycol, poly- decanedioic acid hexylene glycol-butyl glycol ester diol or poly- decanedioic acid second
One kind in glycol-butyl glycol ester diol, PolyTHF-propylene oxide copolymer glycol or polytetrahydrofuran polyol (PTMG)
Or two kinds of object mixed above.
The molecular weight of polymer polyatomic alcohol is 1000-3000.
Isocyanates is 4,4 '-methyl diphenylene diisocyanate (MDI), naphthalene -1,5- diisocyanate (NDI), hexichol
Methane -3,3 '-dimethoxy-4 ', 4 '-diisocyanate, toluene di-isocyanate(TDI) (TDI), 1,4- cyclohexyl-diisocyanate
(CHDI) or decane -1,10- diisocyanate, one kind in 3,3 '-dimethyl -4,4 '-biphenyl diisocyanate (TODI) or
Two or more mixtures.
Chain extender is ethylene glycol, propylene glycol, methyl propanediol, diethylene glycol, 1,4- butanediols, 1,6-HD or new penta
The mixture of one or more of glycol.
Antioxidant is 2,6 di tert butyl 4 methyl phenol (246), 3,5- di-tert-butyl-hydroxy phenyls propionic acid 18
Ester (1076), triethylene-glycol bis- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionic ester] (245), four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), the bis- [3- (3,5- di-t-butyl -4- hydroxyls of thio diethylene
Phenyl) propionic ester] (1035), one or both of triphenyl phosphite (TTP) or phosphorous acid three (nonyl phenyl ester) (TNP) with
On mixture.
Mixture of the catalyst for one or more of organo-bismuth, organotin or titanate ester.
The preparation method of antistatic urethane elastomer of the present invention, includes the following steps：
(1) polymer polyatomic alcohol, antioxidant and catalyst are mixed and are kept the temperature at 95-105 DEG C, isocyanates heat preservation
40-60 DEG C of temperature；
(2) modified graphene is added in chain extender, under ultrasound condition, forms modified graphene-chain extender dispersion
Liquid, is heated to 50-60 DEG C of heat preservation, and ultrasonic time is 2-5 hours.
(3) by the isocyanates and modified graphite after the mix products of polymer polyatomic alcohol, antioxidant and catalyst, heat preservation
Antistatic urethane elastomer is obtained by the reaction by double screw extruder in alkene-chain extension agent dispersing liquid three.
(4) by the isocyanates and modified graphite after the mix products of polymer polyatomic alcohol, antioxidant and catalyst, heat preservation
Antistatic urethane elastomer is obtained by the reaction by double screw extruder in alkene-chain extension agent dispersing liquid three.
Step (3) is：Under the conditions of 180-210 DEG C, by the mix products of polymer polyatomic alcohol, antioxidant and catalyst,
Isocyanates and modified graphene-chain extension agent dispersing liquid three after heat preservation is obtained by the reaction antistatic poly- by double screw extruder
Urethane elastomer, the screw speed of double screw extruder is 180-200rmp.
As a preferred technical solution, the preparation method of antistatic urethane elastomer of the present invention uses one
Footwork synthesizes, including following synthesis step：
(1) polymer polyatomic alcohol of metering, antioxidant, catalyst etc. are added to the reaction equipped with mechanical agitation and temperature control
In kettle A, set temperature is 95-105 DEG C；Diisocyanate is positioned in reaction kettle B, set temperature is 40-60 DEG C；
(2) chain extender, modified graphene are positioned in reaction kettle C, ultrasonic disperse 2-5 hours, form antistatic agent-expansion
Chain agent dispersing liquid, set temperature are 50-60 DEG C；
(3) treat that each temperature of reaction kettle is stablized, by carrying the perfusion system of accurate measurement, by the original in reaction kettle A, B and C
Expect component, after being thoroughly mixed by metering pump according to the weight percent accurate measurement shared by every component, implantation temperature is
It is reacted in 180-210 DEG C of double screw extruder, and passes through twin-screw reactive extrursion, granulation underwater obtains anti-static thermoplastic and gathers
Urethane adhesive particle, wherein screw speed are 180-200rmp.
Compared with prior art, the present invention has the following advantages：
(1) modified graphene and chain extender are formed into stable modified graphene-chain extension agent dispersing liquid by ultrasonic disperse,
And hydroxyl that modified graphene surface is contained, carboxyl, amino groups are reacted with-NCO during the reaction, pass through in-situ polymerization
The obtained antistatic urethane elastomer of method.Such material has relatively low surface resistivity and volume resistivity, higher
Mechanical property, preferable wear-resisting and thermal stability, the surface resistivity of polyurethane elastomer of the present invention is 1.2 × 104Ω-106
Ω；Volume resistivity is 1.4 × 104-106Ω·m；Tensile strength is up to 58.2Mpa, can be applied and polyurethane textile field.
(2) modified graphene is as antistatic agent, and additive amount is few, and antistatic effect is apparent, by the method for in-situ polymerization,
And antistatic agent is allowed to participate in reaction, good dispersion effect can not only be reached in this way, increase conductive path, improve antistatic energy
Power, and antistatic agent is embedded into polyurethane elastomer strand, hence it is evident that improve mechanical property.
(3) present invention makes modified graphene participate in segment reaction, the dispersibility of modified graphene is improved, even if very little adds
Dosage can also form continuous conductive path in elastic polyurethane body.
Specific embodiment
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of antistatic urethane elastomer, by weight score meter are mainly prepared by the following raw material：
(1) polybutylene glyool adipate (M-1000), antioxidant 1010, organotin are added to instead by weight percentage
It answers in kettle A, nitrogen protection, it is 95 DEG C to keep reaction kettle A temperature, and is stirred in reaction kettle A.By MDI by weight
Percentage is added in reaction kettle B, and nitrogen protection, it is 40 DEG C to keep temperature of reaction kettle.
(2) 1,4-butanediol, graphene oxide are added to according to weight percent in reaction kettle C, and in ultrasonic disperse 2
Hour, graphene oxide-Isosorbide-5-Nitrae butanediol dispersion liquid is formed, nitrogen protection, it is 55 DEG C to keep temperature of reaction kettle.
(3) treat that each temperature of reaction kettle is stablized, by carrying the perfusion system of accurate measurement, by the original in reaction kettle A, B and C
Expect component, by metering pump according to the weight of raw material in weight percent accurate measurement three kettles A, B and C shared by every component,
And after being delivered to and being thoroughly mixed at pouring head, reactive extrursion in 180 DEG C of double screw extruder is injected into, by making under water
Antistatic urethane elastomer particle is made in grain, and wherein screw speed is 200rmp.
Embodiment 2
A kind of antistatic urethane elastomer, by weight score meter are mainly prepared by the following raw material：
Specific preparation process is same as Example 1, and difference is：Reaction kettle A holding temperatures are 100 DEG C, and reaction kettle B is protected
Temperature is 50 DEG C, and reaction kettle C holding temperatures are 50 DEG C, and hydroxylating modified graphene and 1,6- hexylene glycol ultrasonic disperse time is
4 hours, form hydroxylating modified graphene -1,6- hexylene glycol dispersion liquid；The temperature of double screw extruder is 210 DEG C, and screw rod turns
Speed is 190rmp.
Embodiment 3
A kind of antistatic urethane elastomer, by weight score meter are mainly prepared by the following raw material：
Specific preparation process is same as Example 1, and difference is：Reaction kettle A holding temperatures are 98 DEG C, and reaction kettle B is protected
Temperature is 60 DEG C, and reaction kettle C holding temperatures are 58 DEG C, and amination modified graphene and 1,6- hexylene glycol ultrasonic disperse time is
4 hours, form amination modified graphene -1,6- hexylene glycol dispersion liquid；The temperature of double screw extruder is 180 DEG C, and screw rod turns
Speed is 180rmp.
Embodiment 4
A kind of antistatic urethane elastomer, by weight score meter are mainly prepared by the following raw material：
Specific preparation process is same as Example 1, and difference is：Reaction kettle A holding temperatures are 105 DEG C, and reaction kettle B is protected
Temperature is 55 DEG C, and reaction kettle C holding temperatures are 60 DEG C, when silane coupler modified graphene is with Isosorbide-5-Nitrae butanediol ultrasonic disperse
Between for 5 hours, form silane coupler modified graphene -1,4-butanediol dispersion liquid；The temperature of double screw extruder is 210
DEG C, screw speed 180rmp.
Comparative example 1
A kind of adhesive for polyurethane, by weight score meter are mainly prepared by the following raw material：
For specific preparation process with embodiment 4, difference is that C reaction kettles are not added with modified graphene.
Product prepared by embodiment 1-4 and comparative example 1 is tested for the property, the results are shown in Table 1.
1 properties of product testing result of 1 embodiment 1-4 of table and comparative example
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Hardness (Shao A) | 70D | 93A | 80A | 73A | 70A |
| Tensile strength (MPa) | 58.2 | 45.4 | 38.7 | 36.1 | 30.6 |
| Elongation at break (%) | 453 | 534 | 562 | 592 | 643 |
| Surface resistivity (Ω) | 1.4×106 | 5.3×105 | 4.6×104 | 1.2×104 | 3.8×1014 |
| Volume resistivity (Ω m) | 2.3×06 | 8.5×105 | 6.2×104 | 1.3×104 | 6.9×1014 |
Anti-static thermoplastic polyurethane elastomer provided by the invention has compared with existing thermoplastic polyurethane：It is higher
Strength pull intensity, hardness range is wide, especially with relatively low surface resistivity and volume resistivity, has good anti-quiet
Electrical property can be widely used in the fields such as textile clothing, medical instrument.
Claims (10)
1. a kind of antistatic urethane elastomer, it is characterised in that：It is made of the raw material of following weight percent：
The addition manner of modified graphene is：Modified graphene is added in chain extender, under ultrasound condition, forms modified stone
Black alkene-chain extension agent dispersing liquid.
2. antistatic urethane elastomer according to claim 1, it is characterised in that：Modified graphene is graphite oxide
In alkene, silane coupler modified graphene, hydroxylating modified graphene, amination modified graphene or alkylamine modified graphene
One or more kinds of mixtures.
3. antistatic urethane elastomer according to claim 1, it is characterised in that：Polymer polyatomic alcohol is polyadipate
Glycol ester glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyadipate ethylene glycol-butanediol
Esterdiol, polybutyleneadipate-hexylene glycol esterdiol, polyethylene terephthalate glycol, poly terephthalic acid fourth two
Alcohol esterdiol, polyethylene terephthalate-butyl glycol ester diol, poly terephthalic acid hexylene glycol esterdiol, poly- terephthaldehyde
Sour butanediol-hexylene glycol esterdiol, polydiethylene glycol sebacate glycol, poly- decanedioic acid hexylene glycol esterdiol, poly- decanedioic acid second two
Alcohol esterdiol, poly- decanedioic acid hexylene glycol-butyl glycol ester diol or poly- decanedioic acid ethylene glycol-butyl glycol ester diol, PolyTHF-
The object mixed above of one or both of propylene oxide copolymer glycol or polytetrahydrofuran polyol.
4. antistatic urethane elastomer according to claim 3, it is characterised in that：The molecular weight of polymer polyatomic alcohol is
1000-3000。
5. antistatic urethane elastomer according to claim 1, it is characterised in that：Isocyanates is 4,4 '-diphenyl
Methane diisocyanate, naphthalene -1,5- diisocyanate, diphenyl-methane -3,3 '-dimethoxy-4 ', 4 '-diisocyanate, toluene
Diisocyanate, 1,4- cyclohexyl-diisocyanate, decane -1,10- diisocyanate or 3,3 '-dimethyl -4,4 '-biphenyl
The mixture of one or more of diisocyanate.
6. antistatic urethane elastomer according to claim 1, it is characterised in that：Chain extender for ethylene glycol, propylene glycol,
The mixing of one or more of methyl propanediol, diethylene glycol, 1,4- butanediols, 1,6-HD or neopentyl glycol
Object.
7. antistatic urethane elastomer according to claim 1, it is characterised in that：Antioxidant for 2,6- di-t-butyls-
Bis- [the β-(3- tertiary butyl -4- hydroxyls of 4- methylphenols, 3,5- di-tert-butyl-hydroxy phenyl propionic acid octadecyl ester, triethylene-glycol
Base -5- aminomethyl phenyls) propionic ester], four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, thio diethyl
In support bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic esters], triphenyl phosphite or phosphorous acid three (nonyl phenyl ester)
One or more kinds of mixtures.
8. antistatic urethane elastomer according to claim 1, it is characterised in that：Catalyst is organo-bismuth, organotin
Or the mixture of one or more of titanate ester.
9. a kind of preparation method of any antistatic urethane elastomers of claim 1-8, it is characterised in that：Including with
Lower step：
(1) polymer polyatomic alcohol, antioxidant and catalyst are mixed and are kept the temperature at 95-105 DEG C, isocyanates is heated to
40-60 DEG C of heat preservation of temperature；
(2) modified graphene is added in chain extender, under ultrasound condition, forms modified graphene-chain extension agent dispersing liquid, add
Heat to 50-60 DEG C heat preservation；
(3) by the mix products of polymer polyatomic alcohol, antioxidant and catalyst, heat preservation after isocyanates and modified graphene-
Antistatic urethane elastomer is obtained by the reaction by double screw extruder in chain extension agent dispersing liquid three.
10. the preparation method of antistatic urethane elastomer according to claim 9, it is characterised in that：
Ultrasonic time is 2-5 hours in step (2)；
Step (3) is：Under the conditions of 180-210 DEG C, by the mix products of polymer polyatomic alcohol, antioxidant and catalyst, heat preservation
Antistatic polyurethane is obtained by the reaction by double screw extruder in isocyanates and modified graphene-chain extension agent dispersing liquid three afterwards
Elastomer, the screw speed of double screw extruder is 180-200rmp.
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