CN102731731A - Preparation method of hyperbranched polyurethane/polyacrylate damping material - Google Patents
Preparation method of hyperbranched polyurethane/polyacrylate damping material Download PDFInfo
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Abstract
The invention discloses a preparation method of hyperbranched polyurethane/polyacrylate damping material, which comprises the following preparation steps: (1) partially end capped waterborne polyurethane prepolymer is synthesized by a traditional method; (2) the self-made hydroxyl-terminated hyperbranched polyurethane is reacted with isocyanate group to be grafted to the waterborne polyurethane prepolymer, thereby obtaining hyperbranched waterborne polyurethane prepolymer; (3) triethylamine and partial vinyl monomer are added in the prepolymer to ionize, and added with water to disperse to obtain polyurethane/vinyl monomer dispersing liquid under high-speed stirring; (4) the temperature of the dispersing liquid is raised to 65-80 DEG C, and the dispersing liquid is dripped with residual vinyl monomer, initiator and a crosslinking agent to react for 2-6h in heat preservation; and the reacted liquid is cooled to obtain the hyperbranched polyurethane/polyacrylate emulsion. The material obtained by coating the hyperbranched polyurethane/polyacrylate emulsion and curing has the characteristics of excellent damping performance and heat resistance, can be used in the fields such as automobile industry and constructional engineering, and has wide application prospect.
Description
One, technical field
The present invention relates to a kind of preparation method of damping material, the preparation method of specifically a kind of super branched polyurethane/polyacrylic ester damping material.
Two, background technology
The harm of sound pollution and generation thereof more and more receives people's attention; Damping material and Study on Technology exploitation also more and more receive scholar's extensive concern, are widely used in fields such as automotive industry, construction work, mechanical industry, space flight and aviation, naval vessels.Damping material is meant and changes the solid mechanical vibrational energy into heat energy and the material that dissipates, is mainly used in vibration and noise reducing.The high molecular polymer damping material be a kind of be that matrix suppresses vibration and reduces the functional materials of noise with the polymkeric substance.In polymer damping material; It is narrow that the Tg of general homopolymer and random copolymers changes warm territory; Applicable temperature territory is limited, and effective damping temperature territory (tan δ >=0.3) often has only 20-30 ℃, therefore need carry out the polymkeric substance of different Tg transformation ranges compound.As far back as the 1950's; At first develop excellent property, superpolymer damping material easy to use by West Germany; The vibration and noise reducing that is widely used in various device, one of salient features that polymer damping material possessed of getting up of this development in period is the damping temp field width, damping factor is high.Subsequently, states such as the U.S., West Europe, Japan have also carried out the research of damping material aspect successively and have obtained the excellent research achievement.The domestic research work of carrying out damping material before and after the seventies is started late but progress is very fast, from different aspects development damping materials, has obtained very big achievement such as Qingdao Haiyang coating institute, China Engineering Physics Research Institute etc.
Urethane itself has a large amount of hydrogen bonds, micro phase separation structure to a certain degree and higher damping factor by the soft section block polymer of forming with hard section, in the damping field application is arranged in recent years more.Hyperbranched polymer has highly branched structure; Viscosity is low; Characteristics such as good solubility, and contain a large amount of active function groups and be prone to carry out terminal groups modification, so can realize and the programmable consistency of linear molecule; Carried out its as the additive of polymer blending improving the rheological property of polymer processing, the research of the toughness of polymkeric substance etc.The molecular structure of hyperbranched polymer is special, and is dispersed big and have a large amount of side chains and end group, and molecular motion has multiplicity, is expected to have good damping performance.In addition, it is low that it has viscosity, and solvability is high, characteristics such as good film-forming property, and synthesis technique is simple, and cost is low, helps scale operation, so hyperbranched polymer has important theoretical research value and wide application prospect.
The technology of preparation high damping damping material with wide-temperature range has a lot, like blend, grafting, block, crosslinked and interpenetrating polymer networks (IPN).Wherein IPN technology nearly two obtains fast development and application during the last ten years; It is preparation high-performance damping material effective means; Owing to running through each other, tangling to produce to force and dissolve each other and synergistic effect between the interpenetrating(polymer)networks; Make the IPN material have the characteristics that are separated on not phase-splitting and the microcosmic on the macroscopic view, thereby created condition for preparation wide temperature (wideband) damping material.Interpenetrating net polymer latex (LIPN) is dispersion medium with water, compliance with environmental protection requirements, and Chinese scholars is more as the matrix research of damping system with PS, polyurethane-base and polyacrylate based.Existing many about the research of polyurethane/polyacrylate latex interpenetrating(polymer)networks IPN in recent years, but the preparation of relevant super branched polyurethane/polyacrylic ester LIPN does not also appear in the newspapers.
Three, summary of the invention
The present invention aims to provide the preparation method of a kind of super branched polyurethane/polyacrylic ester damping material, and technical problem to be solved is to improve the damping capacity and the resistance toheat of polymkeric substance, obtains the damping material of the high dissipation factor in water-based wide temperature territory.
The present invention passes through homemade superbrnaching end-hydroxy urethane as polyurethane cross-linking agent; Add in the polyurethane prepolymer; Obtain the hyperbranched aqueous polyurethane performed polymer; The polymerization of re-initiation acrylate monomer makes hyperbranched aqueous polyurethane/polyacrylate interpenetrating network polymer (HBPUA-IPN), has good damping property and resistance toheat.
The preparation method of super branched polyurethane of the present invention/polyacrylic ester damping material comprises the preparation of base polyurethane prepolymer for use as, each unit process of preparation, latex interpenetrating polymerization and curing of hyperbranched aqueous polyurethane performed polymer:
1) preparation of said base polyurethane prepolymer for use as is with vulcabond and mixed 60-100 ℃ of reaction 0.5-4 hour that be incorporated in of oligopolymer divalent alcohol in nitrogen atmosphere; Add chainextender subsequently; Continue reaction 0.5-3 hour in 60-100 ℃; Add end-capping reagent then, obtained base polyurethane prepolymer for use as in 1-4 hour in 40-80 ℃ of reaction;
Said vulcabond is selected from isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI) or hexamethylene diisocyanate (HDI);
Said oligopolymer divalent alcohol is selected from polyether Glycols N210, THF homopolymer (PTMEG), polyoxytrimethylene (PPO), polyoxyethylene glycol (PEG), poly-epsilon-caprolactone glycol (PCL), polyethylene glycol adipate glycol (PEA), gathers adipate glycol-propylene glycol ester glycol (PEPA), poly adipate succinic acid ester glycol (PBA) or gathers carbonic acid pinakon esterdiol (PCDL);
Said chainextender comprises hydrophilic chain extender and non-hydrophilic chain extender;
Said end-capping reagent is selected from Rocryl 400 (HEMA), Propylene glycol monoacrylate (HPA) or NMA;
2) preparation of said hyperbranched aqueous polyurethane performed polymer is that superbrnaching end-hydroxy urethane is added in the base polyurethane prepolymer for use as of step 1) preparation, obtains the hyperbranched aqueous polyurethane performed polymer in 1-4 hour in 60-90 ℃ of reaction;
3) said latex interpenetrating polymerization is that the vinyl monomer of hyperbranched aqueous polyurethane performed polymer and 1/3 is mixed and stirs; Add then and add deionized water emulsification behind the neutralizing agent neutralization reaction 5-20min and disperse to obtain dispersion liquid; Under the nitrogen protection said dispersion liquid is warming up to 65-80 ℃; Drip the vinyl monomer of initiator, linking agent and surplus, insulation reaction 2-6 hour, obtain super branched polyurethane/polyacrylate emulsion that solid content is 25-40%;
Said vinyl monomer is made up of hard monomer and soft monomer; Said hard monomer is selected from vinylbenzene (St), TEB 3K (MMA) or vinyl cyanide (AN), and said soft monomer is selected from Bing Xisuandingzhi (BA), ethyl propenoate, vinylformic acid ethylhexyl or NSC 20956; The mol ratio of said hard monomer and soft monomer is 1:0.5-4;
Said neutralizing agent is selected from triethylamine (TEA), ammoniacal liquor or sodium hydroxide;
Said initiator is selected from ammonium persulphate, Potassium Persulphate, azo isobutyronitrile (AIBN) or Lucidol;
Said linking agent is selected from divinylbenzene (DVB), diacrylate diethyl alcohol ester or diacrylate binaryglycol ester;
Each raw material is constructed as follows by mass fraction:
Said hydrophilic chain extender is selected from dimethylol propionic acid (DMPA) or 1,4-butyleneglycol-2-sodium sulfonate; Said non-hydrophilic chain extender is selected from 1,4-butyleneglycol (BDO), 1,3 butylene glycol, glycol ether or terepthaloyl moietie.
Said superbrnaching end-hydroxy urethane prepares as follows:
Under nitrogen protection, vulcabond and the divalent alcohol that contains hydrophilic radical are mixed in the solvent; In 70-90 ℃ of reaction 1-4 hour; Obtain midbody, be cooled to-5 ~ 0 ℃ then, drip the secondary amine that contains two hydroxyls; Be warming up to 40-100 ℃ of reaction 0.5-5 hour after dripping, obtain superbrnaching end-hydroxy urethane (HBPU);
Said vulcabond is selected from isophorone diisocyanate (IPDI), tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI) or hexamethylene diisocyanate (HDI);
The said divalent alcohol that contains hydrophilic radical is selected from dimethylol propionic acid (DMPA) or 1,4-butyleneglycol-2-sodium sulfonate;
Wherein containing the divalent alcohol of hydrophilic radical and the mol ratio of vulcabond is 1:1.5-6; Containing the secondary amine of two hydroxyls and the mol ratio of midbody is 1:1.5-6.
The present invention has the following advantages:
1, to have viscosity low for super branched polyurethane, good film-forming property, and cost is low, raw material characteristics such as be easy to get, technology is simple when therefore preparing, and is convenient to operation.
2, super branched polyurethane has highly branched structure, contains a plurality of hydroxyls in the macromole, and through terminal hydroxy group and-NCO reaction, branch point is more, can the spheroidal compact form of type of obtaining, so can too big influence not arranged to the system viscosity with the increase of molecular weight; In addition, the intramolecular cavity structure of super branched polyurethane helps product and water molecules associates, and has also increased the water dispersible of product;
3, add preceding end-capping reagent and the part-NCO of using of super branched polyurethane and react, make to be difficult for gel in the reaction process.
4, synthetic aqueous polyurethane/polyacrylate latex interpenetrating network emulsion has good damping property and resistance toheat, for the research of super branched polyurethane provides theoretical foundation; In addition, hyperbranched polymer viscosity is little, and reaction is prone to carry out, and helps scale operation, has certain practical value.
Four, description of drawings
Fig. 1 is the TG spectrogram of super branched polyurethane-polyacrylate interpenetrating network polymer of the present invention when different PA content (being differing ethylene base monomer addition).As can beappreciated from fig. 1, along with PA content increases, the heat decomposition temperature of HBPUA-IPN raises, and resistance toheat is good more.Compare with pure urethane; The resistance toheat of HBPUA-IPN obviously improves; Explain that the adding of propenoate can improve the resistance toheat of urethane; The synergistic effect of interpenetrating(polymer)networks makes its thermotolerance be higher than the thermal property of independent a certain component, mainly shows as temperature of initial decomposition and improves temperature raising corresponding when reaching certain percentage with thermal weight loss.PA content increases, and more acrylate monomer can enter into PU micelle inside and carry out polymerization, forms more fine and close network structure, and temperature required when making thermolysis increases, and thermotolerance improves.
Fig. 2 is at St/BA=1/2, under the condition of initiator 1%, and the tan δ-temperature curve of the HBPUA-IPN of different ratios of raw materials under 10Hz.Visible from Fig. 2; A peak appears in the pure urethane (WHBPU) that does not add PA about-30 ℃; Correspond to soft section second-order transition temperature; And damping factor tan δ＜0.4, its damping capacity is compared very poor with the PU/PA matrix material, explain that the adding of propenoate can obviously improve the damping capacity of urethane.The maximum damping factor tan δ max that also can be found out sample HBPUA-IPN-3 and HBPUA-IPN-2 by Fig. 2 is respectively 1.25 and 1.18, and the warm territory of damping factor tan δ＞0.3 is respectively 57 ℃ and 66 ℃, all has the damping temperature domain of damping factor and broad preferably.It can also be seen that, a peak only occurs, explain that PU and PA have fabulous consistency; Increase along with PA component content; Tan δ max and effective damping temperature territory all increase, and the effect of the enhancing damping that has except PA, IPN tangles and makes structure tightr between PU and PA network; Molecule segment motion difficulty increases; Make material when receiving stress, produce distortion and consume more multimachine tool vibrational energy, that is to say to make mechanical vibrational energy more be converted into heat energy, make to have than good damping property.
Five, embodiment
Below in conjunction with embodiment the present invention is done explanation further.Content involved in the present invention is not limited only to following examples.Embodiment 1: the preparation of superbrnaching end-hydroxy urethane
1, each raw material is constructed as follows by mass fraction:
2, specifically prepare process:
Take by weighing IPDI and DMPA is dissolved in N, among the N '-N (DMF), the back that stirs feeds nitrogen; Air in the eliminating system is warming up to 85 ℃ of reaction 1.5h, is cooled to-5 ~ 0 ℃ then; Slowly drip the DMF solution of DEOA; Drip continued and stir 30min, be warming up to 60 ℃ of reaction 2.0h subsequently, obtain super branched polyurethane (HBPU) through underpressure distillation.Measuring its number-average molecular weight with vapour pressure osmometry (VPO) is 3912.
Embodiment 2:
Each raw material is constructed as follows by mass fraction:
1, the preparation of base polyurethane prepolymer for use as
TDI and N210 (relative molecular mass 1000) are added there-necked flask, feed the air in the nitrogen eliminating system,, add DMPA and BDO subsequently, in 75 ℃ of reactions 2.5 hours in 80 ℃ of reactions 2.5 hours; Be cooled to 60 ℃, add HEMA and carry out partially end-blocked reaction 1.5 hours, make base polyurethane prepolymer for use as.
2, the preparation of hyperbranched aqueous polyurethane performed polymer
In the base polyurethane prepolymer for use as of step 2 preparation, add HBPU, obtained the hyperbranched aqueous polyurethane performed polymer in 2 hours, add small amount of acetone and reduce system viscosity in 75 ℃ of reactions.
3, polyreaction
After in the super branched polyurethane performed polymer of step 2 preparation, adding 1/3 St and 1/3 BA below 45 ℃, stirring 20min, add TEA neutralization reaction 15min, in system, add deionized water emulsification then and disperse to obtain dispersion liquid; Under nitrogen protection, dispersion liquid is warming up to 75 ℃, adds the St of surplus, BA, AIBN and the DVB of surplus, insulation reaction 5 hours obtains super branched polyurethane/polyacrylate emulsion after reducing to room temperature.
Super branched polyurethane/the polyacrylate emulsion for preparing is poured in the tetrafluoroethylene mould, was at room temperature left standstill 2-4 days, 60-80 ℃ dry 6-8 hour, prepare the glued membrane that thickness is about 1mm.
Embodiment 3:
Each raw material is constructed as follows by mass fraction:
The preparation method is with embodiment 2.
Embodiment 4:
Each raw material is constructed as follows by mass fraction:
1, the preparation of base polyurethane prepolymer for use as
TDI and PTMEG (relative molecular mass 1000) are added there-necked flask, feed the air in the nitrogen eliminating system,, add DMPA and BDO subsequently, in 75 ℃ of reactions 2.5 hours in 80 ℃ of reactions 2.5 hours; Be cooled to 60 ℃, add HEMA and carry out partially end-blocked reaction 2 hours, make base polyurethane prepolymer for use as.
2, the preparation of hyperbranched aqueous polyurethane performed polymer
In the base polyurethane prepolymer for use as of step 2 preparation, add HBPU, obtained the hyperbranched aqueous polyurethane performed polymer in 2 hours, add small amount of acetone and reduce system viscosity in 75 ℃ of reactions.
3, polyreaction
After in the super branched polyurethane performed polymer of step 2 preparation, adding 1/3 St and 1/3 BA below 45 ℃, stirring 20min, add TEA neutralization reaction 15min, in system, add deionized water emulsification then and disperse to obtain dispersion liquid; Under nitrogen protection, dispersion liquid is warming up to 75 ℃, adds the St of surplus, BA, AIBN and the DVB of surplus, insulation reaction 5 hours obtains super branched polyurethane/polyacrylate emulsion after reducing to room temperature.
Super branched polyurethane/the polyacrylate emulsion for preparing is poured in the tetrafluoroethylene mould, was at room temperature left standstill 2-4 days, 60-80 ℃ dry 6-8 hour, prepare the glued membrane that thickness is about 1mm.
Embodiment 5:
Each raw material is constructed as follows by mass fraction:
The preparation process:
1, the preparation of base polyurethane prepolymer for use as
TDI and N210 (relative molecular mass 1000) are added there-necked flask, feed the air in the nitrogen eliminating system,, add DMPA and BDO subsequently, in 75 ℃ of reactions 2.5 hours in 80 ℃ of reactions 2.5 hours; Be cooled to 60 ℃, add HPA and carry out partially end-blocked reaction 3 hours, make base polyurethane prepolymer for use as.
2, the preparation of hyperbranched aqueous polyurethane performed polymer
In the base polyurethane prepolymer for use as of step 2 preparation, add HBPU, obtained the hyperbranched aqueous polyurethane performed polymer in 2 hours, add small amount of acetone and reduce system viscosity in 75 ℃ of reactions.
3, polyreaction
After in the super branched polyurethane performed polymer of step 2 preparation, adding 1/3 AN and 1/3 BA below 45 ℃, stirring 20min, add TEA neutralization reaction 15min, in system, add deionized water emulsification then and disperse to obtain dispersion liquid; Under nitrogen protection, dispersion liquid is warming up to 75 ℃, adds the AN of surplus, BA, AIBN and the DVB of surplus, insulation reaction 5 hours obtains super branched polyurethane/polyacrylate emulsion after reducing to room temperature.
Super branched polyurethane/the polyacrylate emulsion for preparing is poured in the tetrafluoroethylene mould, was at room temperature left standstill 2-4 days, 60-80 ℃ dry 6-8 hour, prepare the glued membrane that thickness is about 1mm.
Claims (3)
1. the preparation method of super branched polyurethane/polyacrylic ester damping material comprises the preparation of base polyurethane prepolymer for use as, each unit process of preparation, latex interpenetrating polymerization and curing of hyperbranched aqueous polyurethane performed polymer, it is characterized in that:
1) preparation of said base polyurethane prepolymer for use as is with vulcabond and mixed 60-100 ℃ of reaction 0.5-4 hour that be incorporated in of oligopolymer divalent alcohol in nitrogen atmosphere; Add chainextender subsequently; Continue reaction 0.5-3 hour in 60-100 ℃; Add end-capping reagent then, obtained base polyurethane prepolymer for use as in 1-4 hour in 40-80 ℃ of reaction;
Said vulcabond is selected from isophorone diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate or hexamethylene diisocyanate;
Said oligopolymer divalent alcohol is selected from polyether Glycols N210, THF homopolymer, polyoxytrimethylene, polyoxyethylene glycol, poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, gathers adipate glycol-propylene glycol ester glycol, poly adipate succinic acid ester glycol or gathers carbonic acid pinakon esterdiol;
Said chainextender comprises hydrophilic chain extender and non-hydrophilic chain extender;
Said end-capping reagent is selected from Rocryl 400, Propylene glycol monoacrylate or NMA;
2) preparation of said hyperbranched aqueous polyurethane performed polymer is that superbrnaching end-hydroxy urethane is added in the base polyurethane prepolymer for use as of step 1) preparation, obtains the hyperbranched aqueous polyurethane performed polymer in 1-4 hour in 60-90 ℃ of reaction;
3) said latex interpenetrating polymerization is that the vinyl monomer of hyperbranched aqueous polyurethane performed polymer and 1/3 is mixed and stirs; Add then and add deionized water emulsification behind the neutralizing agent neutralization reaction 5-20min and disperse to obtain dispersion liquid; Under the nitrogen protection said dispersion liquid is warming up to 65-80 ℃; Drip the vinyl monomer of initiator, linking agent and surplus, insulation reaction 2-6 hour, obtain super branched polyurethane/polyacrylate emulsion that solid content is 25-40%;
Said vinyl monomer is made up of hard monomer and soft monomer, and said hard monomer is selected from vinylbenzene, TEB 3K or vinyl cyanide, and said soft monomer is selected from Bing Xisuandingzhi, ethyl propenoate, vinylformic acid ethylhexyl or NSC 20956; The mol ratio of said hard monomer and soft monomer is 1:0.5-4;
Said neutralizing agent is selected from triethylamine, ammoniacal liquor or sodium hydroxide;
Said initiator is selected from ammonium persulphate, Potassium Persulphate, azo isobutyronitrile or Lucidol;
Said linking agent is selected from divinylbenzene, diacrylate diethyl alcohol ester or diacrylate binaryglycol ester;
Each raw material is constructed as follows by mass fraction:
2. preparation method according to claim 1 is characterized in that: said hydrophilic chain extender is selected from dimethylol propionic acid or 1,4-butyleneglycol-2-sodium sulfonate; Said non-hydrophilic chain extender is selected from 1,4-butyleneglycol, 1,3 butylene glycol, glycol ether or terepthaloyl moietie.
3. preparation method according to claim 1 and 2 is characterized in that said superbrnaching end-hydroxy urethane prepares as follows:
Under nitrogen protection, vulcabond and the divalent alcohol that contains hydrophilic radical are mixed in the solvent; In 70-90 ℃ of reaction 1-4 hour; Obtain midbody, be cooled to-5 ~ 0 ℃ then, drip the secondary amine that contains two hydroxyls; Be warming up to 40-100 ℃ of reaction 0.5-5 hour after dripping, obtain superbrnaching end-hydroxy urethane;
Said vulcabond is selected from isophorone diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate or hexamethylene diisocyanate;
The said divalent alcohol that contains hydrophilic radical is selected from dimethylol propionic acid or 1,4-butyleneglycol-2-sodium sulfonate;
Wherein containing the divalent alcohol of hydrophilic radical and the mol ratio of vulcabond is 1:1.5-6; Containing the secondary amine of two hydroxyls and the mol ratio of midbody is 1:1.5-6.
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| CN107922522A (en) * | 2015-08-17 | 2018-04-17 | 日立化成株式会社 | Composite material, solder resist photosensitive polymer combination and photosensitive element |
| CN105064036A (en) * | 2015-09-08 | 2015-11-18 | 广东德美精细化工股份有限公司 | Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent |
| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
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