CN1752140A - Preparation of wide temperature range polyacry late/polyurethane/polysiloxane damping latex - Google Patents
Preparation of wide temperature range polyacry late/polyurethane/polysiloxane damping latex Download PDFInfo
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- CN1752140A CN1752140A CN 200410051529 CN200410051529A CN1752140A CN 1752140 A CN1752140 A CN 1752140A CN 200410051529 CN200410051529 CN 200410051529 CN 200410051529 A CN200410051529 A CN 200410051529A CN 1752140 A CN1752140 A CN 1752140A
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Abstract
A damping polyacrylate/polyurethane/polysiloxane latex with wide temp range for the vibration damping and silencing is prepared through self-emulsifying of polyurethane to obtain a prepolymer emulsion A with active vinyl radicals, polymerizing organic siloxane in the A to obtain the semi-interpenetratic network type prepolymer emulsion B, and copolymerizing acrylate in B to obtain the grafted-crosslinked network type damping latex C. Its advantages are high damping factor, wide vitrification temp range, high antiageing performance and excellent adhesion and mechanical performance.
Description
Technical field:
The present invention relates to the preparation method of a kind of wide temperature territory polyacrylic ester/urethane/polysiloxane damping latex, belong to functional high polymer material field.More particularly, the present invention relates to show the technology of preparing of the polyacrylic ester/urethane/polysiloxane interpenetrating(polymer)networks damping latex of broad damping use temperature scope, the high damping factor, excellent adhesiveproperties and mechanical property.
Background technology:
Damping just is meant that changing thermal dissipation into by the energy with mechanical vibration and sound vibration falls, thereby reaches the purpose of vibration-absorbing and silencing.Along with the raising of science and technology development, quality of life and the reinforcement of environmental protection consciousness; the damping material is had higher requirement; be subjected to increasing attention, be widely used in fields such as space flight, aviation, shipbuilding, military project, building, automobile, electronic instrument.Polymkeric substance viscoelastic damping material damping is best, has better mechanical property simultaneously, uses extensively, and development is fast.
At present, polymkeric substance viscoelastic damping material great majority are matrix with urethane, polyacrylic ester, carry out modification.For example patent publication No. CN1033814A provides the method for a kind of synthesizing new damping material-AB-cross-linked polymer, utilizes the end capped polyurethane prepolymer of thiazolinyl to be the B chain, is that the A chain has synthesized the AB-cross-linked polymer with polystyrene, polymethacrylate etc.And CN 85104749A has reported the urethane that is formed by poly-cyclopropane dibasic alcohol by forming the damping material that a step IPN makes with Resins, epoxy, and damping temperature domain is greater than 100 ℃, and damping value (tg δ) has good clinging power greater than 0.4 to substrate.The disclosed interpenetrating polymer networks wide temperature band damping adhesive of disclosure of the Invention CN1400270A is to be formed by base polyurethane prepolymer for use as and acrylate copolymer blended glue and polyurethane curing agent and the blending of polyacrylic ester solidifying agent, two component tackiness agent force blend, form interpenetrating polymer networks wide temperature band damping adhesive.The damping material of these patent reports has good damping performance and heat-resisting, mechanical toughness, but be simple urethane, polyacrylic ester and material modified, do not relate to compounding technology fully with organosilicon polymer, the damping temperature range of material is still broad inadequately, simultaneously, the damping material of patent report is a solvent-borne type, has problem of environmental pollution.
Round development of new aqueous, environmental protective, high-performance wide temperature range damping polymer materials, people have carried out unremitting effort, and advanced polymer interpenetration network technology (IPN technology) is the effective way of the wide temperature of preparation high-performance territory polymkeric substance viscoelastic damping material.Patent CN 85104739A has reported the method for utilizing L-IPN latex preparation one class wide temperature territory or assigned temperature region clustering thing viscoelastic damping material earlier, system is chosen as polystyrene network and polyacrylic ester network, can also prepare more polynary network structure as required.CN 85104741 A then provide a kind of method that can improve cross-linked emulsion polymer (IPN) damping material damping capacity and mechanical property, when being synthetic latex IPN damping material, in the monomer of an one component or two components, add a certain amount of unsaturated fatty acids, add a certain amount of alkali or salts solution behind synthetic the finishing again in emulsion, then its damping capacity and mechanical property all are significantly increased behind the emulsion film forming.Though these patents have adopted the IPN synthetic technology, but these patented materials are not polyacrylic ester/urethane/polysiloxane matrix materials, do not relate to compounding technology with organosilicon polymer yet, more be not the technology of preparation polyacrylic ester/urethane/polysiloxane damping IPN latex, it is not enough that the damping temperature domain scope of material and mechanical property are still disliked.
Organo-silicone rubber second-order transition temperature (Tg) is-120 ℃, is a kind of polymer materials of effectively widening the damping function district, and is at present few to the patent report of organosilicon damping material, to the report of organosilicon damping latex still less.The open CN 1410485A of Chinese patent reports a kind of preparation method of wide temperature wide spectrum polyacrylic acid ester ester/polysiloxane composite damping rubber, be characterized in adopting the sulfuration of polysiloxane and polyacrylate blending, widen the low temperature damping district of polyacrylic ester, be that parent passes through mutually with poly-(methyl) acrylate sequence again with the blended rubber, widen the high temperature damping district of compounded rubber, make the height and the controllable broad temperature, broadband composite damping rubber of width in polysiloxane/polyacrylic ester damping function district.This patent has prepared polysiloxane/polyacrylic ester damping material, but what adopt is the technology that blend is extruded, and the material that obtains is the damping rubber piece, rather than damping latex.Publication number CN 1376736A has reported the preparation method of polysiloxane/poly-(methyl) alkyl acrylate damping material, be characterized in α, alpha, omega-dihydroxy polysiloxane oligomer and (methyl) alkyl acrylate, in the presence of linking agent, catalyzer and initiator, add in the same reactor that has a stirring, mix mold, vacuum high-temperature reaction 24 hours, the interpenetrating polymer networks damping material at a glass transition peak of acquisition.Have problem of environmental pollution in the preparation process of this patent report, damping capacity is still good inadequately simultaneously.In addition, patent CN1410485A report adopts the S-IPN technology to prepare a kind of novel PMPS/ polymethacrylate (PMAc) damping material, and tan δ is 0.35 ~ 1.2, and the damping temperature domain scope can reach-80 ℃～250 ℃.Though this damping material has adopted the IPN technology, has good damping performance, application performances such as other mechanical strength are undesirable.
Generally speaking, yet there are no the preparation method's of the described polycomponent urethane/polysiloxane of this patent/polyacrylate interpenetrating network damping polymer latex report.
According to molecular structure Design Theory principle, the design requirements of damping material with wide-temperature range is that the Tg of each component is separated by and is wanted far away, and each component is suitably compatible simultaneously, makes in the each component Tg and moves.Therefore, adopt organosilicon and multicomponent polymeric copolymerization, the mode of Tg linking designed, to prepare wide temperature territory, high damping material is very favourable.For this reason, the present invention is directed to the deficiencies in the prior art and a kind of preparation method of novel polycomponent urethane/polysiloxane/polyacrylate interpenetrating network damping polymer latex is provided, it is characterized in that whole process of preparation was broadly divided into for three steps: 1, at first be to prepare a kind of polyurethane prepolymer latex A with active ethylene group functional group by the urethane self-emulsifying; 2, secondly in pre-polymer emulsion, carry out the monomeric polymerization of organo-siloxane, form semi-intercrossing network prepolymer urethane/polysiloxane emulsion B; 3, then, in pre-polymer emulsion B, carry out and the acrylate monomer copolymerization.Preparation process root a tree name practical situation can set-up procedure, and step 2 and step 3 can be changed.According to the present invention, the preparation method of this novel urethane/polysiloxane/polyacrylate interpenetrating network polymer, based on the actual application requirements, can be that any one multiple component polymer is a cross-linked network structure, for example, urethane and polysiloxane macromolecular chain are crosslinking structure, and the polyacrylic ester macromolecular chain is a linear structure, perhaps polyacrylic ester and polysiloxane macromolecular chain are crosslinking structure, and the polyurethane component macromolecular chain is a linear structure, or three kinds of component polymer molecular chains all are cross-linked network structure.
This novel urethane/polysiloxane/polyacrylate interpenetrating network polymer preparation process and target product all are dispersion medium with water, pollution-free, belong to green material, simultaneously, urethane/polysiloxane/polyacrylate interpenetrating network polymer effectively combines urethane, polysiloxane, polyacrylate polymers advantage separately, glass transition peak width and highly can regulating as required, tan δ is 0.4～1.5, the damping temperature domain scope can reach-80 ℃～200 ℃, water-fast weather-proof, adhesiveproperties and mechanical property are good.
Summary of the invention:
Purpose of the present invention is realized by following technical measures, and raw materials used mark removes special instruction and is massfraction.
1. the preparation of the polyurethane prepolymer latex A of active ethylene group functional group
Isocyanate-monomer, polyethers or polyester, dihydroxymethyl vinylformic acid, vinyl hydroxy acrylate, dibutyl tin laurate are added reactor by proportioning, 60 ℃～90 ℃ reaction 3～6h, add chainextender, linking agent, triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.
The isocyanate-monomer of wherein selecting for use comprises tolylene diisocyanate (TDI), ditan-4,4 '-vulcabond (MDI), poly methylene poly phenyl poly isocyanate (PAPI), 1, oneself two different acid esters (HDI) of 6-, isophorone two different acid esters (IPDI), xylylene diisocyanate (XDI), Methylcyclohexyl diisocyanate (HTDI), dicyclohexyl methane diisocyanate (HMDI).
Selected polyethers or polyester comprise polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene-castor oil polyhydric alcohol, polytetrahydrofuran diol, tetrahydrofuran (THF)-propylene oxide copolymerization glycol, polyethylene glycol adipate glycol (PEA), poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol (PDA), poly-hexanodioic acid-1,4 butanediol ester glycol, poly-adipate glycol-1,4 butanediol ester glycol, poly-hexanodioic acid Viscotrol C ester polyol, poly-epsilon-caprolactone glycol, poly-carbonic acid 1,6-hexylene glycol esterdiol (PHC).
Selected vinyl hydroxy acrylate comprises hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate, pentaerythritol triacrylate.Available linking agent be quadrol, glycerol, quadrol, glycerine, sorbyl alcohol, 3,3 ' two chloro-4,4 '-diamino-ditan.
Entire reaction course is the progressively condensation reaction of functional group-NCO and functional group-OH, because functional group-NCO and water molecules have strong reaction, therefore reaction process should avoid contacting water, the polyethers that strict simultaneously control is selected or the water content of polyester, avoid isocyanic ester and water generation side reaction, in order to avoid influence quantitatively carrying out of reaction.In reaction system, added the vinyl hydroxy acrylate monomer, like this, have active vinyl group in the polyurethane molecular chain, this active ethylene group group can participate in the reaction of back.In addition, in reaction process, according to actual needs, can add linking agent glycerol etc., polymer molecular chain is made network structure, like this, the viscosity of system can increase gradually, before self-emulsifying, can suitably add the small amount of acetone solvent and make viscosity controlled.In the self-emulsifying process, control stirring velocity well, self-emulsifying obtains pale blue polyurethane prepolymer latex A, and this polyurethane prepolymer latex A maybe can enter next preparation section after can placing certain hour.
2, the preparation of urethane/polysiloxane prepolymers emulsion B
Get 30～90 parts of the polyurethane prepolymer emulsions that prepared, with 5～60 parts of adding reactors of multiple organo-siloxane mix monomer, mix with the polyurethane prepolymer emulsion in the reactor, add initiator and emulsifying agent synchronously, at 50 ℃～90 ℃ reaction 4～48h.
Selected organo-siloxane monomer comprises a kind of vinyl ring body siloxanes at least, can be following one or more organo-siloxane monomers: hexamethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenyl cyclotetrasiloxane, trimethyl triphenyl cyclotrisiloxane, trimethylammonium trivinyl cyclotrisiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, tetramethyl-triphenyl vinyl cyclotetrasiloxane, tetramethyl divinyl disiloxane.
In reaction, add a certain amount of Organoalkyl Phenylsulfonic acid or its esters compound, be used as initiator, also can play the effect of emulsifying agent simultaneously, can use one or more Organoalkyl Phenylsulfonic acids or its esters compound.
After the organosilane monomer swelling polyurethane prepolymer emulsion, under action of evocating, carry out the ring-opening reaction of organosilicon ring body,, therefore, have active vinyl group on the organosilicon molecular chain that reaction generates owing to contain the vinyl ring body in the organosilane monomer.If add initiator cause on the organosilicon molecular chain active ethylene group can with the active ethene on the polyurethane prepolymer molecular chain, then obtain grafting or crosslinked polyurethane/organosilicon polymer emulsion.If control temperature of reaction and time well, make the active ethylene group that can not cause in this reaction process on the prepolymer molecular chain, then vinyl group can participate in the copolyreaction of back and acrylate monomer.
3, the preparation of urethane/polysiloxane/polyacrylate interpenetrating network polymer damping latex
At first add deionized water, negatively charged ion and nonionic blending emulsifiers in another pre-emulsion reactor, add and mix acrylate monomer, stirring and emulsifying obtains acrylate pre-emulsion D, and is standby; Be seed with the prepared urethane of step 2 in the reactor/polysiloxane prepolymers emulsion B then, dropwise addition of acrylic acid ester pre-emulsion D and initiator react 2～6h, insulation reaction 1～3h then at 65 ℃～90 ℃ synchronously, carry out the oxidation-reduction aftertreatment at last, cooling is filtered the back discharging and is got final product.
The mixing acrylate monomer that preparation process is used, be selected from following two or more monomer, comprise methyl methacrylate, methyl acrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl acrylate, 2-EHA, methacrylic acid 2-ethylhexyl, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid, methacrylic acid, diacrylate 1, the 4-butanediol ester, trimethyol propane triacrylate diacrylate 1, the 4-butanediol ester, trimethyol propane triacrylate, γ-glycidyl methacrylate, glycidyl acrylate.
Negatively charged ion and nonionic blending emulsifiers that reaction is added, can be the mixture of following one or more the moon, nonionogenic tenside: 1,2-dodecyl diether disulfonic acid disodium, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, ethoxy alcohol disodium sulfosuccinate, polyethers nonyl phenol succinate, ester succinic acid salt, Nonyl pheno (4) ether ammonium sulfate, Nonyl pheno (30) ether, Nonyl pheno (40) ether, alkyl alkyl polyether sulphur acid sodium-salt, acrylamido methyl propane sulfonic acid sodium.
In addition, the initiator in the reaction is selected from persulphate compounds and organo-peroxide or organic azo compound, and for example Ammonium Persulfate 98.5, Potassium Persulphate, benzoyl peroxide, azo two isobutyls are fine.
Product of the present invention has good physical and chemical performance, and all technical indicator meets national environmental protection rules and national Specification.Emulsion microcosmic oyster white, little blue light-emitting, reaction does not have residue substantially, does not have cohesion, the stability in storage excellence, Calcium ion stability and freeze-thaw stability pass through national standard.The latex film water-tolerant, damping factor is big by 0.4～1.5, and the damping temperature domain scope can reach-80 ℃～150 ℃, and is water-fast weather-proof, and adhesiveproperties is good.In purpose product preparation process, by the weight fraction of adjusting each component and the crosslinking degree that changes the each component polymkeric substance, change consistency and the glass transition zone and the height of each component, can effectively control the polymer performance of product of the present invention.
The required monomer of the preparation of urethane/polysiloxane of the present invention/polyacrylate interpenetrating network polymer damping latex generally can arrive on the market to be buied, three steps of whole process can also can discontinuously be operated in operate continuously, use again and following preparation after for example the urethane pre-emulsion of preparation can be placed a couple of days earlier, therefore, whole process operation is flexible, and each step can be adjusted according to practical situation.
Specific implementation method:
Below in conjunction with example the present invention is described in further detail, but not as a limitation of the invention.
Embodiment 1
Tolylene diisocyanate, poly-third diether, dimethylol propionic acid, 2-hydroxyl vinylacrylic acid ester, dibutyl tin laurate are added reactor, 80 ℃-90 ℃ reaction 4～6h, add butyleneglycol, TriMethylolPropane(TMP), triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.Then, add multiple organo-siloxane monomer, add initiator and emulsifying agent simultaneously, mix, at 80 ℃-90 ℃ reaction 2～6h with the polyurethane prepolymer latex A.
In pre-emulsion reactor, add deionized water, negatively charged ion and nonionic blending emulsifiers, add again and mix acrylate monomer, stir pre-emulsification and obtain acrylate pre-emulsion D; Be seed with the prepared urethane of step 2 in the reactor/polysiloxane prepolymers emulsion B then, synchronous dropwise addition of acrylic acid ester pre-emulsion D and initiator, at 65 ℃～90 ℃ reaction 2～6h, insulation reaction 1～3h then, lowering the temperature at last 30 ℃-60 ℃ adds post-treatment agents and handles and filtered discharging in 0.5-1.5 hour.
Embodiment 2
Tolylene diisocyanate, poly-third diether, dihydroxymethyl vinylformic acid, 2-hydroxyl vinylacrylic acid ester, dibutyl tin laurate are added reactor, 80 ℃-90 ℃ reaction 4～6h, add triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.Then, add hexamethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, add initiator and emulsifying agent simultaneously, mix, at 60 ℃-90 ℃ reaction 6～28h with the polyurethane prepolymer latex A.Then, add sodium peroxydisulfate, at 70 ℃-90 ℃ reaction 3～10h.Cooling, discharging obtain polyurethane/organosilicon polymer latex B, and be standby.
In another pre-emulsion reactor, add deionized water, negatively charged ion and nonionic blending emulsifiers, add methacrylic ester, acrylic ester monomer and functional monomer again, stir pre-emulsification and obtain acrylate pre-emulsion D; Get urethane/polysiloxane polymer latex that the front prepared then as seed, dropwise addition of acrylic acid ester pre-emulsion D and initiator, at 65 ℃～90 ℃ reaction 2～8h, insulation reaction 1～3h then, lowering the temperature at last 30 ℃-60 ℃ adds post-treatment agents and handles and filtered discharging in 0.5-1.5 hour and promptly get target product.
Embodiment 3
With ditan-4,4 '-vulcabond (MDI), 1, oneself two different acid esters (HDI) of 6-, polyoxytrimethylene-castor oil polyhydric alcohol and polyethylene glycol adipate glycol (PEA), dimethylol propionic acid, 2-hydroxyl vinylacrylic acid ester, dibutyl tin laurate add reactor, 80 ℃-90 ℃ reaction 4～8h, add butyleneglycol, TriMethylolPropane(TMP), triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.Then, add multiple organo-siloxane ring body, add Organoalkyl Phenylsulfonic acid or its esters compound simultaneously, mix with the polyurethane prepolymer latex A, at 50 ℃-80 ℃ reaction 6～36h, obtain containing the urethane/polysiloxane prepolymers emulsion B of active ethylene group.
In another pre-emulsion reactor, add deionized water, negatively charged ion and nonionic blending emulsifiers, add again and mix acrylate monomer, stir pre-emulsification and obtain acrylate pre-emulsion D; Be seed with prepared urethane/polysiloxane prepolymers emulsion B then, synchronous dropwise addition of acrylic acid ester pre-emulsion D and initiator, at 65 ℃～90 ℃ reaction 2～6h, insulation reaction 1～3h then, lowering the temperature at last 30 ℃-60 ℃ adds post-treatment agent processing filtration in 0.5-1.5 hour discharging, and total overall reaction needed finish altogether in 10-48 hour.
Embodiment 4
Tolylene diisocyanate, isophorone two different acid esters (IPDI), polyoxytrimethylene-castor oil polyhydric alcohol, dimethylol propionic acid, 2-hydroxyl vinylacrylic acid ester, dibutyl tin laurate are added reactor, 80 ℃-90 ℃ reaction 4～6h, add butyleneglycol, TriMethylolPropane(TMP), triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.Standby.
Add deionized water, negatively charged ion and nonionic blending emulsifiers in the pre-emulsion reactor, add again and mix acrylate monomer, contain glycidyl methacrylate, stir pre-emulsification and obtain acrylate pre-emulsion D; Be seed with prepared polyurethane prepolymer emulsion B then, synchronous dropwise addition of acrylic acid ester pre-emulsion D and initiator, at 65 ℃～90 ℃ reaction 2～6h, insulation reaction 1～3h then, lowering the temperature at last 30 ℃-60 ℃ adds post-treatment agent processing filtration in 0.5-1.5 hour discharging, obtains polyurethane/polyacrylate interpenetrating network latex E.
Then, add hexaphenyl cyclotrisiloxane, octamethylcyclotetrasiloxane monomer, fully after the swelling, add initiator and emulsifying agent, at 50 ℃-90 ℃ reaction 8～25h toward polyurethane/polyacrylate interpenetrating network latex E.The after-filtration discharging of lowering the temperature then promptly gets target product.
Embodiment 5
Tolylene diisocyanate, isophorone two different acid esters (IPDI), polyoxytrimethylene-castor oil polyhydric alcohol, dimethylol propionic acid, 2-hydroxyl vinylacrylic acid ester, dibutyl tin laurate are added reactor, 80 ℃-90 ℃ reaction 4～6h, add butyleneglycol, TriMethylolPropane(TMP), triethylamine and deionized water then, powerful stirring self-emulsifying is the polyurethane prepolymer latex A.Standby.
Add deionized water, negatively charged ion and nonionic blending emulsifiers in the pre-emulsion reactor, add again and mix acrylate monomer, contain glycidyl methacrylate, stir pre-emulsification and obtain acrylate pre-emulsion D; Be seed with part propylene acid esters pre-emulsion D then, drip residual acrylic acid ester pre-emulsion D and initiator synchronously, at 75 ℃～90 ℃ reaction 2～6h, insulation reaction 1～3h then, lowering the temperature at last 30 ℃-60 ℃ adds post-treatment agent processing filtration in 0.5-1.5 hour discharging, obtains polyacrylic ester network latex F.
Mix polyurethane prepolymer latex A and polyacrylic ester network latex F, mix, then, in this blend latex F, add hexaphenyl cyclotrisiloxane, octamethylcyclotetrasiloxane monomer, fully after the swelling, add initiator and emulsifying agent, at 50 ℃-90 ℃ reaction 8～25h.The after-filtration discharging of lowering the temperature then promptly gets target product.
Claims (9)
1, the preparation method of the adjustable urethane/polysiloxane with broad use temperature scope/polyacrylic ester (PU/PSi/PA) interpenetrating net polymer damping latex (LIPN) is characterized in that whole preparation can be divided into three steps: step 1, at first be that self-emulsifying by urethane prepares a kind of polyurethane prepolymer latex A with active ethylene group functional group; Secondly step 2, in pre-polymer emulsion, carry out the monomeric polymerization of organo-siloxane, form urethane/polysiloxane prepolymers emulsion B; Step 3, is then carried out in pre-polymer emulsion B and the acrylate monomer copolymerization, promptly obtains urethane/polysiloxane/polyacrylate interpenetrating network polymer damping latex C.The molecular chain in this polymkeric substance damping glue Ruzhong can be that any one multiple component polymer is a cross-linked network structure, for example, urethane and polysiloxane macromolecular chain are crosslinking structure, and the polyacrylic ester macromolecular chain is a linear structure, perhaps polyacrylic ester and polysiloxane macromolecular chain are crosslinking structure, and the polyurethane component macromolecular chain is a linear structure, or three kinds of component polymer molecular chains all are cross-linked network structure.In addition, root a tree name practical situation can be adjusted the step of preparation process, and step 2 and step 3 can be changed.
2, damping latex C according to claim 1, it is characterized in that the damping polymkeric substance is urethane, polysiloxane, polyacrylic ester polycomponent interpenetrating net polymer, the molecular chain in polymkeric substance damping glue Ruzhong can be that any one multiple component polymer is a cross-linked network structure, effectively combine urethane, polysiloxane, polyacrylate polymers advantage separately, have other application performances such as excellent damping capacity and mechanical property.
3, damping latex C according to claim 1, this novel urethane/polysiloxane/polyacrylate interpenetrating network polymer preparation process and target product all with water are dispersion medium, and be pollution-free, belongs to green material.
4, step 1 according to claim 1, it is characterized in that preparation technology is: isocyanate-monomer, polyethers or polyester, dihydroxymethyl vinylformic acid, active ethylene group hydroxy acrylate, dibutyl tin laurate are added reactor by proportioning, 60 ℃～90 ℃ reaction 3～6h, can add chainextender, linking agent participation reaction as required again, triethylamine and deionized water then, powerful to stir self-emulsifying be the polyurethane prepolymer latex A.
5, step 2 preparation process according to claim 1, it is characterized in that preparation technology is: multiple organo-siloxane monomer is added reactor, and the polyurethane prepolymer latex A in the swelling reactor mixes, add initiator and emulsifying agent, at 50 ℃～90 ℃ reaction 4～48h.After this can enter step 3.
6, organo-siloxane monomer according to claim 5 is made up of two or more organo-siloxane monomer, comprises one or more C at least
2-3The unsaturated silica C of olefinic
1-3Alkane.It comprises: hexamethyl cyclotrisiloxane, hexaphenyl cyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenyl cyclotetrasiloxane, trimethyl triphenyl cyclotrisiloxane, trimethylammonium trivinyl cyclotrisiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, tetramethyl-triphenyl vinyl cyclotetrasiloxane, tetramethyl divinyl disiloxane, vinyl triisopropyl siloxanes, vinyl methyl dimethoxy oxygen radical siloxane, vinyl-three-(2-methoxy ethoxy) siloxanes.
7, preparation process step 3 according to claim 1, it is characterized in that preparation technology is: at first in pre-emulsion reactor, add deionized water, negatively charged ion and nonionic blending emulsifiers, add again and mix acrylate monomer, stir pre-emulsification and obtain acrylate pre-emulsion D; Be seed with the prepared urethane of step 2 in the reactor/polysiloxane prepolymers emulsion B then, dropwise addition of acrylic acid ester pre-emulsion D and initiator react 2～6h, insulation reaction 1～3h then at 65 ℃～90 ℃ synchronously, carry out the oxidation-reduction aftertreatment at last, cooling is filtered the back discharging and is got final product.
8, mixing acrylate monomer according to claim 7, be selected from following two or more monomer, comprise methyl methacrylate, methyl acrylate, Jia Jibingxisuanyizhi, ethyl propenoate, butyl acrylate, 2-EHA, methacrylic acid 2-ethylhexyl, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid, methacrylic acid, γ-glycidyl methacrylate, γ-glycidyl acrylate, diacrylate 1, the 4-butanediol ester, trimethyol propane triacrylate.
9, negatively charged ion according to claim 7 and nonionic blending emulsifiers, it can be the mixture of following one or more the moon, nonionogenic tenside: 1, and 2-dodecyl diether disulfonic acid disodium, Witco 1298 Soft Acid, Sodium dodecylbenzene sulfonate, ethoxy alcohol disodium sulfosuccinate, polyethers nonyl phenol succinate, ester succinic acid salt, Nonyl pheno (4) ether ammonium sulfate, Nonyl pheno (30) ether, Nonyl pheno (40) ether, alkyl alkyl polyether sulphur acid sodium-salt, acrylamido methyl propane sulfonic acid sodium.
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| CNB2004100515292A CN100368476C (en) | 2004-09-21 | 2004-09-21 | Preparation of wide temperature range polyacry late/polyurethane/polysiloxane damping latex |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103074025A (en) * | 2013-01-17 | 2013-05-01 | 武汉理工大学 | Polysiloxane/silylated castor oil polyurethane IPN (Interpenetrating Polymer Network) sealant |
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