CN105542174A - Silicone-modified hyperbranched polyurethane and preparation method and application thereof - Google Patents
Silicone-modified hyperbranched polyurethane and preparation method and application thereof Download PDFInfo
- Publication number
- CN105542174A CN105542174A CN201610021217.XA CN201610021217A CN105542174A CN 105542174 A CN105542174 A CN 105542174A CN 201610021217 A CN201610021217 A CN 201610021217A CN 105542174 A CN105542174 A CN 105542174A
- Authority
- CN
- China
- Prior art keywords
- organic
- silicon
- super branched
- branched polyurethane
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
Abstract
The invention discloses silicone-modified hyperbranched polyurethane. The structural formula I of the silicone-modified hyperbranched polyurethane is shown in the description, wherein the hyperbranched polyurethane structural part is shown in the structural formula I, C is the silicon chain segment part, the branching degree is 0.3-0.85, and the molecular weight is 104-106. According to the silicone-modified hyperbranched polyurethane (HPU-Si), the branched part is the hyperbranched polyurethane and can have the good interfacial compatibility with polyurethane materials, the outer end of the branched chain is the silicon chain segment end and can have the good interfacial compatibility with silicone rubber, the silicone-modified hyperbranched polyurethane is added into a polyurethane/silicone rubber mixed system as a bulking agent, and therefore the polyurethane/silicone rubber mixed system can have the excellent interfacial compatibility; the viscosity of the melt can be effectively lowered, processing of the polyurethane/silicone rubber mixed system is facilitated, the molecular weight is large, effective capacity expansion is achieved, and the whole mechanical property of the materials will not be lowered.
Description
Technical field
The present invention relates to matrix material expanding material and preparing technical field thereof, particularly organic-silicon-modified super branched polyurethane of one and preparation method thereof and application.
Background technology
Polymkeric substance simple blend is a kind of common material modification mode, carrys out improving SNR, to reaching desired effect by the mutual supplement with each other's advantages of two kinds or two or more materials.Carry out blending and modifying for uncompatibility polymkeric substance, needing to improve consistency could improve performance, and adding expanding material is a kind of normal method.Silicon rubber is a kind of use temperature wide ranges, has the excellent macromolecular material of high temperature resistant, cold-resistant, weather-proof, excellent dielectricity and special surface property, but silicon rubber oil-proofness is poor and physical strength is not high limits its application.Polyurethane material physical strength is high, oil-proofness good, will both blended and use, can obtain the excellent properties that both are common.Urethane and silicon rubber are two kinds of thermodynamics incompatible materials, need to add expanding material, reduce its micron-scale phase separation, improve blended and use performance.
Hyperbranched polymer has highly branched structure, has the active end group of a large amount of correctability, and the less entanglement of molecular chain, non-crystallizable, favorable solubility, low viscosity, the speciality of high reaction activity.The building-up process of hyperbranched polymer is relatively simple, efficiency is high, cost is low, be conducive to industrialized production, hyperbranched polymer all shows tempting prospect at many Applied research fields, hyperbranched polymer can be used as the processing aid of various different purposes in polymer modification, such as: rheology modifier, compatilizer etc.Hyperbranched polymer, in polymer blending modification, because of the Structure and Properties feature of its uniqueness, makes it achieve excellent modified effect.
Chinese patent CN104650591A discloses a kind of preparation method of urethanes/silicon rubber gross rubber, the method technique is simple, directly add vulcanizing agent and make rubber unvulcanizate sulfuration, but owing to not adding expanding material in this rubber unvulcanizate preparation process, thus make bi-material bad at micromorphologic interface compatibility, cause Blend rubber mechanical property poor.Chinese patent CN102153853A discloses a kind of polyurethane/silicon rubber thermoplastic elastomer and preparation method thereof, synthesize the block linear copolymer of a kind of urethane and silicone oil, for increase-volume polyurethane/silicon rubber, the method improve polyurethane/silicon rubber interface compatibility, but the polymericular weight of this kind of preparation method's synthesis is less, and can reduce the overall mechanical property of material.
Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, primary and foremost purpose of the present invention is to provide a kind of and has excellent interface compatibility, molecular weight is large, and can not reduce the organic-silicon-modified super branched polyurethane of the overall mechanical property of material.
Another object of the present invention is to provide the preparation method of above-mentioned organic-silicon-modified super branched polyurethane.
Another object of the present invention is to provide the purposes of above-mentioned organic-silicon-modified super branched polyurethane.
Another object of the present invention is to provide the polyurethane/silicon rubber co-mixing system comprising above-mentioned organic-silicon-modified super branched polyurethane.
The present invention is achieved through the following technical solutions:
A kind of organic-silicon-modified super branched polyurethane, has following structural formula I:
Ⅰ；
Wherein,
for super branched polyurethane structure division, C is silicone segments part, and the degree of branching is 0.3 ~ 0.85, and molecular weight is 10
4~ 10
6.
A preparation method for above-mentioned organic-silicon-modified super branched polyurethane, comprises the steps:
A) oligomers of glycols, vulcabond are added reactor, and add the non-protonic solvent accounting for system total mass 68 ~ 72wt%, pass into rare gas element protection, react 3 ~ 5 hours under the condition of 75 DEG C; 2 ~-2 DEG C are cooled to after reaction terminates, dioxane hydramine reaction 20 ~ 40 minutes are dripped in solution after terminating to reaction, after reaction terminates, add catalyzer and be warming up to 40 ~ 80 DEG C, continue reaction 10 ~ 50 hours, after reaction terminates, it is dry that the solution after reaction being terminated carries out separation by Rotary Evaporators, obtains super branched polyurethane;
B) after organic silicone oil, vulcabond being dissolved in benzene class organic solvent, add reactor, pass into rare gas element protection, react 1 ~ 5 hour under the condition of 40 ~ 80 DEG C, be cooled to 25 DEG C after question response terminates, the mixture adding alkanamine and benzene class organic solvent continues reaction 30 minutes, after reaction terminates, solution after reaction being terminated puts into Rotary Evaporators, except desolventizing, obtains modified organic silicon;
C) modified organic silicon that super branched polyurethane step a) obtained and step b) obtain adds reactor, passes into rare gas element protection, adds mixed organic solvents as reaction solvent; Add catalyzer, temperature control 40 ~ 80 DEG C, react 20 ~ 100 hours, it is that 95 ~ 105 DEG C of vacuum drying ovens carry out drying that the solution after reaction being terminated puts into temperature control, and removing mixed organic solvents, obtains organic-silicon-modified super branched polyurethane HPU-Si.
Wherein, in described step a), described oligomers of glycols is selected from one or more in polytetramethylene ether diol PTMG, polycarbonate diol PCDL, polyoxyethylene glycol PEG, polyethylene oxide PEO; Described non-protonic solvent is selected from one or more in dimethyl sulfoxide (DMSO), acetonitrile, butanone, hexamethylphosphoramide, dimethyl formamide; Described dioxane hydramine is selected from diethanolamine and/or diisopropanolamine (DIPA).
Wherein, in described step a), the mol ratio of oligomers of glycols and vulcabond is 1:1 ~ 1:5; The mol ratio of dioxane hydramine and oligomers of glycols is 1:1 ~ 1:2.
Wherein, step a) and b) in, described vulcabond is selected from one or more in hexamethylene vulcabond HDI, tolylene diisocyanate TDI, diphenylmethanediisocyanate MDI, isophorone diisocyanate IPDI; Step a) and c) in, described catalyzer is selected from dibutyl tin laurate and/or zinc naphthenate, and the addition of described catalyzer is 0.1 ~ 2wt% of system total mass.
Wherein, in step b), described organic silicone oil is selected from one or more in hydroxy silicon oil, hydroxypropyl silicone oil, amido silicon oil; Described benzene class organic solvent is selected from one or more in toluene, dimethylbenzene, benzene; Described alkanamine is selected from one or more in diethylamine, propylamine, triethylamine; The addition of the mixture of described alkanamine and benzene class organic solvent is 40 ~ 60wt% of system total mass.
Wherein, in step c), the mol ratio of super branched polyurethane and modified organic silicon is 1:2 ~ 2:1.
Wherein, in step c), described mixed organic solvents two kinds of being selected from butanone, dimethyl formamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene form by 1:1 ~ 1:10 is composite, and the addition of described mixed organic solvents is the 48wt%-82wt% of system total mass.
The organic-silicon-modified super branched polyurethane that the preparation method that the invention also discloses above-mentioned organic-silicon-modified super branched polyurethane obtains is used as the purposes of expanding material.
A kind of polyurethane/silicon rubber co-mixing system prepared by the organic-silicon-modified super branched polyurethane that the preparation method that the invention also discloses above-mentioned organic-silicon-modified super branched polyurethane obtains, by weight, comprise 1 ~ 3 part of organic-silicon-modified super branched polyurethane, 20 ~ 80 parts of urethane, 20 ~ 80 parts of silicon rubber; Wherein, organic-silicon-modified super branched polyurethane has following structural formula I,
Ⅰ；
Wherein,
for super branched polyurethane structure division, C is silicone segments part, and the degree of branching is 0.3 ~ 0.85, and molecular weight is 10
4~ 10
6.
The preparation method of above-mentioned polyurethane/silicon rubber co-mixing system, comprises the steps:
Urethane, silicon rubber, organic-silicon-modified super branched polyurethane (HPU-Si) being added in twin screw extruder according to proportioning carries out extruding blended, and granulation, obtains polyurethane/silicon rubber co-mixing system.
The present invention compared with prior art, has following beneficial effect:
1) organic-silicon-modified super branched polyurethane (HPU-Si) of the present invention, its branched moiety is super branched polyurethane, good interface compatibility can be had with polyurethane material, be the organosilicon end of the chain in the outer end of branched chain, good interface compatibility can be had with silicon rubber, it can be used as expanding material to add in polyurethane/silicon rubber co-mixing system, polyurethane/silicon rubber co-mixing system can be made to have excellent interface compatibility.
2) organic-silicon-modified super branched polyurethane (HPU-Si) of the present invention, because it has unique structure, effectively can reduce the entanglement between molecular chain, expanding material is it can be used as to add in polyurethane/silicon rubber co-mixing system, effectively can reduce the viscosity of melt, be conducive to the processing of polyurethane/silicon rubber co-mixing system.
3) organic-silicon-modified super branched polyurethane (HPU-Si) of the present invention, molecular weight is large, can effectively increase-volume, and can not reduce the overall mechanical property of material.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the organic-silicon-modified super branched polyurethane HPU-Si of embodiment 3 gained.
Fig. 2 is the microcosmic scanning electronic microscope comparison diagram of comparative example 1;
Fig. 3 is the microcosmic scanning electronic microscope comparison diagram of application examples 3.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
The structure of organic-silicon-modified super branched polyurethane HPU-Si is composed by following nuclear-magnetism carbon, the infrared spectra shown in Fig. 1 can be confirmed, and its molecular weight is by following laser scattering method:
Nuclear-magnetism carbon is composed:
13c-NMR is that solvent measures with DMSO;
Infrared spectra: the FT-IR205 type Fourier transform infrared spectrometer that infrared spectra Nicolet company produces measures;
Molecular weight: the molecular weight laser light scattering instrument of the BI-200SM type that Brookhaven company of the U.S. produces measures.
The degree of branching: measured by nmr analysis.
The testing standard of each performance or method:
Interface compatibility: observe appearance form by scanning electron microscope (SEM);
The viscosity of melt: measured by Haake torque rheometer;
Tensile strength and elongation at break: according to GB/T528-2009 test, draw speed 300mm/min.
Embodiments of the invention and comparative example adopt following raw material, but are not limited only to these raw materials:
Oligomers of glycols: polytetramethylene ether diol PTMG: analytical pure, the Japanese rising sun becomes chemical industry;
Polycarbonate diol PCDL: analytical pure, the Japanese rising sun becomes chemical industry;
Polyoxyethylene glycol PEG: analytical pure, the Japanese rising sun becomes chemical industry;
Polyethylene oxide PEO: analytical pure, the Japanese rising sun becomes chemical industry;
Vulcabond: hexamethylene vulcabond HDI: analytical pure, Tianjin great Mao chemical reagent factory;
Tolylene diisocyanate TDI: analytical pure, Tianjin great Mao chemical reagent factory;
Diphenylmethanediisocyanate MDI: analytical pure, Tianjin great Mao chemical reagent factory;
Isophorone diisocyanate IPDI: analytical pure, Tianjin great Mao chemical reagent factory;
Dioxane hydramine: diethanolamine: analytical pure, Aladdin reagent;
Diisopropanolamine (DIPA): analytical pure, Aladdin reagent;
Organic silicone oil: hydroxy silicon oil: analytical pure, Shenzhen thousand capital Science and Technology Ltd.
Amido silicon oil: analytical pure, Shenzhen thousand capital Science and Technology Ltd.
Hydroxypropyl silicone oil: analytical pure, Shenzhen thousand capital Science and Technology Ltd.
Alkanamine: diethylamine: analytical pure, Aladdin reagent
Propylamine: analytical pure, Aladdin reagent
Triethylamine: analytical pure, Aladdin reagent
Urethane: TPU90A, ten thousand China's chemistry;
Silicon rubber (VSR): contents of ethylene 0.15%, Guangzhou is polymerized to million industry organosilicon materials centers.
Embodiment 1 ~ 6: the preparation of organic-silicon-modified super branched polyurethane HPU-Si
A) oligomers of glycols, vulcabond are added reactor, and add the non-protonic solvent accounting for system total mass 68-72wt%, pass into rare gas element protection, react 3 ~ 5 hours under the condition of 70 ~ 80 DEG C; 2 ~-2 DEG C are cooled to after reaction terminates, dioxane hydramine reaction 20 ~ 40 minutes are dripped in solution after terminating to reaction, after reaction terminates, add catalyzer and be warming up to 40 ~ 80 DEG C, continue reaction 10 ~ 50 hours, after reaction terminates, it is dry that the solution after reaction being terminated carries out separation by Rotary Evaporators, obtains super branched polyurethane;
B) after organic silicone oil, vulcabond being dissolved in benzene class organic solvent, add reactor, pass into rare gas element protection, react 1 ~ 5 hour under the condition of 40 ~ 80 DEG C, be cooled to normal temperature after question response terminates, the mixture adding alkanamine and benzene class organic solvent continues reaction 30 minutes, after reaction terminates, solution after reaction being terminated puts into Rotary Evaporators, except desolventizing, obtains modified organic silicon;
C) modified organic silicon that super branched polyurethane step a) obtained and step b) obtain adds reactor, passes into rare gas element protection, adds mixed organic solvents as reaction solvent; Add catalyzer, temperature control 40 ~ 80 DEG C, react 20 ~ 100 hours, it is that 95 ~ 105 DEG C of vacuum drying ovens carry out drying that the solution after reaction being terminated puts into temperature control, and removing mixed organic solvents, obtains organic-silicon-modified super branched polyurethane HPU-Si; The structure of the organic-silicon-modified super branched polyurethane HPU-Si prepared can be confirmed by the infrared spectra shown in Fig. 1, and performance index are as shown in table 1;
Wherein, embodiment 1 ~ 6 to prepare concrete technology condition as shown in table 1, and the oligomers of glycols in embodiment 1 ~ 6 is polycarbonate diol (PCDL), in step a), vulcabond is tolylene diisocyanate (TDI), dioxane hydramine is diethanolamine (DEOA), organic silicone oil is hydroxy silicon oil, the vulcabond of step b) is isophorone diisocyanate (IPDI), alkanamine is diethylamine (DEA), step a) and step b) used catalyst are dibutyl tin laurate, and its quality is the 0.1wt% of system total mass; Aprotic solvent in step a) is one or more in dimethyl sulfoxide (DMSO), acetonitrile, butanone, hexamethylphosphoramide, dimethyl formamide; In step b), benzene class organic solvent is one or more in toluene, dimethylbenzene, benzene; Mixed organic solvents used in step c) is that two kinds in butanone, dimethyl formamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene form by 1:1 ~ 1:10 is composite.
Table 1
Embodiment 7 ~ 11: the preparation of organic-silicon-modified super branched polyurethane HPU-Si
The raw material of embodiment 7 ~ 11 is as shown in table 2, and the aprotic solvent in step a) is one or more in dimethyl sulfoxide (DMSO), acetonitrile, butanone, hexamethylphosphoramide, dimethyl formamide; In step b), benzene class organic solvent is one or more in toluene, dimethylbenzene, benzene; Mixed organic solvents used in step c) is that two kinds in butanone, dimethyl formamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene form by 1:1 ~ 1:10 is composite; Step a) and step c) used catalyst are zinc naphthenate, and its quality is the 0.5wt% of system total mass, and other preparation process condition is all identical with embodiment 3; The performance index of the organic-silicon-modified super branched polyurethane HPU-Si prepared are as shown in table 2.
Table 2
Application examples 1-5 and comparative example 1-4: the preparation of polyurethane/silicon rubber co-mixing system
According to table 3 proportioning by urethane, silicon rubber, organic-silicon-modified super branched polyurethane (HPU-Si) according to proportioning add in twin screw extruder carry out extruding blended, granulation, obtain polyurethane/silicon rubber co-mixing system, the performance index result of the polyurethane/silicon rubber co-mixing system prepared is as shown in table 3.
Table 3
| Comparative example 1 | Application examples 1 | Application examples 2 | Application examples 3 | Comparative example 2 | Comparative example 3 | Application examples 4 | Comparative example 4 | Application examples 5 | |
| TPU（phr） | 80 | 80 | 80 | 80 | 80 | 40 | 40 | 20 | 20 |
| VSR(phr) | 20 | 20 | 20 | 20 | 20 | 60 | 60 | 80 | 80 |
| HPU-Si(phr) | 0 | 1 | 2 | 3 | 4 | 0 | 2 | 0 | 3 |
| Melt viscosity (Nm) | 12.3 | 12.1 | 11.8 | 11.6 | 10.2 | 13.7 | 11.2 | 16.9 | 14.4 |
| Tensile strength (MPa) | 10.4 | 15.5 | 19.8 | 13.26 | 7.2 | 10.8 | 13.2 | 4.3 | 6.6 |
| Elongation at break (%) | 302 | 493 | 577 | 378 | 249 | 212 | 346 | 126 | 203 |
As can be seen from application examples 1-5 and comparative example 1-4 relatively: when adding the organic-silicon-modified super branched polyurethane HPU-Si of 1-3 part as expanding material in polyurethane/silicon rubber co-mixing system, as application examples 1 ~ 5, polyurethane/silicon rubber co-mixing system can be made to have the interface compatibility of excellence as shown in Figures 2 and 3, effectively can reduce the viscosity of melt, be conducive to the processing of polyurethane/silicon rubber co-mixing system, and the overall mechanical property of material can not be reduced.When adding very few organic-silicon-modified super branched polyurethane HPU-Si in polyurethane/silicon rubber co-mixing system, as 0 part of comparative example 1,3 and 4, the interface compatibility of polyurethane/silicon rubber co-mixing system is bad; And in polyurethane/silicon rubber co-mixing system, add too much organic-silicon-modified super branched polyurethane HPU-Si, as 4 parts of comparative example 2, polyurethane/silicon rubber co-mixing system melt viscosity is too reduced and not easily disperses on the contrary, cause overall mechanics degradation.
Claims (10)
1. an organic-silicon-modified super branched polyurethane, is characterized in that, has following structural formula I:
Ⅰ；
Wherein,
for super branched polyurethane structure division, C is silicone segments part, and the degree of branching is 0.3 ~ 0.85, and molecular weight is 10
4~ 10
6.
2. a preparation method for organic-silicon-modified super branched polyurethane as claimed in claim 1, is characterized in that, comprise the steps:
A) oligomers of glycols, vulcabond are added reactor, and add the non-protonic solvent accounting for system total mass 68-72wt%, pass into rare gas element protection, react 3 ~ 5 hours under the condition of 70 ~ 80 DEG C;-2 ~ 2 DEG C are cooled to after reaction terminates, dioxane hydramine reaction 20 ~ 40 minutes are dripped in solution after terminating to reaction, after reaction terminates, add catalyzer and be warming up to 40 ~ 80 DEG C, continue reaction 10 ~ 50 hours, after reaction terminates, it is dry that the solution after reaction being terminated carries out separation by Rotary Evaporators, obtains super branched polyurethane;
B) after organic silicone oil, vulcabond being dissolved in benzene class organic solvent, add reactor, pass into rare gas element protection, react 1 ~ 5 hour under the condition of 40 ~ 80 DEG C, be cooled to 25 DEG C after question response terminates, the mixture adding alkanamine and benzene class organic solvent continues reaction 30 minutes, after reaction terminates, solution after reaction being terminated puts into Rotary Evaporators, except desolventizing, obtains modified organic silicon;
C) modified organic silicon that super branched polyurethane step a) obtained and step b) obtain adds reactor, passes into rare gas element protection, adds mixed organic solvents as reaction solvent; Add catalyzer, temperature control 40 ~ 80 DEG C, react 20 ~ 100 hours, it is that 95 ~ 105 DEG C of vacuum drying ovens carry out drying that the solution after reaction being terminated puts into temperature control, and removing mixed organic solvents, obtains organic-silicon-modified super branched polyurethane HPU-Si.
3. the preparation method of organic-silicon-modified super branched polyurethane according to claim 2, it is characterized in that, in described step a), described oligomers of glycols is selected from one or more in polytetramethylene ether diol PTMG, polycarbonate diol PCDL, polyoxyethylene glycol PEG, polyethylene oxide PEO; Described non-protonic solvent is selected from one or more in dimethyl sulfoxide (DMSO), acetonitrile, butanone, hexamethylphosphoramide, dimethyl formamide; Described dioxane hydramine is selected from diethanolamine and/or diisopropanolamine (DIPA).
4. the preparation method of organic-silicon-modified super branched polyurethane according to claim 2, is characterized in that, in described step a), the mol ratio of oligomers of glycols and vulcabond is 1:1 ~ 1:5; The mol ratio of dioxane hydramine and oligomers of glycols is 1:1 ~ 1:2.
5. the preparation method of the organic-silicon-modified super branched polyurethane according to Claims 2 or 3, it is characterized in that, step a) and b) in, described vulcabond is selected from one or more in hexamethylene vulcabond HDI, tolylene diisocyanate TDI, diphenylmethanediisocyanate MDI, isophorone diisocyanate IPDI; Step a) and c) in, described catalyzer is selected from dibutyl tin laurate and/or zinc naphthenate, and the addition of described catalyzer is 0.1 ~ 2wt% of system total mass.
6. the preparation method of organic-silicon-modified super branched polyurethane according to claim 2, is characterized in that, in step b), described organic silicone oil is selected from one or more in hydroxy silicon oil, hydroxypropyl silicone oil, amido silicon oil; Described benzene class organic solvent is selected from one or more in toluene, dimethylbenzene, benzene; Described alkanamine is selected from one or more in diethylamine, propylamine, triethylamine; The addition of the mixture of described alkanamine and benzene class organic solvent is 40 ~ 60wt% of system total mass.
7. the preparation method of organic-silicon-modified super branched polyurethane according to claim 2, is characterized in that, in step c), the mol ratio of super branched polyurethane and modified organic silicon is 1:2 ~ 2:1.
8. the preparation method of organic-silicon-modified super branched polyurethane according to claim 2, it is characterized in that, in step c), described mixed organic solvents two kinds of being selected from butanone, dimethyl formamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene form by 1:1 ~ 1:10 is composite, and the addition of described mixed organic solvents is the 48wt%-82wt% of system total mass.
9. the organic-silicon-modified super branched polyurethane that the preparation method as the organic-silicon-modified super branched polyurethane according to claim 2-8 obtains is used as the purposes of expanding material.
10. a kind of polyurethane/silicon rubber co-mixing system prepared by the organic-silicon-modified super branched polyurethane that the preparation method of the organic-silicon-modified super branched polyurethane as described in claim 2-8 obtains, by weight, comprise 1 ~ 3 part of organic-silicon-modified super branched polyurethane, 20 ~ 80 parts of urethane, 20 ~ 80 parts of silicon rubber; Wherein, organic-silicon-modified super branched polyurethane has following structural formula I,
Ⅰ；
Wherein,
for super branched polyurethane structure division, C is silicone segments part, and the degree of branching is 0.3 ~ 0.85, and molecular weight is 10
4~ 10
6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021217.XA CN105542174A (en) | 2016-01-13 | 2016-01-13 | Silicone-modified hyperbranched polyurethane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021217.XA CN105542174A (en) | 2016-01-13 | 2016-01-13 | Silicone-modified hyperbranched polyurethane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105542174A true CN105542174A (en) | 2016-05-04 |
Family
ID=55821758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610021217.XA Pending CN105542174A (en) | 2016-01-13 | 2016-01-13 | Silicone-modified hyperbranched polyurethane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105542174A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250449A (en) * | 2017-12-19 | 2018-07-06 | 广东省石油与精细化工研究院 | A kind of line style end-silicane-group block polyether and its preparation method and application |
| CN111763370A (en) * | 2020-07-16 | 2020-10-13 | 广东国立科技股份有限公司 | EVA/TPU supercritical foaming composite shoe material and preparation method thereof |
| CN113101418A (en) * | 2020-01-09 | 2021-07-13 | 北京化工大学 | Breast prosthesis shell material, preparation method and application |
| CN115558070A (en) * | 2022-10-09 | 2023-01-03 | 美瑞新材料股份有限公司 | Compatilizer suitable for modification processing of biodegradable material and preparation and application thereof |
| WO2024067890A1 (en) * | 2022-09-27 | 2024-04-04 | 浙江康隆达特种防护科技股份有限公司 | Functional modification of recycled rubber material and application thereof in safety gloves |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
| CN103834038A (en) * | 2014-03-13 | 2014-06-04 | 江西省科学院应用化学研究所 | Method for preparing pectinate organic silicon-modified polyurethane grafted ethylene-vinyl acetate (EVA) water emulsion |
| CN104448200A (en) * | 2014-12-19 | 2015-03-25 | 江南大学 | Preparation method of plant oil-based UV-curable waterborne organosilicone polyurethane resin |
| CN104448235A (en) * | 2014-12-19 | 2015-03-25 | 江南大学 | Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin |
| CN105113255A (en) * | 2015-09-07 | 2015-12-02 | 杭州美高华颐化工有限公司 | Organosilicone modification polyurethane color fixing agent and preparation method thereof |
-
2016
- 2016-01-13 CN CN201610021217.XA patent/CN105542174A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504293A (en) * | 2011-11-03 | 2012-06-20 | 杭州吉华高分子材料有限公司 | Preparation method of hyperbranched polyester modified organic silicon resin and coating comprising resin |
| CN103834038A (en) * | 2014-03-13 | 2014-06-04 | 江西省科学院应用化学研究所 | Method for preparing pectinate organic silicon-modified polyurethane grafted ethylene-vinyl acetate (EVA) water emulsion |
| CN104448200A (en) * | 2014-12-19 | 2015-03-25 | 江南大学 | Preparation method of plant oil-based UV-curable waterborne organosilicone polyurethane resin |
| CN104448235A (en) * | 2014-12-19 | 2015-03-25 | 江南大学 | Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin |
| CN105113255A (en) * | 2015-09-07 | 2015-12-02 | 杭州美高华颐化工有限公司 | Organosilicone modification polyurethane color fixing agent and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250449A (en) * | 2017-12-19 | 2018-07-06 | 广东省石油与精细化工研究院 | A kind of line style end-silicane-group block polyether and its preparation method and application |
| CN113101418A (en) * | 2020-01-09 | 2021-07-13 | 北京化工大学 | Breast prosthesis shell material, preparation method and application |
| CN113101418B (en) * | 2020-01-09 | 2022-07-19 | 北京化工大学 | Breast prosthesis shell material, preparation method and application |
| CN111763370A (en) * | 2020-07-16 | 2020-10-13 | 广东国立科技股份有限公司 | EVA/TPU supercritical foaming composite shoe material and preparation method thereof |
| WO2024067890A1 (en) * | 2022-09-27 | 2024-04-04 | 浙江康隆达特种防护科技股份有限公司 | Functional modification of recycled rubber material and application thereof in safety gloves |
| CN115558070A (en) * | 2022-10-09 | 2023-01-03 | 美瑞新材料股份有限公司 | Compatilizer suitable for modification processing of biodegradable material and preparation and application thereof |
| CN115558070B (en) * | 2022-10-09 | 2024-03-12 | 美瑞新材料股份有限公司 | Compatilizer suitable for modification processing of biodegradable material, preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105542174A (en) | Silicone-modified hyperbranched polyurethane and preparation method and application thereof | |
| CN110591542A (en) | Disulfide bond and hydrogen bond containing dual self-repairing polyurethane coating for invisible car cover and preparation method thereof | |
| EP2295490A1 (en) | Solvent-free crosslinked polyrotaxane material and process for production of same | |
| WO2012165402A1 (en) | Material comprising crosslinked polyrotaxane, and process for producing same | |
| CN1208365C (en) | Method for preparing amino silicone oil modified polyurethane | |
| WO2011108515A1 (en) | Material having cross-linked polyrotaxane, and method for producing same | |
| CN102432818A (en) | Preparation method of1,5-naphthalene diisocyanate-based polyurethane microcellular elastomer | |
| CN106700021A (en) | Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof | |
| Zou et al. | Hyperbranched polyurethane as a highly efficient toughener in epoxy thermosets with reaction-induced microphase separation | |
| CN111607055A (en) | High molecular weight polyurethane based on dynamic reversible covalent bond and preparation method and application thereof | |
| CN102634031A (en) | Heat-resisting poly (silazane-siloxane) polymer and preparation method thereof | |
| LU101916B1 (en) | Use of low-phosphorus crosslinker in preparation of polyurethane film | |
| Song et al. | Properties and morphology of interpenetrating polymer networks based on poly (urethane-imide) and epoxy resin | |
| CN110669203B (en) | Intramolecular polyacetylene polyurethane and polytriazole curing system | |
| CN109575233B (en) | Polysiloxane polyether type polyurethane elastomer with high mechanical property and preparation method thereof | |
| CN113105608B (en) | Self-healing hyperbranched polyurethane with high mechanical strength and preparation method and application thereof | |
| CN108047698B (en) | Mesoporous molecular sieve doped polyvinylidene fluoride/polyurethane piezoelectric damping material and preparation method thereof | |
| CN113999609B (en) | Polyurethane/epoxy sliding ring damping coating and preparation method thereof | |
| CN111733478A (en) | Preparation method of high-elasticity polyurethane elastic fiber | |
| KR101893728B1 (en) | Polyurethane-based shape-memory polymers and composition containing the same | |
| CN110294832A (en) | A kind of polyurethane termoplastic elastomer and preparation method thereof of amino POSS modification | |
| CN114276517B (en) | Preparation method of epoxy-terminated polybutadiene series liquid rubber | |
| CN109627414B (en) | High-temperature post-curing polyurethane composite material | |
| CN116199855B (en) | Polyether-polyester mixed polyurethane and preparation method thereof | |
| CN115124920B (en) | Transparent self-repairing anti-contamination polyurethane coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination |