CN1664006A - Polyurethane and process for preparing nano composite materials thereof - Google Patents
Polyurethane and process for preparing nano composite materials thereof Download PDFInfo
- Publication number
- CN1664006A CN1664006A CN200510037794.XA CN200510037794A CN1664006A CN 1664006 A CN1664006 A CN 1664006A CN 200510037794 A CN200510037794 A CN 200510037794A CN 1664006 A CN1664006 A CN 1664006A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polymerization
- reaction
- heating
- reactor
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims description 27
- 239000002114 nanocomposite Substances 0.000 title claims description 14
- 239000004814 polyurethane Substances 0.000 title abstract description 11
- 229920002635 polyurethane Polymers 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 6
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 12
- -1 poly methylene Polymers 0.000 claims description 11
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000005844 autocatalytic reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 229920001451 polypropylene glycol Polymers 0.000 description 8
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 101100010166 Mus musculus Dok3 gene Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the polyurethane and its nanometer composite material and the preparing method, comprising putting the polyisocyanates, oligomer polyhydric alcohol, inorganic nano material, chain-enlarging solvent, catalyst and dissolvant into the reactor promptly after intimate mixing with process for front end polymerization, heating the system at one side of the reactor for a short time, then stopping heating, accomplishing the monomer polymerization by means of thermal autocatalysis of the exothermal reaction and getting the product with good stability. The invention is characterized by the same heat stability compared with the traditional kettle type polymerization process, and the simpler process and the reduced reaction time and an excellent energy-saving reaction pattern.
Description
Technical field
The present invention relates to the preparation method of a kind of urethane and nano composite material thereof, relate in particular to a kind of method for preparing urethane and nano composite material thereof with the front end polyreaction.
Background technology
Urethane is easy to design and processes be the material faster of versatile development in the synthetic materials that the product of making has kinds such as porous plastics, rubber, coating, tackiness agent with its structure.Polyurethane synthetic material has than any other industrial rubbers and all good performance of plastics, for example elastomeric property, wear-resistant, high strength, oil resistant, acid and alkali-resistance and have good adhesiveproperties.Simultaneously, the polymer-based nano hybrid material has been widely used in the research of Materials science, for polyether(poly)urethane, because its molecular chain is flexible big, the secondary valence bond reactive force is little, insufficient strength can strengthen urethane by adding nano material, and its mechanical property is improved a lot on original basis.At present, the production technique of urethane and matrix material thereof mainly adopts traditional kettle-typed polymerization method both at home and abroad, the specific equipment that required level of automation is higher, and output investment ratio is bigger, cost height, technology more complicated, long reaction time.Nonlinear chemical kinetics develops into a sophisticated scientific research field gradually at present, and the front end polymerization is its important application that has development potentiality in field of polymer technology.Researchers find to use nonlinear chemical kinetics can obtain various unusual beautiful pattern such as space patterns such as vibration ripple, spirals, the more important thing is through further investigation and found the dynamic (dynamical) many important application of nonlinear chemical, in science and technology and daily life, play a role.The front end polymerization is different from traditional reaction pattern, it is a kind of by local reaction zone moving and polymer monomer is changed into a kind of reaction pattern of polymkeric substance in polymer monomer, be mainly used in the thermopositive reaction, carry out the heating of short period of time in the reaction starting stage, then stop to heat by the caloric autocataiysis effect of thermopositive reaction and finish monomeric polymerization, therefore this is a kind of fast simple and economic reaction pattern, more and more attracts scientist scholars' attention.According to the differential responses mechanism of front end polyreaction, the front end polyreaction can be divided into following two classes: heat difference front end polymerization (thermal frontalpolymerization) and isothermal front end polymerization (isothermal frontal polymerization).Heat difference front end polyreaction is a kind of front reaction that the thermodiffusion that will produce owing to the ununiformity of heat in the reaction process combines with the Arrhenius reaction kinetics.For example in Physics and Chemistry Dokl 1975 the 221st volume, look into slow Lip river (Chechilo) and Ai Neikelaopu speech (Enikolopyan) and influence in the process of the initiator type of methyl methacrylate polymerization and initiator concentration and find hot poor front end polymerization first by research.But do not see with this method synthesis of polyurethane product and matrix material thereof.
Summary of the invention
The technical problem to be solved in the present invention is to overcome traditional still formula polyreaction to prepare shortcoming such as urethane and matrix material manufacturing cost height thereof, complex process, long reaction time and a kind of saving cost, heat difference front end polymeric method simply fast are provided, and is used to prepare urethane and nano composite material thereof.
Technical scheme of the present invention is that reference front end polyreaction is a kind of autocatalysis process, it is a kind of splendid energy-conservation reaction pattern, have the advantage that needs the less reaction times, use traditional still formula polyreaction instead the front end polyreaction and prepare urethane and matrix material thereof.Its steps in sequence comprises:
A, following component is mixed, wherein the weight percent of the shared total amount of each component is
Polyisocyanates 10%～20%
Oligomer polyol 60%～80%
Inorganic nano material 0%～2%
Chainextender 2%～5%
Catalyzer 0.1%～0.8%
Solvent 5%～20%
B, pour in the reactor rapidly after above-mentioned component mixed, liquid level front end at reactor carries out the short period of time heating to above-mentioned system, stop heating then, the method for finishing monomer polymerization by the caloric autocataiysis of thermopositive reaction is front end polymeric method preparation and getting.
Wherein said oligomer polyol is wherein one or more of polyether glycol, polyester polyol, Viscotrol C, Resins, epoxy.
Described isocyanic ester is a tolylene diisocyanate (TDI), 4, wherein one or more of 4 '-diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), poly methylene poly phenyl poly isocyanate (PAPI).
Described inorganic nano material is wherein one or more of silicon oxide, zinc oxide, aluminum oxide, titan oxide particles shape nano-powder material or sol system.
Described chainextender is 1, and the 4-butyleneglycol (1,4-BG), 2, wherein one or more of 3-butyleneglycol, glycol ether, glycerine, TriMethylolPropane(TMP) (TMP), sorbyl alcohol.
Described catalyzer is stannous octoate or dibutyl tin laurate.
Described solvent is toluene or N-BUTYL ACETATE.
Reaction process as shown in Figure 1.Pour in the reactor rapidly after described polyisocyanates, oligomer polyol, inorganic nano material, chainextender, catalyzer, solvent mixed by above-mentioned weight percent, liquid level front end at reactor carries out the short period of time heating to above-mentioned system, stop heating then, finish the method preparation of monomer polymerization by the caloric autocataiysis of thermopositive reaction and get.
Described front end polymeric reaction is undertaken by following processing parameter:
A) Heating temperature: 60 ℃～160 ℃
B) heat-up time: 30～60 (seconds)
Beneficial effect of the present invention is:
1, the front end polymerization process is compared with traditional kettle-typed polymerization method, the urethane and the nano composite material thereof of preparation have close second-order transition temperature, and operation is simpler on preparation technology, the required reaction times shortens greatly, required 3～6 hours of traditional kettle-typed polymerization method, and about 1 minute required for the present invention, be a kind of splendid energy-conservation reaction pattern.
2, reaction process medium power consumption of the present invention is low, and the cost of made urethane and nano composite material product thereof is low.
3, the present invention utilizes heat difference front end polymeric method to prepare polyurethane products and nano composite material thereof, and the material that makes has good abrasion resistance and luster performance, is widely used, and can be used for coating, tackiness agent etc.
Description of drawings
Fig. 1 is a front end polymerization synthesis of polyurethane synoptic diagram.
Embodiment
List non-restrictive example below, further specify the present invention.
Embodiment 1
With 1 of the propanediol polyoxypropylene ether of TDI, the 10g of 2.3g, 0.45g, the toluene of 4-butyleneglycol and 1.5g stirs in the presence of the stannous octoate of 0.07g, pour in the reactor rapidly then, as shown in Figure 1, adopt well heater such as torch liquid upper end in reactor that above-mentioned system is carried out short period of time heating 50s, Heating temperature is 110 ℃, stop heating then, by the caloric autocataiysis of thermopositive reaction is front end polyreaction and finish monomer polymerization, direction of polymerization is prepared polyurethane material shown in the direction of arrow among Fig. 1.The second-order transition temperature that this material is measured is listed in the table 1.
Embodiment 2
With 0.25g nanometer SiO
21 of the TDI of powder and 2.3g, the propanediol polyoxypropylene ether of 10g, 0.45g, the toluene of 4-butyleneglycol and 1.5g is pre-dispersed in the presence of the stannous octoate of 0.07g, pour in the reactor rapidly after stirring evenly, end at reactor carries out short period of time heating 50s to above-mentioned system, Heating temperature is 110 ℃, stop heating then, finish monomer polymerization, prepare urethane and polyurethane nano composite material thereof with good stability by the caloric autocataiysis of thermopositive reaction.The second-order transition temperature that this material is measured is listed in the table 1.
Embodiment 3
With 0.1g nanometer SiO
21 of the TDI of colloidal sol and 2.3g, the propanediol polyoxypropylene ether of 10g, 0.45g, the toluene of 4-butyleneglycol and 1.5g is pre-dispersed in the presence of the stannous octoate of 0.02g, pour in the reactor rapidly after stirring evenly, end at reactor carries out short period of time heating 50s to above-mentioned system, Heating temperature is 110 ℃, stop heating then, finish monomer polymerization, prepare urethane and polyurethane nano composite material thereof with good stability by the caloric autocataiysis of thermopositive reaction.The decomposition temperature that this material is measured is listed in the table 1.
Embodiment 4
With 0.1g nanometer SiO
21 of the TDI of powder and 3.4g, the propanediol polyoxypropylene ether of 15g, 0.68g, the toluene of 4-butyleneglycol and 4.5g is pre-dispersed in the presence of the stannous octoate of 0.08g, pour in the reactor rapidly after stirring evenly, end at reactor carries out short period of time heating 30s to above-mentioned system, Heating temperature is 155 ℃, stop heating then, finish monomer polymerization, prepare urethane and polyurethane nano composite material thereof with good stability by the caloric autocataiysis of thermopositive reaction.
Embodiment 5
With 0.23g nanometer SiO
21 of the TDI of colloidal sol and 3.4g, the propanediol polyoxypropylene ether of 15g, 0.68g, the toluene of 4-butyleneglycol and 4.3g is pre-dispersed in the presence of the stannous octoate of 0.04g, pour in the reactor rapidly after stirring evenly, end at reactor carries out short period of time heating 60s to above-mentioned system, Heating temperature is 65 ℃, stop heating then, finish monomer polymerization, prepare urethane and polyurethane nano composite material thereof with good stability by the caloric autocataiysis of thermopositive reaction.
The above-mentioned matrix material that obtains is compared with traditional kettle-typed polymerization method has identical thermostability.
Comparative example 1 (polymerization of still formula)
With 1 of the propanediol polyoxypropylene ether of TDI, the 10g of 2.3g, 0.45g, the 4-butyleneglycol mixes in there-necked flask; The toluene that adds 1.5g simultaneously is solvent, and the stannous octoate catalyst of 0.07g, and 80 ℃ were reacted 3 hours down, finish reaction.Second-order transition temperature and decomposition temperature that this material is measured are listed in the table 1.
Comparative example 2 (polymerization of still formula)
With 0.25g nanometer SiO
21 of the TDI of powder and 2.3g, the propanediol polyoxypropylene ether of 10g, 0.45g, the 4-butyleneglycol is pre-dispersed, mixes in there-necked flask then; The toluene that adds 1.5g simultaneously is solvent, and the stannous octoate catalyst of 0.07g, and 80 ℃ were reacted 3 hours down, finish reaction.The second-order transition temperature that this material is measured is listed in the table 1.
Comparative example 3 (polymerization of still formula)
With 0.1g nanometer SiO
21 of the TDI of colloidal sol and 2.3g, the propanediol polyoxypropylene ether of 10g, 0.45g, the 4-butyleneglycol is pre-dispersed, mixes in there-necked flask then; The toluene that adds 1.5g simultaneously is solvent, and the stannous octoate catalyst of 0.07g, and 80 ℃ were reacted 3 hours down, finish reaction.The decomposition temperature that this material is measured is listed in the table 1.
Table 1
| The embodiment sequence number | Second-order transition temperature ℃ | Decomposition temperature ℃ |
| Embodiment 1 | ????-43.5 | ????- |
| Embodiment 2 | ????-42.9 | ????- |
| Embodiment 3 | ????- | ????370 |
| The comparative example 1 | ????-43.3 | ????350 |
| The comparative example 2 | ????-42.5 | ????- |
| The comparative example 3 | ????- | ????368 |
Claims (8)
1, the preparation method of a kind of urethane and nano composite material thereof, its steps in sequence comprises:
A, following component is mixed, wherein the weight percent of the shared total amount of each component is
Polyisocyanates 10%～20%
Oligomer polyol 60%～80%
Inorganic nano material 0%～2%
Chainextender 2%～5%
Catalyzer 0.1%～0.8%
Solvent 5%～20%
B, pour in the reactor rapidly after above-mentioned component mixed, liquid level front end at reactor carries out the short period of time heating to above-mentioned system, stop heating then, by the caloric autocataiysis of thermopositive reaction and finish monomer polymerization, promptly front end polymeric method prepares urethane and nano composite material thereof.
2, preparation method according to claim 1 is characterized in that the method for front end polyreaction is undertaken by following processing parameter:
A) Heating temperature: 60 ℃～160 ℃
B) heat-up time: 30～60 seconds.
3, preparation method according to claim 1 is characterized in that described oligomer polyol is wherein one or more of polyether glycol, polyester polyol, Viscotrol C, Resins, epoxy.
4, preparation method according to claim 1, it is characterized in that it being that described isocyanic ester is a tolylene diisocyanate (TDI), 4, wherein one or more of 4 '-diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), poly methylene poly phenyl poly isocyanate (PAPI).
5,, it is characterized in that described inorganic nano material is wherein one or more of silicon oxide, zinc oxide, aluminum oxide, titan oxide particles shape nano-powder material or sol system according to the described preparation method of claim 1.
6, preparation method according to claim 1 is characterized in that described chainextender is 1, and the 4-butyleneglycol (1,4-BG), 2, wherein one or more of 3-butyleneglycol, glycol ether, glycerine, TriMethylolPropane(TMP) (TMP), sorbyl alcohol.
7, preparation method according to claim 1 is characterized in that described catalyzer is stannous octoate or dibutyl tin laurate.
8, preparation method according to claim 1 is characterized in that described solvent is toluene or N-BUTYL ACETATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510037794.XA CN1272355C (en) | 2005-02-05 | 2005-02-05 | Polyurethane and process for preparing nano composite materials thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510037794.XA CN1272355C (en) | 2005-02-05 | 2005-02-05 | Polyurethane and process for preparing nano composite materials thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1664006A true CN1664006A (en) | 2005-09-07 |
| CN1272355C CN1272355C (en) | 2006-08-30 |
Family
ID=35035327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510037794.XA Expired - Fee Related CN1272355C (en) | 2005-02-05 | 2005-02-05 | Polyurethane and process for preparing nano composite materials thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1272355C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985542A (en) * | 2010-10-25 | 2011-03-16 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN102115657A (en) * | 2010-12-31 | 2011-07-06 | 广州鹿山新材料股份有限公司 | High-hardness quickly-setting polyurethane hot melt adhesive and preparation method thereof |
| CN101597461B (en) * | 2009-07-10 | 2011-11-09 | 浙江东化实业有限公司 | Multiple curable aqueous hyperbranched polyurethane inorganic nanomaterial hybrid coating agent and preparation method thereof |
| CN101550224B (en) * | 2009-05-07 | 2012-01-11 | 四川大学 | Preparation method of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent |
| CN101503502B (en) * | 2008-02-04 | 2012-03-28 | 上海巨安科技有限公司 | Thermoplastic hard polyurethane foam plastic and preparation thereof |
| CN101368079B (en) * | 2008-09-25 | 2012-05-09 | 广州鹿山新材料股份有限公司 | Polyurethane hot melt adhesive with fast crystallization and preparation method thereof |
| CN102027032B (en) * | 2008-05-16 | 2013-03-27 | 拜尔材料科学股份公司 | Stable polyisocyanates comprising nanoparticles |
| CN103881013A (en) * | 2014-03-18 | 2014-06-25 | 南京工业大学 | Method for quickly preparing fluorine-containing hydrogel by adopting frontal plasma polymerization |
| CN103936896A (en) * | 2013-01-21 | 2014-07-23 | 王超 | Preparation method of polymeric material |
| CN105367750A (en) * | 2015-12-22 | 2016-03-02 | 合肥仲农生物科技有限公司 | In-situ polymerizing composite |
| CN109294431A (en) * | 2018-09-27 | 2019-02-01 | 佛山九陌科技信息咨询有限公司 | A kind of marine antifouling coating |
| CN113214451A (en) * | 2021-04-08 | 2021-08-06 | 东莞市米儿塑胶原料有限公司 | TPU preparation method based on front-end polymerization process |
| CN115651522A (en) * | 2022-12-28 | 2023-01-31 | 广州豫顺新材料有限公司 | Polyurethane coating containing nano silicon dioxide based flame retardant and preparation method thereof |
-
2005
- 2005-02-05 CN CN200510037794.XA patent/CN1272355C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503502B (en) * | 2008-02-04 | 2012-03-28 | 上海巨安科技有限公司 | Thermoplastic hard polyurethane foam plastic and preparation thereof |
| CN102027032B (en) * | 2008-05-16 | 2013-03-27 | 拜尔材料科学股份公司 | Stable polyisocyanates comprising nanoparticles |
| CN101368079B (en) * | 2008-09-25 | 2012-05-09 | 广州鹿山新材料股份有限公司 | Polyurethane hot melt adhesive with fast crystallization and preparation method thereof |
| CN101550224B (en) * | 2009-05-07 | 2012-01-11 | 四川大学 | Preparation method of cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent |
| CN101597461B (en) * | 2009-07-10 | 2011-11-09 | 浙江东化实业有限公司 | Multiple curable aqueous hyperbranched polyurethane inorganic nanomaterial hybrid coating agent and preparation method thereof |
| CN101985542A (en) * | 2010-10-25 | 2011-03-16 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN101985542B (en) * | 2010-10-25 | 2013-06-05 | 北京首创纳米科技有限公司 | Wind blade coating and preparation method thereof |
| CN102115657A (en) * | 2010-12-31 | 2011-07-06 | 广州鹿山新材料股份有限公司 | High-hardness quickly-setting polyurethane hot melt adhesive and preparation method thereof |
| CN102115657B (en) * | 2010-12-31 | 2013-05-15 | 广州鹿山新材料股份有限公司 | High-hardness quickly-setting polyurethane hot melt adhesive and preparation method thereof |
| CN103936896A (en) * | 2013-01-21 | 2014-07-23 | 王超 | Preparation method of polymeric material |
| CN103881013A (en) * | 2014-03-18 | 2014-06-25 | 南京工业大学 | Method for quickly preparing fluorine-containing hydrogel by adopting frontal plasma polymerization |
| CN105367750A (en) * | 2015-12-22 | 2016-03-02 | 合肥仲农生物科技有限公司 | In-situ polymerizing composite |
| CN109294431A (en) * | 2018-09-27 | 2019-02-01 | 佛山九陌科技信息咨询有限公司 | A kind of marine antifouling coating |
| CN113214451A (en) * | 2021-04-08 | 2021-08-06 | 东莞市米儿塑胶原料有限公司 | TPU preparation method based on front-end polymerization process |
| CN115651522A (en) * | 2022-12-28 | 2023-01-31 | 广州豫顺新材料有限公司 | Polyurethane coating containing nano silicon dioxide based flame retardant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1272355C (en) | 2006-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1272355C (en) | Polyurethane and process for preparing nano composite materials thereof | |
| CN106366636B (en) | The polyurethane foam of carried metal organic frame nanocrystal and its preparation and application | |
| Rao et al. | UV-driven self-replenishing slippery surfaces with programmable droplet-guiding pathways | |
| Pattanayak et al. | Synthesis of thermoplastic polyurethane nanocomposites of reactive nanoclay by bulk polymerization methods | |
| Choi et al. | Synthesis of exfoliated polyacrylonitrile/Na− MMT nanocomposites via emulsion polymerization | |
| CN110845952B (en) | Fluorinated polyurethane coating and preparation method of super-hydrophobic coating | |
| CN104151516B (en) | A kind of preparation method of the grade polyureas mono-dispersion microballoon of size tunable | |
| CN100503757C (en) | Ultraviolet light solidifying paint containing POSS and its preparation method | |
| CN103980449A (en) | Composite material for 3D printing and preparation method thereof | |
| CN110105532A (en) | Thermoplasticity selfreparing polyurethane resin and preparation method thereof for 3D printing composite material | |
| CN110713706A (en) | Self-repairing MXene/polyurethane thermoelectric composite material and preparation method thereof | |
| CN107418420A (en) | A kind of hydrophobic polyurethane hybrid coating and preparation method thereof | |
| CN1958711A (en) | Energy storage material of solid - solid phase change in opal / polyurethane type, and preparation method | |
| CN1204170C (en) | Preparation method of nano particles with high refractive index and polymer nano composite film material | |
| Wang et al. | Understanding the mechanism in aggregation ability between aerobic and anammox granular sludge from the perspective of exopolysaccharides | |
| Chen et al. | Positional assembly of hybrid polyurethane nanocomposites via incorporation of inorganic building blocks into organic polymer | |
| WO2020068720A1 (en) | Dual cure resins for additive manufacturing | |
| Xu et al. | Tough self-healing polyurethane elastomers based on interpenetrating networks containing multiple hydrogen bond networks, flexible blocks, metal coordination and covalent cross-linking | |
| CN1860144A (en) | Statistic comb polymers, method for producing the same and their use | |
| CN109627413A (en) | A kind of high abrasion polyurethane material and preparation method thereof | |
| Rus | Effect of titanium dioxide on material properties for renewable rapeseed and sunflower polyurethane | |
| Ke et al. | Research progress in intrinsic self-healing polyurethane materials based on dynamic reversible non-covalent bonds | |
| CN101367945A (en) | Interpenetration network prepared with in situ interesterification method and uses thereof | |
| CN115322332A (en) | Fluorescent bio-based polyurethane capable of being rapidly self-repaired and preparation method thereof | |
| CN113307938A (en) | Polyurethane elastomer composition, polyurethane elastomer 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU SANLTY NEWWIN LIGHT INDUSTRIAL CO., LTD. Free format text: FORMER OWNER: NANJING UNIVERSITY OF TECHNOLOGY Effective date: 20140218 |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 210009 NANJING, JIANGSU PROVINCE TO: 211200 NANJING, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140218 Address after: 211200 No. 8 Qinhuai North Road, Lishui Economic Development Zone, Nanjing, Jiangsu Patentee after: Jiangsu Shuntian Xinying Light Industry Co., Ltd. Address before: 210009 Zhongshan North Road, Jiangsu, No. 200, Patentee before: Nanjing University of Technology |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060830 Termination date: 20160205 |