CN105001389A - Polyurethane material and preparation method thereof - Google Patents
Polyurethane material and preparation method thereof Download PDFInfo
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- CN105001389A CN105001389A CN201510475330.0A CN201510475330A CN105001389A CN 105001389 A CN105001389 A CN 105001389A CN 201510475330 A CN201510475330 A CN 201510475330A CN 105001389 A CN105001389 A CN 105001389A
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
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Abstract
The invention provides a polyurethane material which is obtained through a reaction of a first polyurethane prepolymer, a second polyurethane prepolymer and a chain extender. The first polyurethane prepolymer is obtained through a reaction of a polyhydroxy compound and one or two kinds of toluene diisocynate and benzene diisocyanate. The second polyurethane prepolymer is obtained through a reaction of a polyhydroxy compound and one or two kinds of 4,4'-diphenylmethane diisocyanate and naphthalene diisocyanate. The polyurethane material can be decomposed through the effect of water or microorganisms, and pollution is avoided; meanwhile, on the basis of the combination of the specific aromatic diisocyanate and the chain extender, the finally-obtained polyurethane material has the good strength and toughness.
Description
Technical field
The present invention relates to coating field, especially relate to a kind of polyurethane material and preparation method thereof.
Background technology
At present, China's fertilizer amount accounts for 1/3 of world Fertilizer total amount.But according to pertinent data display, the utilization rate of nitrogen fertilizer that China is most widely used is only 30% ~ 35%, differs more greatly different with the utilization ratio of 50% ~ 55% of developed country.Chemical fertilizer utilization ratio low causing needs repeatedly to apply fertilizer in a growth cycle of crop, excess fertilizer accumulates at plant rhizosphere, not only can destroy root system of plant cellularstructure, cause salt damage, cause crop failure even dead, also can spoiled soil structure, cause Soil degradation and earth's surface and body of groundwater pollution etc.Therefore, country, in " 15 ", Eleventh Five-Year Plan, all points out to need Development of Novel fertilizer.One of major fields wherein developed are exactly slow release fertilizer.
Slow release fertilizer (Slow release fertilizers) is called for short SRFs, after being characterized in incorporation of fertilizerin the soil, the rate of release changing the available nutrients that plant can directly absorb into is more much smaller than conventional instant fertilizer, long to the fertilizer efficiency of the effective sex ratio common fertilizer of crop.Meet the requirement of energy-saving and emission-reduction, meet the needs of China's national situation.From using value and the long-term interest of slow release fertilizer, development sustained-controll-release fertiliser will become the inexorable trend of fertilizer industry development.
The main direction of studying of current slow release fertilizer is the enveloped slow release fertilizer of macromolecular material parcel.Large quantity research shows, uses organic high molecular polymer coated slow release fertilizer and can significantly improve fertilizer utilization efficiency, reduces nutrient loss and pollution on the environment.But the development of the enveloped slow release fertilizer of macromolecular material parcel also exists following problem: 1. organic high molecular polymer coated fertilizer nutrient controlled-release effect is good, but its nutrient-lapsed time still can not need the fertile time well to coincide with crop; 2. its nutrients release complete after, the organic polymer ghost remained in soil is difficult to degraded, and using for many years can pollute edatope; 3. the film forming material of domestic development is main mainly with organic solvent, and toxicity is higher, damages the ozone layer, and causes topsoil.In view of above problem, greatly limit the practical application of enveloped slow release fertilizer.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is for providing a kind of polyurethane material, and polyurethane material provided by the invention has good intensity and toughness, nontoxic, degradable.
The invention provides a kind of polyurethane material, be obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender;
Described first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol to be prepared;
Described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol to be prepared.
Preferably, described polyol is selected from hydroxyl vegetable oil.
Preferably, described hydroxyl vegetable oil is selected from Viscotrol C, the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.
Preferably, described chainextender is selected from one or more in 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acids and 3,5-dihydroxymethyl phenylformic acid.
Preferably, the molecular weight of the first base polyurethane prepolymer for use as is 1500 ~ 3000.
The invention provides a kind of preparation method of polyurethane material, comprising:
A) one or more and polyol in tolylene diisocyanate and PPDI react, and obtain the first base polyurethane prepolymer for use as;
4, one or more and polyol in 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate react, and obtain the second base polyurethane prepolymer for use as;
B) the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender reaction, obtains polyurethane material.
Preferably, described steps A) in the mol ratio of one or more and polyol in tolylene diisocyanate and PPDI be 1 ~ 4:1.
Preferably, described step B) after also comprise described polyurethane material and triethylamine be obtained by reacting water-base polyurethane material.
Preferably, described steps A) in obtain the first base polyurethane prepolymer for use as temperature of reaction be 70 ~ 80 DEG C, the reaction times is 3 ~ 5h.
Preferably, described step B) in the mol ratio of the first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as be 1:1 ~ 2.
Compared with prior art, the invention provides a kind of polyurethane material, be obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender; Described first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol to be prepared; Described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol to be prepared.And polyurethane material of the present invention, by degrading under the effect of water or microorganism, is avoided polluting; The present invention simultaneously, by the combination between specific aromatic diisocyanate and chainextender, makes the polyurethane material finally prepared have good intensity and toughness.
Embodiment
The invention provides a kind of polyurethane material, it is characterized in that, be obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender;
Described first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol to be prepared;
Described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol to be prepared.
Polyurethane material provided by the invention is obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender; Wherein, the first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol and prepares.The source of the present invention to described tolylene diisocyanate and PPDI does not limit, and can be commercially available.
In the present invention, described polyol is preferably selected from hydroxyl vegetable oil, and described hydroxyl vegetable oil comprises natural polyhydroxy vegetables oil and the hydroxyl vegetable oil through modification; Described natural polyhydroxy vegetables oil includes but not limited to Viscotrol C; The described hydroxyl vegetable oil through modification includes but not limited to the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.Above-mentioned hydroxylation modification mode can be hydroxylation modification mode well known to those skilled in the art; Concrete, as soybean oil carries out hydroxylation modification preferably by maleic anhydride, glycol ether, obtain soybean oil polyol, shown in (I) structure; Tung oil carries out hydroxylation modification preferably by glycerol, sodium methylate, obtains dihydroxyl eleostearic acid, shown in (II) structure; Sunflower seed oil, preferably by formic acid, Tai-Ace S 150, hydrogen peroxide, fluoroboric acid modification, obtains sunflower seed oil polyvalent alcohol, shown in (III) structure.
formula (I);
formula (II);
formula (III).
In the present invention, the mol ratio of one or more and polyol in described tolylene diisocyanate and PPDI is preferably 1 ~ 4:1, preferred, the mol ratio of described tolylene diisocyanate or PPDI and polyol is 1 ~ 4:1.
In the present invention, the molecular weight of described first base polyurethane prepolymer for use as is preferably 1500 ~ 3000, is more preferably 1600 ~ 2800.
In the present invention, described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol and prepares.The present invention is to described 4, and the source of 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate does not limit, and can be commercially available.
In the present invention, described polyol is preferably selected from hydroxyl vegetable oil, includes but not limited to Viscotrol C, the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.Above-mentioned hydroxylation modification mode can be hydroxylation modification mode well known to those skilled in the art; Concrete, as soybean oil carries out hydroxylation modification preferably by maleic anhydride, glycol ether, obtain soybean oil polyol, shown in (I) structure; Tung oil carries out hydroxylation modification preferably by glycerol, sodium methylate, obtains dihydroxyl eleostearic acid, shown in (II) structure; Sunflower seed oil, preferably by formic acid, Tai-Ace S 150, hydrogen peroxide, fluoroboric acid modification, obtains sunflower seed oil polyvalent alcohol, shown in (III) structure.
In the present invention, described 4, the mol ratio of one or more and polyol in 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate is preferably 1 ~ 4:1, preferred, described 4, the mol ratio of 4 '-diphenylmethanediisocyanate or naphthalene diisocyanate and polyol is 1 ~ 4:1.
In the present invention, the molecular weight of described second base polyurethane prepolymer for use as is preferably 1500 ~ 3000, is more preferably 1600 ~ 2800.
In the present invention, described chainextender is preferably selected from one or more in 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acids and 3,5-dihydroxymethyl phenylformic acid.The present invention does not limit for the source of above-mentioned chainextender, can be commercially available.
The invention provides a kind of preparation method of polyurethane material, comprising:
A) one or more and polyol in tolylene diisocyanate and PPDI react, and obtain the first base polyurethane prepolymer for use as;
4, one or more and polyol in 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate react, and obtain the second base polyurethane prepolymer for use as;
B) the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender reaction, obtains polyurethane material.
First one or more in phenylene diisocyanate and PPDI and polyol react by the present invention, obtain the first base polyurethane prepolymer for use as.
In the present invention, described polyol is preferably selected from hydroxyl vegetable oil, includes but not limited to Viscotrol C, the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.Above-mentioned hydroxylation modification mode can be hydroxylation modification mode well known to those skilled in the art; Concrete, as soybean oil carries out hydroxylation modification preferably by maleic anhydride, glycol ether, obtain soybean oil polyol, shown in (I) structure; Tung oil carries out hydroxylation modification preferably by glycerol, sodium methylate, obtains dihydroxyl eleostearic acid, shown in (II) structure; Sunflower seed oil, preferably by formic acid, Tai-Ace S 150, hydrogen peroxide, fluoroboric acid modification, obtains sunflower seed oil polyvalent alcohol, shown in (III) structure.
In the present invention, the mol ratio of one or more and polyol in described tolylene diisocyanate and PPDI is preferably 1 ~ 4:1, preferred, the mol ratio of described tolylene diisocyanate or PPDI and polyol is 1 ~ 4:1.
In the present invention, the molecular weight of described first base polyurethane prepolymer for use as is preferably 1500 ~ 3000, is more preferably 1600 ~ 2800.
In the present invention, described reaction solvent is preferably acetone; Described reaction is preferably stirring reaction, and described temperature of reaction is preferably 70 ~ 80 DEG C, is more preferably 72 ~ 78 DEG C; Described reaction pressure is preferably normal pressure; The time of described stirring reaction is preferably 3 ~ 5h.
In the present invention, one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol are reacted, obtains the second base polyurethane prepolymer for use as.
In the present invention, described polyol is preferably selected from hydroxyl vegetable oil, includes but not limited to Viscotrol C, the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.Above-mentioned hydroxylation modification mode can be hydroxylation modification mode well known to those skilled in the art; Concrete, as soybean oil carries out hydroxylation modification preferably by maleic anhydride, glycol ether, obtain soybean oil polyol, shown in (I) structure; Tung oil carries out hydroxylation modification preferably by glycerol, sodium methylate, obtains dihydroxyl eleostearic acid, shown in (II) structure; Sunflower seed oil, preferably by formic acid, Tai-Ace S 150, hydrogen peroxide, fluoroboric acid modification, obtains sunflower seed oil polyvalent alcohol, shown in (III) structure.
In the present invention, described 4, the mol ratio of one or more and polyol in 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate is preferably 1 ~ 4:1, preferred, described 4, the mol ratio of 4 '-diphenylmethanediisocyanate or naphthalene diisocyanate and polyol is 1 ~ 4:1.
In the present invention, the molecular weight of described second base polyurethane prepolymer for use as is preferably 1500 ~ 3000, is more preferably 1600 ~ 2800.
In the present invention, described reaction solvent is preferably acetone; Described reaction is preferably stirring reaction, and described temperature of reaction is preferably 70 ~ 80 DEG C, is more preferably 72 ~ 78 DEG C; Described reaction pressure is preferably normal pressure; The time of described stirring reaction is preferably 3 ~ 5h.
After preparing above-mentioned first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as, the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender react, and obtain polyurethane material.Be specifically as follows first by above-mentioned first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as mix and blend reaction after, then with described chainextender hybrid reaction.Described temperature of reaction is preferably 70 ~ 80 DEG C; Described first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as mix and blend reaction times are preferably 1 ~ 2h, and the described and described chainextender hybrid reaction time is preferably 2 ~ 3h.
Described chainextender is preferably selected from one or more in 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acids and 3,5-dihydroxymethyl phenylformic acid.The present invention does not limit for the source of above-mentioned chainextender, can be commercially available.
In the present invention, the mol ratio of described first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as is 1:1 ~ 2.The ratio of the amount of substance of the amount of substance of described chainextender and described first base polyurethane prepolymer for use as and the remaining isocyano of the second polyurethane prepolymer precursor reactant is preferably 1:1.
In the present invention, after described step B, described polyurethane material and triethylamine are obtained by reacting water-base polyurethane material by preferred also comprising.
Be specifically as follows: polyurethane material and triethylamine are reacted, then adds water, steam acetone and obtain water-base polyurethane material.
The mol ratio of described triethylamine and described chainextender is preferably 1:0.5 ~ 1.5, and the described reaction times is preferably 0.5 ~ 1.5h, is more preferably 1h.
In the polyurethane material prepared, add triethylamine can improve the hydrophilicity of the polyurethane material that the present invention prepares and not affect all the other performances.The present invention does not limit for the described mode steaming acetone, the mode steaming acetone well known to those skilled in the art.
The invention provides a kind of polyurethane material, be obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender; Described first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol to be prepared; Described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol to be prepared.And polyurethane material of the present invention, by degrading under the effect of water or microorganism, is avoided polluting; The present invention simultaneously, by the combination between specific aromatic diisocyanate and chainextender, makes the polyurethane material finally prepared have good intensity and toughness.The present invention simultaneously, by specific reaction between aromatic diisocyanate and chainextender in aromatic diisocyanate specific in the first performed polymer, the second performed polymer, makes the polyurethane material finally prepared have good intensity and toughness.Polyurethane material provided by the invention is applicable to the coating field of chemical fertilizer.Degradable polyurethane film material can not work the mischief to soil, and by regulating and controlling degradation time to the control of mould material structure, the object that the deenergized period reaching control internal package nutrient needs the fertile cycle consistent with crop, can reduce the fertilising frequency and intensity, improve chemical fertilizer utilization ratio.
The present invention carries out performance measurement preferably by with under type to the polyurethane material prepared:
1, (1) tensile strength and elongation at break (toughness)
Poured into by aqueous polyurethane emulsion in molded polytetrafluoroethylarticle template, keep natural horizontal after dry 2-3 days, in loft drier, 90 DEG C of dry 2h, take off film for subsequent use after cooling.
The AG-X plus universal electrical material-testing machine of Japanese Shimadzu Corporation is adopted at room temperature to test, rate of extension 100mm/min.
With reference to QB/T2415-1998 standard, on film, cut three samples with dumbbell shape cut-off knife, size should meet the regulation of 2 types in GB/T528-1992.
Tensile strength: X=F/S
X in formula---film stretching intensity, MPa;
F---load value when film is broken, N;
S---film average traversal area, mm
2.
Results averaged.
Elongation at break: X=(L
1-L)/L × 100
X in formula---film elongation at break rate, %;
1---film breaks markers wire spacing, mm;
---the former distance between bench marks of film is from, mm.
Results averaged.
(2) degradation property
In degradation process, the performance of material the most directly shows both is the change of rate of weight loss.The Weight lose of degraded is all broadly divided into three phases: the weight of (a) sample slowly reduces; B the loss of () sample weight is accelerated; C the loss of () sample weight slows down.So the mensuration of degradation property can be converted into the mensuration of material sample rate of weight loss.Between general first stage and subordinate phase, rate of weight loss curve can produce flex point, and about this time period, the appearance of material film is that large fold or slight crack appear in surface, and the nutrients release of internal package now can be made to go out.So, this curve be there is the defining standard of the time of flex point as material degradation performance of the present invention.
The buffered soln of room temperature preparation pH=7.6, is mixed in soil.The material film sample taking certain mass is embedded in wherein, and regular taking-up sample carries out test and weighs.Each time point adopts three samples to average.Rate of weight loss in material degradation process calculates as follows:
In formula, m0 represents the original weight of sample, and mt represents the dry weight after sample degradation t days respectively.
In order to further illustrate the present invention, below in conjunction with embodiment, polyurethane material provided by the invention and preparation method thereof is described in detail
Embodiment 1
First crude soya bean oil is carried out modification, be processed into soybean oil polyol: add 218g soybean oil (SO) and 73.5g maleic anhydride (MA), four-hole bottle is placed in heating jacket, installs stirring, water of condensation, thermometer and nitrogen protection.210 DEG C of reaction 3h, obtain the maleic anhydride modified soybean oil of intermediate (SOMA).In four-hole boiling flask, add 238.5g glycol ether and 0.12gKOH again, heating jacket is warming up to 220 DEG C of reaction 6h, obtains crude soybean oil polyvalent alcohol.By repeatedly washing, separatory remove unreacted glycol ether; Add the water of 3%, water removes by underpressure distillation, by suction filtration by sorbent material and sylvite removing, obtains reacting required soybean oil polyol (SOP), containing hydroxyl 3mol in 1mol SOP.
The SOP obtained is mixed with the ratio of tolylene diisocyanate according to mol ratio 1:2, add acetone as solvent, 70 DEG C, stirring reaction 4 hours under normal pressure, keep temperature by uncovered for container reaction 1h removal acetone, complete the synthesis of the first base polyurethane prepolymer for use as, take out for subsequent use;
By the SOP and 4 obtained, 4 '-diphenylmethanediisocyanate mixes according to the ratio of mol ratio 1:2.5, adds acetone as solvent, and 70 DEG C, stirring reaction 5 hours under normal pressure, complete the synthesis of the second base polyurethane prepolymer for use as;
First base polyurethane prepolymer for use as 1mol is joined in the reaction soln of the second base polyurethane prepolymer for use as 2mol, keep the temperature of reaction of 70 DEG C to stir 1 hour, then add chainextender 2, the 2-dimethylolpropionic acid that amount of substance is 3mol, stirring reaction carries out chain extension in 3 hours, generates macromolecule polyurethane material;
In the acetone soln of the macromolecule polyurethane material of synthesis, add triethylamine introduce hydrophilic radical, triethylamine and chainextender 2, the mol ratio of 2-dimethylolpropionic acid is 1:1,70 DEG C of stirring reactions 1 hour, temperature of reaction is kept to add water gradually afterwards in acetone soln, steam acetone, complete the preparation of the polyurethane material of water-based.
Carry out performance measurement according to the method described in the present invention to the above-mentioned water-base polyurethane material prepared, result is as shown in table 1, the performance measurement result of the water-base polyurethane material that table 1 prepares for the embodiment of the present invention.
Embodiment 2
First natural tung oil is carried out modification, be processed into dihydroxyl eleostearate: tung oil, glycerol with the ratio of mol ratio 1:2, and massfraction to be 0.5% sodium methylate be that catalyst mix joins that stirrer is housed, prolong, temperature are taken into account in the four-hole boiling flask of nitrogen conduit.Under 200 DEG C of conditions, reaction 4h.In reaction process, with N
2protection.40ml saturated sodium-chloride water solution is added in the mixture prepared, utilize the character that tung oil and the water insoluble and glycerol of dihydroxyl eleostearate and sodium methylate are water-soluble, tung oil and dihydroxyl eleostearate can be made to be suspended in waterborne, utilize separating funnel to be separated, obtain the mixture of tung oil and dihydroxyl eleostearate.This mixture is heated 8h in vacuum drying oven, can obtain the layering thing that upper strata is tung oil, lower floor is dihydroxyl eleostearate, separating funnel is separated.Repeat above process for several times, the dihydroxyl eleostearate that can obtain purity higher is for subsequent use.
The dihydroxyl eleostearate obtained is mixed with the ratio of tolylene diisocyanate according to mol ratio 1:1.5, add acetone as solvent, 75 DEG C, stirring reaction 5 hours under normal pressure, keep temperature by uncovered for container reaction 1h removal acetone, complete the synthesis of the first base polyurethane prepolymer for use as, take out for subsequent use;
By the dihydroxyl eleostearate and 4 obtained, 4 '-diphenylmethanediisocyanate mixes according to the ratio of mol ratio 1:3, adds acetone as solvent, and 75 DEG C, stirring reaction 5 hours under normal pressure, complete the synthesis of the second base polyurethane prepolymer for use as;
First base polyurethane prepolymer for use as is joined in the reaction soln of the second base polyurethane prepolymer for use as, two kinds of performed polymers are the ratio mixing of 1:1.5 according to mol ratio, the temperature of reaction of 75 DEG C is kept to stir 1 hour, add chainextender 2 again, 2-dimethylol propionic acid, the ratio of the amount of substance of isocyano reserved in its amount of substance and the first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as is 1:1, and stirring reaction carries out chain extension in 3 hours, generates macromolecule polyurethane material;
In the acetone soln of the macromolecule polyurethane material of synthesis, add triethylamine introduce hydrophilic radical, triethylamine and chainextender 2, the mol ratio of 2-dimethylol propionic acid is 1:1,75 DEG C of stirring reactions 1 hour, temperature of reaction is kept to add water gradually afterwards in acetone soln, steam acetone, complete the preparation of the polyurethane material of water-based.
Carry out performance measurement according to the method described in the present invention to the above-mentioned water-base polyurethane material prepared, result is as shown in table 1, the performance measurement result of the water-base polyurethane material that table 1 prepares for the embodiment of the present invention.
Embodiment 3
Viscotrol C is mixed according to the ratio of mol ratio 1:1.7 with PPDI (PPDI), add acetone as solvent, 75 DEG C, stirring reaction 5 hours under normal pressure, keep temperature by uncovered for container reaction 1h removal acetone, complete the synthesis of the first base polyurethane prepolymer for use as, take out for subsequent use;
Mixed according to the ratio of mol ratio 1:2.5 with naphthalene diisocyanate (NDI) by Viscotrol C, add acetone as solvent, 75 DEG C, stirring reaction 4 hours under normal pressure, complete the synthesis of the second base polyurethane prepolymer for use as;
First base polyurethane prepolymer for use as is joined in the reaction soln of the second base polyurethane prepolymer for use as, two kinds of performed polymers are the ratio mixing of 1:2 according to mol ratio, the temperature of reaction of 75 DEG C is kept to stir 1 hour, add chainextender 2 again, 2-dimethylolpropionic acid, the ratio of the amount of substance of isocyano reserved in its amount of substance and the first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as is 1:1, and stirring reaction carries out chain extension in 4 hours, generates macromolecule polyurethane material;
Step 4: add triethylamine and introduce hydrophilic radical in the acetone soln of the macromolecule polyurethane material of synthesis, triethylamine and chainextender 3, the mol ratio of 5-dihydroxymethyl phenylformic acid is 1:1,75 DEG C of stirring reactions 1 hour, temperature of reaction is kept to add water gradually afterwards in acetone soln, steam acetone, complete the preparation of the polyurethane material of water-based.
Carry out performance measurement according to the method described in the present invention to the above-mentioned water-base polyurethane material prepared, result is as shown in table 1, the performance measurement result of the water-base polyurethane material that table 1 prepares for the embodiment of the present invention.
Embodiment 4
First natural sunflower seed seed oil is carried out modification, be processed into sunflower seed oil polyvalent alcohol: sunflower seed oil 210g, formic acid 27.4g, Tai-Ace S 150 21.7g, cetyl trimethylammonium bromide 0.44g are joined in the there-necked flask of 500ml; Hydrogen peroxide 189g joins in the equalizing addition device of 250ml; Install agitator, thermometer and balance feeder, drip hydrogen peroxide when 35 DEG C, when being added dropwise to complete, temperature of reaction controls at about 60 DEG C, isothermal reaction 3h.Remove spent acid and vacuum hydro-extraction, obtain epoxy sunflower seed oil.
By gained epoxy sunflower seed oil in equalizing addition device, (mol ratio of the epoxy group(ing) of anhydrous methanol and epoxy sunflower seed oil is 14.6:1 to take anhydrous methanol and distilled water, the mol ratio of methyl alcohol and distilled water is 5:1) in 250ml there-necked flask, after question response liquid temp reaches preset temp, start to drip epoxy sunflower seed oil, time for adding is 5min, after being added dropwise to complete, 2.5g sodium bicarbonate is added, stopped reaction after continuing reaction 25min.Desolvation more afterwards, obtains sunflower seed oil polyvalent alcohol.
The sunflower seed oil polyvalent alcohol obtained is mixed according to the ratio of mol ratio 1:4 with PPDI (PPDI), add acetone as solvent, 75 DEG C, stirring reaction 5 hours under normal pressure, keep temperature that uncovered for container reaction 1h is removed acetone, complete the synthesis of the first base polyurethane prepolymer for use as, take out for subsequent use;
Mixed according to the ratio of mol ratio 1:3.5 with naphthalene diisocyanate (NDI) by the sunflower seed oil polyvalent alcohol obtained, add acetone as solvent, 75 DEG C, stirring reaction 5 hours under normal pressure, complete the synthesis of the second base polyurethane prepolymer for use as;
First base polyurethane prepolymer for use as is joined in the reaction soln of the second base polyurethane prepolymer for use as, two kinds of performed polymers are the ratio mixing of 1:1.8 according to mol ratio, the temperature of reaction of 75 DEG C is kept to stir 1 hour, add chainextender 2 again, 2-dimethylol propionic acid, the ratio of the amount of substance of isocyano reserved in its amount of substance and the first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as is 1:1, and stirring reaction carries out chain extension in 3 hours, generates macromolecule polyurethane material;
In the acetone soln of the macromolecule polyurethane material of synthesis, add triethylamine introduce hydrophilic radical, triethylamine and chainextender 2, the mol ratio of 2-dimethylol propionic acid is 1:1,75 DEG C of stirring reactions 1 hour, temperature of reaction is kept to add water gradually afterwards in acetone soln, steam acetone, complete the preparation of the polyurethane material of water-based.
Carry out performance measurement according to the method described in the present invention to the above-mentioned water-base polyurethane material prepared, result is as shown in table 1, the performance measurement result of the water-base polyurethane material that table 1 prepares for the embodiment of the present invention.
The performance measurement result of the water-base polyurethane material that table 1 embodiment of the present invention prepares
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a polyurethane material, is characterized in that, is obtained by reacting by the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender;
Described first base polyurethane prepolymer for use as is reacted by one or more in tolylene diisocyanate and PPDI and polyol to be prepared;
Described second base polyurethane prepolymer for use as is reacted by one or more in 4,4 '-diphenylmethanediisocyanate and naphthalene diisocyanate and polyol to be prepared.
2. polyurethane material according to claim 1, is characterized in that, described polyol is selected from hydroxyl vegetable oil.
3. polyurethane material according to claim 2, is characterized in that, described hydroxyl vegetable oil is selected from Viscotrol C, the soybean oil through hydroxylation modification, the tung oil through hydroxylation modification and one or more in the sunflower seed oil of hydroxylation modification.
4. polyurethane material according to claim 1, is characterized in that, described chainextender is selected from one or more in 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acids and 3,5-dihydroxymethyl phenylformic acid.
5. polyurethane material according to claim 1, is characterized in that, the molecular weight of the first base polyurethane prepolymer for use as is 1500 ~ 3000.
6. a preparation method for polyurethane material, comprising:
A) one or more and polyol in tolylene diisocyanate and PPDI react, and obtain the first base polyurethane prepolymer for use as;
4, one or more and polyol in 4 '-diphenylmethanediisocyanate and naphthalene diisocyanate react, and obtain the second base polyurethane prepolymer for use as;
B) the first base polyurethane prepolymer for use as, the second base polyurethane prepolymer for use as and chainextender reaction, obtains polyurethane material.
7. the preparation method of polyurethane material according to claim 6, is characterized in that, described steps A) in the mol ratio of one or more and polyol in tolylene diisocyanate and PPDI be 1 ~ 4:1.
8. the preparation method of polyurethane material according to claim 6, is characterized in that, described step B) after also comprise described polyurethane material and triethylamine be obtained by reacting water-base polyurethane material.
9. the preparation method of polyurethane material according to claim 6, is characterized in that, the temperature of reaction obtaining the first base polyurethane prepolymer for use as in described steps A is 70 ~ 80 DEG C, and the reaction times is 3 ~ 5h.
10. the preparation method of polyurethane material according to claim 6, is characterized in that, described step B) in the mol ratio of the first base polyurethane prepolymer for use as and the second base polyurethane prepolymer for use as be 1:1 ~ 2.
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|---|---|---|---|---|
| CN106012567A (en) * | 2016-07-28 | 2016-10-12 | 东莞市雄林新材料科技股份有限公司 | Environment-friendly antibacterial TPU (thermoplastic polyurethanes) synthetic leather and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0867422A2 (en) * | 1997-03-26 | 1998-09-30 | Central Glass Company, Limited | Coated granular fertilizer and method for producing same |
| CN1813013A (en) * | 2003-07-02 | 2006-08-02 | 诺沃恩Ip控股公司 | Water dispersions of core-shell polyurethanes |
| CN101671425A (en) * | 2009-09-11 | 2010-03-17 | 中国海洋石油总公司 | Polyurethane coated controlled-release fertilizer with improved mechanical property, preparation method thereof and special coating material |
| CN101723754A (en) * | 2009-02-19 | 2010-06-09 | 施可丰化工股份有限公司 | High-efficient controlled release compound fertilizer and preparation method thereof |
| CN102924164A (en) * | 2012-04-24 | 2013-02-13 | 中国科学院南京土壤研究所 | Water-based polymer polyacrylate coated fertilizer modified based on biochar, and preparation method thereof |
| CN103304772A (en) * | 2013-06-27 | 2013-09-18 | 上海永通化工有限公司 | Controlled release fertilizer coated by vegetable oil based polyurethane and preparation method thereof |
| CN103772646A (en) * | 2013-12-31 | 2014-05-07 | 山东茂施生态肥料有限公司 | Biodegradation sustained-release fertilizer coating material containing soybean oil polyhydric alcohol and preparation process thereof |
-
2015
- 2015-08-06 CN CN201510475330.0A patent/CN105001389A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0867422A2 (en) * | 1997-03-26 | 1998-09-30 | Central Glass Company, Limited | Coated granular fertilizer and method for producing same |
| CN1813013A (en) * | 2003-07-02 | 2006-08-02 | 诺沃恩Ip控股公司 | Water dispersions of core-shell polyurethanes |
| CN101723754A (en) * | 2009-02-19 | 2010-06-09 | 施可丰化工股份有限公司 | High-efficient controlled release compound fertilizer and preparation method thereof |
| CN101671425A (en) * | 2009-09-11 | 2010-03-17 | 中国海洋石油总公司 | Polyurethane coated controlled-release fertilizer with improved mechanical property, preparation method thereof and special coating material |
| CN102924164A (en) * | 2012-04-24 | 2013-02-13 | 中国科学院南京土壤研究所 | Water-based polymer polyacrylate coated fertilizer modified based on biochar, and preparation method thereof |
| CN103304772A (en) * | 2013-06-27 | 2013-09-18 | 上海永通化工有限公司 | Controlled release fertilizer coated by vegetable oil based polyurethane and preparation method thereof |
| CN103772646A (en) * | 2013-12-31 | 2014-05-07 | 山东茂施生态肥料有限公司 | Biodegradation sustained-release fertilizer coating material containing soybean oil polyhydric alcohol and preparation process thereof |
Non-Patent Citations (6)
| Title |
|---|
| 刘益军: "《聚氨酯树脂及其应用》", 31 January 2012 * |
| 周顺祥: "葵花籽油多元醇的合成工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王林瑞: "大豆油多元醇的合成及聚氨酯慢回弹泡沫性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王正祥，等: "桐油基多元醇的制备及表征", 《包装学报》 * |
| 许戈文 等: "《水性聚氨酯材料》", 28 February 2007 * |
| 钱伯章: "《石油化工技术进展与市场分析（2008-2011年）》", 30 September 2011 * |
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