Come from the aqueous polyurethane and preparation method thereof of the silicon hybridization of natural acid
Technical field
The invention belongs to the polyurethane field of macromolecular material, particularly aqueous polyurethane of a kind of silicon hybridization that comes from natural acid and preparation method thereof.
Background technology
That aqueous polyurethane has is nontoxic, do not fire, characteristic free from environmental pollution.Yet, owing to containing hydrophilic radical in aqueous polyurethane molecular structure, cause the as easy as rolling off a log absorption moisture of water-base polyurethane material.Moisture penetration is delivered in aqueous polyurethane molecular structure, and water-base polyurethane material is caused to two kinds of impacts: (1) water produces plastification to water-base polyurethane material.After plasticising, in aqueous polyurethane molecule and intermolecular hydrogen bond action decline, cause water-base polyurethane material mechanical properties decrease, material shape also may be out of shape.This is reversing process.(2) aqueous polyurethane molecular backbone chain ruptures.After backbone structure fracture, the molecular weight of aqueous polyurethane reduces, and has reduced mechanical strength, even can make polyurethane material complete failure.This is non-reversible process.The problems such as the bad and hydrolytic resistance of water tolerance is poor have all hindered the large-scale application of aqueous polyurethane in industrial circle, also make aqueous polyurethane in use may become potential dangerous body.
Present stage, the raw material of aqueous polyurethane is from petrochemical industry resource.Yet, along with petrochemical industry resource day by day totally, the development of aqueous polyurethane is certain to be affected.Utilize natural reproducible resource all to replace or partly replace the petrochemical material of urethane, can solve and be limited to this bottleneck of petrochemical industry resource.
Lipid acid is a kind of in numerous biomass resources, is mainly present in vegetable and animals oils.Fatty acid source is abundant, cheap.Dimeracid full name is dimer (fatty acid) yl, by two C18 unsaturated fatty acidss (as oleic acid, linolic acid etc.) under catalyzer exists, the di-carboxylic acid generating through Diels-Alder polyreaction.Commodity dimeracid is to take C36 dimer as main mixture (dimeric molar content >=92% of C36), wherein, contains a small amount of C54 tripolymer, the isomerized C18 monomer of part.In preparing the process of dimeracid, owing to containing the oleic acid of two keys and the linolic acid of two two keys in raw materials used C18 unsaturated fatty acids, the dimeracid of in fact producing will contain non-ring structure and ring texture.Its ratio is depending on the oleic acid in raw material and linoleic content.Oleic acid content height non-ring structure is many, and linoleic acid content height ring texture is many, and commodity dimeracid is actually the mixture of Various Complex structure.The long-chain fat hydrocarbon structure of dimeracid and the property such as noncrystalline, give dimer acid type macromolecular material and have snappiness and the oilness under height water tolerance, hydrolytic resistance and utmost point low temperature.In addition, saturated hydroxy-fatty acid molecular structure contains hydroxyl and carboxyl, by forming the poly-hydroxy fatty acid of a series of different molecular weights from condensation polymerization reaction.With respect to other lipid acid, saturated hydroxy-fatty acid is introduced Polymer Systems, can improve the thermostability of resin.And saturated hydroxy-fatty acid can form microcrystalline cellulose structure by self-assembly behavior in Polymer Systems.Dimeracid and saturated hydroxy-fatty acid all derive from natural resource, renewable, degradable, in order to prepare macromolecular material, reduce the pollution of environment and the use of petrochemical industry resource.
Silicone resin is to take Si-O-Si as main chain, connects cross-linking type half inorganic polymer of organic group on Siliciumatom, by multi-functional organosilicon, through hydrolytie polycondensation, is made.Silicone resin has excellent thermotolerance and weathering resistance, has good electrical insulating property, chemical proofing, hydrophobic nature and flame retardant resistance concurrently, also can obtain other performances by modification.Polyhedron oligomeric silsesquioxanes (POSS) is the organic/inorganic thing of a class 3-D solid structure.Molecular formula is (RSiO
1.5)
n(n=6,8,12 etc.), R can be alkyl, aryl, amino, hydroxyl, thiazolinyl, isocyanate group etc.Typical POSS is cage type cube structure, and 8 R bases can identical, also can be different.POSS, as organic/inorganic hybridization material, has the special propertys such as surface effects, small-size effect, nanometer quantum size effect.POSS is introduced in Polymer Systems, can be polymer-modified on nanoscale, improve the performances such as water tolerance, hydrolytic resistance, weathering resistance, thermostability and mechanical strength of macromolecular material.
Along with people exhaust day by day to the reinforcement of environmental protection consciousness and petrochemical industry resource; not only to low-carbon energy-saving, pollute less, the product cry of high added value, multifunction is day by day strong; requirement to material is also more and more higher, and green and high performance biomass-based macromolecular material will be subject to more and more higher attention.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, and a kind of preparation method of aqueous polyurethane of the silicon hybridization that comes from natural acid is provided.
Another object of the present invention is to provide the aqueous polyurethane of the silicon hybridization that comes from natural acid preparing by above-mentioned preparation method.
Object of the present invention is achieved through the following technical solutions: a kind of preparation method of aqueous polyurethane of the silicon hybridization that comes from natural acid, comprises the steps:
(1) come from the preparation of polyester polyol of the silicon hybridization of natural acid: 100 parts of dimeracids, 10~25 part of ten dihydroxystearic acid, 5~17 part of eight hydroxypropyl silsesquioxane and 18~25 parts of neopentyl glycol are carried out to the polyester polyol that polycondensation obtains coming from the silicon hybridization of natural acid.
(2) come from the preparation of aqueous polyurethane of the silicon hybridization of natural acid: by 100 parts of above-mentioned polyester polyol decompression dehydration 1~3h, be cooled to 55~70 ℃, the dihydroxyl compound and 40~46 parts of organic solvents that add 11~15 parts of carboxyls, the system for the treatment of is equal phase time, the isocyanic ester and 0.01~0.1 part of catalyzer that add 28~32Fen functional group degree to equal 2, 55~70 ℃ are reacted 2~4 hours, be cooled to 40~50 ℃, add 1~3 part of chainextender reaction 1~2h, add again 4~10 parts of neutralizing agent reaction 0.5~1h, under 600~1000rpm stirring velocity, add 220~360 parts of emulsifying waters to disperse, remove the silicon hybridization water-based urethane that acetone obtains coming from natural acid.
Above-mentioned umber is weight part.
Eight hydroxypropyl silsesquioxanes described in step (1) are preferably by the following method and prepare: in the aqueous sodium hydroxide solution of 1mol/L that is 1:1 in volume ratio by prestox acryloyl-oxy propyl group silsesquioxane and the mixed solvent of DMF, 70 ℃ of hydrolysis 12~24h obtain.Wherein, prestox acryloyl-oxy propyl group silsesquioxane preparation method is: the Virahol of 10 parts of methyl allyl acyloxypropyl trimethoxysilanes and 100 parts mixes, add again 8 parts of water and 3 parts of Tetramethylammonium hydroxide, at 40~50 ℃ of Water Under solution 24h, concentrated by rotary evaporation solution at 50 ℃; Then concentrated solution is added in toluene with saturated common salt solution washing toluene solution to neutral, add anhydrous magnesium sulfate drying toluene solution, obtain siloxanes oligopolymer toluene solution; Further in reflux in toluene condensation, obtain.Above-mentioned umber is weight part.
The condition optimization of the polycondensation described in step (1) is 130 ℃ of reaction 1h, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 8~12h.
The number-average molecular weight of the polyester polyol of the silicon hybridization that comes from natural acid described in step (1) is 1000~6000, is preferably 2900~4600.
Decompression dehydration described in step (2) is preferably at 120 ℃ of decompression dehydrations.
The dihydroxyl compound of the carboxyl described in step (2) is preferably one or both in 2,2-dimethylol propionic acid and 2,2-dimethylolpropionic acid.
Organic solvent described in step (2) is preferably the combination of acetone and DMF or N-Methyl pyrrolidone.The weight ratio of acetone and DMF or N-Methyl pyrrolidone is 6~10:1.
Functional group's degree described in step (2) equals 2 isocyanic ester and is preferably at least one in aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate; More there is choosing, it is diphenylmethanediisocyanate, tolylene diisocyanate, polyphenyl polymethylene polyisocyanates, 1 that described functional group's degree equals 2 isocyanic ester, 6-hexamethylene diisocyanate, 1,3,3-trimethylammonium-5-isocyanato-1-isocyanato methylcyclohexane and dicyclohexyl methyl hydride-4, at least one in 4 '-vulcabond.
Catalyzer described in step (2) is preferably machine metallic tin class; More have choosing, described catalyzer is dibutyl tin laurate or stannous octoate.
Chainextender described in step (2) is preferably BDO, ethylene glycol, neopentyl glycol, 1, at least one in 6-hexylene glycol, glycol ether, dipropylene glycol, quadrol, diethylenetriamine and triethylene tetramine.
Neutralizing agent described in step (2) is preferably at least one in triethylamine, sodium hydroxide and potassium hydroxide.
A kind of aqueous polyurethane that comes from the silicon hybridization of natural acid prepares by above-mentioned preparation method, and its weight solid content is 30~40%.
A kind of aqueous polyurethane that comes from the silicon hybridization of natural acid has advantages of that viscosity is low, tack is high and cohesive strength is large, can be applied to the surface treatment of soft polymer and bonding.
Dimeracid, ten dihydroxystearic acids, eight hydroxypropyl silsesquioxanes and neopentyl glycol prepare by polycondensation the polyester polyol that certain molecular weight distributes, and this polyester polyol is introduced to aqueous polyurethane by chemical bonding.The hydrophobic aliphatic hydrocarbon structure that dimeracid and ten dihydroxystearic acids contain long-chain, and ring-type and non-annularity structure, can improve water tolerance, the snappiness under low temperature, mechanical property and the thermostability of water-base polyurethane material.According to " six atom empirical laws " (Mblvin S.Newman, J.Am.Chem.Soc.72 (1950) 4783-4786), ester group surrounds shielding by two pending methyl groups in neopentyl glycol, and steric hindrance is large, can stop water molecules attack ester group, improve its hydrolytic resistance.In addition, adopting organosilicon chemical modification aqueous polyurethane can overcome organosilicon differs greatly and causes the shortcoming of organosilicon reunion with urethane solubility parameter.Gained organic silicon modified polyurethane material, when maintaining the advantages such as the excellent mechanical property of urethane and solvent resistance, has again excellent weathering resistance, flame retardant properties and thermostability.
The present invention has following advantage and effect with respect to prior art:
(1) take natural reproducible resource dimeracid and ten dihydroxystearic acids as copolycondensation monomer synthesizing polyester polyvalent alcohol.The use of biomass resource can reduce the utilization of petrochemical industry resource, breaks away from the dependence to petrochemical industry resource.The high polyvalent alcohol of this polyester not only synthetic cost is low, and on its molecular structure, contains large hydrophobic aliphatic hydrocarbon structure and part ring texture, can improve its water tolerance and hydrolytic resistance;
(2) cleverly neopentyl glycol is introduced to polyester polyol.Ester group on polyester polyol surrounds shielding by two pending methyl groups in neopentyl glycol, and steric hindrance is large, can stop water molecules attack ester group, has further improved hydrolytic resistance;
(3) eight hydroxypropyl silsesquioxanes (POSS) are introduced polyester polyol, can obtain POSS/ polymer hybridisation body.This product had both had organosilyl flame retardant resistance, thermotolerance, weathering resistance, had again the good snappiness of macromolecule resin, high tack, had organic and inorganic characteristic concurrently;
(4) adopt the aqueous polyurethane of water-dispersion self-emulsifying technology Preparation and storage good stability.Aqueous dispersion has, and zero release environmentally friendly, nontoxic, non-combustible, organic solvent has embodied its green, environmental protection, low-carbon (LC).
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Umber described in following embodiment is weight part.
Embodiment 1
(1) 100 parts of dimeracids, 10 part of ten dihydroxystearic acid, 17 part of eight hydroxypropyl silsesquioxane and 18 parts of neopentyl glycol are reacted to 1h at 130 ℃, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 8h polycondensations obtain the polyester polyol that number-average molecular weight is 4560 the silicon hybridization that comes from natural acid.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 1.5h, be then cooled to 55 ℃, add 11 parts of dimethylol propionic acids, 40 parts of acetone and 6 parts of DMFs; The system for the treatment of was equal phase time, adds 32 parts of diphenylmethanediisocyanates and 0.05 part of dibutyl tin laurate, 55 ℃ of reactions 4 hours.System temperature is reduced to 40 ℃, add 1.5 parts of quadrols at 40 ℃ of chain extending reaction 1.5h.Add again 8 parts of triethylamine neutralizations, reaction 1h.Under 1000rpm stir speed (S.S.), add 354 parts of emulsifying waters to disperse, and acetone removal is obtained coming from the aqueous polyurethane of weight solid content 30% of the silicon hybridization of natural acid.Its water-intake rate and hydrolytic resistance are as shown in table 1.
Embodiment 2
(1) 100 parts of dimeracids, 18 part of ten dihydroxystearic acid, 10 part of eight hydroxypropyl silsesquioxane and 19 parts of neopentyl glycol are reacted to 1h at 130 ℃, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 10h polycondensations obtain the polyester polyol that number-average molecular weight is 4200 the silicon hybridization that comes from natural acid.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 2h, be then cooled to 70 ℃, add 11 parts of dimethylol propionic acids, 36 parts of acetone and 6 parts of N-Methyl pyrrolidone.The system for the treatment of is equal phase time, adds 30 part 1,3, and 3-trimethylammonium-5-isocyanato-1-isocyanato methylcyclohexane and 0.1 part of stannous octoate, 70 ℃ of reactions 4 hours.System temperature is reduced to 50 ℃, add 2 parts of glycol ethers at 50 ℃ of chain extending reaction 2h.Add again 4 parts of sodium hydroxide neutralizations, reaction 0.5h.Under under 900rpm/min stir speed (S.S.), add 273 parts of emulsifying waters to disperse, and acetone removal is obtained coming from the aqueous polyurethane of weight solid content 35% of the silicon hybridization of natural acid.Its water-intake rate and hydrolytic resistance are as shown in table 1.
Embodiment 3
(1) 100 parts of dimeracids, 25 part of ten dihydroxystearic acid, 7 part of eight hydroxypropyl silsesquioxane and 20 parts of neopentyl glycol are reacted to 1h at 130 ℃, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 10h polycondensations obtain the polyester polyol that number-average molecular weight is 3920 the silicon hybridization that comes from natural acid.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 2h, be then cooled to 65 ℃, add 11 parts of dimethylol propionic acids, 40 parts of acetone and 5 parts of DMFs.The system for the treatment of is equal phase time, adds 33 parts of dicyclohexyl methyl hydride-4, and 4 '-vulcabond and 0.05 part of stannous octoate, 65 ℃ of reactions 3 hours.System temperature is reduced to 50 ℃, add 2.5 part 1,6-hexylene glycol is at 50 ℃ of chain extending reaction 2h.Add again 5 parts of sodium hydroxide neutralizations, reaction 0.5h.Under 800rpm/min stir speed (S.S.), add 281 parts of emulsifying waters to disperse, and acetone removal is obtained coming from the aqueous polyurethane of weight solid content 35% of the silicon hybridization of natural acid.Its water-intake rate and hydrolytic resistance are as shown in table 1.
Embodiment 4
(1) 100 parts of dimeracids, 20 part of ten dihydroxystearic acid, 10 part of eight hydroxypropyl silsesquioxane and 24 parts of neopentyl glycol polycondensations are reacted to 1h at 130 ℃, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 12h obtain the polyester polyol that number-average molecular weight is 3460 the silicon hybridization that comes from natural acid.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 3h, be then cooled to 60 ℃, add 15 parts of dimethylolpropionic acids, 40 parts of acetone and 4 parts of DMFs.The system for the treatment of was equal phase time, adds 28 parts of tolylene diisocyanates and 0.03 part of dibutyl tin laurate, 60 ℃ of reactions 2 hours.System temperature is reduced to 45 ℃, add 2 parts of diethylenetriamines at 50 ℃ of chain extending reaction 1h.Add again 10 parts of triethylamine neutralizations, reaction 40min.Under 700rpm/min stir speed (S.S.), add 253 parts of emulsifying waters to disperse, and acetone removal is obtained coming from the aqueous polyurethane of weight solid content 38% of the silicon hybridization of natural acid.Its water-intake rate and hydrolytic resistance are as shown in table 1.
Embodiment 5
(1) 100 parts of dimeracids, 25 part of ten dihydroxystearic acid, 5 part of eight hydroxypropyl silsesquioxane and 25 parts of neopentyl glycol polycondensations are reacted to 1h at 130 ℃, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, 210 ℃ of reaction 11h obtain the polyester polyol that number-average molecular weight is 2920 the silicon hybridization that comes from natural acid.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 2h, be then cooled to 70 ℃, add 15 parts of dimethylolpropionic acids, 36 parts of acetone and 4 parts of DMFs.The system for the treatment of is equal phase time, adds 28 part 1, and 6-hexamethylene diisocyanate and 0.08 part of stannous octoate, 70 ℃ of reactions 4 hours.System temperature is reduced to 40 ℃, add 1.5 parts of triethylene tetramines at 50 ℃ of chain extending reaction 1h.Add again 4 parts of sodium hydroxide neutralizations, reaction 0.5h.Under 600rpm/min stirs, add 223 parts of emulsifying waters to disperse, and acetone removal is obtained coming from the aqueous polyurethane of weight solid content 40% of the silicon hybridization of natural acid.Its water-intake rate and hydrolytic resistance are as shown in table 1.
Embodiment 6(comparative example)
(1) by 100 parts of hexanodioic acids and 80 parts of neopentyl glycol at 130 ℃ of reaction 1h, 150 ℃ of reaction 1h, 175 ℃ of reaction 1h, it is 3100 polyester polyol that 210 ℃ of reaction 12h polycondensation obtains number-average molecular weight.
(2) by 100 parts of above-mentioned polyester polyols at 120 ℃ of decompression dehydration 1.5h, be then cooled to 55 ℃, add 11 parts of dimethylolpropionic acids, 40 parts of acetone and 4 parts of DMFs.The system for the treatment of was equal phase time, adds 32 parts of diphenylmethanediisocyanates and 0.05 part of dibutyl tin laurate, 55 ℃ of reactions 4 hours.System temperature is reduced to 50 ℃, add 1.5 parts of quadrols at 50 ℃ of chain extending reaction 1.5h.Add again 7.5 parts of triethylamine neutralizations, reaction 1h.Under 600rpm/min stirs, add 228 parts of emulsifying waters to disperse, and acetone removal is obtained to the aqueous polyurethane of solid content 40%.Its water-intake rate and hydrolytic resistance are as shown in table 1.
The aqueous polyurethane that the aqueous polyurethane of the silicon hybridization that comes from natural acid that embodiment 1~5 prepares and comparative example (embodiment 6) obtain is poured in tetrafluoroethylene mould, Air drying 48h, 60 ℃ of dry 48h, 70 ℃ of vacuum-drying 24h, obtain aqueous polyurethane film forming matter.Film forming matter is carried out to water-intake rate test, hydrolytic resistance test, and method is as follows:
Water-intake rate testing method: by dried film forming matter, m weighs
0, immerse in 30 ℃ of deionized waters of constant temperature.Soak after certain hour, the surface of taking out and drying film forming matter with filter paper rapidly, m weighs
1.Formula is:
Hydrolytic resistance testing method: by dried film forming matter, m weighs
0, immerse 37 ℃ of 0.1mol/LNaOH(pH=13 of constant temperature) in solution, soak after certain hour, after taking out and being dried, m weighs
2.Formula is:
T-shaped peel strength test: embodiment 1~6 gained aqueous polyurethane emulsion is uniformly coated on polyolefin film, according to GB/T2791-1995 test, tensile strength 300mm/min, replicate(determination) three times, averages.This test is on polyethylene film.
The performance perameter of table 1 embodiment 1~6 gained aqueous polyurethane
Result by performance characterization shows: than the aqueous polyurethane of adipic acid type, the aqueous polyurethane that comes from the silicon hybridization of natural acid has excellent water tolerance and hydrolytic resistance and high T-shaped stripping strength, is suitable for the surface treatment of soft polymer and bonding.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.