CN107540829A - Polycarbonate polyol and aqueous polyurethane resin dispersion - Google Patents
Polycarbonate polyol and aqueous polyurethane resin dispersion Download PDFInfo
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- CN107540829A CN107540829A CN201710432112.8A CN201710432112A CN107540829A CN 107540829 A CN107540829 A CN 107540829A CN 201710432112 A CN201710432112 A CN 201710432112A CN 107540829 A CN107540829 A CN 107540829A
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- polycarbonate polyol
- repeat unit
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Abstract
The present invention provides a kind of polycarbonate polyol and aqueous polyurethane resin dispersion, the polycarbonate polyol can show the useful effect such as flexibility, light resistance when derivative is polyurethane.A kind of polycarbonate polyol, it is characterized in that, the polycarbonate polyol has the repeat unit represented by formula (A) and the repeat unit represented by formula (B), the mol ratio of repeat unit and the repeat unit represented by formula (B) represented by formula (A) is 10/90~90/10, and hydroxyl value is 20~600mgKOH/g.
Description
Technical field
The present invention relates to polycarbonate polyol and the waterborne polyurethane resin of the polycarbonate polyol has been used to disperse
Body.Polycarbonate polyol is the compound useful as the raw material of various polyurethane resins.
Background technology
Polyurethane resin is can be used as artificial leather, synthetic leather, coating, ink, coating material, elastomer, viscous
Connect the useful materials that the raw material of agent, adhesive etc. uses.In the past, the raw material as various polyurethane resins, is widely used
Polycarbonate polyol.
Wherein, disclose by 1,6- hexylene glycols and the PCDL of 1,9- nonanediol composition (for example, with reference to patent text
Offer 1).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-95852 publications
The content of the invention
Invent problem to be solved
Confirmed in above-mentioned patent document, high elastic modulus can be obtained by the PCDL and low-temperature characteristics is excellent
Polyurethane elastomer.
But be also used for due to polyurethane resin in the material of artificial leather, smears, elastomer etc., thus, still
So expect also show the effectively polycarbonate polyol of function and characteristic such as flexibility, light resistance in addition to above-mentioned characteristic
Alcohol.
The present invention problem be solve above-mentioned problem, there is provided one kind can be shown when derivative is polyurethane flexibility,
The polycarbonate polyol of the useful effect such as light resistance, extensibility.
Means for solving the problems
The problem of the present invention is solved by following polycarbonate polyols, and the polycarbonate polyol is characterised by, its
With the repeat unit represented by following formula (A) and the repeat unit represented by following formula (B),
The mol ratio of repeat unit represented by formula (A) and the repeat unit represented by formula (B) is 10/90~90/10,
Hydroxyl value is 20~600mgKOH/g.
[changing 1]
The effect of invention
According to the present invention it is possible to provide a kind of polycarbonate polyol, it can show softness when derivative is polyurethane
The useful effects such as property, light resistance.
Embodiment
[polycarbonate polyol]
The polycarbonate polyol of the present invention is characterised by that the polycarbonate polyol has following formula (A) represented
Repeat unit and following formula (B) represented by repeat unit,
The mol ratio of repeat unit represented by formula (A) and the repeat unit represented by formula (B) is 10/90~90/10,
Hydroxyl value is 20~600mgKOH/g.
[changing 2]
(repeat unit)
On the repeat unit in the polycarbonate polyol of the present invention, repeat unit and formula (B) institute represented by formula (A)
The mol ratio of the repeat unit of expression be 10/90~90/10, more preferably 20/80~80/20, more preferably 30/70~
70/30th, it is particularly preferably 51/49~65/35.
By for the scope, it is derivative turn to polyurethane when can give play to higher flexibility.
(hydroxyl value)
The hydroxyl value of the polycarbonate polyol of the present invention is 20~600mgKOH/g, is preferably 20~300mgKOH/g, more
Preferably 25~60mgKOH/g, particularly preferably 25~50mgKOH/g.
By for the scope, it is derivative turn to polyurethane when can give play to higher extensibility.
(acid number)
The acid number of the polycarbonate polyol of the present invention is preferably below 0.10mgKOH/g, is more preferably
Below 0.08mgKOH/g.
By the way that for the scope, the generation of accessory substance can be suppressed in urethane reaction.It is in addition, poly- with being made
The tendency that fracture strength during urethane film further increases.
(terminal olefin rate)
The end of polycarbonate polyol is usually hydroxyl, but is become sometimes represented by following formula in its manufacturing process
Alkene.
[changing 3]
The terminal olefin rate ratio of whole ends (alkene of end relative to) is preferably 1.5 moles of below %, entered
One step is preferably 1.0 moles of below %.
By the way that urethane reaction for the scope, can be sufficiently carried out.In addition, with when being made polyurethane film
The tendency that fracture strength further increases.
(end alkoxy group rate)
The end of polycarbonate polyol becomes alkoxy represented by following formula (as example sometimes in its manufacturing process
Son, methoxyl group is shown).
[changing 4]
The end alkoxy group rate ratio of whole ends (alkoxy of end relative to) be preferably 0.15 mole of % with
Under, more preferably 0.10 mole of below %.
By the way that urethane reaction for the scope, can be sufficiently carried out.In addition, with when being made polyurethane film
The tendency that fracture strength further increases.
(end alkoxy group carbonic ester rate)
The end of polycarbonate polyol becomes the alkoxy carbonic ester represented by following formula sometimes in its manufacturing process
Base (as an example, shows methoxyl group carbonate group).
[changing 5]
The end alkoxy group carbonic ester rate ratio of whole ends (the alkoxy carbonate group of end relative to) is preferably
For 0.15 mole of below %, more preferably 0.10 mole of below %.
By the way that urethane reaction for the scope, can be sufficiently carried out.
It should be noted that the polycarbonate polyol of the present invention can also have with the degree for not damaging function and characteristic
Ester bond, ehter bond.By with ester bond, it is contemplated that increase to compatibility when polyurethane is made.In addition, by with ehter bond, it is contemplated that
Further increase to flexibility when polyurethane is made.
(number-average molecular weight of polycarbonate polyol)
The number-average molecular weight of the polycarbonate polyol of the present invention can suitably adjust according to purpose, preferably 200~
6000th, it is more preferably 1500~5000, more preferably 2100~4000.
By the way that for the scope, the easy liquid of processing of polycarbonate polyol can be turned into, and by polycarbonate polyol
The low-temperature characteristics of the polyurethane of alcohol derivatization becomes good.In addition, stretched by the polyurethane film of polycarbonate polyol derivatization
Long property improves.
It should be noted that number-average molecular weight is the equal molecule of number calculated based on the hydroxyl value determined according to JIS K 1557
Amount.Specifically, hydroxyl value is determined, (should to calculate using (56.1 × 1000 × valence mumber)/hydroxyl value by end group sizing technique
In formula, the unit of hydroxyl value is [mgKOH/g]).In above formula, valence mumber is the hydroxyl value in a molecule.
(polyalcohol (monomer))
The polyalcohol of repeat unit represented by constitutional formula (A) is 1,6- hexylene glycols, the repetition list represented by constitutional formula (B)
The polyalcohol of member is 1,9- nonanediols.
, can be not damage the work(of the polyurethane of generated polycarbonate polyol or derivatization in these polyalcohols
The degree of energy and characteristic includes other polyalcohols on a small quantity.
(manufacture of polycarbonate polyol)
The manufacture method (hereinafter also referred to as " reaction of the invention ") of the polycarbonate polyol of the present invention is without special
Limit, such as following methods can be applied：
1,6- hexylene glycols, 1,9- nonanediols, carbonic ester and catalyst are mixed, while low boiling point component (example is distilled off
Such as, as alcohol caused by accessory substance etc.) while the method (being also referred to as one-step method sometimes below) for reacting it；
Any of 1,6- hexylene glycols and 1,9- nonanediol polyalcohol, carbonic ester and catalyst are mixed, on one side
Low boiling point component (for example, as alcohol caused by accessory substance etc.) is distilled off while making its reaction, manufactures polycarbonate polyol
(only being synthesized by one of which polyalcohol), and then the method for being reacted another polyalcohol (is also referred to as two sometimes below
Footwork).
It should be noted that the reaction of the present invention can also temporarily obtain the prepolymer of polycarbonate polyol (with mesh
It is low compared to molecular weight to mark polycarbonate polyol) after, make its reaction etc. to further improve molecular weight, reaction is divided into
Carry out more than twice.
On the dosage of above-mentioned 1,6- hexylene glycols and 1,9- nonanediol, meet the scope of above-mentioned prescribed limit in repeat unit
Interior appropriate adjustment.
(carbonic ester)
For example, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate for the carbonic ester used in the reaction of the present invention
The dialkyl carbonates such as ester；The diaryl carbonates such as diphenyl carbonate；Ethylene carbonate, propylene carbonate (4- methyl isophthalic acids, 3- bis-
Butyl oxide link -2- ketone, trimethylene carbonate methyl ester), butylene carbonate (4- ethyl -1,3- dioxolan-2-ones, carbonic acid tetramethylene
Ester), the cyclic carbonate such as 5- methyl isophthalic acids, 3- dioxane-2-ketones, it is preferably sub- using dimethyl carbonate, diethyl carbonate, carbonic acid
Ethyl ester.
It should be noted that these carbonic esters can be used alone or mix two or more uses.
Relative to 1 mole of the total amount of polyalcohol, the dosage of above-mentioned carbonic ester is preferably 0.8~2.0 mole, further preferably
For 0.9~1.5 mole.
By for the scope, can with sufficient reaction speed, be efficiently obtained target polycarbonate polyol.
(reaction temperature and reaction pressure)
Reaction temperature in the reaction of the present invention can suitably adjust according to the species of carbonic ester, preferably 50~250 DEG C,
More preferably 70~230 DEG C, all same in the case of using any of one-step method, two-step method.
In addition, as long as the reaction pressure in the reaction of the present invention, which turns into, removes low boiling point component while making its reaction
Mode as pressure, be just not particularly limited, preferably carry out under normal or reduced pressure.
By the way that target polycarbonate polyol for the scope, can be efficiently obtained without successive reaction, secondary anti-occurs
Should.
(catalyst)
As the catalyst used in the reaction of the present invention, known ester exchange catalyst can be used, can be enumerated
Such as the metal such as lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, strontium, barium, zinc, aluminium, titanium, zirconium, cobalt, germanium, tin, cerium and their hydride, hydrogen
Oxide, alkoxide, carboxylate, carbonate, bicarbonate, sulfate, phosphate, nitrate, organic metal etc., preferably using hydrogen
Change sodium, tetraisopropoxy titanium, four titanium butoxides, tetrabutyl zirconate, acetylacetone,2,4-pentanedione zirconium, zirconyl acetate, dibutyltindilaurylmercaptide cinnamic acid
Ester, dimethoxide base tin, Dibutyltin oxide.
It should be noted that these catalyst can be used alone or mix two or more uses.
Relative to 1 mole of the total amount of polyalcohol, the dosage of above-mentioned catalyst is preferably 0.001~0.1 mM, more preferably
For 0.005~0.05 mM, more preferably 0.03~0.05 mM.
By the way that for the scope, target polycarbonate polyol can be efficiently obtained without making post processing numerous and diverse.
It should be noted that the catalyst can use in the lump when reacting and starting, can also be when reacting beginning and anti-
(addition) is used after should starting in batches.
[polyurethane]
(it is also referred to as sometimes below by the polycarbonate polyol of the invention and polyisocyanates reaction that make as above to obtain
For " polyurethane-reinforcement reaction "), so as to obtain polyurethane.
As the flexible modulus of polyurethane as derived from the polycarbonate polyol of the present invention is low, elongation at break is high
Good flexibility, and light resistance is also excellent, is extremely useful material.
(polyisocyanates)
It as above-mentioned polyisocyanates, can suitably be selected according to purpose, purposes, such as 2,4- toluene two can be used different
Cyanate, 2,6- toluene di-isocyanate(TDI)s, diphenyl methane -4,4 '-diisocyanate, naphthalene -1,5- diisocyanate, 3,3 ' -
Dimethyl -4,4 '-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, XDI
(XDI), the araliphatic diisocyanate such as phenylene diisocyanate；4,4 '-methylene-bis-cyclohexyl diisocyanate, six methylenes
Group diisocyanate, IPDI, hexamethylene -1,3- diyls double (methylene) diisocyanate, trimethyls six
The aliphatic diisocyanates such as methylene diisocyanate.
It should be noted that these polyisocyanates can be used alone or mix two or more uses, the one of its structure
Partly or entirely can be with isocyanurate, carbodiimides or the derivatization such as biuretized.
On the dosage of polyisocyanates, be polyisocyanates NCO and polycarbonate polyol hydroxyl it
Than the amount that (NCO/hydroxyl (mol ratio)) is preferably 0.8~1.5, more preferably 0.9~1.3.
(chain extender)
In polyurethane-reinforcement reaction, for the purpose of increase molecular weight, chain extender can be used.As used chain extension
It agent, can suitably be selected, can be used for example according to purpose, purposes：
Water；
Ethylene glycol, 1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 1,6-HD, neopentyl glycol, the 1,10- last of the ten Heavenly stems two
Alcohol, 1,1-CHDM, 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, benzene dimethanol, double (to hydroxyl) biphenyl,
Double (p-hydroxybenzene) propane, 2,2- double [4- (2- hydroxyl-oxethyls) phenyl] propane, double [4- (2- hydroxyl-oxethyls) phenyl]
The low molecular polylols such as double [4- (2- hydroxyl-oxethyls) phenyl] hexamethylenes of sulfone, 1,1-；
PEPA, polyester amide polyol, PPG, polyester ether polylol, polycarbonate polyol, polyene
The macromolecule polyols such as hydrocarbon polyalcohol；
Ethylenediamine, IPD, 2- methyl isophthalic acids, 5- pentane diamines, amino ethyl ethanolamine, diethylenetriamines,
The polyamines such as trien, tetren, penten.
It should be noted that on chain extender, such as " newest polyurethane application technology " (Co., Ltd. C MC is referred to
Company, issue within 1985), on above-mentioned macromolecule polyol, be referred to for example " polyurethane foam " (meeting of macromolecule publication,
1987).
(urethanation catalyst)
In polyurethane-reinforcement reaction, in order to improve reaction speed, known polymerization catalyst can be used, can be with use example
Such as organic metal salt of tertiary amine, tin or titanium.
It should be noted that on polymerization catalyst, it is referred to Jitian and respects control work " polyurethane resin " (Japanese industry is new
Hear society periodical, 1969) page 23~32.
(solvent)
Polyurethane-reinforcement reaction can be carried out in the presence of the solvent, can use such as ethyl acetate, butyl acetate, acetic acid
The esters such as propyl ester, gamma-butyrolacton, gamma-valerolactone, δ-caprolactone；Dimethylformamide, diethylformamide, dimethylacetamide
The amide-types such as β-alkoxypropan acid amides representated by " Ekuamido " that amine, light extraction Xing Chan companies manufacture；The Asias such as dimethyl sulfoxide (DMSO)
Sulfone class；The ethers such as tetrahydrofuran, dioxane, cellosolvo；The ketones such as methyl iso-butyl ketone (MIBK), cyclohexanone；Benzene, toluene etc.
It is aromatic hydrocarbon.
Reacted for polyurethane-reinforcement, in order to adjust molecular weight, end-capping reagent can be added to carry out.
In addition, according to purpose, there can be thermostabilization in polyurethane with the amount for not damaging the scope of the effect of the present invention
Agent, light stabilizer, plasticizer, inorganic filler, lubricant, colouring agent, silicone oil, foaming agent, fire retardant etc..
Flexible polyurethane foams, hard polyurethane foams, thermoplastic polyurethane, solvent can be made in resulting polyurethane
It is polyurethane solutions, aqueous polyurethane resin dispersion etc..Further, it is possible to use they be processed into artificial leather, synthetic leather,
Formed bodys such as heat-insulating material, padded coaming, bonding agent, coating, smears, film etc..
[aqueous polyurethane resin dispersion]
On above-mentioned aqueous polyurethane resin dispersion, specifically, such as can by carry out successively following processes come
Manufacture：In the presence of the solvent or in the absence of polycarbonate polyol, the polyisocyanates and containing acidity under solvent, making the present invention
The polyol reaction of group, the process that carbamate prepolymer is made；Using nertralizer by the acidic groups in above-mentioned prepolymer
The process that group neutralizes；The process for making the prepolymer after neutralization disperse in water-medium；Make to be dispersed in the pre-polymerization in water-medium
The process of thing and chain extender reaction.
It should be noted that in each operation, catalyst can be used as needed, thus promote reaction, control by-product
Thing.
The aqueous polyurethane resin dispersion as derived from the polycarbonate polyol of the present invention can provide adaptation, softness
The excellent film of property, sense of touch, thus can be particularly suitable for artificial leather, synthetic leather.Further, since light resistance is also excellent,
Thus it is suitable for such as the coating in the material of outdoor application.
Polycarbonate polyol, polyisocyanates, solvent and chain extender can use above described in material.
In the case where manufacturing aqueous polyurethane resin dispersion, in order to be scattered in water-medium, contained using described later
The polyalcohol of acidic-group.Accordingly, with respect to the dosage of above-mentioned polyisocyanates, be polyisocyanates NCO with it is polynary
Alcohol (whole polyalcohols such as polycarbonate polyol, the polyalcohol described later containing acidic-group and low molecular polylol described later)
The ratio between all hydroxyls (NCO/hydroxyl (mol ratio)) are preferably 0.8~2.0, more preferably 0.9~1.8 amount.
(polyalcohol containing acidic-group)
As the above-mentioned polyalcohol containing acidic-group, for example, 2,2- dihydromethyl propionic acids, 2,2- dihydroxymethyls
The dihydroxymethyl alkanoic acid such as butyric acid；The double hydroxyethyl glycine of N, N-, the double hydroxyethyl alanine of N, N-, 3,4- dihydroxy butane
Sulfonic acid, 3,6- dihydroxy -2- toluenesulfonic acids, 12- hydroxy stearic acids etc., from the aspect of dispersiveness, preferably using dihydroxy first
Phenylalkanoic acid, more preferably use the alkanoic acid that the carbon number comprising 2 methylols is 4~12.
From the aspect of flexibility, the hydroxyl chain of 1 hydroxyl and 1~3 carboxyl is included using 12- hydroxy stearic acids etc.
Alkanoic acid.
It should be noted that these polyalcohols containing acidic-group can be used alone or mix two or more uses, its
As long as dosage polyurethane resin can be dispersed in the amount in water-medium, just it is not particularly limited.
(nertralizer)
As above-mentioned nertralizer, for example, trimethylamine, triethylamine, tri-isopropyl amine, tri-n-butylamine, triethanolamine, N-
Methyl diethanolamine, N- ethyldiethanolamines, N- phenyldiethanol-amines, dimethylethanolamine, diethyl ethylene diamine, N- methyl
The organic amines such as quinoline, pyridine；The inorganic base such as sodium hydroxide, potassium hydroxide salt, ammonia, preferably using organic amine, further it is excellent
Choosing uses tertiary amine.
It should be noted that these nertralizers can be used alone or mix two or more uses, as long as its dosage energy
The amount of the acidic-group in polyurethane resin is enough neutralized, is just not particularly limited.
(water-medium)
As above-mentioned water-medium, for example, the water such as running water, ion exchange water, distilled water, ultra-pure water, water with
Blending agent of hydrophilic organic solvent etc..
As above-mentioned hydrophilic organic solvent, for example, the ketones such as acetone, ethyl methyl ketone；N- crassitudes
The pyrrolidinone compounds such as ketone, N- ethyl pyrrolidones；The ethers such as diethyl ether, dimethyl ether；It is methanol, ethanol, normal propyl alcohol, different
The alcohols such as propyl alcohol, ethylene glycol, diethylene glycol；β-alkoxypropan acid amides representated by " kuamido " of the manufacture of light extraction Xing Chan companies
Deng amide-type；The tertiary amine of the hydroxyls such as 2- (dimethylamino) -2- methyl isophthalic acids-propyl alcohol (DMAP).
As the amount of the above-mentioned hydrophilic organic solvent in above-mentioned water-medium, preferably 0~20 mass %.
(low molecular polylol)
In the urethane reaction of the present invention, in order to adjust molecular weight, there may be low molecular polylol.As
Workable low molecular polylol, for example, ethylene glycol, 1,3-PD, 2- methyl isophthalic acids, ammediol, 2,2- diformazans
Base -1,3- propane diols, 1,4- butanediols, 1,5- pentanediols, 3- methyl isophthalic acids, 5- pentanediols, 1,6-HD etc..
It should be noted that these low molecular polylols can be used alone or mix two or more uses.
Embodiment
Then, enumerate embodiment the present invention is specifically described, but the scope of the present invention is not limited to these implementations
Example.
(number-average molecular weight)
The calculating of number-average molecular weight is carried out based on following formula.
Number-average molecular weight=(56100 × 2)/hydroxyl value
It should be noted that the hydroxyl value of polycarbonate polyol is obtained according to JIS K 1557 by titration.Herein, hydroxyl value
Unit is mgKOH/g.
In addition, the acid number of polycarbonate polyol is obtained according to JIS K 1557 by titration.Herein, the unit of acid number is
mgKOH/g。
(repeat unit in polycarbonate polyol)
Polycarbonate polyol 1g, ethanol 30g and potassium hydroxide 4g are mixed, stirred 1 hour at 95~105 DEG C.
After stirring terminates, it is neutralized with hydrochloric acid, after the generated potassium chloride of filtering, dilutes filtrate with ethanol, use gas-chromatography
Analyzed.
For detected polyalcohol (A) and polyalcohol (B), quantified using some calibration curve methods, will be all
The total amount of monomer component is set to 100%, calculates each repeat unit (mole %).
It is as described below using the analysis condition of gas-chromatography.
Device：Gas-chromatography GC-2010 (Shimadzu Seisakusho Ltd.'s manufacture)
Post：DB-WAX (manufacture of J＆W companies of the U.S.), 0.25 μm of thickness, length 30m
Column temperature：60 DEG C (being kept for 5 minutes) → 250 DEG C (holdings)
Programming rate：10 DEG C/min
Carrier gas：Helium
Detector：Flame ionization ditector (FID)
Injection rate：0.5μL
(embodiment 1：The synthesis of polycarbonate polyol)
In the glass system round-bottomed flask for possess rectifying column, agitating device, thermometer and nitrogen ingress pipe mix 1,6- oneself
Glycol 551.24g (4.66 moles), 1,9- nonanediols 498.73g (3.11 moles), dimethyl carbonate 719.02g (7.98 moles,
More than 99%) and four titanium butoxide 0.096g (0.28 mM), low boiling point component is distilled off at ambient pressure while
95~185 DEG C are reacted 11 hours.
And then under normal pressure~decompression (below 13.3kPa), while will include 1,6- hexylene glycols and 1,9- nonanediol into
Divide and be distilled off, while carrying out reacting for 10 hours at 165~190 DEG C, obtain the polycarbonate polyol as thick liquid
(1)。
The number-average molecular weight of resulting polycarbonate polyol is 2000, hydroxyl value 56.1mgKOH/g, acid number are
0.04mgKOH/g, composition are as follows.
Repeat unit (A)：54.5 mole %
Repeat unit (B)：45.5 mole %
(embodiment 2：The synthesis of polycarbonate polyol)
In the glass system round-bottomed flask for possess rectifying column, agitating device, thermometer and nitrogen ingress pipe mix 1,6- oneself
Glycol 242.21g (2.05 moles), 1,9- nonanediols 268.35g (1.67 moles), dimethyl carbonate 342.61g (3.80 moles,
More than 99%) and four titanium butoxide 0.046g (0.14 mM), low boiling point component is distilled off at ambient pressure while
100~190 DEG C are reacted 7 hours.
And then under normal pressure~decompression (below 13.3kPa), while will include 1,6- hexylene glycols and 1,9- nonanediol into
Divide and be distilled off, while carrying out reacting for 12 hours at 165~200 DEG C, obtain the polycarbonate polyol as thick liquid
(2)。
The number-average molecular weight of resulting polycarbonate polyol is 1945, hydroxyl value 57.7mgKOH/g, acid number are
0.06mgKOH/g, composition are as follows.
Repeat unit (A)：48.4 mole %
Repeat unit (B)：51.6 mole %
(embodiment 3：The synthesis of polycarbonate polyol)
In the glass system round-bottomed flask for possess rectifying column, agitating device, thermometer and nitrogen ingress pipe mix 1,6- oneself
Glycol 512.67g (4.34 moles), 1,9- nonanediols 539.11g (3.36 moles), dimethyl carbonate 710.21g (7.88 moles,
More than 99%) and four titanium butoxide 0.104g (0.31 mM), low boiling point component is distilled off at ambient pressure while
95~190 DEG C are reacted 8 hours.
And then under normal pressure~decompression (below 13.3kPa), while will include 1,6- hexylene glycols and 1,9- nonanediol into
Divide and be distilled off, while carrying out reacting for 25 hours at 165~205 DEG C, obtain the polycarbonate polyol as thick liquid
(3)。
The number-average molecular weight of resulting polycarbonate polyol is 3024, hydroxyl value 37.1mgKOH/g, acid number are
0.04mgKOH/g, composition are as follows.
Repeat unit (A)：49.3 mole %
Repeat unit (B)：50.7 mole %
By the viscosity (cP) when the composition of resulting polycarbonate polyol, molecular weight and 75 DEG C, terminal olefin
Rate, end alkoxy group rate and end alkoxy group carbonic ester rate are concluded and are shown in table.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| The repeat unit (mole %) of formula (A) | 54.5 | 48.4 | 49.3 |
| The repeat unit (mole %) of formula (B) | 45.5 | 51.6 | 50.7 |
| Number-average molecular weight | 2000 | 1945 | 3024 |
| Hydroxyl value (mgKOH/g) | 56.1 | 57.7 | 37.1 |
| Acid number (mgKOH/g) | 0.04 | 0.06 | 0.04 |
| Viscosity (75 DEG C) | 1916 | 1767 | 6436 |
| Terminal olefin rate (%) | 0.032 | 0.208 | 0.552 |
| Terminal methoxy group rate (%) | 0.001 | 0.002 | 0.001 |
| Terminal methoxy group carbonic ester rate (%) | 0.058 | 0.044 | 0.003 |
(comparative example 1：The preparation of polycarbonate polyol)
Polycarbonate polyol (3) (the emerging production strain in space portion obtained from preparation makes 1,6-HD and dimethyl carbonate
The manufacture of formula commercial firm, ETERNACOLL (registration mark) UH-200 (molecular weight 2000, hydroxyl value 56.1mgKOH/g, acid number
0.03mgKOH/g)。
(comparative example 2：The synthesis of polycarbonate polyol)
1,9- nonyls are mixed in the glass system round-bottomed flask for possess rectifying column, agitating device, thermometer and nitrogen ingress pipe
Glycol 2356.05g (14.70 moles), dimethyl carbonate 1286.48g (14.28 moles, more than 99%) and four titanium butoxides
0.21g (0.62 mM), low boiling point component is distilled off at ambient pressure while being reacted 12 hours at 95~190 DEG C.
And then under normal pressure~decompression (below 13.3kPa), while the composition that will include 1,9- nonanediols is distilled off,
While carrying out reacting for 23 hours at 165~215 DEG C, the polycarbonate polyol (4) as thick liquid is obtained.
(comparative example 3：The preparation of polycarbonate polyol)
Polycarbonate polyol (5) (the emerging production strain in space portion obtained from preparation makes 1,6-HD and dimethyl carbonate
The manufacture of formula commercial firm, ETERNACOLL (registration mark) UH-300 (molecular weight 2907, hydroxyl value 38.6mgKOH/g, acid number
0.03mgKOH/g)。
(synthesis 1 of aqueous polyurethane resin dispersion)
In possessing the reaction unit of mixer and heater, by embodiment 1~2 and the makrolon of comparative example 1~2
Polyalcohol 257g and 2,2- dihydromethyl propionic acids 8.1g, dicyclohexyl methyl hydride -4,4 '-diisocyanate 88g, 12- hydroxy stearate
Sour 34g, dimethyl ether 157g and dibutyl tin (IV) dilaurate 0.3g are mixed respectively, in a nitrogen atmosphere, in
80~90 DEG C of reactions, 5 hours (isocyanate group contents at the end of reaction：1.33 mass %).
Resulting reaction solution is cooled to 80 DEG C, adds triethylamine 17.9g thereto, is stirred 30 minutes.It is mixed in reaction
Extract 531g among compound out, be added in the water 700g being stirred vigorously.
And then 35 mass % diethylenetriamines aqueous solution 15.1g are added, obtain aqueous polyurethane resin dispersion.
(synthesis 2 of aqueous polyurethane resin dispersion)
In possessing the reaction unit of mixer and heater, by embodiment 3 and the polycarbonate polyol of comparative example 3
Alcohol 260g, 2,2- dihydromethyl propionic acid 7.8g, dicyclohexyl methyl hydride -4,4 '-diisocyanate 74g, 12- hydroxy stearic acid 34g,
Dimethyl ether 118g and dibutyl tin (IV) dilaurate 0.3g mixing, it is in a nitrogen atmosphere, anti-in 80~90 DEG C
Answer 5 hours (isocyanate group contents at the end of reaction：1.31 mass %).
Resulting reaction solution is cooled to 80 DEG C, adds triethylamine 17.4g thereto, is stirred 30 minutes.It is mixed in reaction
Extract 471g among compound out, be added in the water 692g being stirred vigorously.
And then 35 mass % diethylenetriamines aqueous solution 13.2g are added, obtain aqueous polyurethane resin dispersion.
(synthesis of urethane resin film)
Above-mentioned aqueous polyurethane resin dispersion is equably applied on polyethylene terephthalate (PET) film,
It is about 80 μm to make dried thickness.Next, after placing 15 hours at room temperature, dried 2 hours at 60 DEG C, it is dry at 120 DEG C
Dry 2 hours, form polyurethane resin.
Next, from PET film peeling strength polyurethane resin, conserve 10 hours at room temperature, thus obtain urethane resin film.
It should be noted that the water-based poly- ammonia on having used the polycarbonate polyol obtained in embodiment and comparative example
Ester resin dispersion and the aqueous polyurethane resin dispersion for having used commercially available polycarbonate polyol, also carry out equally
Operation, has obtained urethane resin film.
(flexibility)
Using the method according to JIS K 7113, the modulus of elasticity, elongation at break, fracture of above-mentioned polyurethane film are determined
Intensity.
(light resistance)
Ultraviolet is irradiated to polyurethane film with following conditions.Utilize the film obtained by being determined according to JIS K 7113 method
Fracture strength, observe the change of fracture strength.
Use lamp：Xenon lamp
Irradiation level：765W/m2
Time：138 hours
Radiant exposure：380MJ/m2
Wavelength：300~800nm
Blackboard temperature：100℃
(result)
○：Fracture strength does not change.
×：It was observed that the reduction of fracture strength.
[table 2]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| The repeat unit (mole %) of formula (A) | 54.5 | 48.4 | 49.3 | 100 | 0 | 100 |
| The repeat unit (mole %) of formula (B) | 45.5 | 51.6 | 50.7 | 0 | 100 | 0 |
| Modulus of elasticity (MPa) | 7 | 7 | 8 | 9 | 12 | 12 |
| 100% modulus (MPa) | 1.2 | 1.1 | 1.7 | 1.4 | 1.2 | 2.3 |
| Elongation at break (%) | 900 | 770 | 940 | 740 | 930 | 740 |
| Fracture strength (MPa) | 25 | 18 | 22 | 37 | 32 | 32 |
| Light resistance (uv-resistance) | ○ | ○ | ○ | ○ | ○ | ○ |
From result above, aqueous polyurethane resin dispersion derived from the polycarbonate polyol as the present invention is used
The modulus of elasticity of obtained urethane resin film is low, flexibility is excellent, and has good light resistance.
Therefore, the aqueous polyurethane resin dispersion of the polycarbonate polyol of the present invention has been used specifically to may be used as people
The raw material of work leather, synthetic leather, coating, ink, coating material, elastomer, bonding agent, adhesive etc..
Industrial applicibility
The present invention relates to new polycarbonate polyol and the aqueous polyurethane tree of the polycarbonate polyol is used
Fat dispersion.The polycarbonate polyol of the present invention is the compound useful as the raw material of various polyurethane resins.
Claims (9)
1. a kind of polycarbonate polyol, it is characterised in that the polycarbonate polyol has the repetition represented by following formula (A)
Repeat unit represented by unit and following formula (B),
The mol ratio of repeat unit represented by formula (A) and the repeat unit represented by formula (B) is 10/90~90/10,
Hydroxyl value is 20~600mgKOH/g,
[changing 6]
2. polycarbonate polyol as claimed in claim 1, its hydroxyl value is 25~60mgKOH/g.
3. polycarbonate polyol as claimed in claim 1, its hydroxyl value is 25~50mgKOH/g.
4. such as polycarbonate polyol according to any one of claims 1 to 3, its acid number is below 0.10mgKOH/g.
5. such as polycarbonate polyol according to any one of claims 1 to 4, its terminal olefin rate be 1.5 moles of % with
Under.
6. such as polycarbonate polyol according to any one of claims 1 to 5, its end alkoxy group rate is 0.15 mole of %
Below.
7. such as polycarbonate polyol according to any one of claims 1 to 6, its end alkoxy group carbonic ester rate is 0.15
Mole below %.
8. a kind of polyurethane, it is that usage right requires that the polycarbonate polyol any one of 1~7 obtains.
9. a kind of aqueous polyurethane resin dispersion, it is the polycarbonate polyol any one of usage right requirement 1~7
What alcohol obtained.
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Cited By (2)
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|---|---|---|---|---|
| CN111019079A (en) * | 2019-12-20 | 2020-04-17 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane urea and preparation method and application thereof |
| CN115011300A (en) * | 2021-12-14 | 2022-09-06 | 烟台德邦科技股份有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
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| JPH0335054A (en) * | 1989-07-01 | 1991-02-15 | Kuraray Co Ltd | Thermoplastic polyurethane composition |
| JPH04239024A (en) * | 1991-01-11 | 1992-08-26 | Asahi Chem Ind Co Ltd | Production of hydroxyl-terminated polycarbonate |
| CN103347923A (en) * | 2011-02-10 | 2013-10-09 | 宇部兴产株式会社 | Waterborne polyurethane resin dispersion and use thereof |
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| CN111019079A (en) * | 2019-12-20 | 2020-04-17 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane urea and preparation method and application thereof |
| CN111019079B (en) * | 2019-12-20 | 2022-02-18 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane urea and preparation method and application thereof |
| CN115011300A (en) * | 2021-12-14 | 2022-09-06 | 烟台德邦科技股份有限公司 | High-temperature-resistant polyurethane hot melt adhesive and preparation method thereof |
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