CN107556452A - A kind of castor oil-base hydrophilic chain extender and its preparation method and application - Google Patents
A kind of castor oil-base hydrophilic chain extender and its preparation method and application Download PDFInfo
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- CN107556452A CN107556452A CN201710832189.4A CN201710832189A CN107556452A CN 107556452 A CN107556452 A CN 107556452A CN 201710832189 A CN201710832189 A CN 201710832189A CN 107556452 A CN107556452 A CN 107556452A
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Abstract
The present invention discloses a kind of castor oil-base hydrophilic chain extender and its preparation method and application.The present invention is from one of renewable resource castor oil, hydroxyl, which is introduced, using sulfydryl alkene light click-reaction obtains intermediate, again by hydrolysis of ester group react generation carboxyl (or first pass through castor oil hydrolysis of ester group reaction generation castor oil acid, sulfydryl alkene light click-reaction is recycled to introduce hydroxyl), the hydrophilic chain extender containing at least two hydroxyls and a carboxyl is prepared, and is applied to the preparation of anion aqueous polyurethane emulsion.Castor oil is applied to hydrophilic chain extender raw material by the present invention, for widening natural oil lipid products application and improving its added value, by with positive reference value, and for reducing or serving positive effect instead of environmental problem caused by the use of petroleum-type non-renewable resources.All it is liquid under castor oil-base hydrophilic chain extender normal temperature prepared by the present invention, bigger with the contact area of other raw materials during reaction, evenly, reaction speed is faster for mixing.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of castor oil-base hydrophilic chain extender and preparation method thereof and
Using.
Background technology
Polyurethane is widely used in national economy various fields because of its remarkable performance, as coating, foam, adhesive
Deng.Solvent borne polyurethane produces substantial amounts of VOC, including toluene, butanone etc. in use, and environment and workmen are caused
Greatly injury, therefore it is imperative to develop aqueous polyurethane emulsion.Aqueous polyurethane is typically by polyalcohol, isocyanates, parent
Water chain extender is prepared for raw material, and polyalcohol, the species of isocyanates are all very more, and the pass prepared as aqueous polyurethane emulsion
The hydrophilic chain extender of one of key monomer, but only dimethylolpropionic acid (DMBA), 2,2- dihydromethyl propionic acids (DMPA) etc. are several.
Solubility is low in acetone for DMPA, DMBA these petrochemical industry base hydrophilic chain extenders, and fusion temperature is high so that aqueous polyurethane it is equal
Even property fluctuation is extremely strong, and preparation process greatly relies on the experience of operator, has had a strong impact on the stability production of aqueous polyurethane.
On the other hand, because fossil resources increasingly depleted and its price are influenceed by external factors such as politics, larger, Yi Jixian is fluctuated
Active demand of the generation life to environmental protection, development renewable resource prepare green polyurethane production as the substitute of fossil resources
Product turn into a main trend of domestic and international scientific research and industrial quarters.
Vegetable oil is wide as a kind of typical renewable biomass resources, (mainly triglycerides) simple in construction, source
It is general, cheap.And China's vegetable oil resource is very abundant, possesses huge advantage in terms of Developing Biomass material.It is many
Contain 1-7 unsaturated double-bond and 3 ester bonds, and the active reactive group such as more hydroxyls in plant oil structure, it is convenient to carry out
Chemical modification and synthesis, possess the architecture basics of structure high polymer monomer and its material system in theory.U.S. Pittsburgh
State University, Iowa State University, French Institut Charles Gerhardt
The unit such as Montpellier and domestic South China Science ＆ Engineering University is in vegetable oil Efficient Conversion chemical products with high added-value and its high score
Sub- material (coating, lubricating oil, adhesive, plasticizer etc.) has done substantial amounts of work.
From vegetable oil, the renewable content of aqueous polyurethane can further be improved by preparing hydrophilic chain extender, and due to
The fusing point of vegetable oil is low, is liquid under prepared hydrophilic chain extender normal temperature, is expected to further improve the performance of aqueous polyurethane.
Such as Ruqi Chen (2014) successfully prepare the anionic polyhydroxy that can substitute DMPA, DMBA etc. with epoxy linseed oil
Base aliphatic acid hydrophilic chain extender.Jiangxi Science ＆ Technology Normal University pays Changqing etc. and utilizes sulfydryl-alkene click-reaction, with castor oil and 3- mercaptos
Base propionic acid reacts, and synthesizes a kind of novel hydrophilic chain extender：Castor oil-base polybasic carboxylic acid (MCO).
It is seldom that the patent of novel hydrophilic chain extender is prepared at present, and not using recyclable materials as matrix, such as disclose
Number a kind of carboxylic acid type aqueous polyurethane chain extender and preparation method thereof is invented for CN104356330A Chinese invention patent, it is public
The number of opening is that CN106046288A Chinese invention patent has invented a kind of hydrophilic chain extender and preparation method and application, the above two
Although kind of a patent of invention is all successfully prepared the more excellent chain extender of performance, it is expected to substitute traditional chain extender, is all with oil
Sill is matrix.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, primary and foremost purpose of the invention are to provide a kind of castor oil-base hydrophilic
Chain extender.
Another object of the present invention is to provide the preparation method by above-mentioned castor oil-base hydrophilic chain extender.
Further object of the present invention is in the application in the above-mentioned castor oil-base hydrophilic chain extender of offer in aqueous polyurethane.
The purpose of the present invention is achieved through the following technical solutions：
A kind of castor oil-base hydrophilic chain extender, shown in its structural formula such as formula (1)：
Wherein, the natural number of n=1~5, R are alkyl of the main chain less equal than 10 carbon；Preferably, n=1 or 2, R are
Straight chained alkyl of the length in 2~10 carbon.
The preparation method of described castor oil-base hydrophilic chain extender, comprises the following steps：
(1) light trigger measured, castor oil and mercaptan are sequentially added, under magnetic agitation and ultraviolet light react 1~
5h；Using organic solvent not soluble in water as solvent, salt solution washing reaction product 3~5 times, aqueous phase is abandoned, is removed water with drier, is taken out
Filter, revolving, obtain intermediate product light yellow viscous liquid castor oil-base polyalcohol (CO-SH or CO-TG), first step reaction knot
Beam；
(2) intermediate product made from step (1) is put into 60~80 DEG C, dries 0~14h；Appropriate intermediate product is taken, 60
Appropriate bases are added under~80 DEG C of magnetic agitations, react 1~10h, acid is added and reaction system is adjusted to acidity；Have with not soluble in water
Solvent is solvent, salt solution washing reaction product 3~5 times, abandons aqueous phase, is removed water with drier, is filtered, and revolving, obtains hydrophilic expansion
Chain agent, i.e. castor oil-base hydrophilic chain extender.
Or
(A) castor oil is taken, appropriate bases are added under 60~80 DEG C of magnetic agitations, reacts 1~10h, adds acid by reactant
System is adjusted to acidity；Using organic solvent not soluble in water as solvent, salt solution washing reaction product 3~5 times, aqueous phase is abandoned, uses drier
Water removal, filter, revolving, obtain intermediate product castor oil acid；
(B) sequentially add light trigger, intermediate product castor oil acid and mercaptan made from step (A), in magnetic agitation and
1~5h is reacted under ultraviolet light；Using organic solvent not soluble in water as solvent, salt solution washing reaction product 3~5 times, aqueous phase is abandoned, used
Drier removes water, and filters, and revolving, obtains hydrophilic chain extender, i.e. castor oil-base hydrophilic chain extender.
The preparation method of described castor oil-base hydrophilic chain extender also includes first carrying out step (2) with castor oil, obtains
Intermediate product substitutes castor oil and carries out step (1), i.e. step (A) (B) again.
The dosage of light trigger described in step (1) is (quality of quality+mercaptan of castor oil) × 2%~(castor-oil plant
The quality of quality+mercaptan of oil) × 3%.
The sulfydryl mol ratio in the double bond and mercaptan in castor oil described in step (1) is 1:1.5~1:5.5.
The ester group of intermediate product described in step (2) and the mol ratio of alkali are 1:1~1:3.
The mol ratio of ester group in castor oil and alkali described in step (A) is 1:1~1:3.
The dosage of light trigger described in step (B) be (quality of quality+mercaptan of intermediate product castor oil acid) ×
2%~(quality of quality+mercaptan of intermediate product castor oil acid) × 3%.
Sulfydryl mol ratio in the double bond and mercaptan of intermediate product castor oil acid described in step (B) is 1:1.5~1:
5.5。
Light trigger described in step (1), (B) refers to that one kind can trigger monomer polymerization crosslinking to solidify under ultraviolet light
Compound, including light trigger 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone, abbreviation HMPP), 184,907,369,
1490th, 1700, BP, 261, NS-1, NS-2, PBCP, CCP, NCP, BCP, CS-1, CS-2, Photobase generator ketoxime ester, cobalt-amine network
Compound, formamide, quaternary ammonium salt, alkali multiplication agent benzene fulfonic amide carbamate, 9- fluorenes carbamates, 3-Nitropentane Ji Anjijia
Acid esters etc., preferably light trigger 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone, abbreviation HMPP)；
Mercaptan described in step (1), (B) refers to the unitary mercaptan containing one or more hydroxyls, including mercaptoethanol, sulphur
For glycerine, 1- sulfydryl -2- propyl alcohol, 2- sulfydryl -3- butanol, 6- sulfydryl hexanols etc., preferably mercaptoethanol or thioglycerol；
Step (1), (2), (A), the organic solvent not soluble in water described in (B) include ethyl acetate, dichloromethane, stone
Oily ether, ether, carbon tetrachloride etc., preferably ethyl acetate；
Step (1), (2), (A), the drier described in (B) include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride
Deng preferably anhydrous magnesium sulfate；
Acid described in step (2), (A) includes hydrochloric acid, sulfuric acid, acetic acid, nitric acid, carbonic acid, phosphoric acid etc., preferably hydrochloric acid；
Alkali described in step (2), (A) includes sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydrogensulfite, potassium carbonate
Deng preferably sodium hydroxide；
Application of the described castor oil-base hydrophilic chain extender in aqueous polyurethane is prepared.
A kind of Anionic Water-borne Polyurethane Emulsion, including following components in parts by weight：
20~130 parts of castor oil-base hydrophilic chain extenders, 100 parts of polyalcohols, 40~210 parts of diisocyanate, 0.25~3.4
Part catalyst, 125~680 parts of organic solvents, 250~1700 parts of water, 4~40 parts of nertralizers.
Described polyalcohol includes PEPA, PPG and natural oil polyols；PEPA includes poly-
Carbonic ester dihydric alcohol (PCDL), dimer acid polyester dihydric alcohol (PDFA), phthalic acid polyester dihydric alcohol (PPA), polyadipate-
1,4- butanediol esters dihydric alcohol (PBA), polycaprolactone diols (PCL), polyadipate -1,6-HD esterdiol (PHA) etc.；
PPG includes PTMG (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG) etc.；Natural oil is polynary
Alcohol includes castor oil and vegetable oil-based polyols, and wherein vegetable oil-based polyols include linseed oil polylol, soybean oil base
Polyalcohol, corn based oil, coconut based oil, cauliflower based oil etc., preferably in natural oil polyols
Castor oil；
Described diisocyanate include isoflurane chalcone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), two
Methylenebis phenyl isocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), hexamethylene diisocyanate
(HMDI), lysine diisocyanate (LDI), 1, hexamethylene-diisocyanate (HDI) etc., preferably isoflurane chalcone diisocyanate
(IPDI)；
Described catalyst includes dibutyl tin laurate (DBTDL), stannous octoate, triethylenediamine, N-ethyl
Morpholine, triethylenediamine, N, N-dimethyl cyclohexyl amine etc., preferably dibutyl tin laurate (DBTDL)；
Described organic solvent includes butanone, acetone, toluene, dimethylbenzene, butyl acetate, cyclohexanone etc., preferably butanone；
Described nertralizer includes triethylamine (TEA), dimethylethanolamine (DMEA), ammoniacal liquor, sodium hydroxide, hydroxide
Potassium, sodium acid carbonate, triethanolamine etc., preferably triethylamine (TEA).
The preparation method of described Anionic Water-borne Polyurethane Emulsion, comprises the following steps：
Castor oil-base hydrophilic chain extender, polyalcohol and diisocyanate are taken, 100~300r/min in 50~80 DEG C of oil bath
5~20min is stirred, adds catalyst, continues the stirring reaction in 60~80 DEG C of oil bath；Almost flowed not when solution viscosity increases to
When dynamic, organic solvent to be added, continues 1~7h of stirring in 60~80 DEG C, reaction system is changed into clear, stops heating, etc.
After solution is cooled to room temperature, nertralizer is added, continues to stir, after rotating speed is adjusted to 300~500r/min, adds water emulsification, continue to stir
Mix 1~4h；40~60 DEG C of revolving 30min~1h of product are obtained into Anionic Water-borne Polyurethane Emulsion.
The preparation principle of described castor oil-base hydrophilic chain extender, including following chemical reaction：
The preparation principle of castor oil-base hydrophilic chain extender also includes the ester group in first hydrolyzed castor oil, then connects sulfydryl
Mercaptoethanol in principle (3) is changed to thioglycerol.
The present invention mechanism be：
The present invention introduces hydroxyl from one of typical renewable resource castor oil using sulfydryl-alkene light click-reaction
Obtain intermediate, then generation carboxyl is reacted by hydrolysis of ester group and (or first passes through the hydrolysis of ester group reaction generation castor-oil plant of castor oil
Oleic acid, sulfydryl-alkene light click-reaction is recycled to introduce hydroxyl), prepare the hydrophilic chain extension containing at least two hydroxyls and a carboxyl
Agent, and it is applied to the preparation of anion aqueous polyurethane emulsion, and the performance of the aqueous polyurethane class coating material to preparation
Characterized.The influence that intensity of illumination, reaction rate of charge, light application time hit product structure to sulfydryl-alkene luminous point has been probed into simultaneously,
Fully improve double bond conversion rate.
The present invention is had the following advantages and effect relative to prior art：
(1) castor oil is applied to hydrophilic chain extender raw material by the present invention, for widen natural oil lipid products application with
Its added value is improved, by with positive reference value, and for reducing or making instead of petroleum-type non-renewable resources
Environmental problem serves positive effect caused by.
(2) all it is liquid under hydrophilic chain extender COFA-SH and COFA-TG normal temperature prepared by the present invention, compared under normal temperature
For DMPA, DMBA of solid-state, bigger with the contact area of other raw materials during reaction, evenly, reaction speed is faster for mixing.
Brief description of the drawings
Fig. 1 is the castor oil-base hydrophilic chain extender (COFA-SH) of embodiment 1, intermediate product castor oil-base polyalcohol (CO-
SH) with the GPC spectrograms of castor oil (Castor oil).
Fig. 2 is the castor oil-base hydrophilic chain extender (COFA-TG) of embodiment 2, the castor oil-base hydrophilic chain extender of embodiment 1
(COFA-SH) with the GPC spectrograms of castor oil (CO).
Fig. 3 is the castor oil-base hydrophilic chain extender COFA-SH (c) and its intermediate product castor oil-base polyalcohol of embodiment 1
CO-SH (b), embodiment 2 castor oil-base hydrophilic chain extender COFA-TG (d) and castor oil (a)1H-NMR schemes.
Fig. 4 is castor oil-base hydrophilic chain extension of the castor oil-base hydrophilic chain extender (COFA-SH) with embodiment 2 of embodiment 1
Aqueous polyurethane emulsion grain-size graph prepared by agent (COFA-TG).
Fig. 5 is the film stress-strain diagram of obtained part aqueous polyurethane emulsion in test example 1；Wherein, (a)
Using the COFA-SH of embodiment 1 as hydrophilic chain extender；(b) using the COFA-TG of embodiment 2 as hydrophilic chain extender.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) light trigger 1173 measured, castor oil and mercaptoethanol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:4.5；Light trigger dosage is (oil quality+mercaptoethanol quality) × 2%), it is anti-under magnetic agitation and ultraviolet light
Answer 4.5h.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, rotation
Steam, obtain light yellow viscous liquid castor oil-base polyalcohol CO-SH, first step reaction terminates.
(2) intermediate product made from step (1) is put into 60 DEG C of baking ovens, dries 12h.Take appropriate intermediate product CO-SH in
In single port bottle, appropriate NaOH is added under 80 DEG C of magnetic agitations, and (ester group is 1 with NaOH mol ratios:2) 5h, is reacted, adding HCl will
Reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, is removed with anhydrous magnesium sulfate
Water, filter, revolving, obtain COFA-SH hydrophilic chain extenders.
Gel permeation chromatography (GPC) is tested, and using polystyrene as standard specimen, tetrahydrofuran (THF) is mobile phase, and flow velocity is
0.5mL/min, test temperature are 35 DEG C, are measured using 2414 differential refractometers as detecting instrument.
Fig. 1 is castor oil (CO), castor oil-base polyalcohol (CO-SH), the GPC spectrograms of hydrophilic chain extender (COFA-SH), is gathered
Compound drenches that the time is shorter, and molecular weight is bigger, is known by Fig. 1,3 kinds of polymer, molecular weight it is maximum be CO-SH, castor oil takes second place,
Illustrate that mercaptoethanol reacts with double bond, be successfully introduced into castor oil molecule.And COFA-SH molecular weight is minimum, illustrate CO-SH
In ester group hydrolyzed.
Proton nmr spectra is analyzed, and nuclear-magnetism test is carried out using the type NMRs of Bruker Avance 600, with
CDCl3For solvent.
Fig. 3 is castor oil (a), castor oil-base polyalcohol CO-SH (b), hydrophilic chain extender COFA-SH (c)1H-NMR schemes,
(a) displacement of hydrogen (- CH=CH-) disappears completely in (b), (c) on unsaturated double-bond in castor oil near δ=5.43ppm in
Lose, illustrate that double bond participates in reacting completely.And occurs-CH at δ=2.6ppm (b)2- S- Hydrogen Proton peak, illustrate into
Work(introduces mercaptoethanol molecule.(b), (c) in comparison diagram 3, the displacement of the upper hydrogen of δ=5.27ppm-COO-CH- and δ in (b)=
- COO-CH at 4.31ppm, δ=4.15ppm2The displacement of-upper hydrogen has all been wholly absent in (c), illustrates intermediate product CO-SH
Three ester groups have all been hydrolyzed on strand, generation target product COFA-SH.
Embodiment 2
(1) light trigger 1173 measured, castor oil and thioglycerol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:4.5；Light trigger dosage is (oil quality+thioglycerol quality) × 2%), it is anti-under magnetic agitation and ultraviolet light
Answer 4.5h.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, rotation
Steam, obtain light yellow viscous liquid castor oil-base polyalcohol CO-TG, first step reaction terminates.
(2) intermediate product made from step (1) is put into 60 DEG C of baking ovens, dries 12h.Take appropriate intermediate product CO-TG in
In single port bottle, appropriate NaOH is added under 80 DEG C of magnetic agitations, and (ester group is 1 with NaOH mol ratios:2) 5h, is reacted, adding HCl will
Reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, is removed with anhydrous magnesium sulfate
Water, filter, revolving, obtain COFA-TG hydrophilic chain extenders.
Fig. 2 is the castor oil (CO), hydrophilic chain extender COFA-SH, hydrophilic chain extender COFA- of 2414 differential refractometers measure
TG GPC spectrograms, as seen from the figure, hydrophilic chain extender COFA-TG molecular weight are bigger than hydrophilic chain extender COFA-SH molecular weight,
This is that the molecular weight of thioglycerol is big more caused than mercaptoethanol, illustrates that COFA-TG successfully introduces thioglycerol and divides
In subchain, and hydrophilic chain extender COFA-TG molecular weight is smaller than castor oil, illustrates that the ester group in CO-TG has hydrolyzed.
(d) in Fig. 3 is the hydrophilic chain extender COFA-TG of the type nmr determinations of Bruker Avance 600 core
Magnetic hydrogen spectrogram, the displacement of hydrogen (- CH=CH-) is complete in (d) on unsaturated double-bond in castor oil near δ=5.43ppm in (a)
Mistake is totally disappeared, illustrates that double bond participates in reacting completely.And occurs-CH at δ=2.6ppm (d)2- S- Hydrogen Proton peak, explanation
It has been successfully introduced into mercaptoethanol molecule.Simultaneously the displacement of the upper hydrogen of δ=5.27ppm-COO-CH- and δ=4.31ppm, δ in (a)=
- COO-CH at 4.15ppm2The displacement of-upper hydrogen has all been wholly absent in (d), illustrates on intermediate product CO-TG strands three
Ester group has all been hydrolyzed, generation target product COFA-TG.
Embodiment 3
(1) light trigger 1173 measured, castor oil and mercaptoethanol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:1.5；Light trigger dosage is (oil quality+mercaptoethanol quality) × 2%), it is anti-under magnetic agitation and ultraviolet light
Answer 5h.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, revolving,
Light yellow viscous liquid castor oil-base polyalcohol CO-SH is obtained, first step reaction terminates.
(2) intermediate product CO-SH made from appropriate step (1) is taken in single port bottle, is added under 60 DEG C of magnetic agitations suitable
Measuring NaOH, (ester group is 1 with NaOH mol ratios:1) 1h, is reacted, HCl is added and reaction system is adjusted to acidity.Using ethyl acetate to be molten
Agent, salt solution washing reaction product 3 times, abandons aqueous phase, is removed water with anhydrous magnesium sulfate, filters, and revolving, obtains the hydrophilic chain extensions of COFA-SH
Agent.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 1.
Embodiment 4
(1) light trigger 1173 measured, castor oil and thioglycerol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:1.5；Light trigger dosage is (oil quality+thioglycerol quality) × 3%), it is anti-under magnetic agitation and ultraviolet light
Answer 1h.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, revolving,
Light yellow viscous liquid castor oil-base polyalcohol CO-TG is obtained, first step reaction terminates.
(2) intermediate product made from step (1) is put into 80 DEG C of baking ovens, dries 14h.Take appropriate intermediate product CO-TG in
In single port bottle, appropriate NaOH is added under 60 DEG C of magnetic agitations, and (ester group is 1 with NaOH mol ratios:3) 10h, is reacted, adds HCl
Reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed with anhydrous magnesium sulfate
Water, filter, revolving, obtain COFA-TG hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 2.
Embodiment 5
(1) light trigger 1173 measured, castor oil and mercaptoethanol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:2.5；Light trigger dosage is (oil quality+mercaptoethanol quality) × 3%), it is anti-under magnetic agitation and ultraviolet light
Answer 5h.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, revolving,
Light yellow viscous liquid castor oil-base polyalcohol CO-SH is obtained, first step reaction terminates.
(2) intermediate product made from step (1) is put into 80 DEG C of baking ovens, dries 12h.Take appropriate intermediate product CO-SH in
In single port bottle, appropriate NaOH is added under 60 DEG C of magnetic agitations, and (ester group is 1 with NaOH mol ratios:1.5) 1h, is reacted, adds HCl
Reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed with anhydrous magnesium sulfate
Water, filter, revolving, obtain COFA-SH hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 1.
Embodiment 6
(1) light trigger 1173 measured, castor oil and thioglycerol are sequentially added in test tube, and (double bond and sulfydryl rub
You are than being 1:5.5；Light trigger dosage is (oil quality+thioglycerol quality) × 2%), it is anti-under magnetic agitation and ultraviolet light
Answer 5h.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, filtered, revolving,
Light yellow viscous liquid castor oil-base polyalcohol CO-TG is obtained, first step reaction terminates.
(2) intermediate product made from step (1) is put into 80 DEG C of baking ovens, dries 12h.Take appropriate intermediate product CO-TG in
In single port bottle, appropriate NaOH is added under 60 DEG C of magnetic agitations, and (ester group is 1 with NaOH mol ratios:1.5) 1h, is reacted, adds HCl
Reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 3 times, aqueous phase is abandoned, is removed with anhydrous magnesium sulfate
Water, filter, revolving, obtain COFA-TG hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 2.
Embodiment 7
(1) appropriate castor oil is taken in single port bottle, and appropriate NaOH (ester group and NaOH moles are added under 80 DEG C of magnetic agitations
Than for 1:2.5) 1h, is reacted, HCl is added and reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product
5 times, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, is filtered, revolving obtains intermediate product castor oil acid, and first step reaction terminates.
(2) light trigger 1173 measured is sequentially added in test tube, castor oil acid and sulfydryl second made from step (1)
(double bond is 1 with sulfydryl mol ratio to alcohol:5.5；Light trigger dosage is (castor oil acid quality+mercaptoethanol quality) × 3%),
4.5h is reacted under magnetic agitation and ultraviolet light.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, use is anhydrous
Magnesium sulfate removes water, and filters, and revolving, obtains COFA-SH hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 1.
Embodiment 8
(1) appropriate castor oil is taken in single port bottle, and appropriate NaOH (ester group and NaOH moles are added under 80 DEG C of magnetic agitations
Than for 1:1) 5h, is reacted, HCl is added and reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 5
It is secondary, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, is filtered, revolving obtains intermediate product castor oil acid, and first step reaction terminates.
(2) light trigger 1173 measured is sequentially added in test tube, castor oil acid made from step (1) and thio sweet
(double bond is 1 with sulfydryl mol ratio to oil:4.5；Light trigger dosage is (castor oil acid quality+thioglycerol quality) × 3%),
4.5h is reacted under magnetic agitation and ultraviolet light.Using ethyl acetate as solvent, salt solution washing reaction product 5 times, aqueous phase is abandoned, use is anhydrous
Magnesium sulfate removes water, and filters, and revolving, obtains COFA-TG hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 2.
Embodiment 9
(1) appropriate castor oil is taken in single port bottle, and appropriate NaOH (ester group and NaOH moles are added under 80 DEG C of magnetic agitations
Than for 1:3) 10h, is reacted, HCl is added and reaction system is adjusted to acidity.Using ethyl acetate as solvent, salt solution washing reaction product 4
It is secondary, aqueous phase is abandoned, is removed water with anhydrous magnesium sulfate, is filtered, revolving obtains intermediate product castor oil acid, and first step reaction terminates.
(2) light trigger 1173 measured is sequentially added in test tube, castor oil acid and sulfydryl second made from step (1)
(double bond is 1 with sulfydryl mol ratio to alcohol:5.5；Light trigger dosage is (castor oil acid quality+mercaptoethanol quality) × 2%),
3h is reacted under magnetic agitation and ultraviolet light.Using ethyl acetate as solvent, salt solution washing reaction product 4 times, aqueous phase is abandoned, with anhydrous sulphur
Sour magnesium water removal, filters, revolving, obtains COFA-SH hydrophilic chain extenders.
The hydrophilic chain extender GPC spectrograms that are measured with 2414 differential refractometers and it is total to the type nuclear-magnetisms of Bruker Avance 600
The hydrophilic chain extender nucleus magnetic hydrogen spectrum figure of Vibration Meter measure, acquired results characteristic peak are all same as Example 1.
Test example 1：Each embodiment product all-round property testing
Castor oil-base hydrophilic chain extender prepares aqueous polyurethane emulsion made from each embodiment
Appropriate castor oil-base hydrophilic chain extender, diisocyanate and 6g polyalcohols made from the various embodiments described above are taken in double necks
In round-bottomed flask, 5~20min of electric mixer (rotating speed be 100~300r/min) stirring is used in 50~80 DEG C of oil bath.Add
Add 1~6 drop catalyst, continue the stirring reaction in 60~80 DEG C of oil bath.When solution viscosity, which increases to, almost flows motionless, addition
10~50mL organic solvents, continue 1~7h of stirring in 60~80 DEG C, and reaction system is changed into clear.Stop heating, wait molten
After liquid is cooled to room temperature, appropriate nertralizer is added, continues to stir 30min.After rotating speed is adjusted to 300~500r/min, add 20~
90mL deionized waters emulsify, and continue 1~4h of stirring.Product is transferred to single necked round bottom flask, 40~60 DEG C of revolving 30min~1h
Obtain the Anionic Water-borne Polyurethane Emulsion that solid content is 10.68~57.8wt%.
The hydroxyl in polyalcohol described in above step, the hydroxyl in the NCO and hydrophilic chain extender of diisocyanate
Base mol ratio is 1：(1.5~3)：(0.49~1.99).
The degree of neutralization of nertralizer described in above step is 85%~110%.
Polyalcohol described in above step includes PEPA, PPG and natural oil polyols, polyester polyols
Alcohol include PCDL (PCDL), dimer acid polyester dihydric alcohol (PDFA), phthalic acid polyester dihydric alcohol (PPA),
Polyadipate -1,4- butanediol esters dihydric alcohol (PBA), polycaprolactone diols (PCL), polyadipate -1,6-HD ester two
Alcohol (PHA) etc.；PPG includes PTMG (PTMG), polypropylene glycol (PPG), polyethylene glycol (PEG) etc.；
Natural oil polyols include castor oil and vegetable oil-based polyols, and wherein vegetable oil-based polyols include linseed oil Quito member
Alcohol, soybean oil base polyol, corn based oil, coconut based oil, cauliflower based oil etc., preferably natural oil
Castor oil in polyalcohol；
Diisocyanate described in above step includes isoflurane chalcone diisocyanate (IPDI), toluene di-isocyanate(TDI)
(TDI), methyl diphenylene diisocyanate (MDI), dicyclohexyl methyl hydride diisocyanate (HMDI), the isocyanide of hexa-methylene two
Acid esters (HMDI), lysine diisocyanate (LDI), 1, preferably hexamethylene-diisocyanate (HDI) etc., the isocyanide of isophorone two
Acid esters (IPDI)；
Catalyst described in above step includes dibutyl tin laurate (DBTDL), stannous octoate, triethylene two
Amine, N-dionin quinoline, triethylenediamine, N, N-dimethyl cyclohexyl amine etc., preferably dibutyl tin laurate
(DBTDL)；
Organic solvent described in above step includes butanone, acetone, toluene, dimethylbenzene, butyl acetate, cyclohexanone etc., excellent
Elect butanone as；
Nertralizer described in above step include triethylamine (TEA), dimethylethanolamine (DMEA), ammoniacal liquor, sodium hydroxide,
Potassium hydroxide, sodium acid carbonate, triethanolamine etc., preferably triethylamine (TEA).
Aqueous polyurethane emulsion particle diameter and Zeta potential test, are diluted to 0.01%, at room temperature, respectively by sample by emulsion
It is placed in cuvette and current potential pond, the particle diameter and Zeta potential of aqueous polyurethane emulsion is determined using Malvern nano particle size instrument.
Test result is shown in Fig. 4 and table 1.
The aqueous polyurethane emulsion that as can be seen from Table 1 prepared by novel hydrophilic chain extender, average grain diameter is small, and Zeta potential is exhausted
High to value, stability of emulsion is excellent.Using COFA-SH as aqueous polyurethane emulsion made from hydrophilic chain extender, average grain diameter is 40
Between~154nm, Zeta potential absolute value is in more than 38.2mV；Using COFA-TG as aqueous polyurethane made from hydrophilic chain extender
Emulsion, average grain diameter is between 87~150nm, and Zeta potential absolute value is in more than 37mV.Fig. 4 is the castor oil-base of embodiment 1
Hydrophilic chain extender (COFA-SH) and the aqueous polyurethane breast prepared by the castor oil-base hydrophilic chain extender (COFA-TG) of embodiment 2
Liquid grain-size graph, it can be seen that the particle diameter distribution of emulsion is all concentrated very much, good dispersion.
Each embodiment properties of product test result of table 1
Test example 2
Aqueous polyurethane emulsion prepared by each embodiment castor oil-base hydrophilic chain extender made from test example 1 is cast
Into silica gel mould, 80 DEG C of baking 48h, obtained film dries 24h in 60 DEG C of baking ovens.It is hydrophilic to obtain each embodiment castor oil-base
Aqueous polyurethane emulsion film prepared by chain extender.
Film Analysis of tensile strength, UTM4204 type universal electricals testing machine measure photocuring is used according to GB13022-91
The mechanical property of film, sample thickness 1mm, a width of 10mm, draw speed 100mm/min.Test result is shown in Fig. 5 and table 1.
As can be seen from Table 1 novel hydrophilic chain extender prepare aqueous polyurethane film, have good tensile strength and
Excellent elongation at break.All exist by aqueous polyurethane film made from hydrophilic chain extender, tensile strength of COFA-SH
More than 0.59MPa, elongation at break is more than 310%；Applied by aqueous polyurethane made from hydrophilic chain extender of COFA-TG
Film, tensile strength is all in more than 3.35MPa, and elongation at break is more than 80%.
Fig. 5 (a) is with the aqueous polyurethane film stress-strain diagram of hydrophilic chain extender preparation made from embodiment 1, Fig. 5
(b) it is with the aqueous polyurethane film stress-strain diagram of hydrophilic chain extender preparation made from embodiment 2.As can be seen that with
COFA-SH is that aqueous polyurethane film made from hydrophilic chain extender has excellent ductility, available for equipment diaphragm, rubber cushion
Etc.；There is excellent tensile strength by aqueous polyurethane film made from hydrophilic chain extender of COFA-TG, while have good
Good ductility, application are more extensive.The aqueous polyurethane film excellent in mechanical performance prepared with novel hydrophilic chain extender, energy
Fully meet the demand of practice.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. castor oil-base hydrophilic chain extender, it is characterised in that：Shown in its structural formula such as formula (1)：Wherein, the natural number of n=1~5, R are alkyl of the main chain less equal than 10 carbon.
- 2. the preparation method of the castor oil-base hydrophilic chain extender described in claim 1, it is characterised in that comprise the following steps：(1) light trigger measured, castor oil and mercaptan are sequentially added, 1~5h is reacted under magnetic agitation and ultraviolet light；With Organic solvent not soluble in water is solvent, salt solution washing reaction product 3~5 times, abandons aqueous phase, is removed water with drier, is filtered, rotation Steam, obtain intermediate product light yellow viscous liquid castor oil-base polyalcohol, first step reaction terminates；(2) intermediate product made from step (1) is put into 60~80 DEG C, dries 0~14h；Appropriate intermediate product is taken, 60~80 Appropriate bases are added under DEG C magnetic agitation, react 1~10h, acid is added and reaction system is adjusted to acidity；With not soluble in water organic molten Agent is solvent, salt solution washing reaction product 3~5 times, abandons aqueous phase, is removed water with drier, is filtered, and revolving, obtains hydrophilic chain extender, That is castor oil-base hydrophilic chain extender.
- 3. the preparation method of the castor oil-base hydrophilic chain extender described in claim 1, it is characterised in that comprise the following steps：(A) castor oil is taken, appropriate bases are added under 60~80 DEG C of magnetic agitations, reacts 1~10h, acid is added and adjusts reaction system To acidity；Using organic solvent not soluble in water as solvent, salt solution washing reaction product 3~5 times, aqueous phase is abandoned, is removed water with drier, Filter, revolving, obtain intermediate product castor oil acid；(B) light trigger is sequentially added, intermediate product castor oil acid and mercaptan made from step (A), in magnetic agitation and ultraviolet 1~5h is reacted under light；Using organic solvent not soluble in water as solvent, salt solution washing reaction product 3~5 times, aqueous phase is abandoned, uses drying Agent removes water, and filters, and revolving, obtains hydrophilic chain extender, i.e. castor oil-base hydrophilic chain extender.
- 4. the preparation method of castor oil-base hydrophilic chain extender according to claim 2, it is characterised in that：The dosage of light trigger described in step (1) is (quality of quality+mercaptan of castor oil) × 2%~(castor oil The quality of quality+mercaptan) × 3%；The sulfydryl mol ratio in the double bond and mercaptan in castor oil described in step (1) is 1:1.5~1:5.5；The ester group of intermediate product described in step (2) and the mol ratio of alkali are 1:1~1:3.
- 5. the preparation method of castor oil-base hydrophilic chain extender according to claim 3, it is characterised in that：The mol ratio of ester group in castor oil and alkali described in step (A) is 1:1~1:3；The dosage of light trigger described in step (B) be (quality of quality+mercaptan of intermediate product castor oil acid) × 2%~ (quality of quality+mercaptan of intermediate product castor oil acid) × 3%；Sulfydryl mol ratio in the double bond and mercaptan of intermediate product castor oil acid described in step (B) is 1:1.5~1:5.5.
- 6. the preparation method of the castor oil-base hydrophilic chain extender according to Claims 2 or 3, it is characterised in that：Described light trigger refers to a kind of compound that monomer polymerization crosslinking can be triggered to solidify under ultraviolet light, including light Initiator 1173,184,907,369,1490,1700, BP, 261, NS-1, NS-2, PBCP, CCP, NCP, BCP, CS-1, CS-2, Photobase generator ketoxime ester, cobalt-amine complex, formamide, quaternary ammonium salt, alkali multiplication agent benzene fulfonic amide carbamate, 9- fluorenes amino first Acid esters, 3-Nitropentane aminocarbamic acid ester；Described mercaptan refers to the unitary mercaptan containing one or more hydroxyls, including mercaptoethanol, thioglycerol, 1- sulfydryls -2- Propyl alcohol, 2- sulfydryl -3- butanol, 6- sulfydryl hexanols.
- 7. the preparation method of the castor oil-base hydrophilic chain extender according to Claims 2 or 3, it is characterised in that：Described organic solvent not soluble in water includes ethyl acetate, dichloromethane, petroleum ether, ether, carbon tetrachloride；Described drier includes anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous calcium chloride；Described acid includes hydrochloric acid, sulfuric acid, acetic acid, nitric acid, carbonic acid, phosphoric acid；Described alkali includes sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium hydrogensulfite, potassium carbonate.
- 8. application of the castor oil-base hydrophilic chain extender in aqueous polyurethane is prepared described in claim 1.
- 9. a kind of Anionic Water-borne Polyurethane Emulsion, it is characterised in that including following components in parts by weight：Castor oil-base hydrophilic chain extender, 100 parts of polyalcohols, 40~210 part of two isocyanic acid described in 20~130 parts of claims 1 Ester, 0.25~3.4 part of catalyst, 125~680 parts of organic solvents, 250~1700 parts of water, 4~40 parts of nertralizers.
- 10. the preparation method of the Anionic Water-borne Polyurethane Emulsion described in claim 9, it is characterised in that including following step Suddenly：Castor oil-base hydrophilic chain extender, polyalcohol and diisocyanate are taken, 100~300r/min is stirred in 50~80 DEG C of oil bath 5~20min, catalyst is added, continue the stirring reaction in 60~80 DEG C of oil bath；When solution viscosity increase to almost flow it is motionless When, organic solvent is added, continues 1~7h of stirring in 60~80 DEG C, reaction system is changed into clear, stops heating, waits molten After liquid is cooled to room temperature, nertralizer is added, continues to stir, after rotating speed is adjusted to 300~500r/min, adds water emulsification, continue stirring 1 ~4h；40~60 DEG C of revolving 30min~1h of product are obtained into Anionic Water-borne Polyurethane Emulsion.
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