CN114591489B - Silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane and preparation method thereof - Google Patents
Silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane, which comprises the following steps: the preparation method comprises the following steps of (1) copolymerizing an epoxy compound, an epoxy monomer containing double bonds and carbon dioxide serving as monomers to obtain long-chain double-bond polyether-carbonate polyol, and carrying out click chemistry on the long-chain double-bond polyether-carbonate polyol and a mercapto carboxylic acid monomer to obtain long-chain carboxyl polyether-carbonate polyol; mixing long-chain carboxyl polyether-carbonate polyol, diisocyanate and a polyhydroxy chain extender, reacting to prepare an aqueous polyurethane prepolymer, and performing graft modification by using an aminosilane coupling agent and water chain extension to obtain the silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane. The silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane has high emulsification efficiency and excellent emulsion stability; has excellent mechanical performance, heat resistance and hydrophobicity.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane and a preparation method thereof.
Background
The waterborne polyurethane generally consists of isocyanate, a polyol soft segment and a hydrophilic chain extender, wherein the carboxylic acid type hydrophilic chain extender is dimethylolpropionic acid and dimethylolbutyric acid generally, and the waterborne polyurethane prepolymer obtained by the method contains ionizable group carboxyl; after neutralization, the aqueous polyurethane emulsion can be obtained under high-speed stirring in water. However, the carboxyl group of the ionizable group is a short chain carboxyl group, which is close to the main chain, the carboxyl group has low mobility, and the hydrophilic group is easily folded and wrapped in the process of emulsifying by adding water, so the emulsifying effect is poor, and therefore, the content of the carboxyl group in the prepolymer needs to be further increased, but the water resistance is poor.
Chinese patent document with application publication No. CN 109485815A discloses a preparation method of aqueous polyurethane emulsion, the aqueous polyurethane emulsion prepared by the method and application thereof, the method comprises the steps of firstly, according to the molar parts, heating and stirring 85-95 parts of polyol and 5-15 parts of cyclobutane tetracarboxylic dianhydride, heating to 80-120 ℃, and reacting at constant temperature for 4-5 hours to obtain soft-segment carboxylic acid type polyol; then adding a hydrophilic chain extender such as dimethylolbutyric acid to prepare the self-emulsifying waterborne polyurethane.
According to the technical scheme, the soft segment carboxylic acid type polyol is prepared by modifying the soft segment polyol, and then the soft segment carboxylic acid type polyol is used as a raw material to prepare the waterborne polyurethane, so that the stability of the waterborne polyurethane emulsion is improved. However, the carboxyl group in the soft segment carboxylic acid type polyol is still a short chain carboxyl group, and is easily folded and wrapped by a polymer chain in the emulsification process, so the emulsification efficiency is low, and a carboxylic acid type hydrophilic monomer is still required to be added to improve the emulsification effect, which not only makes the preparation process of polyurethane complicated, but also requires higher carboxylic acid addition amount.
Theoretically, compared with the traditional hydrophilic chain extender and short chain carboxyl, the long side chain carboxyl has stronger activity capability and is expected to have better emulsification efficiency, so that the emulsion stability of the waterborne polyurethane is effectively improved. However, there is no report on this aspect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane, and the prepared waterborne polyurethane has excellent emulsion stability, mechanical property, heat resistance and hydrophobicity.
The specific technical scheme is as follows:
a preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane comprises the following steps:
(1) Taking an epoxy compound, an epoxy monomer containing double bonds and carbon dioxide as monomers, and copolymerizing to obtain long-chain double-bond polyether-carbonate polyol;
the mass ratio of the epoxy compound to the double bond-containing epoxy monomer is 100:4 to 18;
in the long-chain double-bond polyether-carbonate polyol, the double-bond density is 0.5-2.5 mol%;
(2) Mixing the long-chain double-bond polyether-carbonate polyol with a mercapto carboxylic acid monomer, and performing click chemistry to obtain long-chain carboxyl polyether-carbonate polyol;
(3) Mixing the long-chain carboxyl polyether-carbonate polyol, diisocyanate and a polyhydroxy chain extender, reacting to obtain a polyurethane prepolymer with an NCO group at the tail end, and neutralizing with an alkaline substance to obtain a water-based polyurethane prepolymer;
(4) And mixing the waterborne polyurethane prepolymer and an aminosilane coupling agent, reacting to obtain a silicon-modified long-chain carboxyl polyether-carbonate-based waterborne polyurethane prepolymer, mixing with water, and reacting to obtain the silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane.
The invention discloses a preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane, which comprises the steps of firstly adding an epoxy monomer containing double bonds into copolymerization reaction of an epoxy compound and carbon dioxide to serve as a third reaction monomer, and obtaining long-chain double-bond polyether-carbonate polyol after copolymerization; then carrying out click reaction on double bonds in the long-chain double-bond polyether-carbonate polyol and-SH in a mercapto carboxylic acid monomer to obtain long-chain carboxyl polyether-carbonate polyol; the long-chain carboxyl polyether-carbonate polyol is used as a soft segment, reacts with diisocyanate and a polyhydroxy chain extender to prepare a waterborne polyurethane prepolymer, is modified by an amino-containing silane coupling agent, and is subjected to chain extension to obtain the waterborne polyurethane.
In the step (1):
the epoxy compound is selected from ethylene oxide and/or propylene oxide;
the double bond-containing epoxy monomer is selected from allyl glycidyl ether and/or alkene butyl glycidyl ether;
the mass ratio of the epoxy compound to the double bond-containing epoxy monomer is 100:4 to 11;
in the reaction system, the pressure of the carbon dioxide is 2-5 MPa;
the copolymerization is carried out at the temperature of 70-120 ℃ for 5-24 h.
An initiator and a catalyst are also added into the reaction system, and the initiator simultaneously plays a function of a chain transfer agent and is selected from polyhydroxy micromolecules or polyhydroxy polymers;
the polyhydroxy micromolecules are selected from common species such as propylene glycol, butanediol and the like; the polyhydroxy polymer is selected from common types such as polyethylene glycol, polypropylene glycol and the like.
Preferably, the initiator is selected from polypropylene glycol, and tests show that by using polypropylene glycol as the initiator and the chain transfer agent, on one hand, other chain segments can be introduced as little as possible, the chain segments of the product are more regular, and the molecular weight distribution is narrower; on the other hand, the properties are stable, the phase state is not influenced by the experiment temperature and pressure, and the experiment error is reduced.
More preferably, the polypropylene glycol has a number average molecular weight selected from 200 to 1000g/mol. Tests show that the long-chain double-bond polyether-carbonate polyol prepared by using the polypropylene glycol with the number average molecular weight range as the initiator has moderate number average molecular weight, and the waterborne polyurethane film finally prepared by using the polypropylene glycol as a soft segment has better mechanical property.
The catalyst is selected from double metal cyanide complex, specifically zinc-cobalt double metal cyanide complex, tetraphenylporphyrin aluminum complex, and bisphenol zinc oxideComplexes, beta-diimine zinc complexes, bimetallic imine zinc complexes and schiff base (salen) metal complexes, et 2 Zn/protic compound systems, zinc carboxylate systems, rare earth metal in combination with other metals (e.g., zinc) systems, and the like.
Preferably:
the mass ratio of the epoxy compound, the initiator and the catalyst is 100:5 to 30:0.01 to 0.1.
In the step, the mass ratio of the epoxy compound to the double-bond-containing epoxy monomer is particularly important, and the double-bond density in the prepared long-chain double-bond-based polyether-carbonate polyol can be controlled by controlling the mass ratio. Tests show that the mass ratio is controlled to be 100: 4-18 hours, the double bond density in the long-chain double bond polyether-carbonate polyol can be controlled to be 0.5-2.5%, and at the moment, the finally prepared waterborne polyurethane emulsion has excellent stability, and no obvious precipitate is generated after centrifugation at 3000r/min for 15 minutes. The film has good water resistance and the applicable temperature range of the material is wider.
Further preferably, the mass ratio of the epoxy compound to the double bond-containing epoxy monomer is 100:4.3 to 9.1; the double bond density in the long-chain double-bond polyether-carbonate polyol can be controlled to be 0.63-1.34 mol% by controlling the mass ratio, and tests show that if the double bond density is controlled to be within the range, the glass transition temperature of the soft segment of the prepared polyurethane film is lower than-40 ℃, and most application scenes can be met. If the density of the double bonds is too high, for example, 2.3mol%, the glass transition temperature of the soft segment of the prepared polyurethane film is-23 ℃, which greatly limits the application of the polyurethane film.
The double bond density in the invention refers to the molar ratio of allyl glycidyl ether monomer in the molecular chain of polyether-carbonate polyol, mainly through 1 The HNMR spectrogram is obtained by calculation according to the following formula:
wherein A represents the peak area.
In the step (2):
the mercapto carboxylic acid monomer is one or more selected from mercaptopropionic acid, mercaptoacetic acid, mercaptobutyric acid and mercaptopentanoic acid, and is preferably mercaptopropionic acid.
The molar ratio of double bonds in the long-chain double-bond polyether-carbonate polyol to sulfydryl in the sulfydryl carboxylic acid monomer is 1:1.
the click chemistry is carried out under the action of a catalyst, wherein the catalyst is selected from a photoinitiator, the specific type of the catalyst has no special requirement, and the catalyst is selected from the types commonly used in the field, such as 801 photoinitiators, TPO photoinitiators, 907 photoinitiators, 184 photoinitiators and the like.
The click chemistry is performed at room temperature and the reaction is completed.
In the step (3):
the diisocyanate is selected from one or more of 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate;
the polyhydroxy chain extender is selected from one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, pentanediol and 1, 6-hexanediol;
the mass ratio of diisocyanate, long-chain carboxyl polyether-carbonate polyol and polyhydroxy chain extender is 100:150 to 300 parts by weight: 20 to 25;
the reaction is carried out under the action of a catalyst selected from one or more of the usual classes in the art, such as organotin-based catalysts, organomercury-based catalysts, organozinc-based catalysts.
Organic tin catalysts such as dibutyltin dilaurate, stannous octoate and the like;
organic mercury catalysts such as phenylmercuric acetate, phenylmercuric propionate, phenylmercuric octanoate, etc.;
the organic zinc-based catalyst is specifically exemplified by zinc octoate, zinc naphthenate and the like.
Preferably, the mass ratio of diisocyanate to catalyst is 100:0.01 to 0.1.
The reaction, namely the reaction of diisocyanate and polyol, is carried out at the temperature of 75-85 ℃ for 1.5-3 h.
The alkaline substance is selected from one or more of triethylamine, ammonia water and sodium hydroxide;
the molar ratio of the alkaline substance to the polyhydroxy chain extender is 1:0.8 to 1.1;
the temperature for the neutralization reaction is 40-55 ℃ and the time is 20-50 min.
In the step (4), the aqueous polyurethane prepolymer prepared in the step (3) is modified by using an aminosilane coupling agent, and in fact, the inventor previously assumed that long-chain carboxyl groups are grafted on side chains of polyether-carbonate polyol and then used as soft segments for preparing aqueous polyurethane, that is, the aminosilane coupling agent is not modified, but in experiments, it is found that if the aqueous polyurethane prepolymer prepared without modification is used for preparing the aqueous polyurethane after chain extension (diamine chain extender or water), not only the expected effect of improving the emulsification efficiency and the emulsion stability is not obtained, but also the polyurethane emulsion becomes turbid from clear at night, the emulsion stability is obviously reduced, and the inventor subsequently speculates that bridging between the long-chain carboxyl groups and the diamine chain extender is formed through mass analysis, and the emulsion stability is damaged. Based on the discovery, the inventor proposes to modify the long-chain carboxyl group by using a silane coupling agent, and finally, chain extension is performed by using water to prepare the waterborne polyurethane. In the modification process, the silane coupling agent and the long-chain carboxyl are found to generate synergism, so that the emulsification efficiency is further improved.
In the present invention, there is no special requirement for the structure of the aminosilane coupling agent, and it is only necessary to contain both amino and siloxy groups, and the aminosilane coupling agent may be selected from the groups commonly used in the art, such as aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, and the like.
The mass ratio of the amino silane coupling agent to the diisocyanate in the step (3) is 30-50: 100;
the reaction temperature is 25-80 ℃ and the reaction time is 10-90 min.
The mass ratio of the waterborne polyurethane prepolymer to water is 25-60: 100, respectively;
the reaction is carried out at the temperature of 0-30 ℃ for 0.5-3 h.
The invention also discloses the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared by the method. The waterborne polyurethane has smaller emulsion particle size, which shows that the waterborne polyurethane has higher emulsification efficiency and better emulsion stability; meanwhile, the waterborne polyurethane also has excellent mechanical property, hydrophobic property and heat resistance.
Compared with the prior art, the invention has the following advantages:
the invention discloses a preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane, which comprises the steps of adding an epoxy monomer containing double bonds into copolymerization reaction of an epoxy compound and carbon dioxide to serve as a third reaction monomer, controlling the double bond density in the prepared long-chain double-bond polyether-carbonate polyol by controlling the addition amount of the third reaction monomer, completely converting the double bonds into long-chain carboxyl through click reaction to obtain polyether-carbonate polyol with a side chain containing the long-chain carboxyl, reacting the polyether-carbonate polyol with a soft segment, diisocyanate and a polyhydroxy chain extender to prepare a waterborne polyurethane prepolymer, and finally modifying by an amino-containing silane coupling agent and carrying out water chain extension to obtain the waterborne polyurethane; the preparation process can obtain the aqueous polyurethane emulsion with high emulsification efficiency and excellent stability under the condition of not adding a carboxylic acid type hydrophilic chain extender.
The silicon modified long-chain carboxyl polyether-carbonic ester waterborne polyurethane prepared by the invention has smaller emulsion particle size, higher emulsification efficiency and better emulsion stability; meanwhile, the waterborne polyurethane also has excellent mechanical property, hydrophobic property and heat resistance.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a long-chain carboxyl polyether-carbonate polyol prepared in example 1 before and after click chemistry;
FIG. 2 is an IR spectrum of the silicon modified polyether-carbonate waterborne polyurethane prepared in example 1;
FIG. 3 is a graph showing the particle size distribution of the aqueous polyurethane emulsions prepared in comparative examples 1 to 2, respectively;
FIG. 4 is a graph showing the average particle diameters of emulsions of the aqueous polyurethanes of silicon-modified polyether-carbonate prepared in examples 1 to 3, respectively, and the average particle diameters of emulsions of the aqueous polyurethanes prepared in comparative examples 1 and 4 to 5, respectively, are shown as a comparison;
FIG. 5 is an appearance diagram (left diagram) of the aqueous polyurethane emulsion prepared in comparative example 3 and an appearance diagram (right diagram) of the emulsion after being left at 25 ℃ for 24 hours.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
Step 1: preparation of long-chain carboxy polyether-carbonate polyols
Before the reaction started, a 100mL stainless steel autoclave was purged and dried under vacuum at 80 ℃ for 2h to remove the water from the autoclave. 18.6g (0.3202 mol) of propylene oxide, 1.4g (0.0123 mol) of allyl glycidyl ether, 3g (0.0075 mol) of PPG-400 and 20mg of zinc-cobalt double metal cyanide complex were put into a reaction vessel, and a small amount of CO was charged 2 And the temperature is raised to 90 ℃, and then CO is adjusted 2 The pressure is 4MPa, and the reaction is carried out for 12h. After the reaction is finished, cooling the reaction kettle in an ice-water bath, and slowly releasing the gas in the kettle at normal temperature. The crude product was dissolved in 50mL of dichloromethane, transferred to a 100mL single neck flask, charged with 1.315g (0.0123 mol) of mercaptopropionic acid and 0.05g of photoinitiator 810, and irradiated with UV light at room temperature for 60min to obtain the long chain carboxy polyether-carbonate polyol which was noted CAPEC.
FIG. 1 is a nuclear magnetic hydrogen spectrum of the long-chain carboxyl polyether-carbonate polyol prepared in this example before and after click chemistry (labeled AGE-PEC), and it can be seen from the nuclear magnetic hydrogen spectrum that no epoxy group characteristic peak is found in the AGE-PEC, which indicates that both propylene oxide and allyl glycidyl ether are completely reacted; the characteristic peak of chemical shift 6ppm in AGE-PEC belongs to the peak of double bond proton, and after click chemistry, the double bond peak disappears and CH connected with carboxyl appears 2 Characteristic peak 2.7ppm and CH attached to S 2 The characteristic peak is 2.5ppm, which proves that the long-chain carboxyl polyether-carbonate polyol is successfully synthesized.
According to tests, the density of double bonds in the intermediate product AGE-PEC is 1.1mol%, the number average molecular weight of the product CAPEC is 3400g/mol, the PDI is 1.79, the carbonate content is 15.8mol%, and the long-chain carboxyl chain segment content is 1.1mol%.
Step 2: preparation of silicon modified long-chain carboxyl polyether-carbonic ester waterborne polyurethane
Adding 7g (0.0021 mol) of the long-chain carboxyl polyether-carbonate polyol prepared in the step 1, 1g (0.011 mol) of 1, 4-butanediol and 0.004g of dibutyltin dilaurate catalyst into a 100mL four-neck flask, heating to 78 ℃, slowly adding 4.09g (0.0184 mol) of isophorone diisocyanate into the flask, reacting for 3 hours, cooling to 50 ℃, adding 0.34g (0.003 mol) of triethylamine, reacting for 40 minutes, heating to 60 ℃, adding 1.41g (0.0074 mol) of KH902, reacting for 30 minutes, cooling to 25 ℃, adding 30.3g of deionized water, and stirring at 600rpm for 2 hours to obtain the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane.
FIG. 2 is an infrared spectrum of 3400cm in the aqueous polyurethane of silicon-modified long-chain carboxyl polyether-carbonate prepared in this example -1 Is an N-H stretching vibration peak in the urethane bond and is 1600 to 1750cm -1 Is a characteristic peak of carbonyl; and belongs to a silane coupling agent to obtain Si-C (790 cm) -1 ) Condensing the characteristic peak with siloxane to obtain Si-O (1019 cm) -1 ) The characteristic peak is clear and visible, and the successful preparation of the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane is proved.
Through observation, the silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared by the implementation has excellent emulsion stability, and no obvious precipitate is found after the polyurethane is placed at room temperature for half a year; no obvious precipitate is seen after centrifugation for 15min at 3000 r/min.
Pouring the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared in the embodiment into a tetrafluoroethylene mold, curing at room temperature for 48 hours, curing at 40 ℃ for 12 hours in a forced air oven, and then curing at 65 ℃ for 12 hours to obtain a silicon modified polyether-carbonate polyurethane film, which is marked as WPU1.
The tensile strength of the silicone-modified long-chain carboxy polyether-carbonate polyurethane film prepared in this example was tested according to the method specified in GB/T1040.1-2006. The test data are shown in table 1 below, and the data of hydrophobicity, water resistance and heat resistance of the product prepared in this example are shown in table 2 below.
Example 2
Step 1: preparation of long-chain carboxy polyether-carbonate polyols
The preparation process is exactly the same as step 1 in example 1.
Step 2: preparation of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane
9g (0.0026 mol) of the long-chain carboxyl polyether-carbonate polyol prepared in the step 1, 1g (0.011 mol) of 1, 4-butanediol and 0.004g of dibutyltin dilaurate catalyst are added into a 100mL four-neck flask, after the temperature is raised to 78 ℃, 4.28g (0.0192 mol) of isophorone diisocyanate is slowly added into the flask to react for 3h, the temperature is lowered to 50 ℃, 0.44g (0.0044 mol) of triethylamine is added to react for 40min, the temperature is raised to 60 ℃, 1.47g (0.0077 mol) of KH550 is added to react for 30min, the temperature is lowered to 25 ℃, 37.54g of deionized water is added, and the mixture is stirred at 600rpm for 2h, so that the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane is obtained.
An organosilicon modified long-chain carboxyl polyether-carbonate polyurethane film, noted as WPU2, was prepared in the same curing manner as in example 1. The tensile strength test data of the organosilicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared in the embodiment are listed in the following table 1, and the data of hydrophobicity, water resistance and heat resistance are listed in the following table 2.
Example 3
Step 1: preparation of long-chain carboxy polyether-carbonate polyols
The preparation process is exactly the same as step 1 in example 1.
Step 2: preparation of silicon modified long-chain carboxyl polyether-carbonic ester waterborne polyurethane
11g (0.0032 mol) of the long-chain carboxyl polyether-carbonate polyol prepared in the step 1, 1g (0.011 mol) of 1, 4-butanediol and 0.005g of dibutyltin dilaurate catalyst are added into a 100mL four-neck flask, after the temperature is raised to 78 ℃, 4.46g (0.0192 mol) of isophorone diisocyanate is slowly added into the flask to react for 3 hours, the temperature is lowered to 50 ℃, 0.54g (0.0044 mol) of triethylamine is added to react for 40 minutes, the temperature is raised to 60 ℃, 1.54g (0.0081 mol) of KH792 is added to react for 30 minutes, the temperature is lowered to 25 ℃, 42.78g of deionized water is added, and the mixture is stirred for 2 hours at 600rpm, so that the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane is obtained.
An organosilicon modified long-chain carboxy polyether-carbonate polyurethane film, denoted as WPU3, was prepared in the same curing manner as in example 1. The tensile strength test data of the organosilicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared in the embodiment are listed in the following table 1, and the data of hydrophobicity, water resistance and heat resistance are listed in the following table 2.
Examples 4 to 6
Step 1: preparation of long-chain carboxy polyether-carbonate polyols
The preparation process was substantially the same as in example 1 except that the amount of allyl glycidyl ether added was adjusted to 0.8g1.7g and 3g, respectively.
The density of double bonds in the intermediate long-chain double-bonded polyether-carbonate polyol prepared in the above examples was tested to be 0.63mol%1.34mol% and 2.3mol%, respectively.
And 2, step: preparation of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane
The preparation process is exactly the same as step 2 in example 1.
The average particle sizes of the emulsions prepared in examples 1 and 4-6 are 53nm, 105nm, 43nm and 30nm respectively, and no obvious sedimentation is observed after centrifugation at 3000r/min for 15min, which shows that the stability of the aqueous polyurethane emulsions prepared in examples 4-6 is good. Generally, the smaller the carboxylic acid content, the better the water resistance of the film when the emulsion stability is desired. The glass transition temperatures of the soft segments of the polyurethane film are respectively-42 ℃, 45 ℃, 42 ℃ and 23 ℃ by DSC test. When the temperature of the soft section of the polyurethane film is lower than-40 ℃, most application scenes can be met.
Comparative example 1
Step 1: preparation of polyether-carbonate polyols
The preparation is analogous to step 1 in example 1, except that the mass of propylene oxide is replaced by 20g, without addition of allyl glycidyl ether, giving the product a polyether-carbonate polyol.
The number average molecular weight was 3000g/mol, PDI was 1.87, and the carbonate content was 15.9mol%.
Step 2: preparation of silicon modified polyether-carbonate waterborne polyurethane
Adding 7g of the polyether-carbonate polyol prepared in the step 1, 0.68g of 1, 4-butanediol, 0.48g of dimethylolpropionic acid and 0.004g of dibutyltin dilaurate catalyst into a 100mL four-neck flask, heating to 78 ℃, slowly adding 4.09g of isophorone diisocyanate into the flask, reacting for 3h, cooling to 50 ℃, adding 0.34g of triethylamine, reacting for 40min, heating to 60 ℃, adding 1.41g of KH902, reacting for 30min, cooling to 25 ℃, adding 30.3g of deionized water, and stirring at 600rpm for 2h to obtain the silicon modified polyether-carbonate waterborne polyurethane, which is marked as DWPU1.
A silicon-modified polyether-carbonate polyurethane film was prepared in the same curing manner as in example 1, and the tensile strength test data thereof are shown in table 1 below, and the hydrophobicity, water resistance and heat resistance data thereof are shown in table 2 below.
Comparative example 2
Step 1: preparation of polyether-carbonate polyols
The preparation method was the same as in step 1 of comparative example 1.
Step 2: preparation of polyether-carbonate waterborne polyurethane
Adding 7g of the polyether-carbonate polyol prepared in the step 1, 0.68g of 1, 4-butanediol, 0.48g of dimethylolpropionic acid and 0.004g of dibutyltin dilaurate catalyst into a 100mL four-neck flask, heating to 78 ℃, slowly adding 4.09g of isophorone diisocyanate into the flask, reacting for 3h, cooling to 50 ℃, adding 0.34g of triethylamine, reacting for 40min, cooling to 25 ℃, adding 30.3g of deionized water and 0.27g of ethylenediamine mixed solution, and stirring at 600rpm for 2h to prepare the polyether-carbonate waterborne polyurethane, which is recorded as DWPU2.
Particle size distribution diagrams of the aqueous polyurethane emulsions prepared in the comparative examples 1-2 are obtained through particle size characterization, and as can be seen in fig. 3 in detail, observation of fig. 3 shows that the particle size of the emulsion in DWPU1 prepared after the KH902 is terminated is obviously increased, and generally, the smaller the particle size of the emulsion is, the better the stability of the emulsion is, which indicates that when the carboxyl in the soft-segment side chain is short-chain carboxyl, the stability of the polyurethane emulsion is rather reduced after the terminal capping is performed by high-content siloxane such as KH 902.
Comparative example 3
Step 1: preparation of long-chain carboxy polyether-carbonate polyols
The preparation process is exactly the same as step 1 in example 1.
Step 2: preparation of long side chain carboxyl polyether-carbonic ester waterborne polyurethane
7g (0.0021 mol) of the long-chain carboxyl polyether-carbonate polyol prepared in the step 1, 1g (0.011 mol) of 1, 4-butanediol and 0.004g of dibutyltin dilaurate catalyst are added into a 100mL four-neck flask, after the temperature is raised to 78 ℃, 4.09g (0.0184 mol) of isophorone diisocyanate is slowly added into the flask to react for 3 hours, the temperature is lowered to 50 ℃, 0.34g (0.003 mol) of triethylamine is added to react for 40 minutes, the temperature is lowered to 10 ℃, 30.3g of deionized water and 0.27g of ethylenediamine mixed solution are added, and the mixture is stirred for 2 hours at 600rpm, so that the long-side chain carboxyl polyether-carbonate aqueous polyurethane emulsion is obtained.
By observation, the long side chain carboxyl polyether-carbonate waterborne polyurethane prepared by the comparative example obtains a transparent emulsion after high-speed stirring is finished, the emulsion is obviously turbid after being placed at 25 ℃ for 24 hours, a little precipitate is left at the bottom of the emulsion, and the stability is obviously reduced. Therefore, the emulsion particle size was not further measured.
Comparing the stability of the aqueous polyurethane prepared in example 1 and comparative example 3, it can be seen that the non-silicon modification of the long side chain carboxyl group is not beneficial to the emulsification, and the stability of the aqueous polyurethane emulsion prepared by the aqueous polyurethane emulsion can be greatly reduced.
If 0.27g of ethylenediamine added in step 2 of this comparative example 3 is removed, the stability of the aqueous polyurethane prepared is similar to that of comparative example 3, and still a noticeable haze appears after 24 hours of standing at room temperature.
Comparative example 4
Step 1: preparation of polyether-carbonate polyols
The preparation process is exactly the same as in step 1 of comparative example 1.
Step 2: preparation of silicon modified polyether-carbonate waterborne polyurethane
9g of the polyether-carbonate polyol prepared in the step 1, 0.59g of 1, 4-butanediol, 0.61g of dimethylolpropionic acid and 0.004g of dibutyltin dilaurate catalyst are added into a 100mL four-neck flask, after the temperature is raised to 78 ℃, 4.28g of isophorone diisocyanate is slowly added into the flask to react for 3h, the temperature is reduced to 50 ℃, 0.44g of triethylamine is added to react for 40min, the temperature is raised to 60 ℃, 1.47g of KH550 is added to react for 30min, the temperature is reduced to 25 ℃, 37.54g of deionized water is added, and the mixture is stirred at 600rpm for 2h, so that the silicon modified polyether-carbonate waterborne polyurethane is obtained.
A silicon modified polyether-carbonate polyurethane film, designated DWPU4, was prepared in the same curing manner as in example 1.
Tensile strength test data of the silicon-modified polyether-carbonate polyurethane film prepared in this comparative example are listed in table 1 below, and hydrophobicity, water resistance and heat resistance data are listed in table 2 below.
Comparative example 5
Step 1: preparation of polyether-carbonate polyols
The preparation process is exactly the same as in step 1 of comparative example 1.
Step 2: preparation of silicon modified polyether-carbonate waterborne polyurethane
Adding 11g of polyether-carbonate polyol prepared in the step 1, 0.5g of 1, 4-butanediol, 0.74g of dimethylolpropionic acid and 0.005g of dibutyltin dilaurate catalyst into a 100mL four-neck flask, heating to 78 ℃, slowly adding 4.46g of isophorone diisocyanate into the flask, reacting for 3h, cooling to 50 ℃, adding 0.54g of triethylamine, reacting for 40min, heating to 60 ℃, adding 1.54g of KH792, reacting for 30min, cooling to 25 ℃, adding 42.78g of deionized water, and stirring for 2h at 600rpm to obtain the silicon modified polyether-carbonate waterborne polyurethane.
A silicon-modified polyether-carbonate polyurethane film was prepared in the same curing manner as in example 1 and is designated DWPU5.
Tensile strength test data of the silicon-modified polyether-carbonate film prepared in this comparative example are listed in table 1 below, and hydrophobicity, water resistance, and heat resistance data are listed in table 2 below.
TABLE 1
TABLE 2
As can be seen by comparing the data in Table 1, the products prepared in examples 1 to 3 have better tensile strength and elongation at break than the products prepared in comparative examples 1,4 and 5, respectively; as can be seen from a comparison of the data in Table 2, the products prepared in examples 1 to 3 have better hydrophobicity and heat resistance than the products prepared in comparative examples 1,4 and 5, respectively. The silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane prepared by the method disclosed by the invention has better mechanical property, hydrophobicity and heat resistance.
Claims (9)
1. A preparation method of silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane is characterized by comprising the following steps:
(1) Taking an epoxy compound, an epoxy monomer containing double bonds and carbon dioxide as monomers, and copolymerizing to obtain long-chain double-bond polyether-carbonate polyol;
the mass ratio of the epoxy compound to the double bond-containing epoxy monomer is 100:4 to 18;
in the long-chain double-bond polyether-carbonate polyol, the double bond density is 0.5-2.5 mol%;
(2) Mixing the long-chain double-bond polyether-carbonate polyol with a mercapto carboxylic acid monomer, and performing click chemistry to obtain long-chain carboxyl polyether-carbonate polyol;
(3) Mixing the long-chain carboxyl polyether-carbonate polyol, diisocyanate and a polyhydroxy chain extender, reacting to obtain a polyurethane prepolymer with an NCO group at the tail end, and neutralizing with an alkaline substance to obtain a water-based polyurethane prepolymer;
(4) And mixing the aqueous polyurethane prepolymer and an aminosilane coupling agent, reacting to obtain a silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane prepolymer, mixing with water, and reacting to obtain the silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane.
2. The preparation method of the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane as claimed in claim 1, wherein in the step (1):
the epoxy compound is selected from ethylene oxide and/or propylene oxide;
the double bond-containing epoxy monomer is selected from allyl glycidyl ether and/or alkene butyl glycidyl ether;
in the reaction system, the pressure of the carbon dioxide is 2-5 MPa;
the copolymerization is carried out at the temperature of 70-120 ℃ for 5-24 h.
3. The preparation method of the silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane as claimed in claim 1, wherein in the step (1):
an initiator and a catalyst are also added into the reaction system, wherein the initiator is selected from polyhydroxy small molecules or polyhydroxy polymers, and the catalyst is selected from double metal cyanide complexes;
the mass ratio of the epoxy compound, the initiator and the catalyst is 100:5 to 30:0.01 to 0.1.
4. The preparation method of the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane as claimed in claim 1, wherein in the step (2):
the mercapto carboxylic acid monomer is selected from one or more of mercaptopropionic acid, thioglycolic acid, mercaptobutyric acid and mercaptopentanoic acid;
the molar ratio of double bonds in the long-chain double-bond polyether-carbonate polyol to sulfydryl in the sulfydryl carboxylic acid monomer is 1:1;
the click chemistry is carried out under the action of a catalyst selected from photoinitiators;
the click chemistry is performed at room temperature.
5. The preparation method of the silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane as claimed in claim 1, wherein in the step (3):
the diisocyanate is selected from one or more of 2, 4-toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and 1, 6-hexamethylene diisocyanate;
the polyhydroxy chain extender is selected from one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, pentanediol and 1, 6-hexanediol;
the mass ratio of diisocyanate, long-chain carboxyl polyether-carbonate polyol and polyhydroxy chain extender is 100:150 to 300 parts by weight: 20 to 25;
the reaction is carried out under the action of a catalyst, and the catalyst is selected from one or more of an organic tin catalyst, an organic mercury catalyst and an organic zinc catalyst;
the reaction is carried out at the temperature of 55-85 ℃ for 1.5-4 h;
the alkaline substance is selected from one or more of triethylamine, ammonia water and sodium hydroxide;
the molar ratio of the alkaline substance to the polyhydroxy chain extender is 1:0.8 to 1.1.
6. The preparation method of the silicon-modified long-chain carboxyl polyether-carbonate waterborne polyurethane as claimed in claim 1, wherein in the step (4):
the aminosilane coupling agent is selected from one or more of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyldiethoxysiloxane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N-aminoethyl-3-aminopropylmethyldimethoxysilane;
the mass ratio of the amino silane coupling agent to the diisocyanate in the step (3) is 30-50: 100, respectively;
the reaction temperature is 25-80 ℃ and the reaction time is 10-90 min.
7. The preparation method of the silicon-modified long-chain carboxyl polyether-carbonate aqueous polyurethane as claimed in claim 1, wherein in the step (4):
the mass ratio of the waterborne polyurethane prepolymer to water is 25-60: 100.
8. the preparation method of the silicon modified long-chain carboxyl polyether-carbonate waterborne polyurethane as claimed in any one of claims 1 to 7, wherein in the step (1), the mass ratio of the epoxy compound to the double bond-containing epoxy monomer is 100:4.3 to 9.1;
in the long-chain double-bond polyether-carbonate polyol, the double bond density is 0.63-1.34 mol%.
9. A silicon-modified long chain carboxy polyether-carbonate waterborne polyurethane prepared according to the method of any one of claims 1 to 8.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242588A (en) * | 1994-01-14 | 1995-09-19 | Hodogaya Chem Co Ltd | Polyoxyalkylene derivative containing carboxyl group |
| AU3947200A (en) * | 1999-04-23 | 2000-11-10 | Aortech Biomaterials Pty Ltd | Siloxane-containing polyurethane-urea compositions |
| JP2004224868A (en) * | 2003-01-21 | 2004-08-12 | Mitsubishi Chemicals Corp | Aqueous emulsion of resin composition and method for producing the same |
| CN105482677A (en) * | 2015-12-29 | 2016-04-13 | 安徽安大华泰新材料有限公司 | Antifouling polyurethane coating |
| EP3178858A1 (en) * | 2015-12-09 | 2017-06-14 | Covestro Deutschland AG | Polyurethane foams based on polyether carbonate polyols |
| CN111138623A (en) * | 2020-01-10 | 2020-05-12 | 浙江大学 | Organic silicon modified polyether-polycarbonate waterborne polyurethane and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2845871A1 (en) * | 2013-09-05 | 2015-03-11 | Bayer MaterialScience AG | Crosslinking of polyether carbonate polyols containing double bonds by the addition of mercaptans |
| WO2016046110A1 (en) * | 2014-09-23 | 2016-03-31 | Covestro Deutschland Ag | Moisture-curing polyether carbonate containing alkoxysilyl groups |
-
2022
- 2022-03-01 CN CN202210192536.2A patent/CN114591489B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242588A (en) * | 1994-01-14 | 1995-09-19 | Hodogaya Chem Co Ltd | Polyoxyalkylene derivative containing carboxyl group |
| AU3947200A (en) * | 1999-04-23 | 2000-11-10 | Aortech Biomaterials Pty Ltd | Siloxane-containing polyurethane-urea compositions |
| JP2004224868A (en) * | 2003-01-21 | 2004-08-12 | Mitsubishi Chemicals Corp | Aqueous emulsion of resin composition and method for producing the same |
| EP3178858A1 (en) * | 2015-12-09 | 2017-06-14 | Covestro Deutschland AG | Polyurethane foams based on polyether carbonate polyols |
| CN105482677A (en) * | 2015-12-29 | 2016-04-13 | 安徽安大华泰新材料有限公司 | Antifouling polyurethane coating |
| CN111138623A (en) * | 2020-01-10 | 2020-05-12 | 浙江大学 | Organic silicon modified polyether-polycarbonate waterborne polyurethane and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Polyester-Modified Poly ( Ethylene Ether Carbonate) Polyols by Molecular Weight Advancement;ROBERT F. HARRIS;《Journal of Applied Polymer Science》;19931205;第50卷;第793-804页 * |
| 基于聚碳酸亚丙酯二元醇的水性聚氨酯的制备及其在水性木器涂料中的应用研究;徐宁;《中国涂料》;20150630;第31卷(第6期);第31-36页 * |
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