CN112390946A - Non-isocyanate polyurethane and preparation method thereof - Google Patents
Non-isocyanate polyurethane and preparation method thereof Download PDFInfo
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- CN112390946A CN112390946A CN202011271455.9A CN202011271455A CN112390946A CN 112390946 A CN112390946 A CN 112390946A CN 202011271455 A CN202011271455 A CN 202011271455A CN 112390946 A CN112390946 A CN 112390946A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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Abstract
The invention discloses non-isocyanate polyurethane and a preparation method thereof, belonging to the technical field of adhesives2Carrying out reaction; adding a bifunctional aziridine polymer, a double-end allyl compound, 2, 3-epoxysuccinic acid and a solvent, and introducing CO under vacuum condition2Carrying out reaction; then filtering the macroporous cation exchange resin, distilling the solvent, and adjusting the solid content to obtain the non-isocyanate polyurethane. The preparation method does not use isocyanate and uses CO in the preparation of polyurethane2Reacting with aziridine polymer as raw material to synthesize polyurethane, CO2The aziridine polymer is non-toxic, rich in resources, low in price, low in volatility, friendly to operators and environment in the production process, safe and environment-friendly, and prepared by the preparation methodThe obtained polyurethane has excellent performance and can replace the existing isocyanate polyurethane.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to non-isocyanate polyurethane and a preparation method thereof.
Background
Polyurethanes are a class of polymers with a high number of carbamate functional groups in the backbone of the macromolecule, and are among the most widely used polymers to date. Industrially, polyurethanes are generally formed by reacting isocyanates with polyols and other functional monomers in the presence of catalysts. Due to the diversification of raw materials and the adjustability of molecular structures, different polyurethane materials from soft to hard can be prepared according to the requirements of the polyurethane materials. Conventional polyurethane synthesis methods use isocyanate monomers. And isocyanate monomers are generally synthesized by the phosgene method. Phosgene is a highly toxic gas and seriously pollutes the environment. Meanwhile, the isocyanate monomer has strong volatility, and isocyanate groups with high activity have great potential safety hazards to human bodies and the environment.
In order to reduce or avoid the use of isocyanate, the related technical personnel continuously research and develop a synthetic method of non-isocyanate polyurethane, and two main methods are used at present. The first method is to prepare polyurethane by ring opening of cyclic carbonate and amine, and the cyclic carbonate is mostly carbon dioxide, so that the method is environment-friendly, efficient and low in cost. For example, the invention patent of Chinese patent with application number 200910105394.6 is that polycyclic carbonate is synthesized by catalysis of a catalyst, and then the polycyclic carbonate is reacted with organic amine to prepare non-isocyanate polyurethane. However, in this method, the molecular weight of the polyurethane obtained by the reaction of the cyclic carbonate and the amine is small, and many side reactions are often produced in the reaction process, which seriously affects the product quality. The second method is to directly obtain a compound with a carbamate structure by using aziridine and derivatives thereof and carbon dioxide, and the method has the advantages of quick reaction and high yield. However, the alkyl aziridine small molecule has strong volatility and high toxicity, and is not friendly to operators, and the prepared compound containing the carbamate structure may contain a certain amount of highly toxic monomers, which affects the health of subsequent users. Meanwhile, aziridine small molecules are easily self-polymerized under reaction conditions, which affects the functionality of the final product.
Disclosure of Invention
In order to overcome the defects of the prior art, the technical problems to be solved by the invention are as follows: to provide a non-isocyanate polyurethane which is friendly to both producers and users without using a biostimulant isocyanate component and has excellent product quality, and a process for producing the same.
In order to solve the technical problems, the invention adopts the technical scheme that: a method of preparing a non-isocyanate polyurethane comprising the steps of:
step 1, mixing a trifunctional aziridine polymer, a double-end allyl compound, macroporous cation exchange resin and a catalyst, introducing carbon dioxide under a vacuum condition, heating to 65-85 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a first reactant;
the macroporous cation exchange resin is hydrogen type macroporous cation exchange resin containing hydrogen ions;
step 2, adding a bifunctional aziridine polymer, a double-end allyl compound, 2, 3-epoxysuccinic acid and a solvent into the first reactant obtained in the step 1, introducing carbon dioxide under a vacuum condition, heating to 70-95 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a second reactant;
and 3, filtering the macroporous cation exchange resin in the second reactant obtained in the step 2, then adjusting the pH value of the system to be 7-9, adding water until the solid content of the product is 45-55%, heating to 60 ℃, carrying out reduced pressure distillation until the content of the solvent is lower than 0.5%, and then adding water until the solid content of the product is 45-55%, thus obtaining the non-isocyanate polyurethane.
The other technical scheme adopted by the invention is as follows: a polyurethane prepared by the preparation method of the non-isocyanate polyurethane.
The invention has the beneficial effects that: the invention provides a preparation method of non-isocyanate polyurethane, which does not use any compound with biostimulative isocyanate group in the process of preparing polyurethane and uses CO2Reacting with aziridine polymer as raw material to synthesize polyurethane, CO2The polyurethane molecular chain prepared by the preparation method of the non-isocyanate polyurethane provided by the invention is of a Y-shaped structure, and the acting force between the molecular chains is stronger than that of a linear polyurethane molecular chain, so that excellent mechanical properties can be providedAnd particularly, the initial performance is established quickly, and meanwhile, the obtained polyurethane has high molecular weight, narrower molecular chain distribution, less side reaction and stable reaction, and can completely replace the existing isocyanate polyurethane.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
The invention provides a preparation method of non-isocyanate polyurethane, which comprises the following steps:
step 1, mixing a trifunctional aziridine polymer, a double-end allyl compound, macroporous cation exchange resin and a catalyst, introducing carbon dioxide under a vacuum condition, heating to 65-85 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a first reactant;
the macroporous cation exchange resin is hydrogen type macroporous cation exchange resin containing hydrogen ions;
step 2, adding a bifunctional aziridine polymer, a double-end allyl compound, 2, 3-epoxysuccinic acid and a solvent into the first reactant obtained in the step 1, introducing carbon dioxide under a vacuum condition, heating to 70-95 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a second reactant;
and 3, filtering the macroporous cation exchange resin in the second reactant obtained in the step 2, then adjusting the pH value of the system to be 7-9, adding water until the solid content of the product is 45-55%, heating to 60 ℃, carrying out reduced pressure distillation until the content of the solvent is lower than 0.5%, and then adding water until the solid content of the product is 45-55%, thus obtaining the non-isocyanate polyurethane.
From the above description, the beneficial effects of the present invention are: according to the invention, an aziridine polymer is selected as a raw material, the aziridine has lower activity than micromolecule aziridine and derivatives thereof, under the conditions of proper temperature, pH and catalyst, carbon atoms in carbon dioxide attack nitrogen atoms in aziridine, nitrogen and carbon in carbon dioxide form C-N bonds, the aziridine opens rings to form intermediates with polymerization activity, and the intermediates can attack compounds with double bonds to form polymers; in the process, a trifunctional aziridine polymer is specially selected as an initiator, a bifunctional aziridine polymer is selected as a chain extender in a matching manner, and a three-arm long-chain polymer can be finally obtained;
meanwhile, the double-end allyl compound is specifically selected, and because the two end groups both contain double bonds, the two end groups and the intermediate can form a carbamate structure under a proper condition, and the allyl structure is connected to the main chain, so that the flexibility and the degree of freedom of the molecules of the polyurethane compound are increased, and the polyurethane dispersion has better flexibility; the double-terminal alkenyl compound increases the chemical crosslinking sites of the aqueous polyurethane dispersion, improves the self cohesion of the polyurethane dispersion and can endow the product with good mechanical properties;
the specific 2, 3-epoxysuccinic acid of selecting of this application is as hydrophilic agent, provides the stability of product in aqueous, and the alkaline substance of stable aziridine group can be got rid of to hydrogen type macropore cation exchange resin containing hydrogen ion, improves the activity of aziridine polymer and carbon dioxide, very easily gets rid of from the system through simple means such as filtration simultaneously again.
Further, adding A parts of trifunctional aziridine polymer, B parts of double-ended allyl compound, C parts of macroporous cation exchange resin, D parts of carbon dioxide and M parts of catalyst in molar parts in the step 1;
adding E parts of difunctional aziridine polymer, F parts of double-ended allyl compound, G parts of 2, 3-epoxysuccinic acid, H parts of carbon dioxide and N parts of solvent in molar parts in the step 2;
wherein, B is 3A; c is more than or equal to 0.01 and less than or equal to 0.03 and more than or equal to 0.01 and E; d is not less than 10A and not more than 15A; e is more than or equal to 8 and less than or equal to 18; f ═ E; g is not less than 0.1 and not more than 0.25; h is not less than 16A and not more than 24A; m is not less than 0.01 and not more than 0.05; n is not less than 30A and not more than 80A.
Further, the trifunctional aziridine polymer has the formula:
R4is methyl or ethyl.
Further, the trifunctional aziridine polymer is trimethylolpropane-tris [3- (2-methylaziridinyl) ] propionate.
Further, the structure of the difunctional aziridine polymer is as follows:
R5is methyl or ethyl.
Further, the difunctional aziridine polymer is 3, 3-dimethylolpentane-bis [3- (2-methylaziridinyl) ] propionate or 3, 3-dimethylolpentane-bis [3- (2-ethylaziridinyl) ] propionate.
Further, the double-end allyl compound is one or two of the following structural formulas:
R6and R7Is hydrogen or methyl, and m1 and m2 are each an integer of 20 to 100.
Further, the double-end allyl compound is one or more of double-end allyl polyoxyethylene ether-20, double-end allyl polyoxypropylene ether-45 and allyl polyoxyethylene ether-50-methacrylate.
Further, the hydrogen type macroporous cation exchange resin containing hydrogen ions is
NRW160。
Further, the catalyst is bromo-1-butyl-3-methylimidazole ([ BMIM ] Br) or 1-butyl-3-methylimidazolium iodide ([ BMIM ] I).
Further, the solvent is acetone.
Further, the reagent for adjusting the pH of the system in step 3 is triethylamine, trimethylamine or diethanolamine.
Example 1:
the preparation method of the non-isocyanate polyurethane specifically comprises the following steps:
step 1, 1mol of trimethylolpropane-tris [3- (2-methylaziridinyl)]Propionate, 3mol of double-end allyl polyoxyethylene ether-20, 0.27mol of hydrogen-ion-containing
NRW160 and 0.01mol [ BMIM ]]Adding Br into a high-pressure reaction kettle lined with a tetrafluoroethylene film through a feed valve, sealing the high-pressure reaction kettle, closing the feed valve, a discharge valve and an air inlet valve, opening an air outlet valve, and pumping air in the reaction kettle by vacuum filtration; closing the gas outlet valve, opening the gas inlet valve, filling 14mol of carbon dioxide, closing the gas inlet valve, heating to 65 ℃, reacting for 5 hours, cooling to 30 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a first reactant;
step 2, opening a feed valve, quickly adding 8mol of 3, 3-dimethylolpentane-bis [3- (2-methylaziridinyl) ] propionate, 8mol of double-end allyl polyoxyethylene ether-20, 0.1mol of 2, 3-epoxysuccinic acid and 30mol of solvent acetone, closing the feed valve, opening an air outlet valve, opening the air outlet valve, and performing vacuum filtration to pump out air in the reaction kettle; closing the gas outlet valve, opening the gas inlet valve, filling 16mol of carbon dioxide, closing the gas inlet valve, heating to 70 ℃, reacting for 5 hours, cooling to 30 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a second reactant;
step 3, filtering the second reactant through filter cloth to remove
NRW160, transferring the filtrate into a glass reaction kettle, stirring, slowly dropwise adding a triethylamine aqueous solution until the pH value of the system is 7, and dropwise adding water until the solid content of the product is 50%; slowly raising the temperature to 60 ℃ from normal temperature, and distilling under reduced pressure until the acetone content is lower than 0.5%; and adjusting the solid content of the product to 50% by water supplementing to obtain a non-isocyanate polyurethane dispersion P1.
Example 2:
the preparation method of the non-isocyanate polyurethane specifically comprises the following steps:
step 1, 1mol of trimethylolpropane-tris [3- (2-ethyl aziridinyl)]Propionate, 3mol of allyl-bis-oxyethylene-45, containing 0.19mol of hydrogen ions
NRW160 and 0.04mol [ BMIM ]]I, adding the mixture into a high-pressure reaction kettle with a tetrafluoroethylene film inside through a feed valve, sealing the high-pressure reaction kettle, closing the feed valve, a discharge valve and an air inlet valve, opening an air outlet valve, and pumping air in the reaction kettle by vacuum filtration; closing the gas outlet valve, opening the gas inlet valve, filling 10mol of carbon dioxide, closing the gas inlet valve, heating to 85 ℃, reacting for 2 hours, cooling to 35 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a first reactant;
step 2, opening a feed valve, quickly adding 18mol of 3, 3-dimethylolpentane-bis [3- (2-methylaziridinyl) ] propionate, 18mol of double-end allyl polyoxyethylene ether-45, 0.25mol of 2, 3-epoxysuccinic acid and 80mol of solvent acetone, closing the feed valve, opening an air outlet valve, opening the air outlet valve, and performing vacuum filtration to pump out air in the reaction kettle; closing the gas outlet valve, opening the gas inlet valve, filling 16mol of carbon dioxide, closing the gas inlet valve, heating to 95 ℃, reacting for 2 hours, cooling to 40 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a second reactant;
step 3, filtering the second reactant through filter cloth to remove
NRW160, transferring the filtrate into a glass reaction kettle, stirring, slowly dropwise adding a trimethylamine aqueous solution until the pH value of the system is 8, and dropwise adding water until the solid content of the product is 55%; slowly raising the temperature to 60 ℃ from normal temperature, and distilling under reduced pressure until the acetone content is lower than 0.5%; and adjusting the solid content of the product to 55% by water replenishing to obtain a non-isocyanate polyurethane dispersion P2.
Example 3:
the preparation method of the non-isocyanate polyurethane specifically comprises the following steps:
step 1, mixing 1mol of threeHydroxymethyl propane-tris [3- (2-ethyl aziridinyl)]Propionate, 3mol of allylpolyoxyethylene ether-50-methacrylate, containing 0.3mol of hydrogen ions
NRW160 and 0.03mol [ BMIM ]]Adding Br into a high-pressure reaction kettle lined with a tetrafluoroethylene film through a feed valve, sealing the high-pressure reaction kettle, closing the feed valve, a discharge valve and an air inlet valve, opening an air outlet valve, and pumping air in the reaction kettle by vacuum filtration; closing the gas outlet valve, opening the gas inlet valve, filling 15mol of carbon dioxide, closing the gas inlet valve, heating to 88 ℃, reacting for 2.5 hours, cooling to 40 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a first reactant;
step 2, opening a feed valve, quickly adding 14mol of 3, 3-dimethylolpentane-bis [3- (2-ethyl aziridinyl) ] propionate, 14mol of allyl polyoxyethylene ether-50-methacrylate, 0.2mol of 2, 3-epoxysuccinic acid and 50mol of solvent acetone, closing the feed valve, opening an air outlet valve, opening the air outlet valve, and pumping and filtering air in the reaction kettle in vacuum; closing the gas outlet valve, opening the gas inlet valve, filling 20mol of carbon dioxide, closing the gas inlet valve, heating to 85 ℃, reacting for 3 hours, cooling to 40 ℃, opening the gas outlet valve, and discharging residual carbon dioxide to obtain a second reactant;
step 3, filtering the second reactant through filter cloth to remove
NRW160, transferring the filtrate into a glass reaction kettle, stirring, slowly dropwise adding ammonia water until the pH value of the system is 9, and dropwise adding water until the solid content of the product is 45%; slowly raising the temperature to 60 ℃ from normal temperature, and distilling under reduced pressure until the acetone content is lower than 0.5%; and adjusting the solid content of the product to 45% by water supplementing to obtain a non-isocyanate polyurethane dispersion P3.
Experimental example 1:
the non-isocyanate polyurethane dispersions P1-P3 of examples 1-3, the domestic polyurethane dispersion P4 of the same type and the imported polyurethane dispersion P5 of the same type were subjected to Gel Permeation Chromatography (GPC) tests for molecular weight and molecular weight distribution, the results of which are shown in Table 1.
TABLE 1
| Group of | Number average molecular weight Mn, (g/mol) | Weight average molecular weight Mw (g/mol) | Molecular weight distribution DI |
| P1 | 134584 | 185479 | 1.38 |
| P2 | 124293 | 184385 | 1.48 |
| P3 | 139011 | 201915 | 1.45 |
| P4 | 98640 | 158321 | 1.61 |
| P5 | 113849 | 189200 | 1.66 |
It can be seen from table 1 that the number average molecular weight of the non-isocyanate polyurethane dispersion prepared by the preparation method provided by the invention is higher than the molecular weight of the domestic and imported polyurethane dispersions of the same type, the weight average molecular weight is similar, the molecular chain distribution is narrower, and the product performance prepared in the later period is more stable.
Experimental example 2:
the non-isocyanate polyurethane dispersions P1-P3, the domestic polyurethane dispersion P4 of the same type and the imported polyurethane dispersion P5 of the same type of the examples 1-3 were used for manufacturing 30 pairs of shoes respectively in a shoe factory, wherein the soles of the shoes are rubber soles, the vamps are nylon mesh vamps, the soles are treated by a rubber treating agent in advance during gluing, and the vamps are treated by a nylon treating agent; isocyanate curing agent accounting for 5 percent of the weight of the sample is added into the P1-P5, the mixture is uniformly stirred to form adhesive, the adhesive is brushed on the processed sole and vamp, and the mixed solution is used within 2 hours. After the adhesive is cured, the mechanical property and hydrolysis resistance of the sample shoe are measured according to GB/T30779-.
TABLE 2
| Group of | Initial adhesion Strength (N/mm) | Late stage bond Strength (N/mm) | Hydrolysis resistance (N/mm) |
| P1 | 5.32 | 11.34 | 8.71 |
| P2 | 5.03 | 10.98 | 7.92 |
| P3 | 5.19 | 12.01 | 8.13 |
| P4 | 3.64 | 10.76 | 6.89 |
| P5 | 4.05 | 11.43 | 8.19 |
As can be seen from Table 2, the non-isocyanate polyurethane prepared by the preparation method provided by the invention can reach the bonding strength and hydrolysis resistance of the polyurethane sold in the market, and the initial bonding strength of the non-isocyanate polyurethane prepared by the preparation method provided by the invention is obviously higher.
In summary, the preparation method of the non-isocyanate polyurethane provided by the invention does not use any compound with biostimulative isocyanate groups in the process of preparing the polyurethane, and uses CO2Reacting with aziridine polymer as raw material to synthesize polyurethane, CO2The aziridine polymer is non-toxic, rich in resources, low in price, low in volatility, friendly to operators and environment in the production process, greatly improves the production safety, is an environment-friendly polymerization production mode, and is prepared by the methodThe molecular chain of the polyurethane prepared by the preparation method of the non-isocyanate polyurethane is Y-shaped, and the acting force between the molecular chains is stronger than that of a linear polyurethane, so that the polyurethane has excellent mechanical property, particularly has quicker initial performance establishment, and meanwhile, the obtained polyurethane has high molecular weight, narrower molecular chain distribution, less side reaction and stable reaction, and can completely replace the existing isocyanate polyurethane.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or directly or indirectly applied to the related technical field are included in the scope of the present invention.
Claims (9)
1. A method for preparing a non-isocyanate polyurethane, comprising the steps of:
step 1, mixing a trifunctional aziridine polymer, a double-end allyl compound, macroporous cation exchange resin and a catalyst, introducing carbon dioxide under a vacuum condition, heating to 65-85 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a first reactant;
the macroporous cation exchange resin is hydrogen type macroporous cation exchange resin containing hydrogen ions;
step 2, adding a bifunctional aziridine polymer, a double-end allyl compound, 2, 3-epoxysuccinic acid and a solvent into the first reactant obtained in the step 1, introducing carbon dioxide under a vacuum condition, heating to 70-95 ℃, reacting for 2-5 hours, and cooling to 30-40 ℃ to obtain a second reactant;
and 3, filtering the macroporous cation exchange resin in the second reactant obtained in the step 2, then adjusting the pH value of the system to be 7-9, adding water until the solid content of the product is 45-55%, heating to 60 ℃, carrying out reduced pressure distillation until the content of the solvent is lower than 0.5%, and then adding water until the solid content of the product is 45-55%, thus obtaining the non-isocyanate polyurethane.
2. The method of preparing a non-isocyanate polyurethane according to claim 1, wherein a part of the trifunctional aziridine polymer, B part of the double-ended allyl compound, C part of the macroporous cation exchange resin, D part of carbon dioxide, and M part of the catalyst are added in step 1, in molar parts;
adding E parts of difunctional aziridine polymer, F parts of double-ended allyl compound, G parts of 2, 3-epoxysuccinic acid, H parts of carbon dioxide and N parts of solvent in molar parts in the step 2;
wherein, B is 3A;
0.01*(A+E)≤C≤0.03*(A+E)；
10*A≤D≤15*A；
8*A≤E≤18*A；
F＝E；
0.1*A≤G≤0.25*A；
16*A≤H≤24*A；
0.01*A≤M≤0.05*A；
30*A≤N≤80*A。
3. the method of claim 1, wherein the trifunctional aziridine polymer has the formula:
R4is methyl or ethyl.
4. The method of claim 1, wherein the difunctional aziridine polymer has the formula:
R5is methyl or ethyl.
5. The method of claim 1, wherein the double-ended allyl compound is one or both of the following structural formulas:
R6and R7Is hydrogen or methyl, and m1 and m2 are each an integer of 20 to 100.
6. The method of claim 1, wherein the catalyst is bromo 1-butyl-3-methylimidazole or 1-butyl-3-methylimidazolium iodide.
7. The non-isocyanate polyurethane and process of claim 1, wherein the solvent is acetone.
8. The method of claim 1, wherein the agent for adjusting the pH of the system in step 3 is triethylamine, trimethylamine, or diethanolamine.
9. The polyurethane prepared by the method of preparing a non-isocyanate polyurethane according to any one of claims 1 to 8.
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