CN108059705B - Aqueous polyurethane resin hydrolysis-resistant agent and preparation method and application thereof - Google Patents
Aqueous polyurethane resin hydrolysis-resistant agent and preparation method and application thereof Download PDFInfo
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- CN108059705B CN108059705B CN201711333723.3A CN201711333723A CN108059705B CN 108059705 B CN108059705 B CN 108059705B CN 201711333723 A CN201711333723 A CN 201711333723A CN 108059705 B CN108059705 B CN 108059705B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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Abstract
The invention disclosesThe invention relates to a water-based polyurethane resin hydrolysis-resistant agent and a preparation method and application thereof, wherein the water-based polyurethane resin hydrolysis-resistant agent can be used as an additive component during storage of water-based polyurethane resin to improve the storage stability, and can also be used as an additive component during application and processing of water-based polyurethane resin to improve the hydrolysis resistance of a finished product. The general structural formula is shown as formula (1):
Description
Technical Field
The water-soluble waterborne polyurethane resin hydrolysis resistant agent is prepared by the following steps.
Background
Waterborne Polyurethanes (WPU) are binary colloidal systems with water as the medium. The polyurethane emulsion has the advantages of no toxicity, difficult combustion, no environmental pollution and the like, is widely applied in the fields of leather, fiber treatment, adhesives, coatings and the like, and has a tendency of gradually replacing solvent type polyurethane. After the efforts of a large number of researchers, the performance of the WPU is continuously improved, so that the WPU is suitable for more occasions, and the WPU is becoming a novel polymer material which is developed vigorously.
While the development of WPU, the defect of extremely poor hydrolysis resistance of WPU is also exposed, especially the WPU of carboxylic acid type. The WPU adopting the sulfonic acid type aqueous chain extender is greatly improved in hydrolysis resistance, the requirement of practical application is still difficult to meet, and the large-scale application of the WPU in some fields is limited.
Disclosure of Invention
The invention aims to provide a hydrolysis-resistant agent for aqueous polyurethane resin, a preparation method and application thereof, which overcome the defects in the prior art and meet the application requirements of the related fields.
The structural general formula of the hydrolysis-resistant agent for the waterborne polyurethane resin is shown as the formula (1):
wherein:
a. b and C respectively represent hydrogen and alkyl of C1-C4; a. b and c can be the same group or different groups;
preferably, the alkyl of C1-C4 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
n is an integer from 1 to 10, preferably an integer from 1 to 6, most preferably an integer from 1 to 3.
The structural general formula of d is shown as formula (2):
m is an integer of 1 to 50, preferably 6 to 40;
r represents C1-C4 alkyl or aryl;
preferably, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl;
preferably, d is methyl ether polyethylene glycol group, ethyl ether polyethylene glycol group, n-propyl ether polyethylene glycol group, isopropyl ether polyethylene glycol group, n-butyl ether polyethylene glycol group, isobutyl ether polyethylene glycol group, tert-butyl ether polyethylene glycol group, phenyl ether polyethylene glycol group; methyl ether poly-1, 3-propanediol; ethyl ether poly-1, 3-propanediol, n-propyl ether poly-1, 3-propanediol, isopropyl ether poly-1, 3-propanediol, n-butyl ether poly-1, 3-propanediol, isobutyl ether poly-1, 3-propanediol, tert-butyl ether poly-1, 3-propanediol, phenyl ether poly-1, 3-propanediol; methyl ether poly-1, 2-propylene glycol group, ethyl ether poly-1, 2-propylene glycol group, n-propyl ether poly-1, 2-propylene glycol group, isopropyl ether poly-1, 2-propylene glycol group, n-butyl ether poly-1, 2-propylene glycol group, isobutyl ether poly-1, 2-propylene glycol group, tert-butyl ether poly-1, 2-propylene glycol group or phenyl ether poly-1, 2-propylene glycol group;
preferably, the hydrolysis resistance agent of the aqueous polyurethane resin is as follows:
m＝4，n＝3；
m＝7，n＝3；
m＝17，n＝3；
m＝13，n＝3。
the preparation method of the hydrolysis resistant agent for the waterborne polyurethane resin comprises the following steps:
reacting aromatic diisocyanate B with a catalyst for 1-12 hours at 90-180 ℃ in an inert atmosphere, cooling to 40-80 ℃, adding polyethylene glycol monoalkyl ether or polypropylene glycol monoalkyl ether, preferably by a dropwise adding method, wherein the dropwise adding time is 1-4 hours, and reacting until-NCO (isocyanate group) disappears to obtain the waterborne polyurethane resin hydrolysis-resistant agent;
the catalyst is 1-phenyl-3-methylphosphine cyclopentene-1-oxide, 1-methyl-1-oxo-2-phosphinene, phosphino-cyclobutane oxide or diethylphosphino-thiocholine;
the polyethylene glycol monoalkyl ether is polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monoisopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monoisobutyl ether, polyethylene glycol mono-tert-butyl ether and polyethylene glycol monophenyl ether with the molecular weight of 200-2000;
the poly-1, 3-propylene glycol monoalkyl ether is poly-1, 3-propylene glycol monomethyl ether, poly-1, 3-propylene glycol monoethyl ether, poly-1, 3-propylene glycol monopropyl ether, poly-1, 3-propylene glycol monoisopropyl ether, poly-1, 3-propylene glycol monobutyl ether, poly-1, 3-propylene glycol monoisobutyl ether, poly-1, 3-propylene glycol mono-tert-butyl ether and poly-1, 3-propylene glycol monophenyl ether with the molecular weight of 200-2000;
the poly-1, 2-propylene glycol monoalkyl ether is poly-1, 2-propylene glycol monomethyl ether, poly-1, 2-propylene glycol monoethyl ether, poly-1, 2-propylene glycol monopropyl ether, poly-1, 2-propylene glycol monoisopropyl ether, poly-1, 2-propylene glycol monobutyl ether, poly-1, 2-propylene glycol monoisobutyl ether, poly-1, 2-propylene glycol mono-tert-butyl ether and poly-1, 2-propylene glycol monophenyl ether with the molecular weight of 200-2000;
the aromatic diisocyanate B has the following structure:
wherein:
a. b and C respectively represent hydrogen and alkyl of C1-C4; a. b and c can be the same group or different groups
Preferably, the alkyl of C1-C4 is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
preferred aromatic diisocyanates B are selected from 1, 3, 5-trimethyl-2, 4-phenylene diisocyanate, diethyltoluene diisocyanate, 2, 4, 6-triethylbenzene diisocyanate, 2, 4, 6-triisopropylbenzene diisocyanate;
the aromatic diisocyanate B can be prepared by a commercial product or by a method reported in a patent CN 201080037436;
the dosage of the catalyst is 0.0001-2% of the weight of the aromatic diisocyanate B;
preferably, the amount of the catalyst is 0.1-0.5% of the weight of the aromatic diisocyanate B;
the dosage of the polyethylene glycol monoalkyl ether or the polypropylene glycol monoalkyl ether is 0.2-0.8 of the amount (mole number) of the aromatic diisocyanate B substance;
the hydrolysis resistance agent of the waterborne polyurethane resin can be used as an additive component during storage of the waterborne polyurethane resin to improve the storage stability, and can also be used as an additive component during application and processing of the waterborne polyurethane resin to improve the hydrolysis resistance of a finished product, and the application method comprises the following steps:
dropwise adding a certain amount of hydrolysis resistance agent into the aqueous polyurethane resin under the condition of mechanical stirring at 200-500 rpm, stirring for 20min to uniformly disperse the hydrolysis resistance agent, stopping stirring, and filtering with a 120-mesh filter screen to obtain the aqueous polyurethane resin added with the hydrolysis resistance agent. The aqueous polyurethane resin is selected from commercial products such as model JF-PDY-A551 and the like.
The invention has the beneficial effects that:
the storage stability of the waterborne polyurethane resin is effectively improved, and the service life of the material prepared from the polyurethane resin is prolonged by 2-3 times.
Drawings
FIG. 1 is a chart IR spectrum of example 1.
FIG. 2 is an infrared spectrum of a map of example 2.
FIG. 3 is a chart IR spectrum of example 3.
FIG. 4 is an infrared spectrum of a map of example 4.
Detailed Description
The present invention is further described below with reference to specific examples, which are only exemplary and do not limit the scope of the present invention in any way.
Example 1
Adding 50 Kg of 1, 3, 5-trimethyl-2, 4-phenylene diisocyanate and 50 g of 1-phenyl-3-methylphosphine heterocyclopentene-1-oxide into a reaction kettle, reacting at 90 ℃ for 12 hours in a nitrogen atmosphere, cooling to 80 ℃, adding 22Kg of polyethylene glycol monomethyl ether 200(M is 200), and dropwise adding for 4 hours; reacting until-NCO (isocyanate group) disappears to obtain the hydrolysis resistant agent of the waterborne polyurethane resin.
The number average molecular weight Mn was 1100 by GPC. For convenient use, deionized water can be added to prepare 10-50% aqueous solution, the aqueous solution is light yellow to yellow viscous liquid, and the viscosity of the 10% aqueous solution is 60cP (25 ℃).
The structural formula is as follows:
wherein: m is 4 and n is 3.
Example 2
Adding 50 Kg of diethyl toluene diisocyanate and 250 g of diethylphosphinothiocholine into a reaction kettle, reacting for 1 hour at 180 ℃ in a nitrogen atmosphere, cooling to 40 ℃, and dropwise adding 43Kg of polyethylene glycol monophenyl ether 400(M is 400) for 4 hours; reacting until-NCO (isocyanate group) disappears to obtain the product carbodiimide oligomer.
The number average molecular weight Mn was 1700 by GPC. For convenient use, deionized water can be added to prepare 10-50% aqueous solution, the aqueous solution is light yellow to yellow viscous liquid, and the viscosity of the aqueous solution with the weight concentration of 50% is 1680cP (25 ℃).
The structural formula is as follows:
wherein: m is 7 and n is 3.
Example 3
Adding 50 Kg of 2, 4, 6-triethylbenzene diisocyanate and 100 g of 1-methyl-1-oxo-2-phosphine cyclopentene into a reaction kettle, reacting at 120 ℃ for 3 hours in a nitrogen atmosphere, cooling to 60 ℃, and dropwise adding about 110Kg of poly-1, 3-propylene glycol monoethyl ether 1000(M is 1000) for 4 hours; reacting until-NCO (isocyanate group) disappears to obtain the hydrolysis resistant agent of the waterborne polyurethane resin.
The number average molecular weight Mn was 2600 by GPC. For convenient use, deionized water can be added to prepare 10-50% aqueous solution, the aqueous solution is light yellow to yellow viscous liquid, and the viscosity of the aqueous solution with the weight concentration of 20% is 220cP (25 ℃).
The structural formula is as follows:
wherein: m is 17 and n is 3.
Example 4
Adding 50 Kg of 2, 4, 6-triisopropylbenzene diisocyanate and 125 g of phosphine-heterocyclic butane oxide into a reaction kettle, reacting for 2.5 hours at 140 ℃ in a nitrogen atmosphere, cooling to 7060 ℃, and dropwise adding about 80Kg of poly-1, 2-propylene glycol monopropyl ether 800(M ═ 800) for 4 hours; reacting until-NCO (isocyanate group) disappears to obtain the hydrolysis resistant agent of the waterborne polyurethane resin.
The number average molecular weight Mn was 2200 by GPC. For convenient use, deionized water can be added to prepare 10-50% aqueous solution, the aqueous solution is light yellow to yellow viscous liquid, and the viscosity of the aqueous solution with the weight percentage of 30% is 640cP (25 ℃). The structural formula is as follows:
wherein: m is 13 and n is 3.
Example 5
The products of examples 1 to 4 were used as additives for storage of the aqueous polyurethane resin and for processing of the aqueous polyurethane resin, and in order to examine storage stability and hydrolysis resistance of the finished product, a commercially available aqueous polyurethane resin JF-PDY-A551 was selected and the application effects of the products of examples 1 to 4 were verified, and the results are shown in Table 1.
TABLE 1
Note: the storage stability refers to the hydrolysis resistance of the finished product detected after the resin is stored to the listed time points, and the hydrolysis resistance is detected according to the standard GB/T30779-.
Compared with the blank control, the hydrolysis resistant agent in the embodiments 1-4 effectively improves the storage stability of the waterborne polyurethane resin, the effective period of 6 months is prolonged to 18 months, so that the service life of the resin is prolonged by 2-3 times, and the hydrolysis resistance of the material prepared from the resin is remarkably improved, thereby being beneficial to expanding the large-scale application of the waterborne polyurethane resin in some fields.
Claims (7)
1. The hydrolysis-resistant agent of the waterborne polyurethane resin is characterized by comprising the following components in percentage by weight:
m＝4，n＝3；
m＝7，n＝3；
m＝17，n＝3；
m＝13，n＝3。
2. the method for preparing the hydrolysis resistant agent for the aqueous polyurethane resin according to claim 1, comprising the steps of: reacting aromatic diisocyanate B with a catalyst for 1-12 hours at 90-180 ℃ in an inert atmosphere, cooling to 40-80 ℃, adding polyethylene glycol monoalkyl ether or polypropylene glycol monoalkyl ether by a dropwise adding method for 1-4 hours, and reacting until-NCO (isocyanate group) disappears to obtain the aqueous polyurethane resin hydrolysis resistant agent;
the aromatic diisocyanate B is selected from 1, 3, 5-trimethyl-2, 4-benzene diisocyanate, diethyl toluene diisocyanate, 2, 4, 6-triethyl benzene diisocyanate or 2, 4, 6-triisopropyl benzene diisocyanate.
3. The process of claim 2 wherein the catalyst is 1-phenyl-3-methylphosphineopentene-1-oxide, 1-methyl-1-oxo-2-phosphinothioene, phosphinothiobutane oxide or diethylphosphonothiocholine.
4. The method according to claim 2, wherein the polyethylene glycol monoalkyl ether is polyethylene glycol monomethyl ether or polyethylene glycol monophenyl ether with a molecular weight of 200-2000;
the polypropylene glycol monoalkyl ether is poly-1, 3-propylene glycol monoethyl ether with the molecular weight of 200-2000 or poly-1, 2-propylene glycol monomethyl ether with the molecular weight of 200-2000.
5. The process of claim 2 wherein the catalyst is present in an amount of 0.0001 to 2% by weight of the aromatic diisocyanate B.
6. The method according to claim 2, wherein the amount of the polyethylene glycol monoalkyl ether or the polypropylene glycol monoalkyl ether is 0.2 to 0.8 mol based on the amount (mole) of the aromatic diisocyanate B.
7. The use of the hydrolysis resistant agent according to claim 1, wherein the additive is used as an additive for the aqueous polyurethane resin during storage to improve the storage stability or an additive for the aqueous polyurethane resin during application and processing to improve the hydrolysis resistance of the finished product.
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| DE4238046A1 (en) * | 1992-11-11 | 1994-05-19 | Basf Ag | New bis (4-substituted-2,6-diisopropylphenyl) carbodiimides, a process for their preparation and their use and the 4-substituted 2,6-diisopropylphenyl isocyanates which can be used for their preparation |
| JP3432566B2 (en) * | 1994-02-10 | 2003-08-04 | 協和醗酵工業株式会社 | Method for inhibiting hydrolysis of ester, hydrolysis inhibitor and ester composition |
| DE10222348A1 (en) * | 2002-05-21 | 2003-12-04 | Mitsubishi Polyester Film Gmbh | Biaxially oriented, hydrolysis-resistant film made of a thermoplastic with a hydrolysis stabilizer, process for its production, its use and capacitors made from the film |
| US7863440B2 (en) * | 2006-12-28 | 2011-01-04 | Great Eastern Resins Industrial Co., Ltd. | Macrocyclic carbodiimides (MC-CDI) and their derivatives, syntheses and applications of the same |
| US20130131255A1 (en) * | 2011-11-17 | 2013-05-23 | Laurence Pottie | Additives for stabilizing polycondensates with respect to hydrolysis |
| JP5101747B1 (en) * | 2012-01-18 | 2012-12-19 | 日本ペイント株式会社 | Two-component aqueous coating composition |
| CN102702699B (en) * | 2012-07-06 | 2015-02-25 | 上海日之升新技术发展有限公司 | Glass-fiber-reinforced hydrolysis-resistant polyester material and preparation method thereof |
| CN103936954A (en) * | 2014-04-21 | 2014-07-23 | 上海朗亿功能材料有限公司 | Novel polycarbodiimide compound and preparation method thereof |
| CN105778026B (en) * | 2014-12-25 | 2018-11-20 | 上海华峰新材料研发科技有限公司 | Carbodiimides quasi-oligomer containing steric hindrance and its preparation method and application |
| CN106632940A (en) * | 2016-12-29 | 2017-05-10 | 上海华峰新材料研发科技有限公司 | Polycarbodiimide compounds, preparation method thereof and liquid type hydrolysis-resistant agent composition |
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