CN114854004B - Nonionic type double-amino hydrophilic chain extender, preparation method thereof and preparation method of nonionic type aqueous polyurea - Google Patents
Nonionic type double-amino hydrophilic chain extender, preparation method thereof and preparation method of nonionic type aqueous polyurea Download PDFInfo
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- CN114854004B CN114854004B CN202210444013.2A CN202210444013A CN114854004B CN 114854004 B CN114854004 B CN 114854004B CN 202210444013 A CN202210444013 A CN 202210444013A CN 114854004 B CN114854004 B CN 114854004B
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- aqueous polyurea
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- 229920002396 Polyurea Polymers 0.000 title claims abstract description 150
- 239000004970 Chain extender Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 39
- 239000002202 Polyethylene glycol Substances 0.000 claims description 38
- 229920001223 polyethylene glycol Polymers 0.000 claims description 38
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 37
- 229920000570 polyether Polymers 0.000 claims description 34
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 claims description 26
- 125000005442 diisocyanate group Chemical group 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 5
- YMLFYGFCXGNERH-UHFFFAOYSA-K butyltin trichloride Chemical compound CCCC[Sn](Cl)(Cl)Cl YMLFYGFCXGNERH-UHFFFAOYSA-K 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-M 4-aminobenzoate Chemical compound NC1=CC=C(C([O-])=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-M 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 80
- 230000000704 physical effect Effects 0.000 abstract description 19
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 17
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 9
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 8
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229960005274 benzocaine Drugs 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- IWXAZSAGYJHXPX-BCEWYCLDSA-N Bisbentiamine Chemical compound C=1C=CC=CC=1C(=O)OCC/C(SS\C(CCOC(=O)C=1C=CC=CC=1)=C(/C)N(CC=1C(=NC(C)=NC=1)N)C=O)=C(/C)N(C=O)CC1=CN=C(C)N=C1N IWXAZSAGYJHXPX-BCEWYCLDSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
- C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3237—Polyamines aromatic
- C08G18/3243—Polyamines aromatic containing two or more aromatic rings
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a nonionic type double-amino hydrophilic chain extender, a preparation method thereof and a preparation method of nonionic type aqueous polyurea. In particular, the nonionic type double amino hydrophilic chain extender according to the invention can be used for preparing aqueous pure polyurea without urethane chain segments, thereby greatly improving the physical properties of the polyurea product. The method for preparing the nonionic type double-amino hydrophilic chain extender can prepare the nonionic type double-amino hydrophilic chain extender in a mode of simple process, low cost and high reaction rate. In addition, the nonionic aqueous polyurea obtained by using the preparation method according to the present invention has excellent emulsion stability (including mechanical stability and calcium ion stability) and its cured product has good physical properties (such as tensile strength, elongation at break, tear strength, etc.).
Description
Technical Field
The invention relates to the technical field of aqueous polyurea materials, and in particular relates to a nonionic type double-amino hydrophilic chain extender, a preparation method of the nonionic type double-amino hydrophilic chain extender and a preparation method of nonionic type aqueous polyurea.
Background
The aqueous polyurea means an aqueous polyurea dispersion obtained by dispersing polyurea in water. Due to the characteristic of urea groups in the aqueous polyurea molecular structure, the dry film of the aqueous polyurea has excellent physical properties, and has wide application prospects in industries such as building coatings, adhesives, automobile manufacturing, clothing, water conservancy and the like.
The preparation of the nonionic aqueous polyurea mainly adopts the way that hydrophilic chain segments are introduced to a molecular main chain or a side chain, and finally the dispersion of the polyurea in water is realized, and the nonionic aqueous polyurea emulsion is insensitive to electrolyte because of the absence of an electric double layer structure in the ionic polyurea emulsion, so that the nonionic aqueous polyurea emulsion can be randomly blended with other emulsions with different PH values without demulsification and other problems, the application field of the aqueous polyurea emulsion can be expanded, and therefore, the nonionic aqueous polyurea has good development prospect.
However, the aqueous polyurea-based products currently employed are not satisfactory in terms of application properties (e.g., emulsion stability of the aqueous polyurea as an emulsion) and physical properties of the cured product. Thus, there is still an urgent need for aqueous polyurea-based products having good application properties (e.g., emulsion stability of aqueous polyurea as an emulsion) and good physical properties of the product after curing thereof.
Disclosure of Invention
Starting from the technical problems set out above, it is an object of the present invention to provide a nonionic bisaminohydrophilic chain extender, which can be used for preparing aqueous pure polyureas without urethane segments, thereby greatly improving the physical properties of polyurea products. Another object of the present invention is to provide a method for preparing a non-ionic bis-amino hydrophilic chain extender, which can prepare the non-ionic bis-amino hydrophilic chain extender in a manner of simple process, low cost and high reaction rate. In addition, it is still another object of the present invention to provide a method for preparing a nonionic aqueous polyurea, by which the obtained nonionic aqueous polyurea has excellent emulsion stability (including mechanical stability and calcium ion stability) and the cured product thereof has good physical properties (such as tensile strength, elongation at break, tear strength, etc.).
Specifically, according to one aspect of the present invention, there is provided a nonionic type bisaminohydrophilic chain extender having a structure represented by the following general formula (1):
wherein n is an integer of 3 to 60.
According to certain preferred embodiments of the present invention, wherein n is an integer from 3 to 37.
According to another aspect of the present invention, there is provided a method for preparing the above-described nonionic bisaminohydrophilic chain extender, the method comprising mixing trimethylolpropane polyethylene glycol monomethyl ether, ethyl p-aminobenzoate, a main catalyst and a cocatalyst, and heating under reduced pressure distillation conditions to react, wherein:
the number of the ethylene oxide repeating units in the trimethylolpropane polyethylene glycol monomethyl ether is an integer of 3-60;
the main catalyst is selected from one or more of sodium methoxide, sodium ethoxide and sodium tert-butoxide; and
the promoter is selected from one or more of dibutyl tin oxide, butyl tin trichloride and dibutyl tin maleate.
According to certain preferred embodiments of the present invention, the molar ratio of the ethyl p-aminobenzoate to the trimethylolpropane polyethylene glycol monomethyl ether is in the range of 2:1 to 3:1.
According to certain preferred embodiments of the present invention, the weight ratio of the procatalyst to the cocatalyst is in the range of 1:1 to 10:1.
According to certain preferred embodiments of the present invention, the ratio of the sum of the weights of the procatalyst and the cocatalyst to the sum of the weights of the trimethylolpropane polyethylene glycol monomethyl ether and the paraben is 1X 10 -4 1 to 1X 10 -2 In the range of 1.
According to still another aspect of the present invention, there is provided a method for preparing a nonionic aqueous polyurea, the method comprising the steps of:
a) Mixing and heating the steric type amino-terminated polyether, diisocyanate, the nonionic type double-amino hydrophilic chain extender prepared by the preparation method and an organic solvent to react; and
b) Adding water to the product of step a).
According to certain preferred embodiments of the present invention, wherein the structure of the sterically hindered amine-terminated polyether is represented by the following general formula (2):
wherein X is a divalent residue obtained after removal of two hydroxyl groups from a polyether polyol selected from one or more of a polyethylene oxide polyol, a polypropylene oxide polyol and a polytetramethylene ether glycol having a hydroxyl functionality of 2 or 3 and a number average molecular weight of 92 to 10000.
According to certain preferred embodiments of the present invention, wherein the polyether polyol has a number average molecular weight in the range of 650 to 3000.
According to certain preferred embodiments of the present invention, wherein the diisocyanate is selected from one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
According to certain preferred embodiments of the present invention, wherein the organic solvent is selected from one or more of ethyl acetate, acetone and N, N-dimethylformamide.
According to certain preferred embodiments of the present invention, wherein the molar ratio of the diisocyanate to the sterically hindered amine-terminated polyether is in the range of 2:1 to 6:1 and the molar ratio of the diisocyanate to the nonionic bis-amino hydrophilic chain extender is in the range of 2:1 to 10:1.
According to certain preferred embodiments of the present invention, wherein the ratio of the weight of the organic solvent to the sum of the weight of the sterically hindered amine-terminated polyether and the diisocyanate is in the range of 0.1:1 to 0.5:1.
According to certain preferred embodiments of the present invention, wherein in step b) the ratio of the weight of added water to the sum of the weights of the sterically hindered amine-terminated polyether, diisocyanate, nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 4:1.
According to certain preferred embodiments of the invention, the method further comprises, after step b):
c) Removing the organic solvent from the product obtained in step b).
Compared with the prior art in the field, the invention has the advantages that:
1) In the case of the nonionic type bisaminohydrophilic chain extender according to the present invention, the nonionic type bisaminohydrophilic chain extender can be used to prepare aqueous pure polyureas without urethane segments and greatly improve physical properties of polyurea products;
2) As for the method for preparing a nonionic bis-amino hydrophilic chain extender according to the present invention, the method can prepare the nonionic bis-amino hydrophilic chain extender in a manner of simple process, low cost and high reaction rate;
3) In the method for preparing the nonionic aqueous polyurea, the steric type low activity amino terminated polyether is used as a main initial reactant, the specific nonionic type low activity double amino hydrophilic chain extender is used as a hydrophilic chain segment, and the obtained aqueous polyurea has a molecular structure without a carbamate chain segment and is a pure polyurea system. Compared with the aqueous polychloro-urea or aqueous polyurethane containing carbamate chain segments, the physical properties of the obtained nonionic aqueous polyurea emulsion are greatly improved when the emulsion is made into a coating film. Specifically, the nonionic aqueous polyurea obtained by using the preparation method according to the present invention has excellent emulsion stability (including mechanical stability and calcium ion stability) and its cured product has good physical properties (such as tensile strength, elongation at break, tear strength, etc.).
Detailed Description
It is to be understood that other various embodiments can be devised and modifications to the embodiments by those skilled in the art based on the teachings herein without departing from the scope or spirit of this disclosure. The following detailed description is, therefore, not to be taken in a limiting sense.
All numbers expressing feature sizes, amounts, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about" unless otherwise indicated. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the desired properties sought to be obtained by the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
The inventors of the present invention found that when preparing a nonionic aqueous polyurea, the hydrophilic segment is more advantageous in achieving dispersion of the polyurea in water on the side chains than on the main chain. However, the preparation of nonionic aqueous polyureas has been reported to generally employ trimethylol propane polyethylene glycol monomethyl ether bearing two hydroxyl functionalities as the nonionic hydrophilic chain extender. However, since the resultant product has a large amount of urethane segments in its molecular structure, the product belongs to the structure of aqueous polyurethane-urea, rather than pure polyurea, and as the amount of urethane segments in the molecular structure increases, the performance tends to approach that of aqueous polyurethane. Therefore, one of the purposes of the invention is to develop a novel nonionic low-activity double-amino hydrophilic chain extender and use the novel nonionic low-activity double-amino hydrophilic chain extender for preparing nonionic aqueous pure polyurea emulsion so as to meet the requirements of the future aqueous polyurea field.
According to one aspect of the present invention, there is provided a nonionic type bisaminohydrophilic chain extender having a structure represented by the following general formula (1):
wherein n is an integer of 3 to 60.
The active group of the nonionic low-activity double-amino hydrophilic chain extender is double-amino, and when the nonionic low-activity double-amino hydrophilic chain extender is used as the hydrophilic chain extender to synthesize the aqueous polyurea, the aqueous pure polyurea system without carbamate groups can be obtained, thereby laying a foundation for preparing the high-performance aqueous polyurea. In addition, because the electron-withdrawing groups beside the amino groups in the nonionic low-activity double-amino hydrophilic chain extender exist, the amino groups have lower activity when reacting with diisocyanate, so that the reaction speed is lower when reacting with isocyanate groups, side reactions are fewer, a prepolymer with uniform molecular weight distribution is easier to obtain, and the macroscopically obtained aqueous polyurea product has higher physicochemical properties. That is, by employing the nonionic type bisaminohydrophilic chain extender in the preparation process of the nonionic type aqueous polyurea, it is possible to avoid the generation of urethane segments in the molecular structure of the resultant product, thereby improving the physical properties (such as tensile strength, elongation at break, tear strength, etc.) of the resultant polyurea product.
In the structural general formula (1) of the nonionic type double-amino hydrophilic chain extender, n is an integer of 3-60. When n is less than 3, the nonionic bisaminohydrophilic chain extender used to provide hydrophilicity to the polyurea product will not provide sufficient hydrophilicity, resulting in that the produced polyurea is not emulsified well; when n is more than 60, the molecular weight of hydrophilic side chains in the resulting polyurea product is excessively large, resulting in deterioration of physical properties (in particular, tensile strength, etc.) of the polyurea product after curing. In order to achieve a good balance between improving hydrophilicity and improving physical properties of the cured product, n is preferably an integer of 3 to 37.
According to another aspect of the present invention, there is provided a method for preparing a nonionic type bisaminohydrophilic chain extender, the method comprising mixing trimethylolpropane polyethylene glycol monomethyl ether, ethyl p-aminobenzoate, a main catalyst and a cocatalyst, and heating under reduced pressure distillation conditions to react, wherein:
the number of the ethylene oxide repeating units in the trimethylolpropane polyethylene glycol monomethyl ether is an integer of 3-60;
the main catalyst is selected from one or more of sodium methoxide, sodium ethoxide and sodium tert-butoxide; and
the promoter is selected from one or more of dibutyl tin oxide, butyl tin trichloride and dibutyl tin maleate.
Preferably, the trimethylolpropane polyethylene glycol monomethyl ether employed in the above process is a nonionic type linear dihydroxypolyethylene glycol monomethyl ether having a hydroxyl functionality of 2, the structure of which is represented by the following general formula (3):
wherein n is an integer from 3 to 60, preferably n is an integer from 3 to 37.
Commercially available products of trimethylolpropane polyethylene glycol monomethyl ether which can be used in the present invention include, for example, ymerT produced and sold by Beston, sweden M N120 (which has a hydroxyl functionality of 2 and a number average molecular weight of 1000) or Ymer TM N90 (its hydroxyl functionality is 2 and number average molecular weight is 1200).
In the above method according to the present invention, a combination of a main catalyst and a cocatalyst is employed to catalyze the transesterification reaction between trimethylolpropane polyethylene glycol monomethyl ether and ethyl p-aminobenzoate, the main catalyst being selected from one or more of sodium methoxide, sodium ethoxide, sodium tert-butoxide, and the cocatalyst being selected from one or more of dibutyltin oxide, butyltin trichloride, dibutyltin maleate. The inventors of the present invention found that when only one of the above-described main catalysts or one of the cocatalysts is used, a high reaction rate of 90% or more cannot be achieved. According to the present invention, the reaction rate in the preparation method of the nonionic type bisaminohydrophilic chain extender is calculated by mass difference of raw materials (for example, methylol propane polyethylene glycol monomethyl ether) before and after the reaction. In order to increase the reaction rate, it is preferable that the weight ratio of the main catalyst to the cocatalyst is in the range of 1:1 to 10:1. In addition, in order to increase the reaction rate, it is preferable that the weight of the procatalyst and the cocatalyst The ratio of the sum of the weight of the trimethylolpropane polyethylene glycol monomethyl ether and the weight of the para-aminobenzoate is 1 x 10 -4 1 to 1X 10 -2 In the range of 1.
Preferably, in the above-described method for preparing a nonionic bisaminohydrophilic chain extender, a molar ratio of the ethyl p-aminobenzoate to the trimethylolpropane polyethylene glycol monomethyl ether is in a range of 2:1 to 3:1. When the molar ratio of the ethyl p-aminobenzoate to the trimethylolpropane polyethylene glycol monomethyl ether is less than 2:1, the hydroxyl in the trimethylolpropane polyethylene glycol monomethyl ether cannot be completely converted into amino, so that a carbamate chain segment can be generated in the subsequent polyurea synthesis, and the physical properties of the product after polyurea solidification are affected. On the other hand, when the molar ratio of ethyl p-aminobenzoate to the trimethylolpropane polyethylene glycol monomethyl ether is more than 3:1, the ethyl p-aminobenzoate is excessive and remains as a small molecule in the resulting nonionic type bisaminohydrophilic chain extender, resulting in deterioration of physical properties of the polyurea cured product.
According to certain preferred embodiments of the present invention, the method for preparing a nonionic bis-amino hydrophilic chain extender comprises: the trimethylolpropane polyethylene glycol monomethyl ether, ethyl p-aminobenzoate, main catalyst and cocatalyst are mixed and reacted for 2.0 to 4.0 hours at 100 to 170 ℃ under the condition of reduced pressure distillation of 100 to 10000 Pa.
According to still another aspect of the present invention, there is provided a method for preparing a nonionic aqueous polyurea, the method comprising the steps of:
a) Mixing and heating the steric type amino-terminated polyether, diisocyanate, the nonionic type double-amino hydrophilic chain extender prepared by the preparation method and an organic solvent to react; and
b) Adding water to the product of step a).
Preferably, the structure of the sterically hindered amine-terminated polyether is represented by the following general formula (2):
wherein X is a divalent residue obtained after removal of two hydroxyl groups from a polyether polyol selected from one or more of a polyethylene oxide polyol, a polypropylene oxide polyol and a polytetramethylene ether glycol having a hydroxyl functionality of 2 or 3 and a number average molecular weight of 92 to 10000.
The electron withdrawing groups beside the amino groups in the branching mechanism of the steric hindrance type low-activity amino-terminated polyether adopted by the invention enable the amino groups to have lower activity when reacting with diisocyanate, so that the reaction speed is low when reacting with isocyanate, the molecular weight distribution of the prepolymer is more uniform, the obtained polyurea has fewer side reactions, the obtained aqueous polyurea product has higher physicochemical properties, the maximum tensile strength of a polyurea coating film synthesized by the reaction of the aqueous polyurea product and the diisocyanate reaches 55.0MPa, the maximum elongation at break reaches 1300%, and the maximum tearing strength reaches 210.5N/mm.
Specific examples of sterically hindered low activity amino terminated polyethers that may be employed in the present invention include: the family of sterically hindered low-activity amino-terminated polyethers produced and sold by the institute of construction science, shanxi province: DP-1000 (amino-terminated polytetrahydrofuran ether with functionality of 2 and number average molecular weight of 1238) and DP-2000 (amino-terminated polytetrahydrofuran ether with functionality of 2 and number average molecular weight of 2238).
Preferably, the polyether polyol has a number average molecular weight in the range of 650 to 3000.
Preferably, the diisocyanate is selected from one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
Preferably, the organic solvent is selected from one or more of ethyl acetate, acetone and N, N-dimethylformamide.
Preferably, the molar ratio of the diisocyanate to the sterically hindered amine-terminated polyether is in the range of 2:1 to 6:1, preferably 2:1 to 5:1, more preferably 2:1 to 4:1, and the molar ratio of the diisocyanate to the nonionic bis-amino hydrophilic chain extender is in the range of 2:1 to 10:1, preferably 2.5:1 to 10:1, more preferably 3.3:1 to 10:1.
Preferably, the ratio of the weight of the ethyl acetate to the sum of the weight of the sterically hindered amine-terminated polyether and the diisocyanate is in the range of 0.1:1 to 0.5:1, preferably 0.1:1 to 0.4:1, more preferably 0.1:1 to 0.3:1.
In step b) of the process for the preparation of a nonionic aqueous polyurea according to the invention, water is added to the product of step a) in order to achieve emulsification of the aqueous polyurea. Preferably, in step b) above, the ratio of the weight of water added to the sum of the weight of the sterically hindered amine-terminated polyether, diisocyanate, nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 5:1, preferably 1:1 to 4:1, more preferably 1:1 to 3:1. The solids content of the polyurea emulsion formed from the nonionic aqueous polyureas according to the invention after mixing with water can be considerably higher than the solids content of other conventional polyurea emulsions.
Preferably, the preparation method of the nonionic aqueous polyurea further comprises, after the step b):
c) Removing the organic solvent from the product obtained in step b).
The stability of the polyurea emulsion obtained can be further improved by the above step c).
According to certain preferred embodiments of the present invention, the method of preparing a nonionic aqueous polyurea comprises the steps of:
a) Mixing the steric type amino-terminated polyether, diisocyanate, the nonionic type double-amino hydrophilic chain extender and an organic solvent and reacting at 50-70 ℃ for 3.0-6.0 hours;
b) Adding deionized water to the product obtained in step a) and stirring at a speed of 1000-3000 rpm for 0.5 to 1.0 hour; and
c) Removing the organic solvent from the product obtained in step b) by distillation under reduced pressure to obtain the nonionic aqueous polyurea.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate an understanding of the invention and are not intended to limit the invention. The scope of the invention is defined by the appended claims.
Examples
The present invention will be described in further detail with reference to examples and comparative examples. It should be understood that the present invention is not limited to the following examples.
In the present invention, unless otherwise indicated, the reagents employed were all commercially available products and were used directly without further purification treatment. Further, "%" is referred to as "% by weight", and "parts" is referred to as "parts by weight".
Test method
Tensile Strength, elongation at break and tear Strength test after curing of nonionic aqueous polyurea
In the following examples, the tensile strength, elongation at break and tear strength of the nonionic aqueous polyureas obtained in the respective examples and comparative examples after curing were measured. The specific measurement method is as follows:
the resulting nonionic aqueous polyurea emulsion was coated on a polytetrafluoroethylene plate having a size of 350mm×320mm so that the final coating film thickness was 1.5±0.2mm. The polytetrafluoroethylene sheet coated with the coating film was dried at 23 ℃ and 50% humidity for 2 days. Followed by 4 days at a temperature of 23 ℃ and a humidity of 50%. The resulting coating film was then tested for tensile strength, elongation at break and tear strength according to the test methods specified in GB-T16777-2008.
Wherein, if the tensile strength of the coating film is more than or equal to 6.0MPa, the coating film is considered to meet the general industrial application requirements of the aqueous polyurea emulsion material; if the tensile strength of the coating film is 10MPa or more, the tensile strength properties of the aqueous polyurea emulsion material are considered to be excellent. If the elongation at break is greater than or equal to 400%, then the general industrial application requirements of the aqueous polyurea emulsion material are considered to be met; if the elongation at break is 460% or more, the aqueous polyurea emulsion material is considered to be excellent in elongation at break performance. If the tear strength is greater than or equal to 40N/mm, then the general industrial application requirements of the aqueous polyurea emulsion material are considered to be met; if the tear strength is 80N/mm or more, the aqueous polyurea emulsion material is considered to be excellent in tear strength properties.
Solid content test of nonionic aqueous polyurea emulsion
The solids content of the nonionic aqueous polyurea emulsions obtained in the respective examples and comparative examples below was determined according to the test method in the national standard GB/T20623-2006.
Specifically, a flat-bottomed disc (diameter: about 75 mm) was baked in a forced air oven at (150.+ -. 2) ℃ for 15 minutes, cooled to room temperature in a dryer, and weighed (m) 0 ) Accurate to 1mg. The test product (m 1 ) About 1g and ensures that the sample is uniformly dispersed on the disk surface. If the viscosity of the sample is too high, the weighed sample may be diluted with water and homogenized. The discs, weighed samples, were placed in a forced air oven preheated to (150.+ -. 2) ℃ for 15 minutes. The tray was moved into a desiccator, cooled to room temperature and weighed (m 2 ) Accurate to 1mg.
The solids content is calculated according to equation (1):
wherein:
w NV -solids content (%) of the nonionic aqueous polyurea emulsion;
m 2 -the mass of the sample and disc after heating in (g);
m 0 -the mass of the disc in (g);
m 1 the mass of the sample before heating is expressed in (g).
The two tests were performed in parallel, and the difference between the results of the two tests was not more than 1%. The experimental results are expressed as the average of two determinations, accurate to the decimal point one digit later.
Mechanical stability test of nonionic aqueous polyurea emulsionsTest on test
The nonionic aqueous polyurea emulsion obtained by the preparation method has excellent emulsion stability, such as mechanical stability. The mechanical stability of the nonionic aqueous polyurea emulsions obtained in the following examples and comparative examples was determined according to the test method in the national standard GB/T20623-2006.
Specifically, about 1000mL of the emulsion of filtered [ filter screen with a pore size of 17 μm (80 mesh) ] was weighed (400.+ -. 0.52) into a container (diameter 100mm, height 180 mm), placed on a high-speed dispersion machine base, fixed with a clamp, started up to a dispersion machine (stirring head is of a disk-tooth shape, diameter about 40 mm), dispersed for 0.5h at a speed of 2500r/min, filtered again, and the residue on the inner wall of the container was washed into the filter screen with tap water, and the filter screen was washed with tap water to see whether the emulsion was broken and whether there was any obvious flocculate. If the above is not present, mechanical stability is considered.
Calcium ion stability test of nonionic aqueous polyurea emulsions
The nonionic aqueous polyurea emulsions obtained by the preparation process according to the invention have good emulsion stability, for example, against substances present on the application surface which may lead to demulsification (for example, calcium ions). The calcium ion stability of the nonionic aqueous polyurea emulsions obtained in the following examples and comparative examples was measured in accordance with the test method in national standard GB/T20623-2006. Specifically, 30mL of the emulsion was added in a beaker, followed by 0.5% by mass CaCl 2 6mL of solution is stirred evenly and then placed in a 50mL measuring cylinder with a plug, and after 48 hours, the phenomena of delamination, sedimentation, flocculation and the like are observed. The presence or absence of flocs can be observed after the sample has been coated onto a glass plate with the aid of a glass rod in a uniform thin layer. If the above is not present, it is considered to have calcium ion stability.
Example 1
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (its hydroxyl functionality is 2 and number average molecular weight)1000), 33.2 grams of ethyl p-aminobenzoate, 0.012 grams of sodium t-butoxide, and 0.0012 grams of dibutyltin oxide. Maintaining the pressure of the system at 100pa, slowly heating to 130 ℃ from normal temperature, and then continuing to react for 2.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described preparation method for testing the nonionic bis-amino hydrophilic chain extender was 96.5%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 2.42.
Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux device, 40 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, which are manufactured by the company Limited, are added, 35.9 g of isophorone diisocyanate and 13.6 g of ethyl acetate are introduced to be protected, nitrogen is introduced to be stirred for 5.0 hours at 50 ℃, 175.9 g of deionized water is added after the temperature is reduced to be below 40 ℃, then the deionized water is dispersed for 0.5 hour at the rotation speed of 1000r/min in a dispersing machine, and then the ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 2
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (hydroxyl functionality of 2 and number average molecular weight of 1000), 36.3 g of ethyl p-aminobenzoate, 0.04 g of sodium ethoxide and 0.01 g of butyl tin trichloride, the system was maintained at a pressure of 1000Pa, and the reaction was continued after slowly heating from normal temperature to 170 ℃2.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described preparation method for testing the nonionic bis-amino hydrophilic chain extender was 95.5%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 2.65.
50 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 200 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi construction science research institute, inc., 59.5 g of isophorone diisocyanate and 51.9 g of ethyl acetate are added into a four-neck flask provided with a stirrer, a thermometer, a nitrogen inlet and a reflux device, nitrogen is introduced for protection, stirring is carried out at 70 ℃ for 3.0 hours, 350 g of deionized water is added into the flask after the temperature is reduced to below 40 ℃, then the deionized water is dispersed in a dispersing machine at the rotating speed of 3000r/min for 1.0 hour, and then ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 3
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (having a hydroxyl functionality of 2 and a number average molecular weight of 1000), 33.3 g of ethyl p-aminobenzoate, 0.044 g of sodium methoxide and O.022 g of dibutyltin maleate, maintaining the system at a pressure of 100Pa, slowly heating the system from normal temperature to 100 ℃ and then continuing the reaction for 4.0 hours to obtain the nonionic low-activity bis-amino hydrophilic chain extender by the reaction rate of the preparation method for testing the nonionic bis-amino hydrophilic chain extender described in detail aboveThe reaction rate obtained was 98.0%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 2.43.
50 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi construction science research institute, inc., and 71.7 g of isophorone diisocyanate and 34.4 g of ethyl acetate are added into a four-neck flask provided with a stirrer, a thermometer, a nitrogen inlet and a reflux device, nitrogen is introduced for protection, stirring is carried out at 60 ℃ for 6.0 hours, 240.2 g of deionized water is added after the temperature is reduced to below 40 ℃, then the deionized water is dispersed for 0.6 hours at the speed of 1000r/min in a dispersing machine, and then the ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 4
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (which has a hydroxyl functionality of 2 and a number average molecular weight of 1000), 33.3 grams of ethyl p-aminobenzoate, 0.04 grams of sodium t-butoxide, and 0.01 grams of dibutyltin oxide. And (3) maintaining the system pressure at 10000pa, slowly heating to 130 ℃ from normal temperature, and then continuing to react for 3.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described method for testing the preparation of the nonionic bis-amino hydrophilic chain extender was 91.0%. In the raw materials for preparing the nonionic type double amino hydrophilic chain extender, ethyl p-aminobenzoate and trimethylolpropane polyethylene glycol monomethyl ether The molar ratio of (2) was 2.43.
Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux device, 90 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, which are manufactured by the company Limited, are added, 53.8 g of isophorone diisocyanate and 46.1 g of ethyl acetate are introduced, nitrogen is introduced for protection, stirring is carried out at 70 ℃ for 5.0 hours, 298 g of deionized water is added after the temperature is reduced to below 40 ℃, then dispersed for 0.5 hours at the rotation speed of 1000r/min in a dispersing machine, and then ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 5
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000), 33.3 g of ethyl p-aminobenzoate, 0.04 g of sodium tert-butoxide and 0.01 g of dibutyltin oxide, maintaining the system at the pressure of 100pa, slowly heating the system to 130 ℃ from normal temperature, and continuing to react for 3.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described method for testing the preparation of the nonionic bis-amino hydrophilic chain extender was 99.0%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 2.43.
50 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi construction science, inc., 53.8 g of isophorone diisocyanate and 35 g of ethyl acetate are added into a four-neck flask provided with a stirrer, a thermometer, a nitrogen inlet and a reflux device, nitrogen is introduced for protection, stirring is carried out at 80 ℃ for 5.0 hours, 611.4 g of deionized water is added into the flask after the temperature is reduced to below 40 ℃, then the mixture is dispersed for 1.0 hour in a dispersing machine at the rotating speed of 1000r/min, and then ethyl acetate is removed by reduced pressure distillation, so that the nonionic aqueous polyurea emulsion is obtained.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 6
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (which has a hydroxyl functionality of 2 and a number average molecular weight of 1000), 26 grams of ethyl p-aminobenzoate, 0.012 grams of sodium t-butoxide, and 0.0012 grams of dibutyltin oxide. Maintaining the pressure of the system at 100pa, slowly heating to 130 ℃ from normal temperature, and then continuing to react for 2.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described preparation method for testing the nonionic bis-amino hydrophilic chain extender was 96.5%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 1.9.
Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux device, 40 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, which are manufactured by the company Limited, are added, 35.9 g of isophorone diisocyanate and 13.6 g of ethyl acetate are introduced to be protected, nitrogen is introduced to be stirred for 5.0 hours at 50 ℃, 175.9 g of deionized water is added after the temperature is reduced to be below 40 ℃, then the deionized water is dispersed for 0.5 hour at the rotation speed of 1000r/min in a dispersing machine, and then the ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Example 7
Into a four-necked flask equipped with a stirrer, a thermometer and a reduced pressure distillation apparatus, 100 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer was charged TM N120 (which has a hydroxyl functionality of 2 and a number average molecular weight of 1000), 42.5 grams of ethyl p-aminobenzoate, 0.012 grams of sodium t-butoxide, and 0.0012 grams of dibutyltin oxide. Maintaining the pressure of the system at 100pa, slowly heating to 130 ℃ from normal temperature, and then continuing to react for 2.0h to obtain the nonionic low-activity double-amino hydrophilic chain extender. The reaction rate obtained by the above-described preparation method for testing the nonionic bis-amino hydrophilic chain extender was 96.5%. In the raw materials for preparing the nonionic type double-amino hydrophilic chain extender, the molar ratio of ethyl aminobenzoate to trimethylolpropane polyethylene glycol monomethyl ether is 3.1.
Into a four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux device, 40 g of the prepared nonionic low-activity double-amino hydrophilic chain extender, 100 g of steric type low-activity amine-terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences, which are manufactured by the company Limited, are added, 35.9 g of isophorone diisocyanate and 13.6 g of ethyl acetate are introduced to be protected, nitrogen is introduced to be stirred for 5.0 hours at 50 ℃, 175.9 g of deionized water is added after the temperature is reduced to be below 40 ℃, then the deionized water is dispersed for 0.5 hour at the rotation speed of 1000r/min in a dispersing machine, and then the ethyl acetate is removed by reduced pressure distillation, thus obtaining the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Comparative example 1
Into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux apparatus were charged 40 g of trimethylolpropane polyethylene glycol monomethyl ether Ymer (100 g) TM N120 (the hydroxyl functionality of which is 2 and the number average molecular weight of which is 1000), 100 g of steric type low activity amine terminated polyether dp1000 with the functionality of 2 and the number average molecular weight of 1238 produced by Shanxi institute of construction and sciences Limited company, 35.9 g of isophorone diisocyanate and 13.6 g of ethyl acetate, and then stirring for 5.0 hours at 50 ℃, adding 175.9 g of deionized water after cooling to below 40 ℃ and then dispersing for 0.5 hours at the speed of 1000r/min in a dispersing machine, and then distilling off ethyl acetate under reduced pressure to obtain the nonionic aqueous polyurea emulsion.
Then, the respective properties of the nonionic aqueous polyurea emulsion prepared above were tested according to the methods for determining the solid content of the nonionic aqueous polyurea emulsion, the tensile strength, elongation at break and tear strength after the curing of the nonionic aqueous polyurea, the mechanical stability of the nonionic aqueous polyurea emulsion, and the calcium ion stability of the nonionic aqueous polyurea emulsion described in detail above, and the results thereof are shown in table 1 below.
Examples 1 to 7 above demonstrate that the nonionic bis-amino hydrophilic chain extender according to the present invention can be used to prepare an aqueous pure polyurea having no urethane segments, thereby greatly improving physical properties of the polyurea product, and that the nonionic aqueous polyurea obtained by using the preparation method according to the present invention has emulsion stability (including mechanical stability and calcium ion stability) conforming to industry standards and the cured product thereof has physical properties (such as tensile strength, elongation at break, tear strength, etc.) conforming to industry standards.
Further, as is apparent from comparing examples 1 to 5 with examples 6 to 7, when an aqueous pure polyurea is prepared according to the technical scheme of the present invention and the molar ratio of ethyl p-aminobenzoate to the trimethylolpropane polyethylene glycol monomethyl ether in the preparation of the nonionic bisaminohydrophilic chain extender is controlled to be in the range of 2:1 to 3:1, it is possible to achieve balance and optimization of various excellent properties in terms of emulsion stability (including mechanical stability and calcium ion stability) and physical properties (such as tensile strength, elongation at break and tear strength, etc.).
In addition, as is apparent from the results of comparative example 1, when trimethylolpropane polyethylene glycol monomethyl ether is used instead of the nonionic bisaminohydrophilic chain extender, physical properties (such as tensile strength, elongation at break, tear strength, etc.) of the resulting aqueous polyurea are greatly deteriorated, as compared with the method for producing a nonionic aqueous polyurea using the nonionic bisaminohydrophilic chain extender according to the present invention.
Although specific embodiments of the invention have been illustrated and described herein, it will be appreciated by those of ordinary skill in the art that a wide variety of alternate and/or equivalent implementations may be substituted for the specific embodiments shown and described without departing from the scope of the present invention. This application is intended to cover any adaptations or variations of the specific embodiments discussed herein. Therefore, it is intended that this invention be limited only by the claims and the equivalents thereof.
It will be understood by those skilled in the art that various modifications and changes may be made without departing from the scope of the present invention. Such modifications and variations are intended to fall within the scope of the invention as defined in the appended claims.
Claims (15)
1. A nonionic type double amino hydrophilic chain extender has a structure represented by the following general formula (1):
Wherein n is an integer of 3 to 60.
2. The nonionic, bis-amino, hydrophilic chain extender of claim 1, wherein n is an integer from 3 to 37.
3. A process for the preparation of the nonionic bisaminohydrophilic chain extender according to claim 1 or 2, the process comprising mixing trimethylolpropane polyethylene glycol monomethyl ether, ethyl p-aminobenzoate, a procatalyst and a cocatalyst and heating under reduced pressure distillation conditions, wherein:
the number of the ethylene oxide repeating units in the trimethylolpropane polyethylene glycol monomethyl ether is an integer of 3-60;
the main catalyst is selected from one or more of sodium methoxide, sodium ethoxide and sodium tert-butoxide; and
the promoter is selected from one or more of dibutyl tin oxide, butyl tin trichloride and dibutyl tin maleate.
4. The method for preparing a nonionic bis-amino hydrophilic chain extender as claimed in claim 3, wherein the molar ratio of said ethyl p-aminobenzoate to said trimethylolpropane polyethylene glycol monomethyl ether is in the range of 2:1 to 3:1.
5. The method for preparing a nonionic bis-amino hydrophilic chain extender of claim 3, wherein the weight ratio of said procatalyst to said cocatalyst is in the range of 1:1 to 10:1.
6. According to claimThe method for producing a nonionic bisaminohydrophilic chain extender as recited in claim 3, wherein a ratio of a sum of weights of the main catalyst and the cocatalyst to a sum of weights of the trimethylolpropane polyethylene glycol monomethyl ether and the p-aminobenzoate is 1×10 -4 1 to 1X 10 -2 In the range of 1.
7. A method for preparing a nonionic aqueous polyurea, the method comprising the steps of:
a) Mixing and heating a sterically hindered amine-terminated polyether, a diisocyanate, a nonionic bis-amino hydrophilic chain extender prepared according to the preparation method of any one of claims 3 to 6, and an organic solvent to perform a reaction; and
b) Adding water to the product of step a).
8. The method for producing a nonionic aqueous polyurea according to claim 7, wherein the structure of the sterically hindered amine-terminated polyether is represented by the following general formula (2):
wherein X is a divalent residue obtained after removal of two hydroxyl groups from a polyether polyol selected from one or more of a polyethylene oxide polyol, a polypropylene oxide polyol and a polytetramethylene ether glycol having a hydroxyl functionality of 2 or 3 and a number average molecular weight of 92 to 10000.
9. The method for preparing a nonionic aqueous polyurea according to claim 8, wherein the polyether polyol has a number average molecular weight ranging from 650 to 3000.
10. The method for preparing a nonionic aqueous polyurea according to claim 7, wherein the diisocyanate is one or more selected from isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and 4,4' -dicyclohexylmethane diisocyanate.
11. The method for preparing a nonionic aqueous polyurea according to claim 7, wherein the organic solvent is one or more selected from the group consisting of ethyl acetate, acetone and N, N-dimethylformamide.
12. The method of preparing a nonionic aqueous polyurea of claim 7, wherein the molar ratio of said diisocyanate to said sterically hindered amine-terminated polyether is in the range of 2:1 to 6:1, and the molar ratio of said diisocyanate to said nonionic bis-amino hydrophilic chain extender is in the range of 2:1 to 10:1.
13. The method of preparing a nonionic aqueous polyurea of claim 7, wherein the ratio of the weight of said organic solvent to the sum of the weight of said sterically hindered amine-terminated polyether and the weight of said diisocyanate is in the range of 0.1:1 to 0.5:1.
14. The process for the preparation of a nonionic aqueous polyurea according to claim 7, wherein in step b) the ratio of the weight of water added to the sum of the weights of the sterically hindered amine-terminated polyether, diisocyanate, nonionic bis-amino hydrophilic chain extender is in the range of 1:1 to 5:1.
15. The method for preparing a nonionic aqueous polyurea according to claim 7, further comprising, after step b):
c) Removing the organic solvent from the product obtained in step b).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005113487A2 (en) * | 2004-05-14 | 2005-12-01 | Sawyer Kenneth I | Polyurea compositions and compounds for the preparation thereof |
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| CN104530370A (en) * | 2014-12-26 | 2015-04-22 | 上海材料研究所 | Solvent-free method for preparing non-ionic water-borne polyurethane |
| CN109081897A (en) * | 2018-08-01 | 2018-12-25 | 万华化学集团股份有限公司 | The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application |
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| EP3412730A4 (en) * | 2016-02-05 | 2019-02-20 | FUJIFILM Corporation | Aqueous dispersion, production method therefor, and image formation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005113487A2 (en) * | 2004-05-14 | 2005-12-01 | Sawyer Kenneth I | Polyurea compositions and compounds for the preparation thereof |
| CN101638472A (en) * | 2009-09-04 | 2010-02-03 | 安徽大学 | Method for preparing side-chain non-ion aqueous polyurethane emulsion |
| CN104530370A (en) * | 2014-12-26 | 2015-04-22 | 上海材料研究所 | Solvent-free method for preparing non-ionic water-borne polyurethane |
| CN109081897A (en) * | 2018-08-01 | 2018-12-25 | 万华化学集团股份有限公司 | The excellent polyurethane of wet-hot aging performance or the aqueous dispersion of polyurethane-urea and its preparation method and application |
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