CN114479003A - High-stability waterborne polyurethane curing agent and preparation method thereof - Google Patents
High-stability waterborne polyurethane curing agent and preparation method thereof Download PDFInfo
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- CN114479003A CN114479003A CN202210059825.5A CN202210059825A CN114479003A CN 114479003 A CN114479003 A CN 114479003A CN 202210059825 A CN202210059825 A CN 202210059825A CN 114479003 A CN114479003 A CN 114479003A
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- curing agent
- polyurethane curing
- carboxylic acid
- acid solution
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 98
- 239000004814 polyurethane Substances 0.000 title claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000003381 stabilizer Substances 0.000 claims abstract description 42
- 239000012948 isocyanate Substances 0.000 claims abstract description 32
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 25
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 claims abstract description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000008096 xylene Substances 0.000 claims abstract description 8
- HPQUMJNDQVOTAZ-UHFFFAOYSA-N 2,2-dihydroxypropanoic acid Chemical compound CC(O)(O)C(O)=O HPQUMJNDQVOTAZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 15
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 8
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 7
- 229940097265 cysteamine hydrochloride Drugs 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 3
- 239000000243 solution Substances 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 29
- 238000004132 cross linking Methods 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- -1 aliphatic isocyanates Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- 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
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy compounds
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/677—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups
- C08G18/678—Low-molecular-weight compounds containing heteroatoms other than oxygen and the nitrogen of primary or secondary amino groups containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application relates to the technical field of waterborne polyurethane curing agents, and particularly discloses a high-stability waterborne polyurethane curing agent and a preparation method thereof. A high-stability waterborne polyurethane curing agent is mainly prepared from the following raw materials: isocyanate, a polyol-carboxylic acid solution, a stabilizer, a solvent and a pH regulator; the polyhydric alcohol-carboxylic acid solution is prepared by adopting a method comprising the following steps: uniformly mixing neopentyl glycol, trihydroxypropane, trimellitic anhydride, butyl acetate, dihydroxypropionic acid and xylene, refluxing, dehydrating and filtering to obtain the compound; the mass ratio of the polyhydric alcohol to the carboxylic acid in the polyhydric alcohol-carboxylic acid solution is 1 (1.3-1.5); the stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of (7.3-15.5) to (3.6-8.2). The high-stability waterborne polyurethane curing agent has the advantages of high stability and good water resistance.
Description
Technical Field
The application relates to the technical field of production of waterborne polyurethane curing agents, in particular to a high-stability waterborne polyurethane curing agent and a preparation method thereof.
Background
The waterborne polyurethane coating is one of products with larger market demand at present, is suitable for middle-high grade woodware, high-grade architectural decoration, middle coating and surface coating of high-grade automobiles, airplanes, space equipment and the like which are crosslinked and cured at normal temperature with the temperature of heat sensitivity lower than (60-80 ℃), and is widely applied in the industrial field.
When the waterborne polyurethane coating is used, a curing agent needs to be added to accelerate crosslinking and curing, and improve the mechanical properties of the coating, such as structural strength, elasticity and the like. At present, polyurethane curing agents mainly comprise isocyanate-alcohol adducts, HDI biuret, isocyanurate and the like, in order to improve the water solubility of the curing agents, hydrophilic groups are usually introduced, but the stability of the curing agents is reduced while the hydrophilicity is improved, the water resistance of the coating after the curing is poor, and the service performance of the coating is influenced.
Disclosure of Invention
In order to solve the problems of poor stability and poor water resistance of the waterborne polyurethane curing agent, the application provides the high-stability waterborne polyurethane curing agent and the preparation method thereof.
In a first aspect, the present application provides a high-stability waterborne polyurethane curing agent, which adopts the following technical scheme: a high-stability waterborne polyurethane curing agent is mainly prepared from the following raw materials in parts by weight: 230 parts of isocyanate, 20-35 parts of a polyhydric alcohol-carboxylic acid solution, 2-7 parts of a stabilizer, 35-60 parts of a solvent and 2-5 parts of a pH regulator;
the polyhydric alcohol-carboxylic acid solution is prepared by adopting a method comprising the following steps: uniformly mixing neopentyl glycol, trihydroxypropane, trimellitic anhydride, butyl acetate, dihydroxypropionic acid and xylene, refluxing, dehydrating and filtering to obtain the compound;
the mass ratio of the polyhydric alcohol to the carboxylic acid in the polyhydric alcohol-carboxylic acid solution is 1 (1.3-1.5);
the stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of (7.3-15.5) to (3.6-8.2).
By adopting the technical scheme, isocyanate and a polyol-carboxylic acid solution are subjected to a crosslinking reaction to form an ester-alcohol prepolymer, then the ester-alcohol prepolymer is reacted with glycerol allyl ether and methyldiethanolamine in a stabilizer to form a crosslinking system, and the terminal NCO in the crosslinking system is sealed to facilitate amine neutralization and improve the water solubility of a product. In addition, the rest active residues in a crosslinking system can be sealed by active groups on the molecules of the glycerol allyl ether and the methyldiethanolamine in the stabilizer through free hydroxyl and polymerizable double bonds, so that the stability and the water resistance of the waterborne polyurethane curing agent are greatly improved.
Preferably, the mass ratio of the isocyanate to NCO to OH in the polyol-carboxylic acid solution is (6-6.3): 1.
By adopting the technical scheme, the quantity ratio of NCO and OH is optimized and adjusted, the reaction speed of the crosslinking reaction is controlled, and the probability of excessive reaction is reduced. Meanwhile, the crosslinking density is increased, the molecular chain length of a crosslinking system is regulated and controlled, and the film coating performance and stability of the product are improved.
Preferably, the glycerol allyl ether is modified by cysteamine hydrochloride.
By adopting the technical scheme, after modification by cysteamine hydrochloride, groups such as sulfydryl, amino and the like are introduced into a molecular chain of the glycerol allyl ether, so that the hydrophilicity of a crosslinking system is improved, the reaction rate of NCO and water is slowed down, and the stability and the water resistance of the waterborne polyurethane curing agent are further improved.
Preferably, the solvent consists of ethyl acetate and water according to the mass ratio of (1.5-3) to (2-3.5).
By adopting the technical scheme, the composition ratio of the solvent is tested and adjusted, the water dispersibility of a crosslinking system is improved, and the phenomenon of crystallization and agglomeration is not easy to generate.
Preferably, the isocyanate is one of TDI, MDI, XDI and IPDI.
By adopting the technical scheme, aromatic and aliphatic isocyanates are optimally selected as reaction monomers, NCO-OH reaction can be carried out at a lower temperature (120-200 ℃), and the prepared crosslinking system is not easy to yellow, has higher transparency and better environmental stability.
Preferably, the mass ratio of the stabilizer to the isocyanate is (32-100): 1.
By adopting the technical scheme, the composition ratio of the stabilizer and the isocyanate is optimized and adjusted, the blocking amount of the active residues in the reaction product is further adjusted, and the stability of a crosslinking system is improved.
Preferably, the pH regulator is at least one of triethanolamine and N-toluene diethanolamine.
By adopting the technical scheme, at the final stage of reaction, after neutralization is carried out by triethanolamine and N-toluene diethanolamine, the reaction rate of NCO and water is further slowed down, the content of residual NCO in a crosslinking system is properly reduced, and the stability and the water resistance of subsequent use are improved.
In a second aspect, the present application provides a preparation method of a high-stability waterborne polyurethane curing agent, which adopts the following technical scheme:
a preparation method of a high-stability waterborne polyurethane curing agent comprises the following steps:
s1: uniformly mixing toluene and xylene, performing reflux dehydration, heating to 120-135 ℃, and adding isocyanate to react to obtain a prepolymer;
s2: controlling the temperature of the prepolymer below 65 ℃, adding a polyol-carboxylic acid solution, reacting until the NCO conversion rate is more than 96%, adding a 10% dimethyl sulfate solution and a stabilizer, heating to 85-95 ℃, reacting for 15-30min, vacuumizing to remove an organic solvent, adding a hydrophilic solvent to adjust the solid content, and finally adding a pH regulator to adjust the pH value.
By adopting the technical scheme, isocyanate forms a prepolymer in a solvent, then a polyol-carboxylic acid solution is added for a crosslinking reaction, hydrophilic groups such as hydroxyl, carboxyl and the like are introduced into a crosslinking system, the hydrophilicity of the product is improved, and residues in the crosslinking system are sealed by a stabilizer, so that the waterborne polyurethane curing agent with good hydrophilic property and excellent stability is finally prepared.
Preferably, in step S2, after adding the polyol-carboxylic acid solution, reacting until the NCO conversion rate is more than 96%, adding 10% dimethyl sulfate solution, (0.5-0.8) parts by weight of 3- (2,3 glycidoxy) propylmethyldiethoxysilane and stabilizer, heating to 85-95 ℃ and reacting for 15-30 min.
By adopting the technical scheme, the 3- (2, 3-glycidoxy) propyl methyl diethoxysilane and a crosslinking system molecular chain are grafted and crosslinked while the stabilizer is added to seal residues, so that the water resistance and the stability of a reaction product are further improved.
In summary, the present application has the following beneficial effects:
1. because the isocyanate and the polyol-carboxylic acid solution are adopted for reaction, the stability and the water resistance of the product are greatly improved under the sealing action of the stabilizer.
2. In the application, cysteamine hydrochloride is preferably adopted to modify the glycerol allyl ether, so that the stability of the aqueous polyurethane curing agent is further improved.
3. The high-stability waterborne polyurethane curing agent prepared by the production method has high hydrophilicity, high resistance and high stability.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials of the examples, preparation examples and comparative examples of the present application were all generally commercially available unless otherwise specified.
Preparation example
Preparation example 1
The polyol-carboxylic acid solution of the present preparation example was prepared by the following method:
(1) adding 5.207kg of neopentyl glycol (namely 0.5mol of neopentyl glycol), 6.708kg of trihydroxypropane (namely 0.5mol of trihydroxypropane), 3kg of trimellitic anhydride, 5kg of butyl acetate, 13.78kg of dihydroxypropionic acid (namely 1.3mol of trihydroxypropane) and 5kg of dimethylbenzene into a reaction kettle, uniformly mixing, and heating to 80 ℃ until all raw materials are completely dissolved to obtain a mixed solution;
(2) and (2) heating the mixed solution in the step (1) to 148 ℃, refluxing and dehydrating to be transparent, and filtering to obtain the product.
Wherein the mass ratio of the polyol to the carboxylic acid in the polyol-carboxylic acid solution is 1: 1.3.
Preparation example 2
The polyol-carboxylic acid solution of the present preparation example was prepared by the following method:
(1) 5.207kg of neopentyl glycol (namely 0.5mol of neopentyl glycol), 6.708kg of trihydroxypropane (namely 0.5mol of trihydroxypropane), 3kg of trimellitic anhydride, 5kg of butyl acetate, 15.062kg of dihydroxypropionic acid (namely 1.42mol of trihydroxypropane) and 5kg of dimethylbenzene are added into a reaction kettle to be uniformly mixed, and the temperature is raised to 80 ℃ until all raw materials are completely dissolved to obtain a mixed solution;
(2) and (2) heating the mixed solution in the step (1) to 148 ℃, refluxing and dehydrating to be transparent, and filtering to obtain the product.
Wherein the mass ratio of the polyol to the carboxylic acid in the polyol-carboxylic acid solution is 1: 1.42.
Preparation example 3
The polyol-carboxylic acid solution of the present preparation example was prepared by the following method:
(1) adding 5.207kg of neopentyl glycol (namely 0.5mol of neopentyl glycol), 6.708kg of trihydroxypropane (namely 0.5mol of trihydroxypropane), 3kg of trimellitic anhydride, 5kg of butyl acetate, 15.91kg of dihydroxypropionic acid (namely 1.5mol of trihydroxypropane) and 5kg of dimethylbenzene into a reaction kettle, uniformly mixing, and heating to 80 ℃ until all raw materials are completely dissolved to obtain a mixed solution;
(2) and (2) heating the mixed solution in the step (1) to 148 ℃, refluxing and dehydrating to be transparent, and filtering to obtain the product.
Wherein the mass ratio of the polyol to the carboxylic acid in the polyol-carboxylic acid solution is 1: 1.5.
Preparation example 4
The polyol-carboxylic acid solution of the present preparation example was prepared by the following method:
(1) adding 10.414kg of neopentyl glycol (namely 1mol of neopentyl glycol), 13.416kg of trihydroxypropane (namely 1mol of trihydroxypropane), 3kg of trimellitic anhydride, 5kg of butyl acetate, 15.91kg of dihydroxypropionic acid (namely 1.5mol of trihydroxypropane) and 5kg of dimethylbenzene into a reaction kettle, uniformly mixing, and heating to 80 ℃ until all raw materials are completely dissolved to obtain a mixed solution;
(2) heating the mixed solution in the step (1) to 148 ℃, refluxing and dehydrating the mixed solution to be transparent, and filtering the mixed solution to obtain the nano-silver/nano-silver composite material.
Wherein the mass ratio of the polyol to the carboxylic acid in the polyol-carboxylic acid solution is 2: 1.5.
Examples
Example 1
The high-stability waterborne polyurethane curing agent is prepared from the following raw materials in parts by weight: 20kg of isocyanate, 2kg of a polyol-carboxylic acid solution, 0.2 part of a stabilizer, 3.5kg of a solvent and 0.2kg of a pH regulator.
Wherein, the isocyanate is TDI monomer. The polyol-carboxylic acid solution was prepared according to preparation example 1. The solvent was ethyl acetate. The stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of 7.3: 3.6. The pH regulator is 50% ethylenediamine solution.
The preparation method of the high-stability waterborne polyurethane curing agent comprises the following steps:
s1: adding toluene and xylene into a reaction kettle, uniformly mixing, refluxing and dehydrating, then adjusting the temperature of the reaction kettle to 120 ℃, adding isocyanate, reacting for 1.2 hours at a stirring speed of 800rpm under the protection of nitrogen, then slowly dropwise adding a non-heterocyclic phosphine solution with the mass fraction of 10% into the reaction kettle, simultaneously observing the reaction state of the materials, and continuously reacting for 2 hours to obtain a prepolymer;
s2: controlling the temperature of the prepolymer below 65 ℃, slowly adding a polyol-carboxylic acid solution, reacting until the conversion rate of NCO is above 96%, adding a 10% dimethyl sulfate solution and a stabilizer, heating to 85 ℃, reacting for 15min, vacuumizing to remove an organic solvent, adding a solvent to adjust the solid content to 50%, adding a pH regulator to adjust the pH to 8.5, and cooling to obtain the prepolymer.
Example 2
The high-stability waterborne polyurethane curing agent is prepared from the following raw materials in parts by weight: 22kg of isocyanate, 2.8kg of polyol-carboxylic acid solution, 0.5 part of stabilizer, 5.5kg of solvent and 0.35kg of pH regulator.
Wherein, the isocyanate is TDI monomer. The polyol-carboxylic acid solution was prepared according to preparation example 1. The solvent was ethyl acetate. The stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of 7.3: 3.6. The pH regulator is 50% ethylenediamine solution.
The preparation method of the high-stability waterborne polyurethane curing agent comprises the following steps:
s1: adding toluene and xylene into a reaction kettle, uniformly mixing, carrying out reflux dehydration, then adjusting the temperature of the reaction kettle to 130 ℃, then adding isocyanate, reacting for 1.35h under the protection of nitrogen at the stirring speed of 900rpm, then slowly dropwise adding a non-heterocyclic ring phosphine solution with the mass fraction of 10% into the reaction kettle, simultaneously observing the reaction state of materials, and continuously reacting for 2h to obtain a prepolymer;
s2: controlling the temperature of the prepolymer below 65 ℃, then slowly adding a polyol-carboxylic acid solution to react until the NCO conversion rate is more than 96%, then adding a 10% dimethyl sulfate solution and a stabilizer, heating to 90 ℃ to react for 20min, vacuumizing to remove an organic solvent, then adding a solvent to adjust the solid content to 50%, finally adding a pH regulator to adjust the pH to 8.5, and cooling to obtain the prepolymer.
Example 3
The high-stability waterborne polyurethane curing agent is prepared from the following raw materials in parts by weight: 23kg of isocyanate, 3.5kg of polyol-carboxylic acid solution, 0.7 part of stabilizer, 6kg of solvent and 0.5kg of pH regulator.
Wherein, the isocyanate is TDI monomer. The polyol-carboxylic acid solution was prepared according to preparation example 1. The solvent was ethyl acetate. The stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of 7.3: 3.6. The pH regulator is 50% ethylenediamine solution.
The preparation method of the high-stability waterborne polyurethane curing agent comprises the following steps:
s1: adding toluene and xylene into a reaction kettle, uniformly mixing, carrying out reflux dehydration, then adjusting the temperature of the reaction kettle to 135 ℃, then adding isocyanate, reacting for 1.5h under the protection of nitrogen at the stirring speed of 1000rpm, then slowly dropwise adding a non-heterocyclic ring phosphine solution with the mass fraction of 10% into the reaction kettle, simultaneously observing the reaction state of materials, and continuously reacting for 2h to obtain a prepolymer;
s2: controlling the temperature of the prepolymer below 65 ℃, then slowly adding a polyol-carboxylic acid solution to react until the NCO conversion rate is more than 96%, then adding a 10% dimethyl sulfate solution and a stabilizer, heating to 95 ℃ to react for 30min, vacuumizing to remove an organic solvent, then adding a solvent to adjust the solid content to 50%, finally adding a pH regulator to adjust the pH to 8.5, and cooling to obtain the prepolymer.
Example 4
The highly stable aqueous polyurethane curing agent of this example is different from example 2 in that: the stabilizer in the raw material consists of glycerol allyl ether and methyldiethanolamine in a mass ratio of 12:5.7, and the rest is the same as that in the example 2.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 2.
Example 5
The highly stable aqueous polyurethane curing agent of this example is different from example 2 in that: the stabilizer in the raw material consists of glycerol allyl ether and methyldiethanolamine in a mass ratio of 15.5:8.2, and the rest is the same as that in the example 2.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 2.
Example 6
The highly stable aqueous polyurethane curing agent of this example differs from example 4 in that: the polyol-carboxylic acid solution in the starting material was prepared by using preparation example 2, and the rest was the same as in example 4.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 4.
Example 7
The highly stable aqueous polyurethane curing agent of this example differs from example 4 in that: the polyol-carboxylic acid solution of the starting material was prepared according to preparation example 3, and the rest was the same as in example 4.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 4.
Example 8
The highly stable aqueous polyurethane curing agent of this example is different from example 6 in that: the feed is prepared from the following raw materials in parts by weight: 21.6kg of isocyanate, 2kg of a polyol-carboxylic acid solution, 0.2 part of a stabilizer, 3.5kg of a solvent, and 0.2kg of a pH adjuster, and the rest is the same as in example 6.
Wherein the mass ratio of NCO to OH in the isocyanate to polyol-carboxylic acid solution is 6.2: 1.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 4.
Example 9
The highly stable aqueous polyurethane curing agent of this example differs from example 8 in that: the allyl ether of glycerin in the stabilizer in the raw material was modified with cysteamine hydrochloride, and the rest was the same as in example 8.
The method for modifying glycerol allyl ether in the embodiment comprises the following steps:
1) adding glycerol allyl ether and cysteamine hydrochloride into a reaction kettle according to the mass ratio of 1.2:1, uniformly mixing, adding DMPA, and reacting for 30min under the initiation of ultraviolet rays;
2) adding methanol and ether into a reaction kettle, mixing uniformly, and filtering to obtain the product.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 8.
Example 10
The highly stable aqueous polyurethane curing agent of this example is different from that of example 9 in that: the solvent in the raw materials consists of ethyl acetate and water according to the mass ratio of 1.5:2, and the rest is the same as that in the example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 9.
Example 11
The highly stable aqueous polyurethane curing agent of this example is different from that of example 9 in that: the solvent in the raw materials consists of ethyl acetate and water in a mass ratio of 3:3.5, and the rest is the same as that in example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 9.
Example 12
The highly stable aqueous polyurethane curing agent of this example is different from example 1 in that: the isocyanate in the starting material was MDI, the remainder being the same as in example 1.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 1.
Example 13
The high-stability aqueous polyurethane curing agent of the present example is different from that of example 1 in that: the isocyanate in the starting material was XDI, and the rest was the same as in example 1.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 1.
Example 14
The highly stable aqueous polyurethane curing agent of this example is different from example 1 in that: the isocyanate in the starting material was IPDI, and the rest was the same as in example 1.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 1.
Example 15
The highly stable aqueous polyurethane curing agent of this example is different from that of example 9 in that: the pH adjuster in the raw material was triethanolamine, and the rest was the same as in example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 9.
Example 16
The highly stable aqueous polyurethane curing agent of this example is different from that of example 9 in that: the pH adjuster in the raw material was N-toluene diethanolamine, and the rest was the same as in example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 9.
Example 17
The highly stable aqueous polyurethane curing agent of this example is different from that of example 9 in that: the pH regulator in the raw material consists of triethanolamine and N-toluene diethanolamine in a mass ratio of 1.5:0.8, and the rest is the same as in example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this example is the same as that of example 9.
Example 18
The highly stable aqueous polyurethane curing agent of this example differs from that of example 17 in that: in the preparation method of the highly stable aqueous polyurethane curing agent, in step S2, after adding the polyol-carboxylic acid solution and reacting until the NCO conversion rate is 96% or more, 10% dimethyl sulfate solution, 0.075kg of 3- (2,3 glycidoxy) propylmethyldiethoxysilane and the stabilizer are added, and then the temperature is raised to 85 ℃ to react for 15min, the rest is the same as in example 17.
Comparative example
Comparative example 1
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 1 in that: the feed is prepared from the following raw materials in parts by weight: 15kg of isocyanate, 2.2kg of a polyol-carboxylic acid solution, 0.1 part of a stabilizer, 8.2kg of a solvent, and 0.2kg of a pH adjuster, and the rest is the same as in example 1.
The preparation method of the highly stable aqueous polyurethane curing agent of this comparative example is the same as that of example 1.
Comparative example 2
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 2 in that: the stabilizer in the raw material consists of glycerol allyl ether and methyldiethanolamine in a mass ratio of 5.5:9, and the rest is the same as that in the example 2.
The preparation method of the high-stability aqueous polyurethane curing agent of this comparative example is the same as that of example 2.
Comparative example 3
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 2 in that: the stabilizer in the starting material was glycerol allyl ether, the rest being the same as in example 2.
The preparation method of the high-stability aqueous polyurethane curing agent of this comparative example is the same as that of example 2.
Comparative example 4
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 2 in that: the stabilizer in the raw material is methyldiethanolamine, and the rest is the same as that in the example 2.
The preparation method of the high-stability aqueous polyurethane curing agent of this comparative example is the same as that of example 2.
Comparative example 5
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 2 in that: the stabilizer in the raw material is polyethylene glycol monomethyl ether, and the rest is the same as that in the example 2.
The preparation method of the high-stability aqueous polyurethane curing agent of this comparative example is the same as that of example 2.
Comparative example 6
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 4 in that: the polyol-carboxylic acid solution in the starting material was prepared by selecting preparation example 4, and the rest was the same as in example 4.
The preparation method of the high-stability aqueous polyurethane curing agent of this comparative example is the same as that of example 4.
Comparative example 7
The highly stable aqueous polyurethane curing agent of this comparative example differs from example 9 in that: the solvent in the raw materials consists of ethyl acetate and water according to the mass ratio of 5:1.5, and the rest is the same as that in the example 9.
The preparation method of the highly stable aqueous polyurethane curing agent of this comparative example is the same as that of example 9.
Performance test
Detection method
Taking the high-stability waterborne polyurethane curing agents of the examples 1-18 and the comparative examples 1-7, measuring the water resistance of a curing agent coating film by adopting a room temperature soaking method according to the national standard GB/T5209-1985, and testing the whitening time (h) of the surface of the curing agent coating film; the storage stability of the curing agents was tested according to the national standard GB/T6753.3-1986, the time (d) at denaturation was measured and the results are shown in Table 1.
TABLE 1 Performance test data for high Performance waterborne polyurethane curatives of examples 1-18 and comparative examples 1-7
It can be seen from the analysis of examples 1-3 and comparative example 1 in combination with table 1 that the raw material ratio of the aqueous polyurethane curing agent is optimized and adjusted, and experiments show that the curing agent prepared by using the composition ratio of example 2 has better water resistance and stability.
By analyzing examples 1 to 3, examples 4 to 5 and comparative examples 2 to 4 and combining table 1, it can be seen that the water resistance of the curing agent is reduced by 11% and the stability is reduced by 6.8% after too much methyldiethanolamine is added to the stabilizer and less glycerol allyl ether is added to the stabilizer; further tests show that when only glycerol allyl ether or methyldiethanolamine is added into the stabilizer, the water resistance and the stability of the curing agent are both greatly reduced; when the stabilizer is polyethylene glycol monomethyl ether, the stability of the curing agent is reduced by 65%, and the water resistance is reduced by 48.3%, so that the stability and the water resistance of the curing agent are greatly improved compared with those of common commercial curing agents.
As can be seen by analyzing examples 6 to 7, comparative example 6, and by combining Table 1, the ratio of the polyol and the carboxylic acid in the polyol-carboxylic acid solution was further tested and optimized, and the stability and water resistance of the curing agent were better when the mass ratio of the polyol to the carboxylic acid in the polyol-carboxylic acid solution was 1: 1.42.
Analyzing example 8 and example 9 in combination with table 1, it can be seen that the ratio of isocyanate to polyol-carboxylic acid solution is further optimized, and the appropriate NCO: OH ratio is selected to improve the water resistance and stability of the curing agent; and the allyl glycerol ether is modified by cysteamine hydrochloride, so that the water resistance of the curing agent is improved by 9.2%, and the stability is improved by 14.7%.
When the composition ratios of the solvents were tested, it was found that the curing agent stability and water resistance were better when the solvent was composed of ethyl acetate and water at a mass ratio of 1.5:2 as seen in example 10, example 11 and comparative example 7 in combination with table 1.
It can be seen from the analysis of examples 12 to 14 and examples 15 to 17 in combination with Table 1 that the composition ratio of the pH regulator and the kind of isocyanate in the raw materials are further optimized and adjusted to further improve the stability and water resistance of the curing agent.
Analysis of example 18 and table 1 show that when 3- (2, 3-glycidoxy) propylmethyldiethoxysilane is compounded with a stabilizer, the water resistance of the curing agent is improved by 3.3%, and the stability is improved by 4.2%.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. A high-stability waterborne polyurethane curing agent is characterized by being mainly prepared from the following raw materials in parts by weight: 200-230 parts of isocyanate, 20-35 parts of a polyol-carboxylic acid solution, 2-7 parts of a stabilizer, 35-60 parts of a solvent and 2-5 parts of a pH regulator;
the polyhydric alcohol-carboxylic acid solution is prepared by adopting a method comprising the following steps: uniformly mixing neopentyl glycol, trihydroxypropane, trimellitic anhydride, butyl acetate, dihydroxypropionic acid and xylene, refluxing, dehydrating and filtering to obtain the compound;
the mass ratio of the polyhydric alcohol to the carboxylic acid in the polyhydric alcohol-carboxylic acid solution is 1 (1.3-1.5);
the stabilizer consists of glycerol allyl ether and methyldiethanolamine according to the mass ratio of (7.3-15.5) to (3.6-8.2).
2. A highly stable aqueous polyurethane cure according to claim 1 wherein the mass ratio of NCO to OH in the isocyanate to polyol-carboxylic acid solution is (6-6.3): 1.
3. The preparation method of the high-stability waterborne polyurethane curing agent as claimed in claim 2, wherein the glycerol allyl ether is modified by cysteamine hydrochloride.
4. The method for preparing the highly stable aqueous polyurethane curing agent according to claim 1, wherein the solvent comprises ethyl acetate and water in a mass ratio of (1.5-3) to (2-3.5).
5. The method for preparing the highly stable waterborne polyurethane curing agent according to claim 1, wherein the isocyanate is one of TDI, MDI, XDI and IPDI.
6. The method for preparing the high-stability waterborne polyurethane curing agent according to claim 1, wherein the mass ratio of the isocyanate to the stabilizer is (32-100): 1.
7. The method for preparing a highly stable aqueous polyurethane curing agent according to claim 1, wherein the pH adjuster is at least one of triethanolamine and N-toluene diethanolamine.
8. A method for preparing a highly stable aqueous polyurethane curing agent according to any one of claims 1 to 7, comprising the steps of:
s1: uniformly mixing toluene and xylene, performing reflux dehydration, heating to 120-135 ℃, and adding isocyanate to react to obtain a prepolymer;
s2: controlling the temperature of the prepolymer below 65 ℃, adding a polyol-carboxylic acid solution, reacting until the NCO conversion rate is more than 96%, adding a 10% dimethyl sulfate solution and a stabilizer, heating to 85-95 ℃, reacting for 15-30min, vacuumizing to remove an organic solvent, adding a hydrophilic solvent to adjust the solid content, and finally adding a pH regulator to adjust the pH value.
9. The method for preparing a highly stable aqueous polyurethane curing agent according to claim 1, wherein in step S2, after adding a polyol-carboxylic acid solution and reacting until the NCO conversion rate is more than 96%, 10% dimethyl sulfate solution, (0.5-0.8) parts by weight of 3- (2, 3-glycidoxy) propylmethyldiethoxysilane and a stabilizer are added, and the temperature is raised to 85-95 ℃ for reaction for 15-30 min.
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