CN104558467B - A kind of catalysts for polyurethanes and its application - Google Patents
A kind of catalysts for polyurethanes and its application Download PDFInfo
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
- C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
Abstract
A kind of catalysts for polyurethanes, compound including sodium, by percentage to the quality, the compound of the sodium accounts for 1 60wt% of the catalysts for polyurethanes, also include tertiary amines and/or pyridine compounds and their, the compound of sodium acts synergistically with the tertiary amine and/or pyridine compounds and their, when being catalyzed isocyanates with polymerization, improve the speed of polymerisation, and obtained polyurethane material has excellent physical property, it has been entirely free of heavy metal element, it is environment-friendly type catalyst, solve catalysts for polyurethanes while ensure the technical problem of Environmental Safety and catalytic efficiency, particularly useful for making polyurethane synthetic leather resin slurry, polyurethane elastomer (performed polymer), polyurethane coating, adhesive for polyurethane and compound polyurethane material.
Description
Technical field
The present invention relates to a kind of catalyst, and in particular to it is a kind of be used for prepare polyurethane catalyst and the catalyst should
With belonging to polyurethane material synthesis technical field.
Background technology
Polyurethane be on a kind of main chain containing repeat carbamate groups high-molecular compound general designation, this high score
Sub- material can be used for the products such as manufacture rubber, hard and flex foam, binder, coating, paint, wear-resisting because of its brilliance
Property, impact resilience, UV resistant and high and low temperature resistance and be widely used in building, automobile, light industry, weaving, petrochemical industry, smelting
The various fields such as gold, electronics, national defence, medical treatment, machinery.
Polyurethane material is using polyisocyanates, polyalcohol and other stabilizers as raw material, at a certain temperature by being catalyzed
Made from agent catalytic reaction, a kind of catalyst commonly used in polyurethane material synthesis is metallo-organic compound, this kind of organic
Metallic catalyst is earliest lead, the organic compound of mercury, but because lead, mercury are heavy metal, harm to the human body is larger and can cause
Serious environmental pollution, the product prohibitted the use of has been listed in it.
Therefore, Chinese patent literature CN101397359A disclose it is a kind of be used to preparing it is low distribute, be catalyzed again it is stable soft
The amine catalyst of matter polyurethane foam, it include at least one reactive amine catalysts and at least one organic potassium, zinc and/or
Tin compound, there is preferable catalytic activity.But due to having used the compound of tin one as catalyst in above-mentioned catalyst
Kind composition so that containing complete dibutyl tin of unreacted etc. in organic tin catalyst, such accessory substance easily causes biology
Body deformity or slow poisoning, therefore the list for controlling and using is included in by developed countries such as European Union.But if do not add organic
Tin compound, when substituting tin compound with the other organic compounds such as potassium and/or zinc, under the catalytic activity of its catalyst is obvious
Drop, even if on the one hand improving reaction temperature, the decline of reaction speed and the extension in reaction time can not be still avoided, if on the other hand
Want to reach then needs to increase catalyst amount with the approximate reaction speed of tin-containing catalyst, such as in synthetic leather slurry synthesis, makes
Dibutyl tin laurate is substituted completely with organo-bismuth, and dosage is up to 4-5 times of former dosage；Regardless of whether it is that the former extends reaction
Time, reaction temperature is improved, or the scheme of the latter's raising catalyst amount can cause polyurethane material to close to some extent
Into the raising of cost, nonetheless, by the physical property of its polyurethane material catalyzed and synthesized, for example, tensile strength, tear-proof
Intensity is decreased obviously, furthermore, using in above-mentioned document not the formula of sn-containing compound when, be also easy to the light poly- ammonia for making synthesis
Ester material turns yellow；In addition, in the case of containing water in the formula for raw stock of synthesis of polyurethane, the organic compound of bismuth or zinc
It can be inactivated because of hydrolysis so that the Storage period for combining material shortens.
The content of the invention
Therefore, the technical problems to be solved by the invention are the catalyst of not stanniferous class organic metal in the prior art not
Only catalytic activity is low and the polyurethane material performance that catalyzes and synthesizes is bad, so as to provide the poly- ammonia that a kind of catalytic activity is high, prepares
The environment-protecting polyurethane catalyst of ester material good physical performance.
In order to solve the above technical problems, the technical scheme is that：
The present invention provides a kind of catalysts for polyurethanes, includes the compound of sodium, by percentage to the quality, the chemical combination of the sodium
Thing accounts for the 1-60wt% of the catalysts for polyurethanes.
The compound of the sodium is sodium hydroxide, sodium carbonate, sodium acid carbonate, sodium benzoate, sodium formate, sodium acetate, propionic acid
Sodium, sodium butyrate, natrium valericum, sodium n-caproate, Sodium Caprylate, sodium iso-octoate, neodecanoic acid sodium, sodium caprate, sodium salicylate, sodium laurate, oil
Sour sodium, sodium maleate, sodium citrate, sodium oxalate, sodium methoxide, sodium cellulosate, sodium carboxymethylcellulose, Sodium Hyaluronate, marine alga
Sour sodium, the one or more in sodium gluconate.
Further, the compound of the sodium is sodium butyrate, neodecanoic acid sodium, sodium salicylate, enuatrol, sodium citrate, thoroughly
One or more in bright matter acid sodium.
Also include nitrogen-containing compound, the nitrogen-containing compound is tertiary amine compounds and/or pyridine compounds and their.It is described to contain
Nitrogen compound is the one or more in straight polyamine, heterocyclic polyamines or phenyl ring class polyamines, and the nitrogen-containing compound accounts for described poly-
The mass percent of urethane catalyst is 5-70wt%.
The tertiary amine compounds and/or pyridine compounds and their are triethylene diamine, pentamethylene triamine, dimethylamino third
Amine diisopropanol, pentamethyl-diethylenetriamine, tetramethyl dipropylenetriamine, N, N- dimethyl -1,3- diaminopropanes, 3- diformazans
Base aminopropyl urea, (dimethyl amido ethyl) ether, N, N- bis- [3- (dimethylamino) propyl group]-N', N'- dimethyl -1,3- third
Diamines, hexadecylamine, 2- [[3- (dimethylamino) propyl group] methylamino] ethanol, 1,3,5- tri- (DimethylAminopropyl)-
1,3,5- hexahydrotriazine, N, N- dimethylethanolamines, N, N- dimethyl benzylamines, triethanolamine, diethanol amine, 1,8- diaza
Bicyclic [5,4,0] 11 carbon -7- alkene, 6- dimethylamino -1- hexanols, N- methyldicyclohexyl amine, cetylamine, tetramethyl croak, 1-
Isobutyl-2-methyl imidazole, 2- amino-α-[[2- (1,1- dimethylethyloxy) -2- oxoethoxies] imino group] -4- thiazoles
Acetic acid, O, O- diethyl sulfides are for hydrogen phosphate acid anhydrides, N-ethylmorpholine, N-methylmorpholine, benzene methanamine, Diethylaminoethanol, N,
N'- DICs, 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate, 1,2- methylimidazole,
N- methylimidazoles, 2,2- dimorpholine base Anaesthetie Ethers, dimethylaminoethoxyethanol, 2- dimethyl aminopyridines, 2,4- diaminos
Yl pyrimidines, 4,5- di-amino-pyrimidines, 2- dimethylaminopyridines, DMAP, 2,4- double (dimethylamino) pyrimidine -6- carboxylics
Acid, 1- (methylamino) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol, aminopiperazine hydrochloride, 2,2,4- trimethyl -2- silicon generation
Coffee quinoline, 1- (2- dimethyl aminoethyls) piperazine, 1- (3- dimethylamino-propyls) piperazine, (2- morpholines pyridin-4-yl) methylamine, 4-
Chloro- 6- dimethylamino-pyrimidines, N, N- dimethyl (morpholine -2-yl) formamide, N, N- dimethyl (R- morpholine -2s-yl) formamide,
4- methyl morpholine -2- methylamines, N, N- dimethyl (4- methyl isophthalic acids-piperazinyl) ethamine, hexahydro -1,3,5- trimethyl-S- triazines, 1,
The azines of 3,5- triethyl group hexahydro-S- three, N, N'- carbonyl dimidazoles, dicyclohexylcarbodiimide, 3- (diethoxy phosphinylidyne oxygen
Base), 2- (7- azos BTA)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters, the nitrogen of N- hydroxyl -7- azos benzo three
Azoles, tripyrrole alkane base phosphonium bromide hexafluorophosphate, O- BTAs-N, N, N', N'- tetramethylurea tetrafluoro boric acid ester, O- (N-
Succinimide) one or more in -1,1,3,3- tetramethylurea tetrafluoro boric acid esters.
Further, the nitrogen-containing compound is pentamethyl-diethylenetriamine, 2- dimethyl aminopyridines, N, N- diformazans
Base -1,3- diaminopropanes, triethylene diamine, 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydrotriazines, 1,8- phenodiazine
Miscellaneous bicyclic [5,4,0] 11 carbon -7- alkene, 2,2- dimorpholine base Anaesthetie Ethers, (2- morpholines pyridin-4-yl) methylamine, 2,4- diaminos
Yl pyrimidines, the one or more in 1- (methylamino) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol.
Also include the compound of potassium, the mass percent that the compound of the potassium accounts for the catalysts for polyurethanes is 2-
50wt%.
The mass percent that the compound of the potassium accounts for the catalysts for polyurethanes is 2-20wt%.
The compound of the potassium is potassium hydroxide, potassium carbonate, saleratus, Potassium Benzoate, potassium formate, potassium acetate, propionic acid
Potassium, potassium butyrate, valeric acid potassium, caproic acid potassium, potassium octanoate, isooctyl acid potassium, neodecanoic acid potassium, Capric acid potassium salt, potassium salicylate, potassium laurate, oil
Sour potassium, maleic acid potassium, potassium citrate, potassium oxalate, potassium methoxide, cellulose potassium, potassium carboxymethylcellulose, potassium hyaluronate, marine alga
Sour potassium, the one or more in K-IAO.
Further, the compound of the potassium is Potassium Benzoate, potassium laurate, potassium oleate, potassium citrate, potassium alginate,
One or more in cellulose potassium.
Further, in addition to organic solvent and stabilizer, the organic solvent have the structure shown in formula (1)：
X-R-Y (1)
Wherein, R C1~20Alkyl, the polyether-based shown in formula (2), the nitrogen-containing group shown in formula (3), shown in formula (4)
The acid amides shown in acid amides or formula (6) shown in nitrogen-containing group, formula (5)；
-(R1-O)n-R2- (2),
X, Y are identical or are unequally H, OH, R or R1；
N=1-100；
R1, R2It is identical or unequally for H or straight chain, branched or ring-type aliphatic or virtue with 1 to 10 carbon atoms
Fragrant race, saturation or alkyl that is undersaturated unsubstituted or being exchanged for heteroatoms；
Vi, Vi1, Vi2Polyether-based identical or unequally for H, OH or shown in formula (2).
Described catalysts for polyurethanes prepare polyurethane synthetic leather resin slurry, polyurethane elastomer, polyurethane coating,
Application in adhesive for polyurethane or compound polyurethane material.
The present invention also provides a kind of application of compound of sodium in catalysts for polyurethanes is prepared.
The above-mentioned technical proposal of the present invention has advantages below compared with prior art：
(1) catalysts for polyurethanes of the present invention, including the compound of sodium and tertiary amine and/or pyridine compounds and their, institute
The compound and the tertiary amine and/or pyridine compounds and their for stating sodium act synergistically, when being catalyzed isocyanates with polymerization,
Improve the speed of polymerisation；By the reaction sequence of each reactant in rational allocation reaction system, make isocyanate molecule
With polyol molecule preferential reaction；Effectively control isocyanates, polyalcohol and water in reaction system, impurity molecule and disconnected simultaneously
Side reaction between the small molecule split, it effectively prevent because other micromolecular compounds that above-mentioned side reaction is formed randomly press from both sides
It is miscellaneous in the polyurethane molecular system of synthesis.The polyurethane material catalyzed and synthesized using the catalysts for polyurethanes of the application has excellent
Good physical property, resisting etiolation and resistance to tearing are good, tensile strength is big, elasticity is big, ageing-resistant performance is good, poly- available for preparing
Urethane elastomer (performed polymer)；Catalyst provided by the present invention can also make liquid polyurethane material have good mobility,
Without gel, caking phenomenon, and there is good wearability and toughness, be suitable as preparing polyurethane synthetic leather resin slurry and
The catalyst of polyurethane coating, the synthetic leather resin slurry can be used as a kind of finishing agent, for manufacturing artificial leather, artificial muntjac
Skin, synthetic leather, electrostatic spinning, superfine fibre etc., it is resulting product excellent performance, flex endurant, anti-aging, wear-resistant；The poly- ammonia
Ester paint adhesive force is strong, and elasticity is big, and ageing-resistant performance is good, available for high-class woodenware, large-scale engineering machinery, cement, rubber, skin
The covering with paint of the materials such as leather；Meanwhile catalyst provided by the present invention applies also for preparing adhesive for polyurethane, can be glued
Accelerate reaction speed in journey, the adhesive for polyurethane of gained has excellent bonding force, impact resistance, toughness weatherability, to bubble
The porous materials such as foam plastics, timber, leather, fabric, paper, ceramics, and any surface finish such as metal, glass, rubber, plastics
Material has good bond effect；Catalyst provided by the present invention can be additionally used in the preparation technology of compound polyurethane material
In, the combined efficiency of PU and other materials can be effectively improved, obtained composite has excellent tensile properties, anti-impact
Hitting property and corrosion resistance.Catalysts for polyurethanes containing sodium also effectively reduces the yellowing of the polyurethane material of synthesis, makes to gather
Urethane elastomer, synthetic leather resin slurry, coating, adhesive and compound polyurethane material are inhibited from yellowing, and it is poly- not interfere with light color
Urethane product it is attractive in appearance.
(2) catalysts for polyurethanes of the present invention, the compound of potassium is included, its compound and tertiary amines with sodium
And/or pyridine compounds and their synergy, the physical property of the polyurethane material of synthesis is further increased, is improving polyurethane
It ensure that polyurethane material has big intensity and excellent tear resistance while materials synthesis speed.
(3) catalysts for polyurethanes of the present invention, heavy metal element has been entirely free of, but used a large amount of in human body
Existing sodium, the compound of potassium are environmentally safe as main component, to human body fanout free region, are environment-friendly type catalyst, are dropping
The catalytic effect of non-environmental protection class catalyst is in the prior art reached while low catalyst endangers.And the compound price of sodium
The other metallo-organic compounds used more in the prior art are low, so as to effectively reduce being produced into for the catalysts for polyurethanes
This；And in use, because addition is less than the organic matters such as bismuth, zinc, also reduce use cost.
(4) catalysts for polyurethanes of the present invention, hydrolytic resistance is good, can be effectively improved tin, bismuth in the prior art
With the organic compound of zinc because of hydrolysis easy in inactivation, the problem of causing the catalyst storage phase short.
Embodiment
In order that the object, technical solutions and advantages of the present invention are clearer, embodiments of the present invention will be made below
Further it is described in detail.In following examples, wt% represents mass percent；The organic solvent has shown in formula (1)
Structure：
X-R-Y (1)
Wherein, R C1~20Alkyl, the polyether-based shown in formula (2), the nitrogen-containing group shown in formula (3), shown in formula (4)
The acid amides shown in acid amides or formula (6) shown in nitrogen-containing group, formula (5)；
-(R1-O)n-R2- (2),
X, Y are identical or are unequally H, OH, R or R1；
N=1-100；
R1, R2It is identical or unequally for H or straight chain, branched or ring-type aliphatic or virtue with 1 to 10 carbon atoms
Fragrant race, saturation or alkyl that is undersaturated unsubstituted or being exchanged for heteroatoms；
Vi, Vi1, Vi2Polyether-based identical or unequally for H, OH or shown in formula (2).
The stabilizer is silicon class or non-silicon class surfactant.
Embodiment 1
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 1g sodium butyrates, 70g pentamethyl-diethylenetriamines
It is dissolved in 0.5g Di-phosphorus pentonides in 28.5g organic solvents, it is well mixed to produce.In the present embodiment, sodium butyrate accounts for described
The 1wt% of catalysts for polyurethanes, pentamethyl-diethylenetriamine account for the 70wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is pentane.
Embodiment 2
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 40g neodecanoic acids sodium, 20g sodium salicylates, 3.5g
Pentamethyl-diethylenetriamine and 1.5g N, N- dimethyl -1,3- diaminopropanes and it is dissolved in 35g organic solvents, mixing is equal
It is even to produce.In the present embodiment, neodecanoic acid sodium and sodium salicylate account for the 60wt% of the catalysts for polyurethanes, pentamethyl divinyl three
Amine and N, N- dimethyl -1,3- diaminopropanes account for the 5% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is dimethyl ether.
Embodiment 3
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 1g enuatrols, 5g2- dimethyl aminopyridines,
50g Potassium Benzoates and 20g Phosphate of Polyoxyethylene Isooctyl Ether are dissolved in 24g diethylamine, well mixed to produce.The present embodiment
In, enuatrol accounts for the 1wt% of the catalysts for polyurethanes, and 2- dimethyl aminopyridines account for the 5wt% of the catalysts for polyurethanes,
Potassium Benzoate accounts for the 50wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is dimethylamine.
Embodiment 4
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 5g sodium citrates, 5g sodium salicylates, the 10g new last of the ten Heavenly stems
Sour sodium, 10g triethylene diamines, (the DimethylAminopropyl) -1,3,5- of 5g1,3,5- tri- hexahydrotriazines, 10.5g potassium laurates,
4.5g potassium oleates and 5g dimethyl silicone polymers are dissolved in 45g organic solvents, well mixed to produce.In the present embodiment, lemon
Sour sodium, sodium salicylate and neodecanoic acid sodium account for the 20wt% of the catalysts for polyurethanes, triethylene diamine and 1,3,5- tri- (dimethyl
Amine propyl group) -1,3,5- hexahydrotriazines account for the 15wt% of the catalysts for polyurethanes, and potassium laurate and potassium oleate account for the poly- ammonia
The 15wt% of ester catalyst.
Organic solvent described in the present embodiment is triethylamine.
Embodiment 5
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 3.5g sodium citrates, 21.5g Sodium Hyaluronates,
3g 2- dimethyl aminopyridines, the carbon -7- alkene of 8g 1,8- diazabicyclos [5,4,0] 11,2g 2,2- dimorpholine base diethyl
Ether, 2g pentamethyl-diethylenetriamines, 12g potassium oleates, 3g potassium alginates and 5g polyether silicones are dissolved in 40g organic solvents,
It is well mixed to produce.In the present embodiment, sodium citrate and Sodium Hyaluronate account for 25%, the 2- dimethyl of the catalysts for polyurethanes
Aminopyridine, the carbon -7- alkene of 1,8- diazabicyclos [5,4,0] 11,2,2- dimorpholine base Anaesthetie Ethers and pentamethyl divinyl
Triamine accounts for the 15% of the catalysts for polyurethanes, and potassium oleate and potassium alginate account for the 15% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R be formula (5) in amide group, R1For-CH2-, R2For-CH2CH3-, Vi1
For H, Vi2For the structure of formula (2), wherein, n=20, X, Y H.
Embodiment 6
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 25g sodium salicylates, 5g sodium hydroxides, 11g (2-
Morpholine pyridin-4-yl) methylamine, 9g 2,4- di-amino-pyrimidines, 2g celluloses potassium, 8g potassium laurates and 3g dimethyl silicone polymers
It is dissolved in 37g organic solvents, it is well mixed to produce.In the present embodiment, sodium salicylate and sodium hydroxide account for the polyurethane and urged
The 30wt% of agent, (2- morpholines pyridin-4-yl) methylamine and 2,4- di-amino-pyrimidine account for the 20wt% of the catalysts for polyurethanes,
Cellulose potassium and potassium laurate account for the 10wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is acetamide.
Embodiment 7
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 15g sodium benzoates, 18g sodium carbonate, 7g carbonic acid
Hydrogen sodium, 1g pentamethylenes triamine, 1.5g 2,4- di-amino-pyrimidines, 2.5g dimethylaminopropylamines diisopropanol, 1g potassium hydroxide,
6g saleratus and 3g dimethyl silicone polymers are dissolved in 45g organic solvents, well mixed to produce.In the present embodiment, benzene first
Sour sodium, sodium carbonate and sodium acid carbonate account for the 40wt% of the catalysts for polyurethanes, pentamethylene triamine, 2,4- di-amino-pyrimidines and
Dimethylaminopropylamine diisopropanol accounts for the 5wt% of the catalysts for polyurethanes, and potassium hydroxide and saleratus account for the polyurethane
The 7wt% of catalyst.
Organic solvent described in the present embodiment is C15H31OH。
Embodiment 8
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 12g sodium benzoates, 23g sodium formates, 2g tetramethyls
Base dipropylenetriamine, 3.5g3- dimethylaminopropyls urea, 4.5g (dimethyl amido ethyl) ether, 2g potassium carbonate, 8g potassium acetates
It is dissolved in 3g trialkyl phosphites in 47g organic solvents, it is well mixed to produce.In the present embodiment, sodium benzoate and formic acid
Sodium accounts for the 35wt% of the catalysts for polyurethanes, tetramethyl dipropylenetriamine, 3- dimethylaminopropyls urea and (dimethyl amido
Ethyl) ether accounts for the 10% of the catalysts for polyurethanes, and potassium carbonate and potassium acetate account for the 5wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the polyether-based in formula (2), wherein, R1For C6H5-, R2For-CH=
CH-, n=25, X, Y H.
Embodiment 9
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 16g sodium formates, 24g sodium acetates, 10g propionic acid
Sodium, 1g 1- (methylamino) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol, 9g N, N- bis- [3- (dimethylamino) propyl group]-N',
N'- dimethyl -1,3- propane diamine, 1g potassium propionates, 1g valeric acids potassium and 1g alkyl alcohol ether phosphates are dissolved in 37g organic solvents,
It is well mixed to produce.In the present embodiment, sodium formate, sodium acetate and sodium propionate account for the catalysts for polyurethanes 50wt%, 1- (first ammonia
Base) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol and N, N- bis- [3- (dimethylamino) propyl group]-N', N'- dimethyl -1,3- third
Diamines accounts for the 10wt% of the catalysts for polyurethanes, and potassium propionate and valeric acid potassium account for the 2% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is (CH3)2CHNHCH2CH2CH3。
Embodiment 10
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 1g natrium valericums, 1.3g Sodium Caprylates, 2.7g capric acid
Sodium, 30g2- [[3- (dimethylamino) propyl group] methylamino] ethanol, 22g N, N- dimethylethanolamine, 8g N, N- dimethyl
Benzylamine, 1.4g caproic acids potassium, 2.7g potassium octanoates, 0.9g Capric acid potassium salts and 2g polyether silicones are dissolved in 28g organic solvents, and mixing is equal
It is even to produce.In the present embodiment, natrium valericum, Sodium Caprylate and sodium caprate account for the 5wt% of the catalysts for polyurethanes, 2- [[3- (diformazans
Base amino) propyl group] methylamino] ethanol, N, N- dimethylethanolamines and N, N- dimethyl benzylamine account for the catalysts for polyurethanes
60wt%, caproic acid potassium, potassium octanoate and Capric acid potassium salt account for the 5wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the nitrogen-containing group in formula (4), wherein, R1For benzyl, R2For isopropyl
Base, Vi1、Vi2For H, X H, Y OH.
Embodiment 11
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 8g sodium iso-octoates, 17g sodium laurates, 10g horses
Come sour sodium, 12g cetylamines, 2g tetramethyls croak, 1g 4- methyl morpholine -2- methylamines, 4.5g isooctyl acids potassium, 0.5g neodecanoic acids potassium and
3g dimethyl silicone polymers are dissolved in 42g organic solvents, well mixed to produce.In the present embodiment, sodium iso-octoate, sodium laurate
The 35wt% of the catalysts for polyurethanes is accounted for sodium maleate, cetylamine, tetramethyl croak and 4- methyl morpholine -2- methylamines account for described
The 15wt% of catalysts for polyurethanes, isooctyl acid potassium and neodecanoic acid potassium account for the 5wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the amide group in formula (5), wherein, R1For-CH2CHCH2CCl-, R2
For cyclohexyl, Vi1For H, Vi2For the structure of formula (2), n=15, X H, Y OH.
Embodiment 12
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 12.5g sodium oxalates, 7.5g sodium methoxides, 11g1-
Isobutyl-2-methyl imidazole, 7g2- amino-α-[[2- (1,1- dimethylethyloxies) -2- oxoethoxies] imino group] -4- thiophenes
Zole acetic acid, 2g O, O- diethyl sulfides are molten for hydrogen phosphate acid anhydrides, 9g potassium salicylates, 11g potassium oxalates and 3g dimethyl silicone polymers
Solution is well mixed to produce in 37g organic solvents.In the present embodiment, sodium oxalate and sodium methoxide account for the catalysts for polyurethanes
20wt%, 1- isobutyl-2-methyl imidazole, 2- amino-α-[[2- (1,1- dimethylethyloxy) -2- oxoethoxies] imido
Base] -4- thiazolyl acetic acids and O, O- diethyl sulfide account for the 20wt% of the catalysts for polyurethanes, potassium salicylate for hydrogen phosphate acid anhydrides
The 20wt% of the catalysts for polyurethanes is accounted for potassium oxalate.
Organic solvent described in the present embodiment, R are the amide group in formula (6), wherein, R1For n-heptyl, R2For styrene
Base, Vi1For H, X R1, Y OH.
Embodiment 13
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 5g sodium cellulosates, 2g sodium carboxymethylcelluloses,
Double (dimethylamino) pyrimidine -6- carboxylic acids of 2g N-ethylmorpholines, 4g N, N'- DIC, 9g 2,4-, 18g methanol
Potassium, 22g potassium carboxymethylcelluloses and 2g dimethyl silicone polymers are dissolved in 36g organic solvents, well mixed to produce.This implementation
In example, sodium cellulosate and sodium carboxymethylcellulose account for the 7wt%, N-ethylmorpholine, N of the catalysts for polyurethanes, N'- diisopropyls
Base carbodiimide and double (dimethylamino) pyrimidine -6- carboxylic acids of 2,4- account for the 15wt% of the catalysts for polyurethanes, potassium methoxide and carboxylic
Methylcellulose potassium accounts for the 40wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the amide group in formula (6), wherein, R1For 2,2- dimethylhexanyls, R2
For isobutyl group, Vi1For-OH, X H, Y R.
Embodiment 14
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 25g sodium gluconates, 12g1- (methylamino)-
3- (4- methylpiperazine-1-yls) -2- propyl alcohol, 9g 2,2,4- trimethyl -2- silicon are for morpholine, 9g1- (3- dimethylamino-propyls)
Piperazine, 2g potassium hyaluronates, 6g K-IAOs and 2g trialkyl phosphites are dissolved in 35g organic solvents, are well mixed
Produce.In the present embodiment, sodium gluconate accounts for the 25wt% of the catalysts for polyurethanes, 1- (methylamino) -3- (4- methyl piperazines
Piperazine -1- bases) -2- propyl alcohol, 2,2,4- trimethyl -2- silicon accounts for the polyurethane for morpholine and 1- (3- dimethylamino-propyls) piperazine
The 30wt% of catalyst, potassium hyaluronate and K-IAO account for the 8wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the polyether-based in formula (2), wherein, R1For cyclohexyl, R2For n-pentyl, n
=40, X H, Y R1。
Embodiment 15
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 35g sodium butyrates, 20g N, N- dimethyl (
Quinoline -2- bases) formamide, 8g N, N- dimethyl (4- methyl isophthalic acids-piperazinyl) ethamine, 7g hexahydro -1,3,5- trimethyl-S- triazines,
2g Potassium Benzoates and 1g Phosphate of Polyoxyethylene Isooctyl Ether are dissolved in 27g organic solvents, well mixed to produce.The present embodiment
In, sodium butyrate accounts for the 35wt% of the catalysts for polyurethanes, N, N- dimethyl (morpholine -2-yl) formamide, N, N- dimethyl (4-
Methyl isophthalic acid-piperazinyl) ethamine and hexahydro -1,3,5- trimethyl-S- triazines account for the 35wt% of the catalysts for polyurethanes, benzoic acid
Potassium accounts for the 2wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the polyether-based in formula (2), wherein, R1For cyclohexyl, R2For n-pentyl, n
=28, X H, Y H.
Embodiment 16
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 55g sodium salicylates, 1.5g N, N'- carbonyl two
Imidazoles, 3g dicyclohexylcarbodiimides, 5.5g2- (7- azos BTA)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters
It is dissolved in 3g Phosphate of Polyoxyethylene Isooctyl Ether in 32g organic solvents, it is well mixed to produce.In the present embodiment, salicylic acid
Sodium accounts for the 55wt% of the catalysts for polyurethanes, N, N'- carbonyl dimidazoles, dicyclohexylcarbodiimide and 2- (7- azo benzos
Triazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters account for the 10wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the nitrogen-containing group in formula (4), wherein, R1For pyridine radicals, R2For-
CH2CH2-, X H, Y R1。
Embodiment 17
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 35g sodium oxalates, 2g N- hydroxyl -7- azobenzenes
And triazole, 5g tripyrrole alkane base phosphonium bromides hexafluorophosphate, 13g O- BTAs-N, N, N', N'- tetramethylurea tetrafluoros
Borate, 5g potassium oleates and 3g dimethyl silicone polymers are dissolved in 37g organic solvents, well mixed to produce.In the present embodiment,
Sodium oxalate accounts for the 35wt% of the catalysts for polyurethanes, N- hydroxyl -7- azos BTA, tripyrrole alkane base phosphonium bromide hexafluoro
Phosphate and O- BTAs-N, N, N', N'- tetramethylurea tetrafluoro boric acid ester account for the 20wt% of the catalysts for polyurethanes,
Potassium oleate accounts for the 5wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment, R are the amide group in formula (6), wherein, R1For n-pentyl, R2For-
CH2CH2-, Vi1For OH, X H, Y R1。
Embodiment 18
The present embodiment provides a kind of catalysts for polyurethanes, at room temperature, by 5g sodium citrates, 5g sodium salicylates, the 10g new last of the ten Heavenly stems
Sour sodium, 10g triethylene diamines, (the DimethylAminopropyl) -1,3,5- of 5g1,3,5- tri- hexahydrotriazines, 10.5g potassium laurates,
4.5g potassium oleates are dissolved in 50g organic solvents, well mixed to produce.In the present embodiment, sodium citrate, sodium salicylate and the new last of the ten Heavenly stems
Sour sodium accounts for the 20wt% of the catalysts for polyurethanes, triethylene diamine and 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydros
Change the 15wt% that triazine accounts for the catalysts for polyurethanes, potassium laurate and potassium oleate account for the 15wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is triethylamine.
Comparative example 1
This comparative example provides a kind of catalysts for polyurethanes, at room temperature, by 20g dibutyltin dilaurates, the second of 14g tri-
Alkene diamines, (the DimethylAminopropyl) -1,3,5- of 1g1,3,5- tri- hexahydrotriazines, 12g potassium laurates, 3g potassium oleates and 2g poly- two
Methylsiloxane is dissolved in 48g organic solvents, well mixed to produce.In the present embodiment, dibutyltin dilaurate accounts for institute
State the 20wt% of catalysts for polyurethanes, triethylene diamine and 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydrotriazines account for
The 15wt% of the catalysts for polyurethanes, potassium laurate and potassium oleate account for the 15wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is triethylamine.
Comparative example 2
This comparative example provides a kind of catalysts for polyurethanes, at room temperature, by 20g caproic acids zinc, 14g triethylene diamines, 1g1,
(the DimethylAminopropyl) -1,3,5- of 3,5- tri- hexahydrotriazines, 12g potassium laurates, 3g potassium oleates and 2g dimethyl silicone polymers
It is dissolved in 48g organic solvents, it is well mixed to produce.In the present embodiment, caproic acid zinc accounts for the 20wt% of the catalysts for polyurethanes,
Triethylene diamine and 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydrotriazines account for the catalysts for polyurethanes
15wt%, potassium laurate and potassium oleate account for the 15wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is triethylamine.
Comparative example 3
This comparative example provides a kind of catalysts for polyurethanes, at room temperature, by 20g bismuth neodecanoates, 14.5g triethylene diamines,
(the DimethylAminopropyl) -1,3,5- of 0.5g1,3,5- tri- hexahydrotriazines, 8g potassium laurates, 7g potassium oleates and 1g poly dimethyl silicon
Oxygen alkane is dissolved in 49g organic solvents, well mixed to produce.In the present embodiment, bismuth neodecanoate accounts for the catalysts for polyurethanes
20wt%, triethylene diamine and 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydrotriazines account for the catalysts for polyurethanes
15wt%, potassium laurate and potassium oleate account for the 15wt% of the catalysts for polyurethanes.
Organic solvent described in the present embodiment is triethylamine.
Test case
(1) polyurethane synthetic leather resin is prepared using above-described embodiment 4-6 and comparative example 1-3 catalysts for polyurethanes provided
Slurry：
Respectively by the catalysts for polyurethanes described in 0.1g embodiments 4-6 and comparative example 1-3 and 150g PEPAs, 20g
Diethylene glycol in stirred tank be well mixed, then add 30g 4,4- '-diphenylmethane diisocyanates, at 60 DEG C with
300pm/min mixing speed stirs the mixture to completion is reacted, and produces polyurethane synthetic leather resin slurry.
During the catalyst preparation polyurethane synthetic leather resin slurry provided using embodiment 4-6, the synthetic leather is made
The reaction time of resin slurry is 120min, during the catalyst preparation Synthetic Leather slurry provided using comparative example 1-3,
It is 120min in polymerization reaction time, product is mainly PEPA, diethylene glycol, isocyanates and catalysts for polyurethanes
Mixture, the polyurethane synthetic leather resin slurry for meeting industrial requirements is not formed, need to extend to respectively in the reaction time
The polyurethane synthetic leather resin slurry for meeting industrial requirements could be made in 180min, 300min and 280min.
The polyurethane obtained by catalysts for polyurethanes provided respectively use embodiment 4-6 and comparative example 1-3 synthesizes
The sample for removing from office resin slurry carries out physical and mechanical property test：
It is strong according to the tensile strength of national light industry standard QBT2710-2005 test samples, elongation at break and fracture
Degree；Test sample into flesh：Test sample is coated in the glass plate groove of certain depth, the thickness of film forming is determined after drying
It is the as shown in table 1 into flesh numerical value results of sample to spend with the ratio of glass plate depth of groove：
Table 1
It can be seen from the results above that compared with the catalysts for polyurethanes that comparative example 1-3 is provided, using embodiment 4-6 institutes
The catalysts for polyurethanes of offer has higher catalytic activity, under identical reaction conditions isocyanates and polyethers can be made more
The polymerisation of first alcohol is completed faster；Also, while ensure that catalytic activity, using the poly- ammonia of embodiment 4-6 offers
Synthetic leather resin slurry physical property prepared by ester catalyst is more excellent：With higher elongation at break, in elongation
For 100% and 300% when with higher tensile strength and fracture strength, maintain good into flesh, one can be used as
Kind finishing agent, for manufacturing artificial leather, artificial suede, synthetic leather, electrostatic spinning, superfine fibre etc..
(2) adhesive for polyurethane is prepared using above-described embodiment 4-6 and comparative example 1-3 catalysts for polyurethanes provided, institute
It can be the only One-component adhesive containing polyurethane or including polyurethane and other additives to state polyurethane adhesive and cohere
Multicomponent adhesive.
This test case is by taking single-component polyurethane adhesive as an example：Respectively by described in 0.1g embodiments 4-6 and comparative example 1-3
Catalyst is stirring with the degree of functionality PPG of 8000 molecular weight of 300g 2,5g diethanol amine and 5g ethylenediamines, 16g dichloromethane
Mix in kettle and be well mixed, 200g polymethylene multi-phenenyl isocyanates are then added, with 200rpm/min stirring at 80 DEG C
Speed stirs the mixture to completion is reacted, and produces adhesive for polyurethane.
During the catalyst preparation adhesive for polyurethane provided using embodiment 4-6, when the reaction of the adhesive is made
Between be 120min；During the catalyst preparation adhesive for polyurethane provided using comparative example 1-3, it is in polymerization reaction time
During 120min, product is mainly PPG, diethanol amine, ethylenediamine, dichloromethane, polymethylene multi-phenenyl isocyanate
With the mixture of catalysts for polyurethanes, the adhesive for polyurethane for meeting industrial requirements is not formed, needs respectively to prolong in the reaction time
Adhesive for polyurethane could be made by growing to 160min, 180min and 200min.
Adhesive for polyurethane made from the catalysts for polyurethanes provided respectively use embodiment 4-6 and comparative example 1-3
Sample carries out physical and mechanical property test：
According to the elongation at break of the test samples of standard GB/T/T6344-86, according to standard GB/T/T 7124-
The shear strength of 1986 test samples, according to the compression strength and springform of standard GB/T/T 12954-1991 test samples
Amount, according to the shrinkage factor of chemical industry ministerial standard HG/T 2380-1992 test samples, each sample is pressed at 90 DEG C after aging 200h
Yellowing according to the test samples of chemical industry ministerial standard HG/T 3862, the heat resistanceheat resistant according to standard GB/T/T 16998-1997 test samples
Ageing properties, according to the weather resistance of standard GB/T 24264-2009 test samples.As a result it is as shown in table 2：
Table 2
It can be seen from the results above that compared with the catalysts for polyurethanes that comparative example 1-3 is provided, using embodiment 4-6 institutes
The catalysts for polyurethanes of offer has higher catalytic activity, under identical reaction conditions polymethylene polyphenyl can be made different
The polymerisation of cyanate and PPG is completed faster；Also, while ensure that catalytic activity, using embodiment
Adhesive for polyurethane physical property prepared by the catalysts for polyurethanes that 4-6 is provided is more excellent：Compression strength, modulus of elasticity
Higher level is held in shear strength, shrinkage factor is smaller, and elongation at break is higher, resistance at 90 DEG C after aging 200h
Wait it is functional, adhesive deformation it is smaller, outward appearance is without exception, more to foamed plastics, timber, leather, fabric, paper, ceramics etc.
Porous materials, and the material of any surface finish such as metal, glass, rubber, plastics have excellent bond effect.
(3) polyurethane coating is prepared using above-described embodiment 4-6 and comparative example 1-3 catalysts for polyurethanes provided, it is described
It can be the only one-component coating containing polyurethane or more including polyurethane and other additives that polyurethane adhesive, which coheres,
Component coating.
This test case is by taking monocomponent polyurethane paint as an example：0.1g embodiments 4-6 and comparative example 1-3 are provided respectively
Catalyst is well mixed with the PPG that 210g molecular weight is 8000, degree of functionality is 2 in stirred tank, adds the different Buddhists of 80g
That ketone isocyanates (IPDI), the isothermal reaction 2-4h at 80 DEG C, confirm reaction end with n-butanol method, be then cooled to 50
DEG C, dihydromethyl propionic acid (DMPA) and BDO (BDO) the reaction 1-3 hours that addition is dissolved with 1-METHYLPYRROLIDONE,
Add triethylamine react 30 minutes, then under vigorous stirring, add a certain amount of water, finally taken off under conditions of vacuum distillation
Except solvent, that is, obtain aqueous polyurethane coating.
During the catalyst preparation polyurethane coating provided using embodiment 4-6, the reaction time that the coating is made is
120min；It is 120min in the reaction time during catalyst preparation polyurethane coating provided using comparative example 1-3, product master
To be the mixture of PPG, IPDI and catalysts for polyurethanes, not form the polyurethane coating for meeting industrial requirements, need
Reaction time is extended to 150min, 150min and 180min respectively could be made the polyurethane coating for meeting industrial requirements.
Polyurethane coating sample made from the catalysts for polyurethanes provided respectively use embodiment 4-6 and comparative example 1-3
Product carry out physical and mechanical property test：
According to standard GB/T/tensile strength of T23999-2009 test samples, elongation at break, modulus of elasticity, and will
Yellowness index of each sample at 90 DEG C after aging 200h according to the standardized test specimens of HG/T 3862, according to standard GB/T/
The ageing resistace and weather resistance of T23999-2009 test samples.As a result it is as shown in table 3：
Table 3
It can be seen from the results above that compared with the catalysts for polyurethanes that comparative example 1-3 is provided, using embodiment 4-6 institutes
The catalysts for polyurethanes of offer has higher catalytic activity, can make isophorone diisocyanate under identical reaction conditions
(IPDI) polymerisation with PPG is completed faster；Also, while ensure that catalytic activity, using embodiment
Polyurethane coating physical property prepared by the catalysts for polyurethanes that 4-6 is provided is more excellent：With higher tensile strength,
Modulus of elasticity and elongation at break, at 90 DEG C after aging 200h, weather resistance is good, and coating deformation is smaller, and outward appearance is without exception,
Covering with paint available for materials such as high-class woodenware, large-scale engineering machinery, cement, rubber, leathers.
(4) polyurethane elastomer is prepared (in advance using above-described embodiment 4-6 and comparative example 1-3 catalysts for polyurethanes provided
Aggressiveness)：
Respectively by the catalysts for polyurethanes described in 0.15g embodiments 4-6 and comparative example 1-3 and 100g polytetramethylene ethers two
Alcohol (PTMEG) (Mn=1000), three-functionality-degree polyethers (Mn=5000) are well mixed in stirred tank, then add 25g 4,4-
Methyl diphenylene diisocyanate (MDI), the mixture is stirred to having reacted with 200rpm/min mixing speed at 80 DEG C
Into producing polyurethane elastomer (performed polymer)
During catalyst preparation polyurethane elastomer (performed polymer) provided using embodiment, it is (pre- that the elastomer is made
Aggressiveness) reaction time be 120min；The catalyst preparation polyurethane elastomer (performed polymer) provided using comparative example 1-3
When, it is 120min in polymerization reaction time, product is mainly polytetramethylene ether diol (PTMEG), three-functionality-degree polyethers, 4,4-
The mixture of methyl diphenylene diisocyanate (MDI) and catalysts for polyurethanes, do not form the polyurethane for meeting industrial requirements
Elastomer (performed polymer), the reaction time need to extend to 140min, 150min and 180min and could be made meet industrial requirements
Polyurethane elastomer (performed polymer).
Polyurethane coating sample made from the catalysts for polyurethanes provided respectively use embodiment 4-6 and comparative example 1-3
Product carry out physical and mechanical property test：
According to the tensile strength of the test samples of standard GB/T/T528-1998, elongation at break and modulus of elasticity, according to
The density of standard GB/T 50404-2007 test samples, according to the hardness (Shore of standard GB/T/T531-92 test samples
D), by each sample at 90 DEG C after aging 200h according to standard GB/T/T18244-2000 test samples ageing resistace and
Weather resistance.As a result it is as shown in table 4：
Table 4
It can be seen from the results above that compared with the catalysts for polyurethanes that comparative example 1-3 is provided, using embodiment 4-6 institutes
The catalysts for polyurethanes of offer has higher catalytic activity, can under identical reaction conditions, and 4,4- diphenyl methanes two are different
Cyanate (MDI) is completed faster with the polymerisation of polytetramethylene ether diol and three-functionality-degree polyethers；Also, it ensure that
While catalytic activity, the polyurethane coating physical property prepared by catalysts for polyurethanes provided using embodiment 4-6 is excellent
It is different：With less density and hardness, and tensile strength, modulus of elasticity and elongation at break are higher, the aging 200h at 90 DEG C
Afterwards, the weather resistance of elastomer (performed polymer) is good, and deformation is slight, and outward appearance is without exception.
(5) compound polyurethane material is prepared using above-described embodiment 4-6 and comparative example 1-3 catalysts for polyurethanes provided：
Respectively by the catalysts for polyurethanes described in 0.2g embodiments 4-6 and comparative example 1-3 and the official of 5000 molecular weight of 200g 3
Energy degree PPG is well mixed in stirred tank, is added the glass fibre ground, is then added toluene di-isocyanate(TDI), in
The mixture is stirred to completion is reacted with 500rpm/min mixing speed at 80 DEG C, is finally putting into 100 DEG C of mould,
Solidify 4 hours at 130 DEG C, produce as glass fibre compound polyurethane material.
During the catalyst preparation glass fibre compound polyurethane material provided using embodiment 4-6, it is made described compound
The reaction time of material is 120min；The catalyst preparation glass fibre compound polyurethane material provided using comparative example 1-3
When, it is 120min in the reaction time, product is mainly that PPG, glass fibre, toluene di-isocyanate(TDI) and polyurethane are urged
The mixture of agent, the compound polyurethane material for meeting industrial requirements is not formed, need to extend to respectively in the reaction time
The compound polyurethane material for meeting industrial requirements could be made in 150min, 180min and 200min.
The poly- ammonia of glass fibre made from the catalysts for polyurethanes provided respectively use embodiment 4-6 and comparative example 1-3
Ester composite sample carries out physical and mechanical property test：
According to the tensile force, elongation at break and tensile strength of the test samples of standard GB/T/T528-1998, according to state
Family the standard test samples of GB/T529-1999 tearing strength, by each sample at 90 DEG C after aging 200h according to national standard
The ageing resistace and weather resistance of GB/T18244-2000 test samples.As a result it is as shown in table 5：
Table 5
It can be seen from the results above that compared with the catalysts for polyurethanes that comparative example 1-3 is provided, embodiment 4-6 is provided
Catalysts for polyurethanes there is higher catalytic activity, under identical reaction conditions PPG and toluene two can be made different
The polymerisation of cyanate is completed faster；And while ensure that catalytic activity, provided using embodiment 4-6 poly-
Polyurethane coating excellent physical properties prepared by urethane catalyst：It is strong with larger tensile force, tensile strength, tear-proof
Degree, elongation at break and modulus of elasticity, 200h, poly- ammonia that embodiment provide are handled above-mentioned encapsulant heat ageing at 90 DEG C
Compound polyurethane material prepared by ester catalyst has more preferable weatherability, and deformation is slight, and outward appearance is without exception.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (11)
- A kind of 1. catalysts for polyurethanes, it is characterised in that the compound including sodium, by percentage to the quality, the chemical combination of the sodium Thing accounts for the 1-60wt% of the catalysts for polyurethanes；The compound of the sodium is sodium hydroxide, sodium carbonate, sodium acid carbonate, sodium n-caproate, Sodium Caprylate, sodium iso-octoate, neodecanoic acid sodium, Sodium caprate, sodium salicylate, sodium laurate, sodium citrate, sodium methoxide, sodium cellulosate, sodium carboxymethylcellulose, Sodium Hyaluronate, Sodium alginate, the one or more in sodium gluconate；Also include nitrogen-containing compound, the nitrogen-containing compound is tertiary amine compounds and/or pyridine compounds and their.
- 2. catalysts for polyurethanes according to claim 1, it is characterised in that the compound of the sodium is neodecanoic acid sodium, water Poplar acid sodium, sodium citrate, the one or more in Sodium Hyaluronate.
- 3. catalysts for polyurethanes according to claim 2, it is characterised in that the nitrogen-containing compound is straight polyamine, miscellaneous One or more in ring polyamines or phenyl ring class polyamines, the nitrogen-containing compound account for the mass percent of the catalysts for polyurethanes For 5-70wt%.
- 4. catalysts for polyurethanes according to claim 3, it is characterised in that the nitrogen-containing compound is triethylene diamine, Pentamethylene triamine, dimethylaminopropylamine diisopropanol, pentamethyl-diethylenetriamine, tetramethyl dipropylenetriamine, N, N- diformazans Base -1,3- diaminopropanes, 3- dimethylaminopropyl ureas, (dimethyl amido ethyl) ether, [3- (dimethylamino) third of N, N- bis- Base]-N', N'- dimethyl -1,3- propane diamine, hexadecylamine, 2- [[3- (dimethylamino) propyl group] methylamino] ethanol, 1,3,5- tri- (DimethylAminopropyl) -1,3,5- hexahydrotriazines, N, N- dimethylethanolamines, N, N- dimethyl benzylamines, three second Hydramine, diethanol amine, the carbon -7- alkene of 1,8- diazabicyclo [5,4,0] 11,6- dimethylamino -1- hexanols, N- methyl bicyclics oneself Base amine, tetramethyl croak, 1- isobutyl-2-methyl imidazoles, 2- amino-α-[[2- (1,1- dimethylethyloxy) -2- oxo ethoxies Base] imino group] -4- thiazolyl acetic acids, O, O- diethyl sulfides are for hydrogen phosphate acid anhydrides, N-ethylmorpholine, N-methylmorpholine, benzene first Amine, Diethylaminoethanol, N, N'- DICs, 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimine hydrochloric acid Salt, 1,2- methylimidazole, N- methylimidazoles, 2,2- dimorpholine base Anaesthetie Ethers, dimethylaminoethoxyethanol, 2- dimethyl Aminopyridine, 2,4- di-amino-pyrimidines, 4,5- di-amino-pyrimidines, 2- dimethylaminopyridines, DMAP, 2,4- is double (dimethylamino) pyrimidine -6- carboxylic acids, 1- (methylamino) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol, aminopiperazine hydrochloride, 2, 2,4- trimethyl -2- silicon are for morpholine, 1- (2- dimethyl aminoethyls) piperazine, 1- (3- dimethylamino-propyls) piperazine, (2- Quinoline pyridin-4-yl) methylamine, the chloro- 6- dimethylamino-pyrimidines of 4-, N, N- dimethyl (morpholine -2-yl) formamide, N, N- dimethyl (R- morpholine -2s-yl) formamide, 4- methyl morpholine -2- methylamines, N, N- dimethyl (4- methyl isophthalic acids-piperazinyl) ethamine, hexahydro -1, 3,5- trimethyl-S- triazines, the azines of 1,3,5- triethyl group hexahydro-S- three, N, N'- carbonyl dimidazoles, dicyclohexylcarbodiimide, 3- (diethoxy phosphoryl oxy), 2- (7- azos BTA)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid esters, N- hydroxyls Base -7- azo BTAs, tripyrrole alkane base phosphonium bromide hexafluorophosphate, O- BTAs-N, N, N', N'- tetramethyl Urea tetrafluoro boric acid ester, the one or more in the tetramethylurea tetrafluoro boric acid esters of O- (N- succinimides) -1,1,3,3-.
- 5. catalysts for polyurethanes according to claim 4, it is characterised in that the nitrogen-containing compound is pentamethyl divinyl Triamine, 2- dimethyl aminopyridines, N, N- dimethyl -1,3- diaminopropanes, triethylene diamine, 1,3,5- tri- (dimethyl amine Propyl group) -1,3,5- hexahydrotriazines, the carbon -7- alkene of 1,8- diazabicyclo [5,4,0] 11,2,2- dimorpholine base Anaesthetie Ethers, (2- morpholines pyridin-4-yl) methylamine, 2,4- di-amino-pyrimidines, in 1- (methylamino) -3- (4- methylpiperazine-1-yls) -2- propyl alcohol One or more.
- 6. according to any described catalysts for polyurethanes of claim 3-5, it is characterised in that the also compound including potassium, it is described The mass percent that the compound of potassium accounts for the catalysts for polyurethanes is 2-50wt%.
- 7. catalysts for polyurethanes according to claim 6, it is characterised in that the compound of the potassium accounts for the polyurethane and urged The mass percent of agent is 2-20wt%.
- 8. catalysts for polyurethanes according to claim 7, it is characterised in that the compound of the potassium is potassium hydroxide, carbon Sour potassium, saleratus, caproic acid potassium, potassium octanoate, isooctyl acid potassium, neodecanoic acid potassium, Capric acid potassium salt, potassium salicylate, potassium laurate, citric acid Potassium, potassium methoxide, cellulose potassium, potassium carboxymethylcellulose, potassium hyaluronate, potassium alginate, one kind or several in K-IAO Kind.
- 9. catalysts for polyurethanes according to claim 8, it is characterised in that the compound of the potassium is potassium laurate, lemon Lemon acid potassium, potassium alginate, the one or more in cellulose potassium.
- 10. catalysts for polyurethanes according to claim 9, it is characterised in that described also including organic solvent and stabilizer Organic solvent has the structure shown in formula (1)：X-R-Y (1)Wherein, R C1~20The alkyl, polyether-based shown in formula (2), the nitrogen-containing group shown in formula (3), nitrogenous shown in formula (4) The acid amides shown in acid amides or formula (6) shown in group, formula (5)；-(R1-O)n-R2- (2),X, Y are identical or are unequally H, OH, R or R1；N=1-100；R1, R2It is identical or unequally for H or straight chain, branched or ring-type aliphatic or aromatic series with 1 to 10 carbon atoms , saturation or alkyl that is undersaturated unsubstituted or being exchanged for heteroatoms；Vi, Vi1, Vi2It is identical or be unequally H, OH or formula (2) polyether-based shown in.
- 11. a kind of any described catalysts for polyurethanes of claim 1-10 is preparing polyurethane synthetic leather resin slurry, poly- ammonia Application in ester elastomer, polyurethane coating, adhesive for polyurethane or compound polyurethane material.
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| CN201410851449.9A CN104558467B (en) | 2014-12-31 | 2014-12-31 | A kind of catalysts for polyurethanes and its application |
| US15/540,485 US10889681B2 (en) | 2014-12-31 | 2015-12-10 | Polyurethane catalyst and application thereof |
| PCT/CN2015/096944 WO2016107388A1 (en) | 2014-12-31 | 2015-12-10 | Polyurethane catalyst and application thereof |
| EP15875066.1A EP3241856B1 (en) | 2014-12-31 | 2015-12-10 | Polyurethane catalyst and application thereof |
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| EP3241856B1 (en) * | 2014-12-31 | 2021-08-18 | Jiangsu Osic Performance Materials Co. Ltd. | Polyurethane catalyst and application thereof |
| CN105131228A (en) * | 2015-09-24 | 2015-12-09 | 辽宁石油化工大学 | Polyurethane catalyst and application thereof |
| CN105330802B (en) * | 2015-12-11 | 2018-01-19 | 南京林业大学 | A kind of Turpentine catalysts for polyurethanes and its application |
| JP6657921B2 (en) * | 2015-12-21 | 2020-03-04 | Dic株式会社 | Urethane resin composition and synthetic leather |
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| CN106366272A (en) * | 2016-08-28 | 2017-02-01 | 山东成泰化工有限公司 | Polyurethane catalyst composition |
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| CN111748068B (en) * | 2020-07-17 | 2021-01-12 | 佛山市普加化工有限公司 | Composite amine catalyst for preparing ultra-low density flexible polyurethane foam |
| CN115368530A (en) * | 2020-12-30 | 2022-11-22 | 江苏奥斯佳材料科技股份有限公司 | Polyurethane rigid foam composition |
| CN113683759B (en) * | 2021-08-31 | 2023-03-24 | 宁波聚嘉新材料科技有限公司 | High-modulus thermotropic liquid crystal polyarylate film and preparation method and application thereof |
| CN114085373B (en) * | 2021-12-09 | 2023-07-14 | 万华化学集团股份有限公司 | Hyaluronic acid polyether polyol and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026629A (en) * | 1999-07-14 | 2001-01-30 | Nhk Spring Co Ltd | Curable composition of polyurethane foam and preparation thereof |
| CN1720277A (en) * | 2002-12-04 | 2006-01-11 | 约翰森·马瑟公开有限公司 | Organometallic catalyst composition and process for polyurethane manufacture using said catalyst |
| CN101067018A (en) * | 2006-05-04 | 2007-11-07 | 气体产品与化学公司 | New trimerization catalysts from sterically hindered salts |
| CN101070369A (en) * | 2006-05-04 | 2007-11-14 | 气体产品与化学公司 | New trimer catalyst additives for improving foam processability |
| CN101248100A (en) * | 2005-06-14 | 2008-08-20 | 莫门蒂夫功能性材料公司 | Catalyst composition and process using same |
| CN103732645A (en) * | 2011-08-11 | 2014-04-16 | 亨斯迈石油化学有限责任公司 | Use of thickening agents as polyurethane amine catalyst diluents |
-
2014
- 2014-12-31 CN CN201410851449.9A patent/CN104558467B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001026629A (en) * | 1999-07-14 | 2001-01-30 | Nhk Spring Co Ltd | Curable composition of polyurethane foam and preparation thereof |
| CN1720277A (en) * | 2002-12-04 | 2006-01-11 | 约翰森·马瑟公开有限公司 | Organometallic catalyst composition and process for polyurethane manufacture using said catalyst |
| CN101248100A (en) * | 2005-06-14 | 2008-08-20 | 莫门蒂夫功能性材料公司 | Catalyst composition and process using same |
| CN101067018A (en) * | 2006-05-04 | 2007-11-07 | 气体产品与化学公司 | New trimerization catalysts from sterically hindered salts |
| CN101070369A (en) * | 2006-05-04 | 2007-11-14 | 气体产品与化学公司 | New trimer catalyst additives for improving foam processability |
| CN103732645A (en) * | 2011-08-11 | 2014-04-16 | 亨斯迈石油化学有限责任公司 | Use of thickening agents as polyurethane amine catalyst diluents |
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Address after: 215634 410A room, A building, new industry incubator, Zhangjiagang Free Trade Zone, Suzhou, Jiangsu Patentee after: Jiangsu Austa material Polytron Technologies Inc Address before: 215634 410A room, A building, new industry incubator, Zhangjiagang Free Trade Zone, Suzhou, Jiangsu Patentee before: Jiangsu OSiC Material Science & Technology Co., Ltd. |