CN107043447B - A kind of asymmetric latency polyurethane curing agent and preparation method thereof - Google Patents

A kind of asymmetric latency polyurethane curing agent and preparation method thereof Download PDF

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CN107043447B
CN107043447B CN201710257830.6A CN201710257830A CN107043447B CN 107043447 B CN107043447 B CN 107043447B CN 201710257830 A CN201710257830 A CN 201710257830A CN 107043447 B CN107043447 B CN 107043447B
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curing agent
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polyurethane curing
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CN107043447A (en
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周建
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Jiangsu Xiangyuan Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3296—Hydroxyamines being in latent form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/04—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of asymmetric latency polyurethane curing agent and preparation method thereof, the existing oxazolidine group of molecular structure has imine group again, has both oxazolidine and the dual functional group's effect of imines, it is low with viscosity, the features such as easy to operate, reaction speed is moderate, and solution is honored as a queen almost without smell.Its composite character is cyclisation, aldehyde (ketone) imino of primary amino group and the esterification of carboxyl and hydroxyl that ethylol amine can be completed in a reaction kettle, without processes such as purification & isolations to intermediate product, process conditions are mild, no exhaust gas waste sludge discharge, and catalyst is recyclable to be reused.Primary raw material used is the aldehydes or ketones of p-aminobenzoic acid (or ester), diethanol amine and 1-13 carbon.40-150 DEG C of reaction temperature.The latent curing agent that the product can not only be used for polyurethane material is used but also as reactive diluent.

Description

A kind of asymmetric latency polyurethane curing agent and preparation method thereof
Technical field
The present invention relates to a kind of asymmetric latency polyurethane curing agents and preparation method thereof, belong to the dedicated chemistry of functional form Product and field of fine chemical.
Background technique
Latent curing agent is the important component for preparing monocomponent polyurethane material (SPU), and room temperature meets steam can be rapid Deblocking exposes hydroxyl, primary amino group and/or the secondary amino group that can react with isocyanate group (- NCO), can prior to NCO and Water reaction is the key point of this kind of curing agent.Had since the eighties in last century both at home and abroad numerous patents disclose it is a series of The kind of such curing agent is used in polyurethane CASE material, such as United States Patent (USP) US5749627, Deutsche Bundespatent DE4021659, Japan are in the patent EP0965604 of European Union's application, the EP2858965A1 of W. R. Grace & Co (CN104364225A), the EP2948485A1 (CN104903371A), Chinese patent CN103289038A of Switzerland SIKA company, CN105061347A etc., be summed up disclosed by above-mentioned patent be the monocycle oxazolidine of different structure, bicyclic oxazolidine and The latent curing agent of diimine class.Mono-/bis-ring oxazole alkanes latent curing agent and diimine class latent curing agent all have chance water energy enough fast Speed deblocking, an exposing hydroxyl and secondary amino group, one is exposed double primary amino groups, is then reacted with NCO and is exercised chain extension-crosslinking function Characteristic.
But there is differences again from operation and service performance for the two.In general oxazole alkanes latent curing agent to water more Sensitivity, activity is stronger, reacts more rapid, but again relatively slow with the reaction of NCO, and it is too fast that there is surface dryings, what the inside was felt like jelly Drawback, for the middle frame bridge portion of two oxazolidine group classes if aromatic series, product viscosity, which becomes larger, is easy solidification in addition, makes to operate Degradation, EP2493949A1 (CN102648225A) is topic with " amorphous oxazolidine " thus, and disclosing keeps such latent solid The technical measures of mobility are kept under agent room temperature；And diimine class latent curing agent, since two primary amino groups are all shielded, room Temperature is lower to have good mobility, mixes and is very easy to polyurethane component, has good operating characteristics, therefore be commonly used for living Property diluent, what solution was honored as a queen exposing in addition is two primary amino groups, and curability is excellent.Therefore many patents also disclose two Class latent curing agent is used in mixed way, to make up mutual insufficient technology.
Summary of the invention
It is an object of that present invention to provide a kind of asymmetric latency polyurethane curing agents and preparation method thereof.
To achieve the above object, present invention provide the technical scheme that a kind of asymmetric latency polyurethane curing agent, institute It states asymmetric latency polyurethane curing agent and contains the compound for meeting general formula (I) that mass percentage is 93%-98%,
(I)；
R in general formula (I)1And R2In at least one be not hydrogen, R1And R2It is identical or different, R1And R2It is independently represented each other H, the aromatic hydrocarbon group that the linear paraffin group, branched paraffin group or carbon atom number that carbon atom number is 1 ~ 13 are 6 ~ 13；General formula (I) In R3And R4In at least one be not hydrogen, R3And R4It is identical or different, R3And R4Be independently represented each other H, carbon atom number be 1 ~ The aromatic hydrocarbon group that 13 alkane group or carbon atom number is 6 ~ 13.
Preferred technical solution are as follows: the compound for meeting general formula (II) for being also 2%-7% containing mass percentage；
(II)
R in general formula (II)5And R6In at least one be not hydrogen, R5And R6It is identical or different, R5And R6Generation each independently Table H, the alkane group that carbon atom number is 1 ~ 13 or the aromatic hydrocarbon group that carbon atom number is 6 ~ 13；R in general formula (II)7And R8In extremely Few one is not hydrogen, R7And R8It is identical or different, R7And R8Be independently represented each other H, carbon atom number be 1 ~ 13 alkane group or The aromatic hydrocarbon group that carbon atom number is 6 ~ 13.
To achieve the above object, present invention provide the technical scheme that a kind of asymmetric latency polyurethane curing agent Preparation method, composition of raw materials include A, B and C, wherein A is diethanol amine, and B is selected from p-aminobenzoic acid, p-aminobenzoic acid The nalka base ester or isoalkyl ester that carbon atom number is 1 ~ 6, C is selected from the aliphatic aldehyde that carbon atom number is 1 ~ 13, carbon atom number be 1 ~ The ketone with aryl that the aldehyde with aryl or carbon atom number that 13 aliphatic ketones, carbon atom number are 7 ~ 13 are 8 ~ 13；
Preparation method includes: that the B of 10-30 parts by weight is added in reaction kettle, and the organic of 30-90 parts by weight is then added Solvent is heated and is stirred, and after B is completely dissolved, A and C is added, and the catalyst of 0.05-0.2 parts by weight is added, first in 40-80 Back flow reaction 1-2 hours under the conditions of DEG C, it is then warming up to 120-150 DEG C of reaction 2-3 hours, then solvent removed by vacuum, next It is recovered by filtration after catalyst up to product；
The organic solvent is selected from benzene,toluene,xylene, petroleum ether, carbon tetrachloride, Benzene Chloride；
The catalyst is polymer supported titanate.
Preferred technical solution are as follows: the C is selected from formaldehyde, polyformaldehyde, acetaldehyde, propionic aldehyde, isobutylaldehyde, 2- ethyl hexanal, 2- Ethyl octanal, 2,3- diethyl valeral, hexahydrobenzaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, methylbenzene first Aldehyde, phenylacetaldehyde, anisaldehyde；Acetone, methyl ethyl ketone, methyl propyl ketone, dimethyl acetone, methyl sec-butyl ketone, methyl tert-butyl Base ketone, cyclohexanone, cyclopentanone, acetophenone, Propiophenone.
Preferred technical solution are as follows: the C is selected from octanal, benzaldehyde, methyl iso-butyl ketone (MIBK), acetophenone.
Preferred technical solution are as follows: the B is selected from p-aminobenzoic acid, methyl p-aminobenzoate, p-aminobenzoic acid Ethyl ester；
Preferred technical solution are as follows: the B is ethylaminobenzoate.
Preferred technical solution are as follows: the molar ratio between A, B and C three is 1 ︰, 1 ︰, 2~1 ︰, 1 ︰ 2.1.
Preferred technical solution are as follows: the solvent removed by vacuum is at 120-150 DEG C, and overbottom pressure is less than or equal to 10 supporting bar parts Under.
Preferred technical solution are as follows: the organic solvent is selected from benzene and dimethylbenzene.
Since above-mentioned technical proposal is used, the present invention has the advantage, that compared with prior art
1, asymmetric latent curing agent of the invention, Molecule Set oxazolidine and imine and the whole body, both had Oxazolidine to water sensitive, be swift in response the characteristics of, and there is imines solution to be honored as a queen and expose primary amine group, curability is excellent, room Under temperature the advantages of good fluidity, make in formula without compounding several latent curing agents to adjust applicability.
2, synthesis technology provided by the present invention is simple and easy, and achievable multi-step chemical reaction, is not necessarily in a reaction kettle The separating-purifying of intermediate and conveying, the reaction technology of this formula for the treatment of different things alike can greatly save equipment investment and operation running cost With, and be conducive to environmental protection.
3, catalyst of the invention is the solid catalyst of polymer supported titanate, can recycle reuse completely, can not only save About cost, and remain product without catalyst, be conducive to the flexible choice of following process formula.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation Content disclosed by book is understood other advantages and efficacy of the present invention easily.
A kind of embodiment one: asymmetric latency polyurethane curing agent and preparation method thereof
By 82.5g ethylaminobenzoate (also known as benzocainum, white crystalline powder, the industrial goods of purity >=99%) It is added in the three-necked flask for having stirring, return channel and oil water separator, thermometer, 250g dimethylbenzene is added (between adjacency pair respectively Be 15.4%, 21.4%, 63.2%), stirring be allowed to sufficiently dissolve, then be added 120.1g acetophenone (light yellow clear liquid, Purity >=99.5%), stirring 15~after twenty minutes be added 52.5g diethanol amine (industrial goods of purity >=99%), be then added 20g polymer supported titanate catalyst, is warming up to 50 DEG C, is heated to reflux a point water, maintains back flow reaction 2 hours, then temperature rises to 130 DEG C, observation has apparent moisture to separate again, and the reaction was continued at such a temperature 2 hours, when no moisture separates, unlatching vacuum, and by Step increases temperature, and when no liquid flows out, temperature rises to 150 DEG C, and 10 support of vacuum stops heating and releases vacuum, and temperature is down to 70 DEG C, it is carried out by the way of suction filtration overanxious, obtains pale yellowish oil liquid, 250 centipoise of viscosity (25 DEG C), through gas chromatography mass spectrometry point Analysis, basic structure is that chemical name shown in I is N-(1- phenyl-ethylene)-p-aminobenzoic acid-(2- methyl -2- phenyl -1,3- Oxazolidine-N- ethyl) ester content 96.4%, structure is that chemical name shown in II is the bis- (N-(1- of 2,2'- diethanolimine Phenyl-ethylene)-P aminobenzoates) content 3.1%, average molecular weight 430.The two adds up content 99.5%. By-product need not separate, because it is also a kind of excellent polyurethane latent curing agent and reactive diluent.
The present invention rolls into one the functional group of oxazole alkanes latent curing agent and diimine class latent curing agent, on a molecule Existing oxazolidine group has imine group again, makes the mutual supplement with each other's advantages of the two, and shortcoming is complementary to one another again.This spline structure is dived Curing agent is not only easy to use compared with oxazole alkanes latent curing agent and imines latent curing agent to be carried out to compounding, but also can be with It effectively avoids the problem that between the two since compatibility exists, or causes to vulcanize inhomogenous phenomenon hair because mixing unevenly It is raw.In addition, general oxazole alkanes latent curing agent and diimine class class latent curing agent, molecule middle frame bridge portion is mostly carboxylic hydroxyl Ester or carbamate, esterification or transesterification in synthesis process mostly use high efficiency liquid tin catalyst, and this kind of catalyst And exactly polyurethane moulded catalyst adds the catalyst being rolled in curing agent to subsequent due to that can not recycle or remove Machine-shaping have an impact, so that operator is difficult to the design and practical operation of accurate control formula.The present invention is using the negative of solid Carrying titanate catalyst can recycle, and can not only reduce cost, but also will not have an impact to the design of subsequent formula and operation.
Embodiment two；A kind of asymmetric latency polyurethane curing agent and preparation method thereof
By 75.6g methyl p-aminobenzoate (white crystalline powder, the industrial goods of purity >=99%) be added with stirring, Return channel and oil water separator, thermometer three-necked flask in, 250g toluene is added, stirring is allowed to sufficiently dissolve, then be added Acetophenone (oily colourless liquid, purity >=99.5%), the stirring 15~diethanol amine (industry of purity >=99% is added after twenty minutes Product), 20g polymer supported titanate catalyst is then added, is warming up to 80 DEG C, is heated to reflux a point water, maintains back flow reaction 2 hours, then Temperature rises to 120 DEG C, and observation has apparent moisture to separate again, and the reaction was continued at such a temperature 2 hours, when no moisture separates, opens Vacuum is opened, and is stepped up temperature, when no liquid flows out, temperature rises to 140 DEG C, and 10 support of vacuum stops heating and releasing vacuum, Temperature is down to 70 DEG C, is carried out by the way of suction filtration overanxious, obtains pale yellowish oil liquid, 260 centipoise of viscosity (25 DEG C), through gas Matter combination analysis, basic structure are that chemical name shown in I is N-(1- phenyl-ethylene)-p-aminobenzoic acid-(2- methyl -2- Phenyl -1,3-oxazoles alkane-N- ethyl) ester content 97.4%, structure is that chemical name shown in II is 2,2'- iminodiacetic acid (salt) Bis- (N-(1- the phenyl-ethylene)-P aminobenzoates of alcohol) content 2.1%, average molecular weight 428.Diethanol amine, to amino Molar ratio between methyl benzoate and acetophenone three is 1 ︰, 1 ︰ 2.
Embodiment three；A kind of asymmetric latency polyurethane curing agent and preparation method thereof
By 82.5g ethylaminobenzoate (also known as benzocainum, white crystalline powder, the industrial goods of purity >=99%) It is added in the three-necked flask for having stirring, return channel and oil water separator, thermometer, 250g toluene is added, stirring is allowed to abundant Then the benzaldehyde (also known as benzaldehyde, light yellow clear liquid, purity >=99% industrial goods) of 106.2g, stirring is added in dissolution 15~after twenty minutes be added 52.5g diethanol amine (industrial goods of purity >=99%), then be added 20g polymer supported titanate catalysis Agent is warming up to 75 DEG C, is heated to reflux a point water, maintains back flow reaction 2 hours, then temperature rises to 130 DEG C, and observation has apparent water again It separates, the reaction was continued at such a temperature 2 hours, when no moisture separates, opens vacuum, and be stepped up temperature, works as no liquid Outflow, temperature rise to 150 DEG C, and 10 support of vacuum stops heating and releases vacuum, and temperature is down to 70 DEG C, is carried out by the way of suction filtration It is overanxious, pale yellowish oil liquid is obtained, 210 centipoise of viscosity (25 DEG C), through Gc-mss, basic structure is chemistry shown in I Entitled N-(phenyi-methylene)-p-aminobenzoic acid-(2- phenyl -1,3-oxazoles alkane-N- ethyl) ester content 95.8%, knot Structure is that chemical name shown in II is bis- (N-(the phenyi-methylene)-P aminobenzoates of 2,2'- diethanolimine) contain Amount 4.2%.Average molecular weight 405.Molar ratio between diethanol amine, ethylaminobenzoate and benzaldehyde three is 1 ︰, 1 ︰ 2。
Embodiment 4(application example)
(1), the synthesis of performed polymer
With methyl diphenylene diisocyanate (MDI) and polyether Glycols (PPG220) for Material synthesis polyurethane prepolymer Body, specifically:
PPG (Mn1800, the height of 600g are added in three-necked flask of the 1000ml equipped with stirring, thermometer and heating device The GE220 of bridge, hydroxyl value 55mgKOH/g) and 93.6g liquefied mdi (MDI-50 of Yantai Wanhua), be to slowly warm up to 80 DEG C, In It is stirred to react at this temperature 3 hours, surveying NCO content is 4.5%, stops heating, (the dibutyltindilaurylmercaptide osmanthus T-12 of 1.2g is added Acid esters), then it is placed in vacuum desiccator deaeration 15 minutes, when temperature is down to 50 DEG C or less, product one dividing into three, each 231g, Nitrogen charging saves respectively.
(2), stability test
The be performed polymer 1# of above-mentioned test is mixed with the novel latency polyurethane curing agent 32.9g that example 1 is done, is stirred It mixes uniformly mixed, is then placed in deaeration 15 minutes in vacuum desiccator again, surveys its viscosity (25 DEG C), be then sealed in 25 DEG C of guarantors It deposits, every the viscosity change situation of survey in 7~14 days, is recorded in table one.
(3) film-making is tested
A, above-mentioned be performed polymer 2# is mixed with the novel latency polyurethane curing agent 32.9g that example 1 is done, is stirred It is uniformly mixed, then is placed in deaeration 15 minutes in vacuum desiccator, then pour into test piece mold, natural levelling.Record room temperature, wet Surface drying time and the time is fully cured in degree.The surface condition of test piece is observed after demoulding and does static mechanical property test, the examination Piece is denoted as A test piece, and institute's measured data is inserted in table two.
B, above-mentioned be performed polymer 2# is mixed with the novel latency polyurethane curing agent 30.4g that example 3 is done, is stirred It is uniformly mixed, then is placed in deaeration 15 minutes in vacuum desiccator, then pour into test piece mold, natural levelling.Record room temperature, wet Surface drying time and the time is fully cured in degree.The surface condition of test piece is observed after demoulding and does static mechanical property test, the examination Piece is denoted as B test piece, and institute's measured data is inserted in table two.
One stability experiment tables of data of table
Serial number Appearance Interval (day) Viscosity (mPa.s, 25 DEG C)
0 Weak yellow liquid, bubble-free 0 1650
2 Weak yellow liquid, bubble-free 7 1660
3 Weak yellow liquid, bubble-free 7 1660
4 Weak yellow liquid, bubble-free 14 1668
5 Weak yellow liquid, bubble-free 14 1670
6 Weak yellow liquid, bubble-free 14 1675
Two gel-forming property table of table
Appearance Surface drying time (h) The time (h) is fully cured Elongation at break (%) Tensile strength (MPa) Tearing strength (N/mm)
A The smooth bubble-free in surface 13 25 612 12.6 32
B The smooth bubble-free in surface 12 24 620 12.3 31
Note: it is opening vulcanization, is demoulded after 27 hours, 25~32 DEG C of room temperature, humidity 65~85%.Appearance after demoulding Light yellow flat and smooth bubble-free, smell substantially without.
A kind of example IV ~ nine: asymmetric latency polyurethane curing agent
Meet the compound of general formula (I) Meet the compound of general formula (II)
Example IV 93% 7%
Embodiment five 94% 6%
Embodiment six 95% 5%
Embodiment seven 96% 4%
Embodiment eight 97% 3%
Embodiment nine 100%
Example IV: R1:H、R2: methyl, R3:H、R4: methyl, R5:H、R6: methyl, R7:H、R8: methyl.
Embodiment five: R1: isopropyl, R2: phenyl, R3: isopropyl, R4: phenyl, R5: methyl, R6: methyl, R7: amyl, R8: methyl.
Embodiment six: R1: ethyl, R2: methyl, R3: ethyl, R4: methyl, R5: ethyl, R6: methyl, R7: ethyl, R8: Methyl.
Embodiment seven: R1: methyl, R2: benzyl, R3: methyl, R4: benzyl, R5: methyl, R6: benzyl, R7: methyl, R8: benzyl.
Embodiment eight: R1: isopropyl, R2: ethyl, R3: isopropyl, R4: ethyl, R5: isopropyl, R6: ethyl, R7: isopropyl Base, R8: ethyl.
Embodiment nine: R1: methyl, R2: methyl, R3: methyl, R4: methyl, R5: methyl, R6: methyl, R7: methyl, R8: first Base.
A kind of embodiment ten: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials include A, B and C, and wherein A is diethyl Hydramine, B are selected from p-aminobenzoic acid N-butyl, and C is the mixing that isobutylaldehyde and methyl sec-butyl ketone are constituted according to the molar ratio of 1:1 Object；
Preparation method includes: that the B of 10 parts by weight is added in reaction kettle, and the organic solvent of 30 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.05 parts by weight, first flow back under the conditions of 40 DEG C Then reaction 1 hour is warming up to 120 DEG C and reacts 2 hours, then solvent removed by vacuum, is next recovered by filtration after catalyst to obtain the final product Product；
The organic solvent is carbon tetrachloride；
The catalyst is polymer supported titanate.
Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.1.
The solvent removed by vacuum is at 120 DEG C, and overbottom pressure is under the conditions of 9 support.
A kind of embodiment 11: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials include A, B and C, and wherein A is diethyl Hydramine, B are the mixture that p-aminobenzoic acid and methyl p-aminobenzoate are constituted according to the molar ratio of 1:1, and C is methyl tert-butyl Base ketone；
Preparation method includes: that the B of 30 parts by weight is added in reaction kettle, and the organic solvent of 90 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.2 parts by weight, first flow back under the conditions of 80 DEG C Then reaction 2 hours is warming up to 150 DEG C and reacts 3 hours, then solvent removed by vacuum, is next recovered by filtration after catalyst to obtain the final product Product.
The organic solvent is the mixture that benzene and dimethylbenzene are constituted according to the molar ratio of 1:1.
The catalyst is polymer supported titanate.
8, the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that: Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.05.
The solvent removed by vacuum is at 150 DEG C, and overbottom pressure is under the conditions of 10 support.
A kind of embodiment 12: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials include A, B and C, and wherein A is diethyl Hydramine, B are p-aminobenzoic acid isopropyl ester, and C is p-tolyl aldehyde；
Preparation method includes: that the B of 20 parts by weight is added in reaction kettle, and the organic solvent of 60 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.1 parts by weight, first flow back under the conditions of 60 DEG C Then reaction 1.5 hours is warming up to 135 DEG C and reacts 2.5 hours, then solvent removed by vacuum, after catalyst next is recovered by filtration Up to product；
The organic solvent is petroleum ether；
The catalyst is polymer supported titanate.
Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.08.
The solvent removed by vacuum is at 135 DEG C, and overbottom pressure is equal under the conditions of 10 supports.
A kind of embodiment 13: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials include A, B and C, and wherein A is diethyl Hydramine, B ethylaminobenzoate, C are phenylacetaldehyde；
Preparation method includes: that the B of 18 parts by weight is added in reaction kettle, and the organic solvent of 78 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.1 parts by weight, first flow back under the conditions of 70 DEG C Then reaction 2 hours is warming up to 150 DEG C and reacts 2 hours, then solvent removed by vacuum, is next recovered by filtration after catalyst to obtain the final product Product；
The organic solvent is Benzene Chloride；
The catalyst is polymer supported titanate.
Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.1.
The solvent removed by vacuum is at 140 DEG C, and overbottom pressure is equal under the conditions of 9.5 supports.
A kind of embodiment 14: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials include A, B and C, and wherein A is diethyl Hydramine, B are methyl p-aminobenzoate, and C is methyl sec-butyl ketone；
Preparation method includes: that the B of 25 parts by weight is added in reaction kettle, and the organic solvent of 85 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.2 parts by weight, first flow back under the conditions of 80 DEG C Then reaction 2 hours is warming up to 150 DEG C and reacts 2 hours, then solvent removed by vacuum, is next recovered by filtration after catalyst to obtain the final product Product；
The organic solvent is toluene；
The catalyst is polymer supported titanate.
Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.
The solvent removed by vacuum is at 150 DEG C, and overbottom pressure is 10 supports.
A kind of embodiment 15: preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, it is characterised in that: composition of raw materials includes A, B and C, Wherein A is diethanol amine, and B is p-aminobenzoic acid n-pentyl ester, and C is methyl iso-butyl ketone (MIBK)；
Preparation method includes: that the B of 30 parts by weight is added in reaction kettle, and the organic solvent of 80 parts by weight is then added, It heats and stirs, after B is completely dissolved, A and C is added, add the catalyst of 0.2 parts by weight, first flow back under the conditions of 75 DEG C Then reaction 2 hours is warming up to 150 DEG C and reacts 2.5 hours, then solvent removed by vacuum, is next recovered by filtration after catalyst i.e. Obtain product；
The organic solvent is the mixture that benzene and dimethylbenzene are constituted according to the molar ratio of 1:2.
In other embodiments, the organic solvent is selected from benzene,toluene,xylene, petroleum ether, carbon tetrachloride, chlorination Benzene；
The catalyst is polymer supported titanate.
In other embodiments, the C is selected from formaldehyde, polyformaldehyde, acetaldehyde, propionic aldehyde, isobutylaldehyde, 2- ethyl hexanal, 2- Ethyl octanal, 2,3- diethyl valeral, hexahydrobenzaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, methylbenzene first Aldehyde, phenylacetaldehyde, anisaldehyde；Acetone, methyl ethyl ketone, methyl propyl ketone, dimethyl acetone, methyl sec-butyl ketone, cyclohexanone, ring Pentanone, acetophenone, Propiophenone.
More preferably in embodiment: the C is selected from octanal, benzaldehyde, methyl iso-butyl ketone (MIBK), acetophenone.
In other embodiments, the B is selected from p-aminobenzoic acid, methyl p-aminobenzoate, p-aminobenzoic acid Ethyl ester；
More preferably in embodiment: the B is ethylaminobenzoate.
Molar ratio between A, B and C three is 1 ︰, 1 ︰ 2.
The solvent removed by vacuum is at 120-150 DEG C, and overbottom pressure is less than or equal under the conditions of 10 supports.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as At all equivalent modifications or change, should be covered by the claims of the present invention.

Claims (8)

1. a kind of preparation method of asymmetric latency polyurethane curing agent, it is characterised in that: composition of raw materials includes A, B and C, Middle A is diethanol amine, the nalka base ester or isoalkyl that B is selected from p-aminobenzoic acid, the carbon atom number of p-aminobenzoic acid is 1 ~ 6 Ester, it is 7 ~ 13 that C, which is selected from the aliphatic aldehyde, the aliphatic ketone that carbon atom number is 1 ~ 13, carbon atom number that carbon atom number is 1 ~ 13, The ketone with aryl that aldehyde or carbon atom number with aryl are 8 ~ 13；
Preparation method includes: that the B of 10-30 parts by weight is added in reaction kettle, and the organic molten of 30-90 parts by weight is then added Agent is heated and is stirred, and after B is completely dissolved, A and C is added, and the catalyst of 0.05-0.2 parts by weight is added, first at 40-80 DEG C Under the conditions of back flow reaction 1-2 hours, be then warming up to 120-150 DEG C of reaction 2-3 hours, then solvent removed by vacuum, following mistake Up to product after filter recycling catalyst；
The organic solvent is selected from benzene,toluene,xylene, petroleum ether, carbon tetrachloride, Benzene Chloride；
The catalyst is polymer supported titanate.
2. the preparation method of asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that: the C Selected from formaldehyde, polyformaldehyde, acetaldehyde, propionic aldehyde, isobutylaldehyde, 2- ethyl hexanal, 2- ethyl octanal, 2,3- diethyl valeral, cyclohexyl Formaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, tolyl aldehyde, phenylacetaldehyde, anisaldehyde；Acetone, Methylethyl Ketone, methyl propyl ketone, dimethyl acetone, methyl sec-butyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, cyclopentanone, acetophenone, phenyl Ethyl ketone.
3. the preparation method of asymmetric latency polyurethane curing agent according to claim 2, it is characterised in that: the C Selected from benzaldehyde, methyl iso-butyl ketone (MIBK), acetophenone.
4. the preparation method of asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that: the B Selected from p-aminobenzoic acid, methyl p-aminobenzoate, ethylaminobenzoate.
5. the preparation method of asymmetric latency polyurethane curing agent according to claim 4, it is characterised in that: the B For ethylaminobenzoate.
6. the preparation method of asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that: described A, the molar ratio between B and C three is 1 ︰, 1 ︰, 2~1 ︰, 1 ︰ 2.1.
7. the preparation method of asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that: described Solvent removed by vacuum is at 120-150 DEG C, and overbottom pressure is less than or equal under the conditions of 10 supports.
8. the preparation method of asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that: described Organic solvent is selected from benzene and dimethylbenzene.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591819A (en) * 1993-10-26 1997-01-07 Angus Chemical Company Aldimine oxazolidines and polyisocyanates
JP2002206020A (en) * 2000-11-13 2002-07-26 Sanyo Chem Ind Ltd Moisture-curable epoxy resin composition
CN101687775A (en) * 2007-07-16 2010-03-31 Sika技术股份公司 Aldimines and compositions comprising aldamine
CN103923565A (en) * 2014-03-26 2014-07-16 浙江鲁班建筑防水有限公司 Uncured polyurethane waterproofing coating and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5591819A (en) * 1993-10-26 1997-01-07 Angus Chemical Company Aldimine oxazolidines and polyisocyanates
JP2002206020A (en) * 2000-11-13 2002-07-26 Sanyo Chem Ind Ltd Moisture-curable epoxy resin composition
CN101687775A (en) * 2007-07-16 2010-03-31 Sika技术股份公司 Aldimines and compositions comprising aldamine
CN103923565A (en) * 2014-03-26 2014-07-16 浙江鲁班建筑防水有限公司 Uncured polyurethane waterproofing coating and preparation method thereof

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