CN107043447A - 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 PDFInfo
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- CN107043447A CN107043447A CN201710257830.6A CN201710257830A CN107043447A CN 107043447 A CN107043447 A CN 107043447A CN 201710257830 A CN201710257830 A CN 201710257830A CN 107043447 A CN107043447 A CN 107043447A
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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
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- 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
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- 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
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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
- C08G18/3225—Polyamines
- C08G18/3253—Polyamines being in latent form
Abstract
The invention discloses a kind of asymmetric latency polyurethane curing agent and preparation method thereof, its molecular structure not only oxazolidine group but also with imine group, Jian Ju oxazolidines and the dual functional group's effect of imines, it is low with viscosity, easy to operate, reaction speed is moderate, the features such as solution is honored as a queen almost without smell.Its composite character is that cyclisation, the aldehyde of primary amino radical of ethylol amine can be completed in a reactor（Ketone）The esterification of imino and carboxyl and hydroxyl, without processes such as the purification ＆ isolations to intermediate product, process conditions are gentle, no waste gas waste sludge discharge, and catalyst is recyclable to be reused.Primary raw material used is p-aminobenzoic acid（Or ester）, diethanol amine and 1 13 carbon aldehydes or ketones.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
Technical field
The present invention relates to a kind of asymmetric latency polyurethane curing agent and preparation method thereof, belong to the special chemistry of functional form
Product and field of fine chemical.
Background technology
Latent curing agent is to prepare monocomponent polyurethane material（SPU）Important component, room temperature meet steam can be rapid
Deblocking exposes can be with NCO（-NCO）Hydroxyl, primary amino radical and/or the secondary amino group of reaction, can prior to NCO with
Water reaction is the key point of this kind of curing agent.Since the eighties in last century both at home and abroad existing numerous patents disclose it is a series of
The kind of such curing agent, in polyurethane CASE materials, such as United States Patent (USP) US5749627, Deutsche Bundespatent
DE4021659, the patent EP0965604 that Japan applies in European Union, the EP2858965A1 of W. R. Grace ＆ Co
(CN104364225A), the EP2948485A1 (CN104903371A) of Switzerland SIKA companies, Chinese patent CN103289038A,
CN105061347A etc., be summed up disclosed by above-mentioned patent be the Dan Huan oxazolidines of different structure, bicyclo 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 can be fast
Speed deblocking, one is exposed hydroxyl and secondary amino group, and one is exposed double primary amino radicals, is then reacted with NCO and is exercised chain extension-crosslinking function
Characteristic.
But both have difference again from operation and performance.From the point of view of as one oxazole alkanes latent curing agent to water more
Sensitivity, activity is stronger, reacts more rapid, but again relatively slow with NCO reaction, exists that surface drying is too fast, what the inside was felt like jelly
Drawback, if the middle frame bridge portion aromatic series of two oxazole groups classes in addition, product viscosity becomes big easily solidification, makes operation
Degradation is this EP2493949A1 (CN102648225A) with《Noncrystalline oxazolidines》For topic, disclosing makes such latent solid
The technical measures of mobility are kept under agent normal temperature；And diimine class latent curing agent, because two primary amino radicals are all shielded, room
Temperature is lower to have good mobility, mixes and is very easy to polyurethane component, with good operating characteristics, therefore is commonly used for living
Property diluent, solution is honored as a queen in addition, and expose is two primary amino radicals, and curability is excellent.Therefore many patents also disclose two
Class latent curing agent is used in mixed way, to make up the technology of mutual deficiency.
The content of the invention
Present invention aims at provide a kind of asymmetric latency polyurethane curing agent and preparation method thereof.
To achieve the above object, the technical scheme that provides of the present invention is：A kind of asymmetric latency polyurethane curing agent, institute
State asymmetric latency polyurethane curing agent and contain weight/mass percentage composition and meet formula for 93%-98%（Ⅰ）Compound,
（Ⅰ）；
Formula（Ⅰ）In R1And R2In at least one be hydrogen, R1And R2It is identical or different, R1And R2H, carbon are represented independently of one another
Atomicity is that 1 ~ 13 linear paraffin group, branched paraffin group or carbon number are 6 ~ 13 aromatic hydrocarbon group；Formula（Ⅰ）In
R3And R4In at least one be hydrogen, R3And R4It is identical or different, R3And R4It is 1 ~ 13 to represent H, carbon number independently of one another
Alkane group or the aromatic hydrocarbon group that carbon number is 6 ~ 13.
It is preferred that technical scheme be：Also meet formula containing weight/mass percentage composition for 2%-7%（Ⅱ）Compound；
（Ⅱ）
Formula（Ⅱ）In R5And R6In at least one be hydrogen, R5And R6It is identical or different, R5And R6Represent independently of one another H,
The alkane group that carbon number is 1 ~ 13 or the aromatic hydrocarbon group that carbon number is 6 ~ 13；Formula（Ⅱ）In R7And R8In at least one
Individual is not hydrogen, R7And R8It is identical or different, R7And R8It is former as 1 ~ 13 alkane group or carbon that H, carbon number are represented independently of one another
Subnumber is 6 ~ 13 aromatic hydrocarbon group.
To achieve the above object, the technical scheme that provides of the present invention is：A kind of asymmetric latency polyurethane curing agent
Preparation method, composition of raw materials includes A, B and C, and wherein A is diethanol amine, and B is selected from p-aminobenzoic acid, p-aminobenzoic acid
Nalka base ester or isoalkyl ester of the carbon number for 1 ~ 6, C be selected from the aliphatic aldehyde that carbon number is 1 ~ 13, carbon number be 1 ~
The aldehyde with aryl that the aliphatic ketone of 13, carbon number are 7 ~ 13 or the ketone with aryl that carbon number is 8 ~ 13；
Preparation method includes：The B of 10-30 parts by weight is added in reactor, the organic molten of 30-90 parts by weight is then added
Agent, heats and stirs, after B is completely dissolved, and adds A and C, 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 and react 2-3 hours, then solvent removed by vacuum, following mistake
Filter produces product after reclaiming catalyst；
The organic solvent is selected from benzene,toluene,xylene, petroleum ether, carbon tetrachloride, Benzene Chloride；
The catalyst is polymer supported titanate.
It is preferred that technical scheme be：The C is selected from formaldehyde, polyformaldehyde, acetaldehyde, propionic aldehyde, isobutylaldehyde, 2- ethyl hexanals, 2-
Ethyl octanal, 2,3- diethyl valeral, hexahydrobenzaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, a 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.
It is preferred that technical scheme be：The C is selected from octanal, benzaldehyde, methyl iso-butyl ketone (MIBK), acetophenone.
It is preferred that technical scheme be：The B is selected from p-aminobenzoic acid, methyl p-aminobenzoate, p-aminobenzoic acid
Ethyl ester；
It is preferred that technical scheme be：The B is ethylaminobenzoate.
It is preferred that technical scheme be：Mol ratio between A, B and C three is the ︰ 2.1 of 1 ︰, 1 ︰, 2~1 ︰ 1.
It is preferred that technical scheme be：The solvent removed by vacuum is that overbottom pressure is less than or equal to 10 support conditions at 120-150 DEG C
Under.
It is preferred that technical scheme be：The organic solvent is selected from benzene and dimethylbenzene.
Because above-mentioned technical proposal is used, the present invention this have the advantage that compared with prior art：
1st, asymmetric latent curing agent of the invention, its Fen Ji oxazolidine and imine were with all over the body, both having had a You oxazoles
Alkane to water sensitive, be swift in response the characteristics of, again there is imines solution to be honored as a queen and expose primary amine group, curability is excellent, at room temperature
The advantage of good fluidity, makes that several latent curing agents need not be compounded in formula to adjust applicability.
2nd, synthesis technique provided by the present invention is simple and easy to apply, and multi-step chemical reaction can be completed in a reactor, without
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.
3rd, catalyst of the invention is the solid catalyst of polymer supported titanate, and reuse can be reclaimed completely, can not only be saved
About cost, and make product be remained without catalyst, the flexible selection for being conducive to following process to be formulated.
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 understands other advantages and effect of the present invention easily.
Embodiment one：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%）Add
With in stirring, return channel and oil water separator, the three-necked flask of thermometer, 250g dimethylbenzene is added（It is respectively between adjacency pair
15.4%, 21.4%, 63.2%）, stir and be allowed to fully dissolving, then add 120.1g acetophenone（Light yellow clear liquid is pure
Degree >=99.5%）, 52.5g diethanol amine is added after stirring 15~20 minutes（The industrial goods of purity >=99%）, then add 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, sight
Examine and there is obvious moisture to separate, continue to react 2 hours at such a temperature, when no moisture is separated, open vacuum, and be stepped up
Temperature, when no liquid outflow, temperature rises to 150 DEG C, and the support of vacuum 10 stops heating and releasing vacuum, and temperature is down to 70 DEG C, use
The mode of suction filtration carries out overanxious, obtains pale yellowish oil liquid, the centipoise of viscosity 250（25℃）, through Gc-mss, basic knot
Structure is that chemical name shown in I is N-（1- phenyl-ethylenes）- p-aminobenzoic acid-（2- methyl -2- phenyl -1,3- oxazolidines-N-
Ethyl）The content 96.4% of ester, structure is that the chemical name shown in II is the double (N- of 2,2'- diethanolimines（1- phenyl Asia second
Base）- P aminobenzoates) content 3.1%, mean molecule quantity is 430.Both add up content 99.5%.Accessory substance is not
It must 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
Not only oxazolidine group but also with imine group, makes both mutual supplement with each other's advantages, weak point is complementary to one another again.This spline structure it is latent
Curing agent is not only easy to use compared with oxazole alkanes latent curing agent and imines latent curing agent are carried out into compounding, and can be with
Be prevented effectively from the problem of existing between the two due to compatibility, or because mix it is uneven and caused by vulcanize inhomogenous phenomenon hair
It is raw.In addition, logical oxazole alkanes latent curing agent and diimine class class latent curing agent, molecule middle frame bridge portion is generally carboxylic hydroxyl
Using high efficiency liquid tin catalyst more than esterification or ester exchange in ester or carbamate, building-up process, and this kind of catalyst
Exactly polyurethane moulded catalyst again, due to that can not reclaim or remove, plus the catalyst being rolled in curing agent is to follow-up
Machine-shaping have an impact, 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 reclaim, and can not only reduce cost, and follow-up formula will not be designed and operation generation influence.
Embodiment two；A kind of asymmetric latency polyurethane curing agent and preparation method thereof
By 75.6g methyl p-aminobenzoates（White crystalline powder, the industrial goods of purity >=99%）Add with stirring, backflow
In device and oil water separator, the three-necked flask of thermometer, 250g toluene is added, stirring is allowed to fully dissolving, then adds benzene second
Ketone（Oily colourless liquid, purity >=99.5%）, diethanol amine is added after stirring 15~20 minutes（The industrial goods of purity >=99%）,
Then 20g polymer supported titanate catalyst is added, 80 DEG C are warming up to, a point water is heated to reflux, back flow reaction is maintained 2 hours, then temperature
120 DEG C are risen to, observation has obvious moisture to separate again, continue to react 2 hours at such a temperature, when no moisture is separated, open true
Sky, and temperature is stepped up, when no liquid outflow, temperature rises to 140 DEG C, and the support of vacuum 10 stops heating and releasing vacuum, temperature
70 DEG C are down to, is carried out by the way of suction filtration overanxious, pale yellowish oil liquid, the centipoise of viscosity 260 is obtained（25℃）, join through makings
With analysis, basic structure is that chemical name shown in I is N-（1- phenyl-ethylenes）- p-aminobenzoic acid-（2- methyl -2- phenyl -
1,3- oxazolidine-N- ethyls）The content 97.4% of ester, structure is that the chemical name shown in II is that 2,2'- diethanolimines are double
〔N-（1- phenyl-ethylenes）- P aminobenzoates) content 2.1%, mean molecule quantity 428.Diethanol amine, p-aminophenyl first
Mol ratio between sour methyl esters and acetophenone three is the ︰ 2 of 1 ︰ 1.
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%）Add
With 250g toluene in stirring, return channel and oil water separator, the three-necked flask of thermometer, is added, stirring is allowed to fully dissolving,
Then 106.2g benzaldehyde is added（Also known as benzaldehyde, light yellow clear liquid, the industrial goods of purity >=99%）, stirring 15~
52.5g diethanol amine is added after 20 minutes（The industrial goods of purity >=99%）, 20g polymer supported titanate catalyst is then added, is risen
Temperature is heated to reflux a point water to 75 DEG C, maintains back flow reaction 2 hours, then temperature rises to 130 DEG C, and observation has obvious moisture point again
Go out, continue to react 2 hours at such a temperature, when no moisture is separated, open vacuum, and be stepped up temperature, when no liquid outflow,
Temperature rises to 150 DEG C, and the support of vacuum 10, which stops heating, simultaneously releases vacuum, and temperature is down to 70 DEG C, carried out by the way of suction filtration it is overanxious,
Obtain pale yellowish oil liquid, the centipoise of viscosity 210（25℃）, through Gc-mss, basic structure is that chemical name is shown in I
N-（Phenyi-methylene）- p-aminobenzoic acid-（2- phenyl -1,3- oxazolidine-N- ethyls）The content 95.8% of ester, structure is II
Shown chemical name is the double (N- of 2,2'- diethanolimines（Phenyi-methylene）- P aminobenzoates) content
4.2%.Mean molecule quantity 405.Mol ratio between diethanol amine, ethylaminobenzoate and benzaldehyde three is the ︰ 2 of 1 ︰ 1.
Embodiment 4（Application example）
（1）, performed polymer synthesis
With methyl diphenylene diisocyanate（MDI）And polyether Glycols（PPG220）For Material synthesis base polyurethane prepolymer for use as, tool
Body is：
Added in 1000ml is equipped with stirring, the three-necked flask of thermometer and heater 600g PPG (Mn1800, high bridge
GE220, hydroxyl value 55mgKOH/g) and 93.6g liquefied mdi（The MDI-50 of Yantai Wanhua）, 80 DEG C are to slowly warm up to, in the temperature
The lower stirring reaction of degree 3 hours, it is 4.5% to survey NCO content, stops heating, adds 1.2g T-12 (dibutyltindilaurylmercaptide cinnamic acids
Ester), deaeration 15 minutes in vacuum desiccator are then inserted, when temperature is down to less than 50 DEG C, product one dividing into three, each 231g, point
Other nitrogen charging is preserved.
（2）, stability test
The new latency polyurethane curing agent 32.9g that performed polymer 1# is in above-mentioned experiment with example 1 is done is mixed, stirring is mixed
Close uniform, deaeration 15 minutes in vacuum desiccator are then inserted again, its viscosity is surveyed（25℃）, 25 DEG C of preservations are then sealed in, often
A viscosity B coefficent situation was surveyed every 7~14 days, is recorded in table one.
（3）Film-making is tested
A, above-mentioned be performed polymer 2# mixed with the new latency polyurethane curing agent 32.9g that example 1 is done, stirring mixing
Uniformly, then deaeration 15 minutes in vacuum desiccator are inserted, then poured into test piece mould, natural levelling.Recording room epidemic disaster,
Surface drying time and the time is fully cured.The surface condition of test piece is observed after the demoulding and static mechanical property test is done, the test piece
A test pieces are denoted as, data is surveyed and inserts in table two.
B, above-mentioned be performed polymer 2# mixed with the new latency polyurethane curing agent 30.4g that example 3 is done, stirred
It is well mixed, then deaeration 15 minutes in vacuum desiccator are inserted, then pour into test piece mould, natural levelling.Record room temperature, wet
Degree, surface drying time and the time is fully cured.The surface condition of test piece is observed after the demoulding and static mechanical property test is done, the examination
Piece is denoted as B test pieces, surveys data and inserts in table two.
The stability experiment tables of data of table one
| Sequence number | Outward appearance | Interval（My god） | 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 |
The gel-forming property table of table two
| Outward 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 stripped after 27 hours, 25~32 DEG C of its room temperature, humidity 65~85%.Outward appearance is pale yellow after the demoulding
The equal flat smooth bubble-free of color, smell substantially without.
Example IV ~ nine:A kind of asymmetric latency polyurethane curing agent
| Meet formula（Ⅰ）Compound | Meet formula（Ⅱ）Compound | |
| 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 group,
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.
Embodiment ten:A kind of preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials includes A, B and C, and wherein A is diethanol
Amine, B is selected from p-aminobenzoic acid N-butyl, and C is isobutylaldehyde and methyl sec-butyl ketone according to 1：The mixing that 1 mol ratio is constituted
Thing；
Preparation method includes：The B of 10 parts by weight is added in reactor, the organic solvent of 30 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.05 parts by weight is added, first the back flow reaction under the conditions of 40 DEG C
1 hour, then it is warming up to 120 DEG C and reacts 2 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces product；
The organic solvent is carbon tetrachloride；
The catalyst is polymer supported titanate.
Mol ratio between A, B and C three is the ︰ 2.1 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is under the conditions of 9 support at 120 DEG C.
Embodiment 11:A kind of preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials includes A, B and C, and wherein A is diethanol
Amine, B is p-aminobenzoic acid and methyl p-aminobenzoate according to 1：The mixture that 1 mol ratio is constituted, C is methyl-isobutyl
Ketone；
Preparation method includes：The B of 30 parts by weight is added in reactor, the organic solvent of 90 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.2 parts by weight is added, first the back flow reaction 2 under the conditions of 80 DEG C
Hour, then it is warming up to 150 DEG C and reacts 3 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces product.
The organic solvent is benzene and dimethylbenzene according to 1：The mixture that 1 mol ratio is constituted.
The catalyst is polymer supported titanate.
8th, the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：
Mol ratio between A, B and C three is the ︰ 2.05 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is under the conditions of 10 support at 150 DEG C.
Embodiment 12:A kind of preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials includes A, B and C, and wherein A is diethanol
Amine, B is p-aminobenzoic acid isopropyl ester, and C is p-tolyl aldehyde；
Preparation method includes：The B of 20 parts by weight is added in reactor, the organic solvent of 60 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.1 parts by weight is added, first the back flow reaction under the conditions of 60 DEG C
1.5 hours, then it is warming up to 135 DEG C and reacts 2.5 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces
Product；
The organic solvent is petroleum ether；
The catalyst is polymer supported titanate.
Mol ratio between A, B and C three is the ︰ 2.08 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is equal under the conditions of 10 supports at 135 DEG C.
Embodiment 13:A kind of preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials includes A, B and C, and wherein A is diethanol
Amine, B ethylaminobenzoate, C is phenylacetaldehyde；
Preparation method includes：The B of 18 parts by weight is added in reactor, the organic solvent of 78 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.1 parts by weight is added, first the back flow reaction 2 under the conditions of 70 DEG C
Hour, then it is warming up to 150 DEG C and reacts 2 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces product；
The organic solvent is Benzene Chloride；
The catalyst is polymer supported titanate.
Mol ratio between A, B and C three is the ︰ 2.1 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is equal under the conditions of 9.5 supports at 140 DEG C.
Embodiment 14:A kind of preparation method of asymmetric latency polyurethane curing agent
A kind of preparation method of asymmetric latency polyurethane curing agent, composition of raw materials includes A, B and C, and wherein A is diethanol
Amine, B is methyl p-aminobenzoate, and C is methyl sec-butyl ketone；
Preparation method includes：The B of 25 parts by weight is added in reactor, the organic solvent of 85 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.2 parts by weight is added, first the back flow reaction 2 under the conditions of 80 DEG C
Hour, then it is warming up to 150 DEG C and reacts 2 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces product；
The organic solvent is toluene；
The catalyst is polymer supported titanate.
Mol ratio between A, B and C three is the ︰ 2 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is 10 supports at 150 DEG C.
Embodiment 15:A kind of 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：The B of 30 parts by weight is added in reactor, the organic solvent of 80 parts by weight is then added, heated
And stir, after B is completely dissolved, A and C is added, the catalyst of 0.2 parts by weight is added, first the back flow reaction 2 under the conditions of 75 DEG C
Hour, then it is warming up to 150 DEG C and reacts 2.5 hours, then solvent removed by vacuum, next it is recovered by filtration after catalyst and produces production
Product；
The organic solvent is benzene and dimethylbenzene according to 1：The mixture that 2 mol ratio is constituted.
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 hexanals, 2-
Ethyl octanal, 2,3- diethyl valeral, hexahydrobenzaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, a methylbenzene first
Aldehyde, phenylacetaldehyde, anisaldehyde；Acetone, methyl ethyl ketone, methyl propyl ketone, dimethyl acetone, methyl sec-butyl ketone, cyclohexanone, ring
Pentanone, acetophenone, Propiophenone.
In the embodiment being more highly preferred to：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；
In the embodiment being more highly preferred to：The B is ethylaminobenzoate.
Mol ratio between A, B and C three is the ︰ 2 of 1 ︰ 1.
The solvent removed by vacuum is that overbottom pressure is less than or equal under the conditions of 10 supports at 120-150 DEG C.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of asymmetric latency polyurethane curing agent, it is characterised in that：The asymmetric latency polyurethane curing agent contains
There is weight/mass percentage composition to meet formula for 93%-98%（Ⅰ）Compound,
（Ⅰ）；
Formula（Ⅰ）In R1And R2In at least one be hydrogen, R1And R2It is identical or different, R1And R2H, carbon are represented independently of one another
The alkane group that atomicity is 1 ~ 13 or the aromatic hydrocarbon group that carbon number is 6 ~ 13；Formula（Ⅰ）In R3And R4In at least one not
For hydrogen, R3And R4It is identical or different, R3And R4It is 1 ~ 13 alkane group or carbon number to represent H, carbon number independently of one another
For 6 ~ 13 aromatic hydrocarbon group.
2. asymmetric latency polyurethane curing agent according to claim 1, it is characterised in that：Also contain quality percentage
Content meets formula for 2%-7%'s（Ⅱ）Compound；
（Ⅱ）
Formula（Ⅱ）In R5And R6In at least one be hydrogen, R5And R6It is identical or different, R5And R6Represent independently of one another H,
The alkane group that carbon number is 1 ~ 13 or the aromatic hydrocarbon group that carbon number is 6 ~ 13；Formula（Ⅱ）In R7And R8In at least one
Individual is not hydrogen, R7And R8It is identical or different, R7And R8It is former as 1 ~ 13 alkane group or carbon that H, carbon number are represented independently of one another
Subnumber is 6 ~ 13 aromatic hydrocarbon group.
3. 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, its
Middle A is diethanol amine, and B is selected from nalka base ester or isoalkyl of the carbon number of p-aminobenzoic acid, p-aminobenzoic acid for 1 ~ 6
Ester, it is 7 ~ 13 that C, which is selected from the aliphatic aldehyde, the aliphatic ketone that carbon number is 1 ~ 13, carbon number that carbon number is 1 ~ 13,
Aldehyde or carbon number with aryl are 8 ~ 13 ketone with aryl；
Preparation method includes：The B of 10-30 parts by weight is added in reactor, the organic molten of 30-90 parts by weight is then added
Agent, heats and stirs, after B is completely dissolved, and adds A and C, 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 and react 2-3 hours, then solvent removed by vacuum, following mistake
Filter produces product after reclaiming catalyst；
The organic solvent is selected from benzene,toluene,xylene, petroleum ether, carbon tetrachloride, Benzene Chloride；
The catalyst is polymer supported titanate.
4. the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：The C
Selected from formaldehyde, polyformaldehyde, acetaldehyde, propionic aldehyde, isobutylaldehyde, 2- ethyl hexanals, 2- ethyls octanal, 2,3- diethyl valeral, cyclohexyl
Formaldehyde, cyclohexyl acetaldehyde, benzaldehyde, p-tolyl aldehyde, a 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.
5. the preparation method of asymmetric latency polyurethane curing agent according to claim 4, it is characterised in that：The C
Selected from octanal, benzaldehyde, methyl iso-butyl ketone (MIBK), acetophenone.
6. the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：The B
Selected from p-aminobenzoic acid, methyl p-aminobenzoate, ethylaminobenzoate.
7. the preparation method of asymmetric latency polyurethane curing agent according to claim 6, it is characterised in that：The B
For ethylaminobenzoate.
8. the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：It is described
Mol ratio between A, B and C three is the ︰ 2.1 of 1 ︰, 1 ︰, 2~1 ︰ 1.
9. the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：It is described
Solvent removed by vacuum is that overbottom pressure is less than or equal under the conditions of 10 supports at 120-150 DEG C.
10. the preparation method of asymmetric latency polyurethane curing agent according to claim 3, it is characterised in that：It is described
Organic solvent is selected from benzene and dimethylbenzene.
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| CN109111834A (en) * | 2018-07-27 | 2019-01-01 | 德州科顺建筑材料有限公司 | A kind of one-component polyurea modified polyurethane water-proof paint and preparation method thereof |
| CN109251292A (en) * | 2018-07-13 | 2019-01-22 | 重庆科顺化工新材料有限公司 | Latent Curing Agents in Polyurethane and single-component polyurethane water-proof paint and preparation method |
| CN112029063A (en) * | 2020-09-07 | 2020-12-04 | 江苏湘园化工有限公司 | Liquid polyurethane curing agent composition and application method thereof |
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| CN107043447B (en) | 2019-12-03 |
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