CN104356330B - Carboxylic acid waterborne polyurethane chain extender and preparation method thereof - Google Patents
Carboxylic acid waterborne polyurethane chain extender and preparation method thereof Download PDFInfo
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- CN104356330B CN104356330B CN201410508873.3A CN201410508873A CN104356330B CN 104356330 B CN104356330 B CN 104356330B CN 201410508873 A CN201410508873 A CN 201410508873A CN 104356330 B CN104356330 B CN 104356330B
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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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a carboxylic acid waterborne polyurethane chain extender and a preparation method thereof. The preparation method comprises the following steps: dissolving diethanol amine in absolute methanol; reacting for 4-5 h at a temperature of 30-35 DEG C with methyl acrylate in a reactor; conducting vacuum-pumping to remove methanol and excess methyl acrylate to obtain intermediates N,N-dihydroxyethylrutin-2-amino propionic acid methyl ester; adding the N,N-dihydroxyethylrutin-2-amino propionic acid methyl ester, and NaOH aqueous solution into the reactor; carrying out stirring and reaction for 8-10 h at a temperature of 155-160 DEG C to obtain a crude product; adopting an ion-exchange method theory to remove sodium ions in the crude product; conducting vacuum-pumping to remove methanol generated by the reaction to obtain the carboxylic acid waterborne polyurethane chain extender. The preparation method utilizes the theories of Michael additive reaction and alkali hydrolysis of ester, carries out reaction between the diethanol amine and the methyl acrylate to synthesize the intermediates N and N-dihydroxyethylrutin-2-amino propionic acid methyl ester first, and then carries out ester group hydration reaction between the intermediates and the NaOH aqueous solution to obtain the product after the two reactions; the synthesis method is simple and low in cost.
Description
Technical field
The invention belongs to chemical products field is and in particular to a kind of carboxylic acid type aqueous polyurethane and preparation method thereof.
Background technology
Hydrophilic monomer is the critical materials of aqueous polyurethane synthesis, and anionic hydrophilic monomer is always this area research
One of emphasis.The molecular mass of chain extender is smaller, and reaction is relatively more active, therefore can effectively adjust the speed of reaction and make anti-
System is answered promptly to carry out crosslinking, in whole reaction system, the response competition rate of chain extender and isocyanates and polyalcohols system
Relatively strong, therefore can and its regulation system effectively reaction rate, it is good that hydrophilic chain extender can also make aqueous polyurethane have
Good dispersiveness or automatic emulsifying performance.DMPA is the carboxylic acid type chain extender of domestic at present most employing, the therefore carboxylic of synthesizing new
Acid monomers have certain facilitation to field of waterborne polyurethane.
Content of the invention
It is an object of the invention to provide a kind of cheap, preparation method simple carboxylic acid type aqueous polyurethane chain extender and
Its preparation method.
In order to achieve the above object, the chemical name of carboxylic acid type aqueous polyurethane chain extender of the present invention is N, N- dihydroxy second
Base -2- alanine, its chemical structural formula is：
A kind of preparation method of carboxylic acid type aqueous polyurethane chain extender, comprises the following steps：
1) diethanol amine is dissolved in absolute methanol, then drips methyl acrylate, 30～35 DEG C of stirring reactions 4～
5h, then vacuumizes removing methyl alcohol at 80～85 DEG C and excessive methyl acrylate obtains intermediate N, N- dihydroxy ethyl -2-
Aminopropanoate；Wherein, the diethanol amine being added and acrylic acid mol ratio are 1:(1～1.2)；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution, flows back and stir at 155-160 DEG C
Mix reaction 8-10h, obtain product crude product；Sodium ion in product crude product is removed using ion-exchange principle, then vacuumizes
The methyl alcohol generating except dereaction, obtains final product carboxylic acid type aqueous polyurethane chain extender；Wherein, the N being added, N- dihydroxy ethyl -2- ammonia
Base methyl propionate is 1 with the mol ratio of NaOH:(1～1.2).
Described step 1) in every 100mL absolute methanol in add the diethanol amine of 1mol.
Described step 2) in the NaOH aqueous solution concentration be 0.08g/mL～0.10g/mL.
Described step 2) in using ion-exchange principle remove product crude product in sodium ion be to adopt with the following method
Carry out：
Product crude product being passed through cation exchange column chromatography, then constantly washing cation exchange column with distilled water until flowing
Go out liquid colourless till, collect the efflux obtaining pH value=7 being adjusted to efflux, finally at 70～75 DEG C, vacuumize removing
Solvent, obtains carboxylic acid type aqueous polyurethane chain extender.
The pH value of described efflux is to be adjusted using the hydrochloric acid of 0.1mol/L.
Compared with prior art, the beneficial effects of the present invention is：
A kind of carboxylic acid type aqueous polyurethane chain extender and preparation method thereof, diethanol amine is dissolved in absolute methanol, then
React 4～5h in 30～35 DEG C in the reactor with methyl acrylate, then vacuumize and remove methyl alcohol and excessive acrylic acid first
Ester, obtains intermediate N, N- dihydroxy ethyl -2- aminopropanoate；By N, N- dihydroxy ethyl -2- aminopropanoate and NaOH
The aqueous solution adds equipped with stirring reaction 8-10h that in reactor, flows back at 155-160 DEG C, obtains product crude product；Handed over using ion
Change the sodium ion that method principle removes in product crude product, then vacuumize the methyl alcohol generating except dereaction, obtain final product carboxylic acid type aqueous poly-
Urethane chain extender；The present invention utilizes Michael addition reaction and the basic hydrolysis principle of ester, by two-step reaction, first by diethyl
Hydramine is reacted with methyl acrylate, synthesizes intermediate N, N- dihydroxy ethyl -2- aminopropanoate；Again that it is water-soluble in NaOH
Carry out hydrolysis of ester group reaction in liquid and obtain product.Synthetic method of the present invention is simple, and product solid content is high, with low cost.
The present invention will be anti-under conditions of methyl alcohol makees solvent to diethanol amine and methyl acrylate using Michael addition reaction
Intermediate should be obtained；Carry out hydrolysis of ester group reaction in the basic conditions again, obtain carboxylic acid type aqueous polyurethane chain extender.With diethyl
Hydramine, methyl acrylate, absolute methanol, NaOH are raw material, and due to these low in raw material price, toxicity is relatively low, therefore, this
Invention is with low cost, and pollution is little and synthetic method is simple.In addition, the present invention consists of optimizing raw material and proportioning, will prepare
Carboxylic acid type aqueous polyurethane chain extender be applied in the preparation process of polyurethane.
Brief description
Fig. 1 is the process chart of synthesis of carboxylic acid type aqueous polyurethane chain extender of the present invention.
Fig. 2 is the infrared spectrogram of carboxylic acid type aqueous polyurethane chain extender of the present invention.
Fig. 3 is the nuclear magnetic spectrum of carboxylic acid type aqueous polyurethane chain extender of the present invention.
Specific embodiment
Referring to Fig. 1, the preparation method of carboxylic acid type aqueous polyurethane chain extender of the present invention comprises the following steps：
1) diethanol amine is dissolved in absolute methanol, then drips methyl acrylate, 30～35 DEG C of stirring reactions 4～
5h, then vacuumizes removing methyl alcohol at 80～85 DEG C and excessive methyl acrylate obtains intermediate N, N- dihydroxy ethyl -2-
Aminopropanoate；Wherein, the diethanol amine being added and acrylic acid mol ratio are 1:(1～1.2)；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution, flows back and stir at 155-160 DEG C
Mix reaction 8-10h, obtain product crude product；Sodium ion in product crude product is removed using ion-exchange principle, then vacuumizes
The methyl alcohol generating except dereaction, obtains final product carboxylic acid type aqueous polyurethane chain extender；Wherein, the N being added, N- dihydroxy ethyl -2- ammonia
Base methyl propionate is 1 with the mol ratio of NaOH:(1～1.2).
4) sodium ion in product is removed according to ion-exchange principle, then vacuum removes solvent, obtains final product carboxylic acid type aqueous
Polyurethane chain extender；Concrete removing method is as follows：
Product crude product being passed through cation exchange column chromatography, then constantly washing cation exchange column with distilled water until flowing
Go out liquid colourless till, collect the efflux obtaining pH value=7 being adjusted to efflux with the hydrochloric acid of 0.1mol/L, finally at 80 DEG C
Under vacuumize removing solvent, obtain carboxylic acid type aqueous polyurethane chain extender, the chemical name of this chain extender is N, N- dihydroxy ethyl-
2- alanine, its chemical structural formula is：
(1) with reference to embodiment, the present invention is described in further details.
Embodiment 1：
1) 0.1mol diethanol amine is dissolved in 10mL absolute methanol, then drips 0.1mol methyl acrylate, at 30 DEG C
Stirring reaction 4h, then vacuumizes removing methyl alcohol at 85 DEG C and excessive methyl acrylate obtains intermediate N, N- dihydroxy second
Base -2- aminopropanoate；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution of 0.08g/mL, at 155 DEG C
Return stirring reacts 10h, obtains product crude product；Wherein, the N being added, N- dihydroxy ethyl -2- aminopropanoate and hydroxide
The mol ratio of sodium is 1:1；
3) by product crude product pass through cation exchange column chromatography, then with distilled water constantly wash cation exchange column until
Till efflux is colourless, collects the efflux obtaining and be adjusted to pH value=7 with the hydrochloric acid of 0.1mol/L, finally take out true at 70 DEG C
Empty removing solvent, obtains carboxylic acid type aqueous polyurethane chain extender.
Embodiment 2：
1) 0.1mol diethanol amine is dissolved in 10mL absolute methanol, then drips 0.11mol methyl acrylate, at 35 DEG C
Stirring reaction 4h, then vacuumizes removing methyl alcohol at 80 DEG C and excessive methyl acrylate obtains intermediate N, N- dihydroxy second
Base -2- aminopropanoate；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution of 0.08g/mL, at 155 DEG C
Return stirring reacts 9h, obtains product crude product；Wherein, the N being added, N- dihydroxy ethyl -2- aminopropanoate and hydroxide
The mol ratio of sodium is 1:1.1；
3) by product crude product pass through cation exchange column chromatography, then with distilled water constantly wash cation exchange column until
Till efflux is colourless, collects the efflux obtaining and be adjusted to pH value=7 with the hydrochloric acid of 0.1mol/L, finally take out true at 75 DEG C
Empty removing solvent, obtains carboxylic acid type aqueous polyurethane chain extender.
Embodiment 3：
1) 0.1mol diethanol amine is dissolved in 10mL absolute methanol, then drips 0.12mol methyl acrylate, at 35 DEG C
Stirring reaction 5h, then vacuumizes removing methyl alcohol at 80 DEG C and excessive methyl acrylate obtains intermediate N, N- dihydroxy second
Base -2- aminopropanoate；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution of 0.08g/mL, at 160 DEG C
Return stirring reacts 8h, obtains product crude product；Wherein, the N being added, N- dihydroxy ethyl -2- aminopropanoate and hydroxide
The mol ratio of sodium is 1:1.2；
3) by product crude product pass through cation exchange column chromatography, then with distilled water constantly wash cation exchange column until
Till efflux is colourless, collects the efflux obtaining and be adjusted to pH value=7 with the hydrochloric acid of 0.1mol/L, finally take out true at 70 DEG C
Empty removing solvent, obtains carboxylic acid type aqueous polyurethane chain extender.
As seen from Figure 2, vinyl chloride and diethanol amine react and generate N- diethanol allylamine, and in Fig. 2 c
In, 3352.62cm-1The strong and wide absworption peak nearby occurring is the absworption peak of O-H stretching vibration, 2924.78-1、
2885.63cm-1It is nearby CH2Stretching vibration absworption peak, 1751.35cm-1For COOH stretching vibration, 1451.26cm-1For CH2
Deformation vibration, 1065.12cm-1、1045.34cm-1C-O stretching vibration for alcohol.These can tentatively infer that product is N, N- bis-
Ethoxy -2- alanine, i.e. the carboxylic acid type aqueous polyurethane chain extender of present invention synthesis.
From the figure 3, it may be seen that H chemical shift δ is on each group of carboxylic acid type aqueous polyurethane chain extender of present invention synthesis：—
N—C—CH2C=O, 2.20～2.33 (t, 2H)；—N—CH2C O, 2.50～2.53 (t, 4H)；—N—CH2—
C C=O, 2.50～2.61 (t, 2H)；—N—C—CH2O, 3.56～3.60 (m, 4H).This collection of illustrative plates meets target product
Chemical constitution.
The present invention will be anti-under conditions of methyl alcohol makees solvent to diethanol amine and methyl acrylate using Michael addition reaction
Intermediate should be obtained；Carry out hydrolysis of ester group reaction in the basic conditions again, obtain carboxylic acid type aqueous polyurethane chain extender.The present invention
Synthetic method is simple, with low cost, and pollution is little, has a wide range of applications in the field of synthesis aqueous polyurethane.
(2) application in polyurethane chain extension of the carboxylic acid type aqueous polyurethane chain extender that the present invention is obtained：
Appropriate polytetrahydrofuran diol (PTMG1000) and IPDI is added in four-hole boiling flask
(IPDI), the mol ratio of PTMG1000 and IPDI is 1.5:1～2:1, cool the temperature to 70 DEG C after 95 DEG C of reaction 2h, add suitable
After amount catalyst, after continuing reaction a period of time at 75 DEG C, obtain performed polymer.Acetone is added to make performed polymer cool to 60 DEG C about,
Add homemade N, N- dihydroxy ethyl -2- alanine carries out chain extension, and the consumption of N, N- dihydroxy ethyl -2- alanine is total matter
The 7%～9% of amount, quick stirring is lower to add deionized water emulsification, and vacuum distillation goes out acetone afterwards, then obtain carboxylic acid type aqueous poly-
Urethane dispersion.Experiment proves that prepared product can play the effect of chain extension.
Claims (5)
1. a kind of preparation method of carboxylic acid type aqueous polyurethane chain extender, the chemical name of this chain extender is N, N- dihydroxy ethyl-
2- alanine, its chemical structural formula is：
It is characterized in that, comprise the following steps：
1) diethanol amine is dissolved in absolute methanol, then drips methyl acrylate, in 30～35 DEG C of stirring reaction 4～5h, so
Vacuumize removing methyl alcohol afterwards and excessive methyl acrylate obtains intermediate N, N- dihydroxy ethyl -2- aminopropan at 80～85 DEG C
Sour methyl esters；Wherein, the diethanol amine being added and acrylic acid mol ratio are 1:(1～1.2)；
2) by N, N- dihydroxy ethyl -2- aminopropanoate is added in the NaOH aqueous solution, is stirred at reflux anti-at 155-160 DEG C
Answer 8-10h, obtain product crude product；Sodium ion in product crude product is removed using ion-exchange principle, then vacuumizes removing
The methyl alcohol that reaction generates, obtains final product carboxylic acid type aqueous polyurethane chain extender；Wherein, the N being added, N- dihydroxy ethyl -2- aminopropan
Sour methyl esters is 1 with the mol ratio of NaOH:(1～1.2).
2. the preparation method of carboxylic acid type aqueous polyurethane chain extender according to claim 1 is it is characterised in that described step
The diethanol amine of 1mol is added in the absolute methanol of every 100mL in rapid 1).
3. carboxylic acid type aqueous polyurethane chain extender according to claim 1 preparation method it is characterised in that：Described step
In rapid 2), the concentration of the NaOH aqueous solution is 0.08g/mL～0.10g/mL.
4. carboxylic acid type aqueous polyurethane chain extender according to claim 1 preparation method it is characterised in that：Described step
Adopted using the sodium ion that ion-exchange principle removes in product crude product in rapid 2) and carry out with the following method：
Product crude product is passed through cation exchange column chromatography, then constantly washs cation exchange column up to efflux with distilled water
Till colourless, collect the efflux obtaining pH value=7 being adjusted to efflux, at 70～75 DEG C, finally vacuumize removing molten
Agent, obtains carboxylic acid type aqueous polyurethane chain extender.
5. carboxylic acid type aqueous polyurethane chain extender according to claim 4 preparation method it is characterised in that：Described stream
The pH value going out liquid is to be adjusted using the hydrochloric acid of 0.1mol/L.
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| CN107141440B (en) * | 2017-06-16 | 2020-07-28 | 北京化工大学 | Rigid ring modified organosilicon polyurethane acrylate water-based oligomer and preparation method thereof |
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| CN101497698A (en) * | 2009-01-22 | 2009-08-05 | 南京大学 | Preparation of chitosan-polyurethane ion complex elastomer material |
| CN101514275A (en) * | 2009-03-20 | 2009-08-26 | 四川大学 | Light/heat curable waterborne polyurethane coating agent with branch type molecular structure and preparation method thereof |
| CN102585154A (en) * | 2012-03-13 | 2012-07-18 | 上海材料研究所 | Method for preparing waterborne polyurethane |
| CN102604023A (en) * | 2012-02-27 | 2012-07-25 | 陕西科技大学 | Sulfoacid/carboxylic acid type hydrophilic chain extender and preparation method thereof |
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN103436155A (en) * | 2013-09-09 | 2013-12-11 | 段宝荣 | Preparation method of light-resistant water-based polyurethane coating |
-
2014
- 2014-09-28 CN CN201410508873.3A patent/CN104356330B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497698A (en) * | 2009-01-22 | 2009-08-05 | 南京大学 | Preparation of chitosan-polyurethane ion complex elastomer material |
| CN101514275A (en) * | 2009-03-20 | 2009-08-26 | 四川大学 | Light/heat curable waterborne polyurethane coating agent with branch type molecular structure and preparation method thereof |
| CN102604023A (en) * | 2012-02-27 | 2012-07-25 | 陕西科技大学 | Sulfoacid/carboxylic acid type hydrophilic chain extender and preparation method thereof |
| CN102585154A (en) * | 2012-03-13 | 2012-07-18 | 上海材料研究所 | Method for preparing waterborne polyurethane |
| CN102775578A (en) * | 2012-08-15 | 2012-11-14 | 中国海洋石油总公司 | Cation-nonionic mixed aqueous polyurethane emulsion and preparation method thereof |
| CN103436155A (en) * | 2013-09-09 | 2013-12-11 | 段宝荣 | Preparation method of light-resistant water-based polyurethane coating |
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