CN101735163A - Hyperbranched compound used as water repellent and synthetic method thereof - Google Patents
Hyperbranched compound used as water repellent and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched compound used as a water repellent and a synthetic method thereof. The hyperbranched compound has a tripolycyanamide nucleus as shown in the figure, wherein, R1 is an alkane group with 1-16 carbon atoms, and R2 is an alkane group with 12-16 carbon atoms; N is 2 or 3; and A is as specified in a specification. The hyperbranched compound is synthesized from cyanuric chloride through two or three steps. The hyperbranched compound has favorable water-repellent effect, and can be used as a fabric waterproof finishing agent. Since no formaldehyde exists in a synthetic reaction process and products, the hyperbranched compound has great advantages in environmental protection.
Description
Technical field
The present invention relates to a kind of hyperbranched compound and synthetic method thereof as water-resisting agent, relate in particular to a kind of hyperbranched compound and synthetic method thereof with trimeric cyanamide nuclear, this hyperbranched compound can be used as the waterproofing that water-resisting agent is applied to fabric.
Background technology
At present, both at home and abroad fabric waterproofing agent mainly contains silicone based, organic fluorine class, senior aliphatic hydrocarbon modified aminoresin class etc.With respect to silicone based and organic fluorine class, senior aliphatic hydrocarbon modified aminoresin class has excellent washing fastness and lower price, and therefore bigger advantage is arranged.This type of water-resisting agent is applied to textile industry already, as the Phobotex FTC series of Switzerland Ciba-Geigy company.Domesticly also get many achievements aspect such water-resisting agent development, just developing NB-501, SGF, DFT type water-resisting agent in the nineties in last century.They are to carry out two kinds of components of modification synthetic by hexamethylolmelamine ethyl etherate and stearic acid, stearyl alcohol and trolamine etc. with the differing molecular ratio, piece together mixed forming with paraffin and emulsifying agent, its water resistance has reached the level of Phobotex FTC, part index number even higher.Wherein, the industrialization of DFT type water-resisting agent is applied to wash, the WATER REPELLENT of fabric such as cotton.But owing to there is formaldehyde to produce in the building-up process of these series product, the meeting removing residue formaldehyde is unfavorable to HUMAN HEALTH in the fabric after the arrangement.Along with the continuous reinforcement of people's environmental consciousness, its market outlook are not expected.
Therefore, prior art awaits improving and development.
Summary of the invention
Problem to be solved by this invention is to provide a kind of hyperbranched compound and synthetic method thereof as water-resisting agent, to solve the formaldehyde residue problem of existing fabric waterproofing agent.
In order to solve the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of hyperbranched compound as water-resisting agent, it has following structure:
Wherein, R
1Alkyl, R for carbonatoms 1-16
2Alkyl for carbonatoms 12-16;
N=2 or 3, when n=2, A is for being selected from-NH (CH
2CH
2)
mHN-or
In a kind of, m=1-3 wherein,
When n=3, A is
Described hyperbranched compound is characterized in that, described R
1=CH
3, C
2H
5, C
12H
25, C
14H
29Or C
16H
33Described R
2=C
12H
25, C
14H
29Or C
16H
33
Described hyperbranched compound is characterized in that, described R
1And R
2Be the straight-chain paraffin base.
A kind of synthetic method that is used as the hyperbranched compound of water-resisting agent, it may further comprise the steps:
A1: 1 part of cyanuric chloride, 2 parts of secondary amine and salt of wormwood are mixed in polar aprotic solvent, and after reacting 1-4 hour respectively under-20 ℃～0 ℃, 0 ℃～40 ℃, refluxing makes its sufficient reacting successively;
B1: in reaction solution, add 1/2 part of quadrol or 1 again, 4-butanediamine or 1, any in 6-hexanediamine or the piperazine 90-100 ℃ of fully reaction, removes and desolvates, and is washed to neutrality, filters;
Wherein, described umber is mol ratio;
At least the alkyl that connects a carbonatoms 12-16 on the amido of described secondary amine.
The described synthetic method that comprises step a1, b1, wherein, the temperature of reacting successively described in the described step a1 is respectively 0 ℃, 25 ℃.
The described synthetic method that comprises step a1, b1, wherein, described polar aprotic solvent is an acetonitrile.
A kind of synthetic method that is used as the hyperbranched compound of water-resisting agent may further comprise the steps:
A2: 1 part of cyanuric chloride, 2 parts of secondary amine and salt of wormwood are mixed in polar aprotic solvent, successively-20 ℃～0 ℃, 0 ℃～40 ℃ react 1-4 hour respectively after, refluxing makes its sufficient reacting; B2: in reaction solution, add excessive quadrol again, and, remove and desolvate and excessive quadrol 90-100 ℃ of fully reaction; C2: in remaining solid, add 1/3 part of cyanuric chloride, salt of wormwood and polar aprotic solvent, successively-20 ℃～0 ℃, 0 ℃～40 ℃ react 1-4 hour respectively after, be back to raw material and disappear, remove and desolvate, be washed to neutral and filter; Wherein, described umber is mol ratio; At least the alkyl that connects a carbonatoms 12-16 on the amido of described secondary amine.
The described synthetic method that comprises step a2-c2, wherein, the temperature of reacting successively described in described step a2 and the c2 is respectively 0 ℃, 25 ℃.
The described synthetic method that comprises step a2-c2, wherein, described polar aprotic solvent is an acetonitrile.
Adopt such scheme, the present invention is by simple synthetic a kind of hyperbranched compound that can be used as water-resisting agent that prepared.Because the synthetic method of this hyperbranched compound does not all have formaldehyde in its reaction raw materials, solvent, centre and the final product, therefore, when this hyperbranched compound is used for the fabric waterproof arrangement, compare with existing common water-resisting agent, have the huge advantage in the environmental protection.
Description of drawings
Fig. 1 is the proton nmr spectra of the embodiment of the invention 1 synthetic compound;
Fig. 2 is the carbon-13 nmr spectra of the embodiment of the invention 1 synthetic compound;
Fig. 3 is the proton nmr spectra of the embodiment of the invention 2 synthetic compounds;
Fig. 4 is the carbon-13 nmr spectra of the embodiment of the invention 2 synthetic compounds;
Fig. 5 is the proton nmr spectra of the embodiment of the invention 3 synthetic compounds;
Fig. 6 is the carbon-13 nmr spectra of the embodiment of the invention 3 synthetic compounds;
Fig. 7 is the proton nmr spectra of the embodiment of the invention 4 synthetic compounds;
Fig. 8 is the carbon-13 nmr spectra of the embodiment of the invention 4 synthetic compounds
Embodiment
Below by embodiment, hyperbranched compound and the synthetic method thereof as water-resisting agent of the present invention is described in further detail.
Hyperbranched compound of the present invention has 2-4 trimeric cyanamide nuclear, and structure is as follows:
Wherein, R
1Alkyl, R for carbonatoms 1-16
2Alkyl for carbonatoms 12-16; Described alkyl can be a straight chain, also can have side chain, preferred straight-chain paraffin; Preferred R
1Be CH
3, C
2H
5, C
12H
25, C
14H
29, C
16H
33R
2Be C
12H
25, C
14H
29, C
16H
33
Because this compound has the alkane chain of at least 4 carbonatoms 12-16, therefore have excellent hydrophobic property, can be used as water-resisting agent, as fabric waterproofing agent, waterproofing agent for leather, waterproof agent for building etc.In the present invention preferably with it as fabric waterproofing agent.
Synthetic above-mentioned hyperbranched compound, solvent is a polar aprotic solvent, for example acetonitrile, acetone, methyl-sulphoxide etc. preferably use acetonitrile.
When synthesizing this hyperbranched compound, at first, cyanuric chloride and secondary amine are mixed in polar aprotic solvent with salt of wormwood with 1: 2 mol ratio, at first-20 ℃～0 ℃ (preferred 0 ℃) reaction 1-4 hour, then 0 ℃～40 ℃ (preferred room temperatures, promptly about 25 ℃) reacted 1-4 hour, fully reflux.This step is step a.In step a, amido has replaced 2 chlorine on the cyanuric chloride.
Wherein, connect the alkyl of a carbonatoms 12-16 on the amido of described secondary amine at least, preferred described alkyl is the straight-chain paraffin base.Described secondary amine can be R
1NHR
2Return time can be 2 days.
After step a, if directly control ratio, as 1/2 mol ratio with former cyanuric chloride, add 1 or 1,4-butanediamine or 1,6-hexanediamine or piperazine are again in 90 ℃-100 ℃ fully reactions (for example 3 days).Remove by ways such as decompressions afterwards and desolvate, residue is washed to neutrality (pH=7) and filters, the compound in the time of can obtaining n=2 of the present invention.Referring to formula (I).
Formula (I)
Wherein, R
1And R
2As previously mentioned,
A1 is for being selected from-NH (CH
2CH
2)
mHN-or
In a kind of, m=1-3 wherein.
If after step a, add excessive quadrol, and fully react (for example 1 day) at 90-100 ℃, remove by methods such as decompressions and desolvate and excessive quadrol; Afterwards, add again a certain amount of cyanuric chloride (as former cyanuric chloride 1/3), salt of wormwood and polar aprotic solvent, at first-20 ℃～0 ℃ (preferred 0 ℃) reaction 1-4 hour, then 0 ℃-40 ℃ (preferred room temperatures, promptly about 25 ℃) reacted 1-4 hour down, be back to raw material and disappear, remove and desolvate, be washed to neutral and filter, the compound in the time of then can obtaining n=3 of the present invention.Referring to formula (II).
Formula (II)
Wherein, R
1And R
2As previously mentioned,
A2 is
According to above-mentioned synthetic method, obtain white solid product at last.In order further to understand the character of institute's synthetic compound, measure its fusing point by melting point detector, and utilize thin layer chromatography in ethyl acetate and sherwood oil blended developping agent, to measure its polarity, determine the ratio of developping agent with this, thus purified product.For the structural formula of definite product, the proton nmr spectra of measurement purified product (
1H NMR, measuring condition are CDCl
3, 400MHz, 25 ℃) and the carbon spectrum (
13C NMR, measuring condition are CDCl
3, 125MHz, 25 ℃), can confirm to have synthesized compound thus with structure of the present invention.
Make water-resisting agent in order to verify that whether this compound is suitable for, this compound is carried out composite, reference standard AATCC22-2001: its water repellency is tested in spray test (Spray Test).Test result shows that compound of the present invention has good water repellency, can be used as the textile finishing water-resisting agent.
Below, be example during with embodiment 1,2 respectively to n=2, the situation of m=1 and m=3 is described; With embodiment 3 is example during to n=2,
Situation be described; Being example with embodiment 4 is described the situation of n=3; Among the described embodiment, R
1And R
2Be C
16H
33(palmityl/hexadecyl).
Embodiment 1
N, N '-two-(four-(hexadecyl)-melamine-based)-quadrol and synthetic method thereof
Step a1-1: 18.4g cyanuric chloride, 93.1g hexadecyl secondary amine and 41.4g salt of wormwood are added in the flask, add the 500ml acetonitrile again, stirring reaction 1 hour under 0 ℃, room temperature respectively successively, refluxed 2 days in the back;
Step b1-1: add the 3.0g anhydrous ethylenediamine in flask, mixed solution is heated to about 100 ℃ reacted 3 days, the solvent of reaction solution is removed in decompression, is washed to neutrality, filters;
Dry afterwards, obtain white solid 91.1g.Productive rate is 88%.
Measure the character of this compound.Its fusing point (mp) is 38～40 ℃.Measure its polarity, in the developping agent of ethyl acetate/petroleum ether=1: 50, climb plate, obtain the value of relatively moving R
f=0.3, thus product is separated purification.
The proton nmr spectra of measurement purified product (
1H NMR, CDCl
3, 400MHz, 25 ℃), obtain spectrogram as shown in Figure 1.Wherein, δ (ppm): 5.11 (br s, 2H), 3.43 (br s, 20H), 1.57 (brs, 16H), 1.27 (br s, 208H), 0.88 (t, 24H, J=6.8Hz).The carbon-13 nmr spectra of measurement product (
13C NMR, CDCl
3, 125MHz, 25 ℃), obtain spectrogram as shown in Figure 2.Wherein, δ (ppm): 166.38,164.90,47.16,41.30,32.65,31.91,29.72,29.66,29.36,28.88,28.23,26.88,22.66,14.06.By analyzing carbon spectrum and hydrogen spectrum, can confirm that product has aforesaid structural formula, promptly successfully synthesize N, N '-two-(four-(hexadecyl)-melamine-based)-quadrol.
In following examples, if no special instructions, the measuring condition of proton nmr spectra/carbon spectrum is identical with present embodiment.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that present embodiment is obtained, reference standard AATCC22-2001: its water repellency is tested in spray test (Spray Test) if carrying out composite.Detected result reaches 100 fens.
Embodiment 2
N, N '-two-(four-(hexadecyl)-melamine-based)-1,6-hexanediamine and synthetic method thereof
Step a1-2: 18.4g cyanuric chloride, 93.1g hexadecyl secondary amine and 41.4g salt of wormwood are added in the flask, add the 500ml acetonitrile again, stirring reaction 4 hours under 0 ℃, room temperature successively, refluxed 2 days in the back;
Step b1-2: add 1 of 5.8g in flask, the 6-hexanediamine was heated to about 100 ℃ reaction 3 days with mixed solution, and the solvent of reaction solution is removed in decompression, is washed to neutrality, filters;
Dry afterwards, obtain white solid 85.2g.Productive rate is 82%.
Measure the character of this compound.Measure its fusing point (mp), be 41-43 ℃.Measure the polarity of product, in the developping agent of ethyl acetate/petroleum ether=1: 50, climb plate, plate than upper/lower positions and hangover, the value of relatively moving R
f=0.3; Ethyl acetate/petroleum ether=1: 20, add 1% volume ratio ammoniacal liquor (NH simultaneously
3H
2O) climb plate in the developping agent, measure the value of relatively moving R
f=0.5, thus product is separated purification.
The proton nmr spectra of measurement product (
1H NMR), obtain as shown in Figure 3 spectrogram.Wherein, δ (ppm): 4.61 (t, 2H, J=5.6Hz), 3.43 (br s, 16H), 3.30 (q, 4H, J=6.4Hz), 1.74 (m, 4H), 1.56 (br s, 20H), 1.27 (br s, 208H), 0.88 (t, 24H, J=6.6Hz).The carbon-13 nmr spectra of measurement product (
13C NMR), obtain as shown in Figure 4 spectrogram.Wherein, δ (ppm): 166.25,164.98,47.12,40.75,38.74,31.94,30.18,29.74,29.69,29.38,28.28,27.38,27.17,22.70,14.11.By analyzing carbon spectrum and hydrogen spectrum, can confirm that product has aforesaid structural formula, promptly successfully synthesize N, N '-two-(four-(hexadecyl)-melamine-based)-1, the 6-hexanediamine.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that present embodiment is obtained, reference standard AATCC22-2001: its water repellency is tested in spray test (Spray Test) if carrying out composite.Detected result reaches 100 fens.
Embodiment 3
N, N '-two-(four-(hexadecyl)-melamine-based)-piperazine and synthetic method thereof
Step a1-3: 18.4g cyanuric chloride, 93.1g hexadecyl secondary amine and 41.4g salt of wormwood are added in the flask, add the 500ml acetonitrile again, stirring reaction 3 hours under 0 ℃, room temperature successively, refluxed 2 days in the back;
Step b1-3: add the Piperazine anhydrous of 4.3g in flask, mixed solution is heated to about 100 ℃ reacted 3 days, the solvent of reaction solution is removed in decompression, is washed to neutrality, filters;
Dry afterwards, obtain white waxy solid 84.0g.Productive rate is 80%.
Measure the character of this compound.Measuring its fusing point (mp), is 52～54 ℃.Measure its polarity, in the developping agent of ethyl acetate/petroleum ether=1: 50, climb plate, need expansion cylinder is uncovered, and repeat to climb plate 2-3 time, measure the value of relatively moving R
f=0.3, thus product is separated purification.
The proton nmr spectra of measurement purified product (
1H NMR), obtain as shown in Figure 5 spectrogram.Wherein, δ (ppm): 3.78 (s, 8H), 3.48 (br s, 16H), 1.59 (br s, 16H), 1.29 (br s, 208H), 0.89 (t, 24H, J=6.8Hz).The carbon-13 nmr spectra of measurement product (
13C NMR), obtain as shown in Figure 6 spectrogram.Wherein, δ (ppm): 165.44,165.10,47.26,43.12,31.97,29.87,29.77,29.62,29.41,28.34,28.21,27.44,27.21,22.72,14.12.By analyzing carbon spectrum and hydrogen spectrum, can confirm that product has aforesaid structural formula, promptly successfully synthesize N, N '-two-(four-(hexadecyl)-melamine-based)-piperazine.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that present embodiment is obtained, reference standard AATCC22-2001: its water repellency is tested in spray test (Spray Test) if carrying out composite.Detected result reaches 100 fens.
Embodiment 4
N, N ', N "-three-(four-(hexadecyl)-melamine-based ethyl)-trimeric cyanamide and synthetic method thereof
Step a2-1: 18.4g cyanuric chloride, 93.1g hexadecyl secondary amine and 41.4g salt of wormwood are added in the flask, add the 500ml acetonitrile again, under 0 ℃, room temperature stirring reaction 1-4 hour successively, refluxed 2 days in the back;
Step b2-1: add the 30.0g anhydrous ethylenediamine in flask, mixed solution is heated to 90-100 ℃ of reaction 1 day, the solvent of reaction solution and excessive quadrol are removed in decompression;
Step c2-1: in remaining solid, add 6.2g cyanuric chloride, 13.8g salt of wormwood and 500ml acetonitrile, under 0 ℃, room temperature stirring reaction 1-4 hour successively, after be back to raw material and disappear, the reaction solution solvent is removed in decompression, is washed to neutral and filters;
Dry afterwards, obtain white powder 87.2g.Productive rate is 82%.
Measure the character of this compound.Measuring its fusing point (mp), is 38～40 ℃.Measure the polarity of product, ethyl acetate/petroleum ether=1: 15, add 1% volume ratio ammoniacal liquor (NH simultaneously
3H
2O) climb plate in the developping agent, measure the value of relatively moving R
f=0.3, thus product is separated purification.
The proton nmr spectra of measurement product (
1H NMR), obtain as shown in Figure 7 spectrogram.Wherein, δ (ppm): 5.06 (m, 6H), 3.53 (br s, 12H), 3.44 (br s, 24H), 1.57 (br s, 24H), 1.27 (br s, 312H), 0.88 (t, 36H, J=7.6Hz).The carbon-13 nmr spectra of measurement product (
13CNMR), obtain as shown in Figure 8 spectrogram.Wherein, δ (ppm): 164.84,47.28,31.94,29.87,29.75,29.69,29.38,28.30,27.43,27.21,22.69,14.09.By analyzing carbon spectrum and hydrogen spectrum, can confirm that product has aforesaid structural formula, promptly successfully synthesize N, N ', N "-three-(four-(hexadecyl)-melamine-based ethyl)-trimeric cyanamide.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that present embodiment is obtained, reference standard AATCC22-2001: its water repellency is tested in spray test (Spray Test) if carrying out composite.Detected result reaches 100 fens.
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (9)
1. hyperbranched compound as water-resisting agent is characterized in that having following structure:
Wherein, R
1Alkyl, R for carbonatoms 1-16
2Alkyl for carbonatoms 12-16;
N=2 or 3, when n=2, A is for being selected from-NH (CH
2CH
2)
mHN-or
In a kind of, m=1-3 wherein,
When n=3, A is
2. hyperbranched compound according to claim 1 is characterized in that, described R
1=CH
3, C
2H
5, C
12H
25, C
14H
29Or C
16H
33Described R
2=C
12H
25, C
14H
29Or C
16H
33
3. hyperbranched compound according to claim 1 and 2 is characterized in that, described R
1And R
2Be the straight-chain paraffin base.
4. synthetic method as the hyperbranched compound of water-resisting agent, it may further comprise the steps:
A1: 1 part of cyanuric chloride, 2 parts of secondary amine and salt of wormwood are mixed in polar aprotic solvent, and after reacting 1-4 hour respectively under-20 ℃～0 ℃, 0 ℃～40 ℃, refluxing makes its sufficient reacting successively;
B1: in reaction solution, add 1/2 part of quadrol or 1 again, 4-butanediamine or 1, any in 6-hexanediamine or the piperazine 90-100 ℃ of fully reaction, removes and desolvates, and is washed to neutrality, filters;
Wherein, described umber is mol ratio;
At least the alkyl that connects a carbonatoms 12-16 on the amido of described secondary amine.
5. synthetic method according to claim 4, wherein, the temperature of reacting successively described in the described step a1 is respectively 0 ℃, 25 ℃.
6. according to claim 4 or 5 described synthetic methods, wherein, described polar aprotic solvent is an acetonitrile.
7. synthetic method as the hyperbranched compound of water-resisting agent may further comprise the steps:
A2: 1 part of cyanuric chloride, 2 parts of secondary amine and salt of wormwood are mixed in polar aprotic solvent, successively-20 ℃～0 ℃, 0 ℃～40 ℃ react 1-4 hour respectively after, refluxing makes its sufficient reacting;
B2: in reaction solution, add excessive quadrol again, and, remove and desolvate and excessive quadrol 90-100 ℃ of fully reaction;
C2: in remaining solid, add 1/3 part of cyanuric chloride, salt of wormwood and polar aprotic solvent, successively-20 ℃～0 ℃, 0 ℃～40 ℃ react 1-4 hour respectively after, be back to raw material and disappear, remove and desolvate, be washed to neutral and filter;
Wherein, described umber is mol ratio;
At least the alkyl that connects a carbonatoms 12-16 on the amido of described secondary amine.
8. synthetic method according to claim 7, wherein, the temperature of reacting successively described in described step a2 and the c2 is respectively 0 ℃, 25 ℃.
9. according to claim 7 or 8 described synthetic methods, wherein, described polar aprotic solvent is an acetonitrile.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941716A (en) * | 2012-11-20 | 2013-02-27 | 吴江市新丝源纺织有限公司 | Water-proof wear-resistant coating fabric |
| CN102941721A (en) * | 2012-11-20 | 2013-02-27 | 吴江市新丝源纺织有限公司 | Waterproof antibiosis fabric |
| CN102965925A (en) * | 2012-11-20 | 2013-03-13 | 吴江市新丝源纺织有限公司 | Waterproof coating fabric |
| US10405543B2 (en) * | 2016-10-31 | 2019-09-10 | Rohm And Haas Company | Microcapsule compositions and the method of their release |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3374235A (en) * | 1963-12-31 | 1968-03-19 | Geigy Chem Corp | S-triazines |
-
2009
- 2009-12-03 CN CN200910188561A patent/CN101735163B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941716A (en) * | 2012-11-20 | 2013-02-27 | 吴江市新丝源纺织有限公司 | Water-proof wear-resistant coating fabric |
| CN102941721A (en) * | 2012-11-20 | 2013-02-27 | 吴江市新丝源纺织有限公司 | Waterproof antibiosis fabric |
| CN102965925A (en) * | 2012-11-20 | 2013-03-13 | 吴江市新丝源纺织有限公司 | Waterproof coating fabric |
| US10405543B2 (en) * | 2016-10-31 | 2019-09-10 | Rohm And Haas Company | Microcapsule compositions and the method of their release |
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