CN103992485A - Hyperbranched compound waterproofing agent and preparation method thereof - Google Patents
Hyperbranched compound waterproofing agent and preparation method thereof Download PDFInfo
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- CN103992485A CN103992485A CN201410206364.5A CN201410206364A CN103992485A CN 103992485 A CN103992485 A CN 103992485A CN 201410206364 A CN201410206364 A CN 201410206364A CN 103992485 A CN103992485 A CN 103992485A
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Abstract
The invention relates to a hyperbranched compound waterproofing agent and a preparation method thereof. The hyperbranched compound is shown in the specification, wherein A is shown in the specification and so forth; R1 is an alkyl with 1-16 carbon atoms and R2 is an alkyl with 8-16 carbon atoms. The preparation method comprises the steps of dissolving a polyamidoamine dendrimer in anhydrous methanol, then dropping 1, 2-epichlorohydrin, replenishing anhydrous methanol, reacting for 3-6h at the temperature of 40-50 DEG C and performing reduced pressure distillation, separation and purification; enabling the polyamidoamine dendrimer of a halogenated grafted epoxy compound, two parts of secondary amine and potassium carbonate in a polar aprotic solvent to respectively react for 1-4h under the conditions of -20-0 DEG C and 0-40 DEG C, refluxing, performing reduced pressure distillation after the end of reaction, separating and purifying so as to obtain the hyperbranched compound waterproofing agent. When the hyperbranched compound is used for waterproof finishing of fabric, compared with an ordinary waterproofing agent containing formaldehyde, the hyperbranched compound waterproofing agent has relatively great environment-friendly advantage.
Description
Technical field
The invention belongs to water-resisting agent and preparation field thereof, particularly a kind of hyperbranched compound water-resisting agent and preparation method thereof.
Background technology
Dendrimer is the Novel polymer of a class three-dimensional, high-sequential. daiamid (PAMAM) dendrimer has highly branched structure, and its molecular structure comprises three parts: i.e. the endosome of active centre, multiple repeating unit composition and have the outer surface layer that enriches functional group.
Because the structure of PAMAM dendrimer is not only the geometrical symmetry of height, and outer surface layer has a large amount of functional groups, therefore can carry out modification to it.PAMAM dendrimer is widely used in the technical fields such as tensio-active agent, support of the catalyst, nano composite material at present.
The superficies of polyamide-amine dendrimer are reaching after certain point of subalgebra and will have a large amount of surperficial terminal functionality; these abundant surperficial terminal functionality not only can provide protection to the internal space of dendrimer, and can play Molecular Recognization to the external reactants of dendrimer and solvent.Can on molecular level, design to control its molecular size, shape, structure and function group, meet different objects and requirement, thereby there is wide potential Application Areas.
Long chain alkane has lower surface can, be grafted on dendrimer with long chain alkane, can improve the hydrophobic performance of dendrimer, the height symmetrical structure of dendrimer can make long chain alkane keep certain configuration simultaneously, be conducive to the permanent maintenance of hydrophobic structure, can be for the waterproofing of fabric.
The tree-shaped macromolecular preparation of part at present will be used formaldehyde, and environment is caused to certain harm, while arranging on fabric, can be unfavorable to HUMAN HEALTH, and along with the enhancing of people's environmental consciousness, will more and more not be accepted containing the preparation method of the hazardous solvents such as formaldehyde.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hyperbranched compound water-resisting agent and preparation method thereof, its reaction raw materials, solvent, centre and final product all do not have formaldehyde, therefore, when this hyperbranched compound is arranged for fabric waterproof, with compare with the common water-resisting agent that has formaldehyde, refuse the larger environment-friendly advantage of oil.
A kind of hyperbranched compound water-resisting agent of the present invention, is characterized in that: the molecular formula of described water-resisting agent is:
wherein A is
the like, be one wherein; R
1for carbonatoms be 1-16 alkyl, R
2for the carbonatoms alkyl that is 8-16.
The preparation method of a kind of hyperbranched compound water-resisting agent of the present invention, comprising:
(1) quadrol is dissolved in anhydrous methanol, then drips methyl acrylate, then at ambient temperature, stirring reaction 12-24h, underpressure distillation, obtains 0.5 generation polyamide-amine dendrimer PAMAM G0.5; Wherein the mol ratio of quadrol, anhydrous methanol, methyl acrylate is 1.5:10:12;
(2) PAMAM G0.5 is dissolved in anhydrous methanol, then drips quadrol, at room temperature magnetic agitation reaction 24-48h, underpressure distillation, obtain 1.0 generation polyamide-amine dendrimer; Repeating step (1), (2) obtain the polyamide-amine dendrimer of different algebraically; Wherein the mol ratio of PAMAM G0.5, anhydrous methanol, quadrol is 0.5:0.02:12;
(3) polyamide-amine dendrimer of step (2) is dissolved in anhydrous methanol, then drip 1,2-epoxy chloropropane, add again anhydrous methanol, obtain daiamid-1,2-epoxy chloropropane dendrimer solution, at 40-50 DEG C of reaction 3-6h, underpressure distillation, separating-purifying, obtains the polyamide-amine dendrimer of grafting epoxy compounds; Wherein polyamide-amine dendrimer, anhydrous methanol summation, 1, the proportionlity of 2-epoxy chloropropane is 0.5mmol:50-100g:4-16mmol;
(4) by the polyamide-amine dendrimer of above-mentioned halo grafting epoxy compounds, secondary amine and salt of wormwood are in polar aprotic solvent, successively under-20～0 DEG C, 0～40 DEG C condition, react respectively after 1-4 hour, reflux, underpressure distillation after completion of the reaction, separating-purifying, obtains hyperbranched compound water-resisting agent; Wherein the mol ratio of the polyamide-amine dendrimer of grafting epoxy compounds, secondary amine is 1:2.
In described step (2), reaction is to react under 40 DEG C of constant temperature water bath conditions.
Separating-purifying is for being dissolved in distilled water centrifugation 3-5 time in described step (2).
One in the polyamide-amine dendrimer that in described step (3), polyamide-amine dendrimer is different algebraically.
The mass ratio of the anhydrous methanol that in described step (3), polyamide-amine dendrimer is dissolved in, the anhydrous methanol of adding is 1:1-2:1.
Daiamid-1 in described step (3), the mass concentration of 2-epoxy chloropropane dendrimer solution is 5%.
In described step (4), the mol ratio of secondary amine and salt of wormwood is 1:1.
Described step (4) Semi-polarity aprotic solvent is one or more in acetonitrile, acetone, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, chloroform, preferably acetonitrile.
Separating-purifying is for being dissolved in distilled water centrifugation 3-5 time in described step (4).
The present invention is core centered by quadrol, and methyl acrylate is branched monomer, grafting epoxy chloropropane, and taking straight-chain paraffin base secondary amine as terminal functionality, a kind of daiamid-straight-chain paraffin dendrimer has been synthesized in design.
The synthetic equation of polyamide-amine dendrimer:
1 generation polyamide-amine dendrimer modification equation:
Wherein A is
R1 is that carbonatoms is the alkyl of 1-16, and R2 is that carbonatoms is the alkyl of 8-16.
beneficial effect
The present invention is by a series of synthetic a kind of hyperbranched compounds that can be used as water-resisting agent of having prepared, in building-up process due to this hyperbranched compound, its reaction raw materials, solvent, centre and final product all do not have formaldehyde, therefore, when this hyperbranched compound is arranged for fabric waterproof, with compare with the common water-resisting agent that has formaldehyde, there is larger environment-friendly advantage.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Synthesizing of polyamide-amine dendrimer:
First 150mmol quadrol is dissolved in 1000mmol anhydrous methanol, slowly drip wherein 1200mmol methyl acrylate, at room temperature magnetic agitation reaction 24h, methyl alcohol and excessive methyl acrylate are removed in underpressure distillation, obtaining 0.5 generation polyamide-amine dendrimer (being denoted as PAMAM G0.5). second step is first 50mmolPAMAM G0.5 to be dissolved in 2.0mol anhydrous methanol, slowly drip wherein again 1200mmol quadrol, at room temperature magnetic agitation reaction 48h, methyl alcohol and excessive quadrol are removed in underpressure distillation, obtain 1.0 generation polyamide-amine dendrimers (being denoted as PAMAM G1.0).
Polyamide-amine dendrimer grafting epoxy compounds:
By about 0.5mmol 1.0 generation polyamide-amine dendrimer be dissolved in 40g anhydrous methanol, drip wherein 1 of about 4mmol, 2-epoxy chloropropane, then add the anhydrous methanol of 20g, make 1.0 generation daiamid-1, the mass concentration of 2-epoxy chloropropane dendrimer is approximately 5% left and right.At 40 DEG C of constant temperature water baths reaction 4h, anhydrous methanol is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Polyamide-amine dendrimer is function modified:
By 0.5mmol polyamide-amine dendrimer, 1mmol secondary amine and salt of wormwood in polar aprotic solvent (acetonitrile), at 0 DEG C, 20 DEG C, react respectively successively after 2 hours, backflow makes its sufficient reacting, react complete, polar aprotic solvent is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Product is after washing, filtration, being dried, and productive rate is 88%.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that the present embodiment is obtained carries out composite, reference standard AATCC22-2001: its water repellency is tested in spray experiment (Spray Test).Detected result is 100 points.
Wherein A is
Embodiment 2
Synthesizing of polyamide-amine dendrimer:
First 150mmol quadrol is dissolved in 1000mmol anhydrous methanol, slowly drip wherein 1200mmol methyl acrylate, at room temperature magnetic agitation reaction 24h, methyl alcohol and excessive methyl acrylate are removed in underpressure distillation, obtaining 0.5 generation polyamide-amine dendrimer (being denoted as PAMAM G0.5). second step is first 50mmolPAMAM G0.5 to be dissolved in 2.0mol anhydrous methanol, slowly drip wherein again 1200mmol quadrol, at room temperature magnetic agitation reaction 48h, methyl alcohol and excessive quadrol are removed in underpressure distillation, obtain 1.0 generation polyamide-amine dendrimers (being denoted as PAMAM G1.0). under felicity condition, repeat the polyamide-amine dendrimer that above two steps obtain 2.0 algebraically.
Polyamide-amine dendrimer grafting epoxy compounds:
By about 0.5mmol 2.0 generation polyamide-amine dendrimer be dissolved in 50g anhydrous methanol, drip wherein 1 of about 8mmol, 2-epoxy chloropropane, then add the anhydrous methanol of 25g, make 2.0 generation daiamid-1, the mass concentration of 2-epoxy chloropropane dendrimer is approximately 5% left and right.At 40 DEG C of constant temperature water baths reaction 4h, anhydrous methanol is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Polyamide-amine dendrimer is function modified:
By 0.5mmol polyamide-amine dendrimer, 1mmol secondary amine and salt of wormwood in polar aprotic solvent (acetonitrile), at-10 DEG C, 20 DEG C, react respectively successively after 2 hours, backflow makes its sufficient reacting, react complete, polar aprotic solvent is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Product is after washing, filtration, being dried, and productive rate is 84%.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that the present embodiment is obtained carries out composite, reference standard AATCC22-2001: its water repellency is tested in spray experiment (Spray Test).Detected result is 100 points.
Embodiment 3
Synthesizing of polyamide-amine dendrimer:
First 150mmol quadrol is dissolved in 1000mmol anhydrous methanol, slowly drip wherein 1200mmol methyl acrylate, at room temperature magnetic agitation reaction 24h, methyl alcohol and excessive methyl acrylate are removed in underpressure distillation, obtaining 0.5 generation polyamide-amine dendrimer (being denoted as PAMAM G0.5). second step is first 50mmolPAMAM G0.5 to be dissolved in 2.0mol anhydrous methanol, slowly drip wherein again 1200mmol quadrol, at room temperature magnetic agitation reaction 48h, methyl alcohol and excessive quadrol are removed in underpressure distillation, obtain 1.0 generation polyamide-amine dendrimers (being denoted as PAMAM G1.0). under felicity condition, repeat the polyamide-amine dendrimer that twice above two step obtain 3.0 algebraically.
Polyamide-amine dendrimer grafting epoxy compounds:
By about 0.5mmol 3.0 generation polyamide-amine dendrimer be dissolved in 55g anhydrous methanol, drip wherein 1 of about 12mmol, 2-epoxy chloropropane, then add the anhydrous methanol of 30g, make 3.0 generation daiamid-1, the mass concentration of 2-epoxy chloropropane dendrimer is approximately 5% left and right.At 40 DEG C of constant temperature water baths reaction 4h, anhydrous methanol is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Polyamide-amine dendrimer is function modified:
By 0.5mmol polyamide-amine dendrimer, 1mmol secondary amine and salt of wormwood in polar aprotic solvent (acetonitrile), at-10 DEG C, 20 DEG C, react respectively successively after 2 hours, backflow makes its sufficient reacting, react complete, polar aprotic solvent is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Product is after washing, filtration, being dried, and productive rate is 82%.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that the present embodiment is obtained carries out composite, reference standard AATCC22-2001: its water repellency is tested in spray experiment (Spray Test).Detected result is 100 points.
Embodiment 4
Synthesizing of polyamide-amine dendrimer:
First 150mmol quadrol is dissolved in 1000mmol anhydrous methanol, slowly drip wherein 1200mmol methyl acrylate, at room temperature magnetic agitation reaction 24h, methyl alcohol and excessive methyl acrylate are removed in underpressure distillation, obtaining 0.5 generation polyamide-amine dendrimer (being denoted as PAMAM G0.5). second step is first 50mmolPAMAM G0.5 to be dissolved in 2.0mol anhydrous methanol, slowly drip wherein again 1200mmol quadrol, at room temperature magnetic agitation reaction 48h, methyl alcohol and excessive quadrol are removed in underpressure distillation, obtain 1.0 generation polyamide-amine dendrimers (being denoted as PAMAM G1.0). under felicity condition, above two steps obtain the polyamide-amine dendrimer of 4.0 algebraically in triplicate.
Polyamide-amine dendrimer grafting epoxy compounds:
By about 0.5mmol 4.0 generation polyamide-amine dendrimer be dissolved in 60g anhydrous methanol, drip wherein 1 of about 16mmol, 2-epoxy chloropropane, then add the anhydrous methanol of 40g, make 4.0 generation daiamid-1, the mass concentration of 2-epoxy chloropropane dendrimer is approximately 5% left and right.At 40 DEG C of constant temperature water baths reaction 4h, anhydrous methanol is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Polyamide-amine dendrimer is function modified:
By 0.5mmol polyamide-amine dendrimer, 1mmol secondary amine and salt of wormwood in polar aprotic solvent (acetonitrile), at-10 DEG C, 20 DEG C, react respectively successively after 2 hours, backflow makes its sufficient reacting, react complete, polar aprotic solvent is removed in underpressure distillation, then product is dissolved in distilled water to centrifugation and repeatedly purifies and obtain light yellow viscous liquid.
Product is after washing, filtration, being dried, and productive rate is 82%.
Whether be suitable for and make water-resisting agent for detecting it, the hyperbranched compound that the present embodiment is obtained carries out composite, reference standard AATCC22-2001: its water repellency is tested in spray experiment (Spray Test).Detected result is 100 points.
Claims (10)
1. a hyperbranched compound water-resisting agent, is characterized in that: the molecular formula of described water-resisting agent is:
wherein A is
the like, be one wherein; R
1for carbonatoms be 1-16 alkyl, R
2for the carbonatoms alkyl that is 8-16.
2. a preparation method for hyperbranched compound water-resisting agent, comprising:
(1) quadrol is dissolved in anhydrous methanol, then drips methyl acrylate, then at ambient temperature, stirring reaction 12-24h, underpressure distillation, obtains 0.5 generation polyamide-amine dendrimer PAMAM G0.5; Wherein the mol ratio of quadrol, anhydrous methanol, methyl acrylate is 1.5:10:12;
(2) PAMAM G0.5 is dissolved in anhydrous methanol, then drips quadrol, at room temperature magnetic agitation reaction 24-48h, underpressure distillation, obtain 1.0 generation polyamide-amine dendrimer; Repeating step (1), (2) obtain the polyamide-amine dendrimer of different algebraically; Wherein the mol ratio of PAMAM G0.5, anhydrous methanol, quadrol is 0.5:0.02:12;
(3) step (2) gained polyamide-amine dendrimer is dissolved in anhydrous methanol, then drip 1,2-epoxy chloropropane, add again anhydrous methanol, obtain daiamid-1,2-epoxy chloropropane dendrimer solution, at 40-50 DEG C of reaction 3-6h, underpressure distillation, separating-purifying, obtains the polyamide-amine dendrimer of grafting epoxy compounds; Wherein polyamide-amine dendrimer, anhydrous methanol summation, 1, the proportionlity of 2-epoxy chloropropane is 0.5mmol:50-100g:4-16mmol;
(4) by the polyamide-amine dendrimer of above-mentioned grafting epoxy compounds, secondary amine and salt of wormwood add in polar aprotic solvent, successively under-20～0 DEG C, 0～40 DEG C condition, react respectively after 1-4 hour, reflux, underpressure distillation after completion of the reaction, separating-purifying, obtains hyperbranched compound water-resisting agent; Wherein the mol ratio of the polyamide-amine dendrimer of grafting epoxy compounds, secondary amine is 1:2.
3. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: in described step (2), reaction is to react under 40 DEG C of constant temperature water bath conditions.
4. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: separating-purifying is for being dissolved in distilled water centrifugation 3-5 time in described step (2).
5. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: the one in the polyamide-amine dendrimer that in described step (3), polyamide-amine dendrimer is different algebraically.
6. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: the mass ratio of the anhydrous methanol that in described step (3), polyamide-amine dendrimer is dissolved in, the anhydrous methanol of adding is 1:1-2:1.
7. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: daiamid-1 in described step (3), the mass concentration of 2-epoxy chloropropane dendrimer solution is 5%.
8. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: in described step (4), the mol ratio of secondary amine and salt of wormwood is 1:1.
9. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: described step (4) Semi-polarity aprotic solvent is one or more in acetonitrile, acetone, methyl-sulphoxide, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, chloroform.
10. the preparation method of a kind of hyperbranched compound water-resisting agent according to claim 2, is characterized in that: separating-purifying is for being dissolved in distilled water centrifugation 3-5 time in described step (4).
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| CN106565967A (en) * | 2016-11-09 | 2017-04-19 | 浙江大学 | Preparation method for hyperbranched polymer with dien as initiator and application of hyperbranched polymer |
| CN108166261A (en) * | 2018-01-18 | 2018-06-15 | 江苏尼美达科技有限公司 | A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof |
| CN108395006A (en) * | 2018-03-30 | 2018-08-14 | 江苏新亿源环保科技有限公司 | A kind of preparation method of oilfield exploitation corrosion inhibiting and descaling agent |
| CN108823987A (en) * | 2018-06-07 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of the floride-free water-proof aagent of reactivity for textile |
| CN113512876A (en) * | 2021-04-29 | 2021-10-19 | 鲁东大学 | Preparation method of crosslinked dendrimer-para-aramid silver-plated conductive fiber |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
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| CN102233249A (en) * | 2010-04-30 | 2011-11-09 | 中国石油天然气集团公司 | Dendritic reverse demulsifier and preparation method thereof |
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| CN102233249A (en) * | 2010-04-30 | 2011-11-09 | 中国石油天然气集团公司 | Dendritic reverse demulsifier and preparation method thereof |
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| CN106565967A (en) * | 2016-11-09 | 2017-04-19 | 浙江大学 | Preparation method for hyperbranched polymer with dien as initiator and application of hyperbranched polymer |
| CN106565967B (en) * | 2016-11-09 | 2019-10-15 | 浙江大学 | Using diethylenetriamines as the preparation method and application of the dissaving polymer of initiator |
| CN108166261A (en) * | 2018-01-18 | 2018-06-15 | 江苏尼美达科技有限公司 | A kind of environment-friendly watertight washes waterproofing agent and preparation method thereof |
| CN108395006A (en) * | 2018-03-30 | 2018-08-14 | 江苏新亿源环保科技有限公司 | A kind of preparation method of oilfield exploitation corrosion inhibiting and descaling agent |
| CN108823987A (en) * | 2018-06-07 | 2018-11-16 | 南通纺织丝绸产业技术研究院 | A kind of preparation method of the floride-free water-proof aagent of reactivity for textile |
| CN113512876A (en) * | 2021-04-29 | 2021-10-19 | 鲁东大学 | Preparation method of crosslinked dendrimer-para-aramid silver-plated conductive fiber |
| CN113512876B (en) * | 2021-04-29 | 2023-05-05 | 鲁东大学 | Preparation method of cross-linked dendrimer para-aramid silver-plated conductive fiber |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
| CN116876221B (en) * | 2023-07-04 | 2024-03-08 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
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Effective date of registration: 20170505 Address after: 528305, Ronggui, Shunde, Guangdong province Foshan Hai tail Industrial Zone Patentee after: FOSHAN SHUNDE GOLDTEX GROUP CO., LTD. Address before: 201620 Shanghai Songjiang new town, North Renmin Road, No. 2999, No. Patentee before: Donghua University |