CN1594388A - Method for preparing nano anionic polyurethane composite water emulsion - Google Patents
Method for preparing nano anionic polyurethane composite water emulsion Download PDFInfo
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- CN1594388A CN1594388A CN 200410025340 CN200410025340A CN1594388A CN 1594388 A CN1594388 A CN 1594388A CN 200410025340 CN200410025340 CN 200410025340 CN 200410025340 A CN200410025340 A CN 200410025340A CN 1594388 A CN1594388 A CN 1594388A
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- nanometer
- nano
- water emulsion
- anionic polyurethane
- compound water
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- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention discloses a method for preparing nano anionic polyurethane composite water emulsion wherein the emulsion is prepared through the reaction between diisocyanate, compounds having reactive amino and hydroxyl, nano material, carboxyl-containing diatomic alcohol, neutralizing agent and frame material.
Description
[technical field]
The present invention relates to chemical technology field, the preparation method of the compound water emulsion of specifically a kind of nanometer anionic polyurethane.
[background technology]
The weakness that mono-component polyurethane water emulsion ubiquity water tolerance is relatively poor, intensity is lower, this has brought very big restriction to its application.In addition, common anionic polyurethane water dispersion mostly is thinlyfluid, and solid content is low, is easy to flow, and uses on non-horizontal basal plane and easily causes became uneven, but also produce sagging, influences effect.The present invention is by having improved its water tolerance and bonding strength in nano material and anionic polyurethane water dispersion original position complex poles the earth; And it is become have thick liquid or body of paste thixotropic, that be easy to smear by adding a kind of body frame material, on non-horizontal basal plane, use not produce became uneven and sagging phenomenon, use very convenient.
[summary of the invention]
The object of the present invention is to provide a kind of preparation method of the novel compound water emulsion of high-strength nano anionic polyurethane.
For achieving the above object, design a kind of preparation method of the novel compound water emulsion of high-strength nano anionic polyurethane, the compound water emulsion of a kind of nanometer anionic polyurethane is by vulcabond (A), have active amino and and or compound (B), the nano material (C) of hydroxyl, to contain carboxyl dibasic alcohol (D), neutralizing agent (E), body frame material substance reactions such as (F) synthetic.Vulcabond (A) is an aliphatics or aromatic, can be TDI-100, TDI-80, MDI, HMDI, IPDI, HDI, NDI, XDI etc.Have active amino and or the compound (B) of hydroxyl contain two active aminos and or the macromole or the low molecule of hydroxyl can be polyethers, polyester, ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, methyl propanediol, quadrol, triethylene diamine, glycol ether etc.Nano material (C) can be nanometer SiO
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer Al
2O
3, inorganic nano materials such as nano imvite, nano clay, that relatively more commonly used is nanometer SiO
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer Al
2O
3, nano imvite, nano clay.The granularity of nano material (C) is necessary for: 10～100nm is preferably in 10～60nm.Dibasic alcohol (D) is the small molecules dibasic alcohol that contains the COOH group, can be dimethylol propionic acid, dimethylolpropionic acid.Neutralizing agent (E) can be mineral alkalis such as sodium hydroxide, lithium hydroxide, also can be organic basess such as triethylamine, trolamine, dimethylethanolamine.Body frame material (F) is a kind of molecular sieve powder, and its chemical formula is Na
2OAl
2O
32SiO
24.5H
2O, main representative physical properties is:
Color and shape: white, powdery
Loose density g/ml:0.4
Relative crystallinity %: ∽ 100
Water adsorptive value % RH-55%: 〉=27
575 ℃ of loss on ignition %, 1h :≤22
PH value 5% floating outstanding thing :≤11.5
(1) polyvalent alcohol (B) nano material (C) of aliphatics or aromatic vulcabond (A) and process original position Combined Processing is part or all of, (2) carried out prepolymerization reaction 1～6 hour with the mol ratio of NCO/OH (NH)=1.5-2.5 at 40～80 ℃, (3) after pre-polymerization finishes, add 2～20% the dibasic alcohol (D) account for the polymkeric substance total amount and add with residue isocyano mol ratio be that 0.5～0.95: 1 low molecular dibasic alcohol or binary amine chainextender carried out chain extending reaction 1～4 hour, (4) after chain extension finishes, system is cooled to 25～35 ℃, the neutralizing agent (E) that adding and dibasic alcohol (D) are complementary and whole body frame material (F) and emulsifying waters, (5) treat to slough solvent after the emulsification fully, the pH value that obtains system through grinding is 6-8, the thick or paste of flowable exquisiteness.Nano material (C) before performed polymer is synthetic by introducing with polyvalent alcohol original position composite methods.
The present invention compared with prior art, the PU water miscible liquid has higher solid content (45%-50%), higher hardness (Shao A90), good solvent resistance (soak in 25 ℃ of acetone 4 hours insoluble), water tolerance (90 ℃ soak do not ftracture half an hour), higher adhesiveproperties, good thixotropy, and have good compatibility and can form stabilized mixture with them with other water miscible liquid, can be used as coating, tackiness agent, textile coating agent etc., be worthy of popularization.
[description of drawings]
Fig. 1 is a process flow sheet of the present invention.
Referring to Fig. 1,1 for get material, 2 for prepolymerization reaction, 3 for chain extending reaction, 4 for emulsifying water, 5 be finished product.
[embodiment]
The present invention is further illustrated below in conjunction with example.
Concrete prescription is: IPDI:120g; Polyester: 80g; Ethylene glycol: 20g; Nanometer SiO
2: 5g; DMPA:20g; TEA:15g; Propyl alcohol: 80g; DMF:20g; Deionized water: 220-380g; Body frame material: 60g.
The preparation method of the compound water emulsion of this kind nano material anionic polyurethane is as follows:
The polyvalent alcohol (B) of aliphatics or aromatic vulcabond (A) and process original position Combined Processing, nano material (C) partly or entirely, mol ratio with NCO/OH (NH)=1.5-2.5 was carried out prepolymerization reaction 1～6 hour at 40～80, after pre-polymerization finishes, add 2～20% the dibasic alcohol (D) account for the polymkeric substance total amount, and to add with remaining the isocyano mol ratio be that 0.5～0.95: 1 low molecular dibasic alcohol or binary amine chainextender carried out chain extending reaction 1～4 hour, after chain extension finishes, system is cooled to 25～35, add the neutralizing agent (E) that is complementary with dibasic alcohol (D), body frame material (F) and whole emulsifying waters, treat to slough solvent after the emulsification fully, the pH value that obtains system is 6-8, outward appearance is for flowing, have thixotropic fine and smooth paste, solid content is 40-50%.
Claims (10)
1, the compound water emulsion of a kind of nanometer anionic polyurethane is characterized in that: by vulcabond (A), have active amino and and or compound (B), the nano material (C) of hydroxyl, to contain carboxyl dibasic alcohol (D), neutralizing agent (E), body frame material substance reactions such as (F) synthetic.
2, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: vulcabond (A) is an aliphatics or aromatic, can be TDI-100, TDI-80, MDI, HMDI, IPDI, HDI, NDI, XDI etc.
3, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: have active amino and or the compound (B) of hydroxyl contain two active aminos and or the macromole or the low molecule of hydroxyl can be polyethers, polyester, ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, methyl propanediol, quadrol, triethylene diamine, glycol ether etc.
4, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1 is characterized in that; Nano material (C) can be nanometer SiO
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer Al
2O
3Inorganic nano material such as nano imvite, nano clay, that relatively more commonly used is nanometer SiO
2, nano-TiO
2, nano-ZnO, nanometer CaCO
3, nanometer Al
2O
3, nano imvite, nano clay.
5, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: the granularity of nano material (C) is necessary for: 10～100nm is preferably in 10～60nm.
6, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: dibasic alcohol (D) is the small molecules dibasic alcohol that contains the COOH group, can be dimethylol propionic acid, dimethylolpropionic acid.
7, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: neutralizing agent (E) can be mineral alkalis such as sodium hydroxide, lithium hydroxide, also can be organic basess such as triethylamine, trolamine, dimethylethanolamine.
8, the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: body frame material (F) is a kind of molecular sieve powder, and its chemical formula is Na
2OAl
2O
32SiO
24.5H
2O, main representative physical properties is:
Color and shape: white, powdery loose density g/ml:0.4
Relative crystallinity %: ∽ 100 water adsorptive value %RH-55%: 〉=27
Loss on ignition %575 ℃, 1h :≤22 pH values 5% floating outstanding thing :≤11.5
9, the preparation method of the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1, it is characterized in that: (1) gets the polyvalent alcohol (B) of aliphatics or aromatic vulcabond (A) and process original position Combined Processing, nano material (C) partly or entirely, (2) carried out prepolymerization reaction 1～6 hour with the mol ratio of NCO/OH (NH)=1.5-2.5 at 40～80 ℃, (3) after pre-polymerization finishes, add 2～20% the dibasic alcohol (D) account for the polymkeric substance total amount, and to add with remaining the isocyano mol ratio be that 0.5～0.95: 1 low molecular dibasic alcohol or binary amine chainextender carried out chain extending reaction 1～4 hour, (4) after chain extension finishes, system is cooled to 25～35 ℃, the neutralizing agent (E) that adding and dibasic alcohol (D) are complementary and whole body frame material (F) and emulsifying waters, (5) treat to slough solvent after the emulsification fully, the pH value that obtains system through grinding is 6-8, the thick or paste of flowable exquisiteness.
10, the preparation method of the compound water emulsion of a kind of nanometer anionic polyurethane as claimed in claim 1 is characterized in that: nano material (C) before performed polymer is synthetic by introducing with polyvalent alcohol original position composite methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025340 CN1594388A (en) | 2004-06-22 | 2004-06-22 | Method for preparing nano anionic polyurethane composite water emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025340 CN1594388A (en) | 2004-06-22 | 2004-06-22 | Method for preparing nano anionic polyurethane composite water emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1594388A true CN1594388A (en) | 2005-03-16 |
Family
ID=34663634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410025340 Pending CN1594388A (en) | 2004-06-22 | 2004-06-22 | Method for preparing nano anionic polyurethane composite water emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1594388A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027032B (en) * | 2008-05-16 | 2013-03-27 | 拜尔材料科学股份公司 | Stable polyisocyanates comprising nanoparticles |
| CN106188482A (en) * | 2016-07-13 | 2016-12-07 | 华南理工大学 | Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method |
-
2004
- 2004-06-22 CN CN 200410025340 patent/CN1594388A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102027032B (en) * | 2008-05-16 | 2013-03-27 | 拜尔材料科学股份公司 | Stable polyisocyanates comprising nanoparticles |
| CN106188482A (en) * | 2016-07-13 | 2016-12-07 | 华南理工大学 | Nano zine oxide grafting water-based ultraviolet (UV) curable polyurethane resin and preparation method |
| CN106188482B (en) * | 2016-07-13 | 2019-07-16 | 华南理工大学 | Nano zine oxide is grafted water-based ultraviolet (UV) curable polyurethane resin and preparation method |
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