CN104789102A - Preparation method of waterborne polyurethane coating and adhesive modified by graphene and rare earth - Google Patents
Preparation method of waterborne polyurethane coating and adhesive modified by graphene and rare earth Download PDFInfo
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Abstract
The invention discloses a preparation method of waterborne polyurethane coating and adhesive which are modified by graphene and rare earth. The preparation method of the waterborne polyurethane coating and adhesive which are modified by graphene and rare earth comprises the following steps: in presence of a dibutyltin dilaurate catalyst, mixing a ytterbium phosphorus flame retardant with hexamethylene diisocyanate, carrying out reaction for 2-3 hours at the temperature of 70-90 DEG C, adding sodium glucoheptonate, and carrying out reaction for 30 minutes at the temperature of 70-90 DEG C, so that a polyurethane prepolymer is obtained; adding a hydrophilic chain extender and butanone into the polyurethane prepolymer, carrying out reaction for 1-3 hours at the temperature of 70-80 DEG C, adding triethylamine for carrying out reaction for 30-60 minutes, and adding water for emulsifying, so that hydrophilic polyurethane is formed; adding a graphene dispersion liquid and phospholipid into the hydrophilic polyurethane, and shearing and stirring for 60-90 minutes under the condition that pH value is 7, so that the waterborne polyurethane coating and adhesive which are modified by graphene and rare earth are obtained, and fire resistance and mechanical properties of the obtained polyurethane coating and adhesive are greatly improved.
Description
technical fieldthe present invention relates to a kind of aqueous polyurethane coating and the preparation method of sizing agent, particularly the preparation method of a kind of Graphene and rare earth modified aqueous polyurethane coating and sizing agent, main purpose is to improve aqueous polyurethane flame retardant resistance.
Background technology
Aqueous polyurethane (also known as waterbased urethane) is a kind of urethane resin containing hydrophilic radical in the molecular chain of urethane, has very strong affinity, adopt specific technique can make it disperse in water and form stable system with glassware for drinking water.Aqueous polyurethane is mainly used in the aspects such as leather finish, textile printing and dyeing, paper-making industry, building coating, tackiness agent, and involved is nearly all inflammable material, and these materials as without fire-retardant finish, must become the potential safety hazard of initiation fire in use.Aqueous polyurethane flame-retarded is one of important directions of aqueous polyurethane functionalization.
The people such as Chen He [1] Chen He, Luo Yunjun, Li Jie. the synthesis and characteries [J] of the aqueous polyurethane that hard section is flame-retardant modified. polymer material science and engineering, 2008,24(6): 79 ~ 84 is chainextender with dibromoneopentyl glycol, by the mode of hard section modification, ignition-proof element is incorporated in aqueous polyurethane, synthesizes the extinguishing waterborn polyurethane of the degree of a series of different modification.Oxygen index test finds, the oxygen index of aqueous polyurethane increases with the degree increase of dibromoneopentyl glycol modification, and the urethane oxygen index of wherein 15% modification has reached 29.6%, makes urethane by the difficult combustion of flammable reduction.But the urethane of bromide fire retardant modification is when burning, produces a large amount of smog and easy etching apparatus, being therefore subject to certain restrictions.And the extinguishing waterborn polyurethane that China sells in the market is based on blended Compositional type, reach flame retardant effect by adding a large amount of fire retardants, this method cost is higher and larger to the performance impact of urethane.Select functional group reactions in the phosphorus flame retardant of inexpensive, environmental protection and urethane, meet the demand of following people to market.
Along with the appearance of European Union RoHS and WEEE two regulations performs, and on January 1st, 2009, the registration of European Union REACH regulation chemical formally started, and the protection of countries in the world to human body and environment is more and more paid attention to, and progressively used decree regulation to carry out specification.This makes the halogenated flame retardant in fire retardant be faced with great environmental protection crisis; continuous for bromide fire retardant at issue; the phosphorus flame retardant having good flame retardant effect and meet environmental protection specification just moves towards foreground; along with the continuous decline of its price, its each series product also just progressively become the mainstream product in the market.
Along with people more and more pay attention to safety; flame retardant properties also becomes the function necessarily required in a lot of Application Areas of macromolecular material gradually; therefore the application of fire retardant is also more and more extensive; the function and application field that environmental protection, flame retardant resistance, high strength, good function synergic etc. are progressively segmented requires more and more higher to anti-flaming function, also requires that fire retardant has better adaptability, specific aim or synergetic property simultaneously.
The outer shell structure of rare earth element uniqueness, demonstrates not only abundant but also unique physical-chemical characteristic, also determines its compound and have much peculiar function, and this is the basis of rare-earth additive application.
At present, the additive agent field of rare earth element successful Application have PVC to combine with calcium zinc and rare earth thermo-stabilizer, PP the beta crystal-type nucleater forming binuclear complex with rare earth multicomponent complex compound or rare earth and IIA race metal.And in flame retardant area, rare earth element there is no application precedent, how by rare earth element with without halogenated flame retardant connected applications, reaching low toxicity, low smog, innoxious requirement while taking into account flame retardant effect, is a research direction upgraded.
Summary of the invention
the present invention adopts rare earth modified to tetrakis hydroxymetyl phosphonium sulfuric, reduce its activity, and react under the effect of catalyzer with the tetrakis hydroxymetyl phosphonium sulfuric of modification and hexamethylene diisocyanate, the catalyzer of sodium glucoheptonate to remnants is selected to be fixed, carry out flame-retardant modified with Graphene, phosphide to urethane, prepared aqueous polyurethane flame retardant resistance is good.
Present invention employs following technical scheme.
The preparation method of Graphene and rare earth modified aqueous polyurethane coating and sizing agent, is characterized in that:
(1) the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20% is added in the reactor, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, use sodium hydroxide solution regulator solution pH value to 7 ~ 8 again, at 20 ~ 30 DEG C, stir 3h, after reaction terminates, filter, dry, be crushed to more than 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) under dibutyltin dilaurate catalyst existent condition, be 2:1 ~ 4 by weight: 1, ytterbium phosphorus fire retardant is mixed with hexamethylene diisocyanate, 2 ~ 3h is reacted at 70 ~ 90 DEG C, add sodium glucoheptonate again, react 30min at 70 ~ 90 DEG C, obtain base polyurethane prepolymer for use as; Described catalyst levels is 0.2 ~ 0.7% of ytterbium phosphorus fire retardant and hexamethylene diisocyanate gross weight, sodium glucoheptonate be ytterbium phosphorus fire retardant, hexamethylene diisocyanate, total catalyst weight 0.1 ~ 0.2%;
(3) in base polyurethane prepolymer for use as, add the hydrophilic chain extender of base polyurethane prepolymer for use as gross weight 2.6 ~ 3.2% and the butanone solvent of base polyurethane prepolymer for use as gross weight 12 ~ 25%, 1 ~ 3h is reacted under 70 ~ 80 DEG C of conditions, the triethylamine adding polyurethane prepolymer body weight 5 ~ 7% carries out neutralization reaction 30 ~ 60min, add water and carry out emulsification, form a kind of hydrophilic urethane for subsequent use;
(4) in 100g water, add 20g Graphene and dispersion agent 6 ~ 8g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) phosphide of the graphene dispersing solution of Hdyrophilic polyurethane solid content 10 ~ 20% and hydrophilic urethane solid content 20 ~ 40% is joined in urethane, the condition down cut being 7 at pH stirs 60 ~ 90min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
Chainextender is any one in 4-acetaminosalicylic acid, norepinephrine, O-(4-hydroxyl-3,5-diiodo-phenyl)-3,5-bis-iodo-TYRs; The dispersion agent of graphene solution is 2-naphthylamines-3,6-disulfonic acid sodium salt, Sodium sulfanilate, succinate sodium 2-ethylhexyl, 2-phosphonobutane-1, any one of 2,4-tricarboxylic acid sodium salt, 3-(4-isobutyl phenenyl)-2,3-epoxy Sodium propanecarboxylate; Phosphide is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, O-ethyl-S-sec-butyl-2-oxo-1, any one in 3-thiazolidine-3-base Thiophosphonate, two (p-nitrophenyl) azide phosphonate, four (2,3-dibromopropyl) ethylene glycol bis phosphonic acid ester; Shear agitation speed is 600 ~ 1100rpm.
The present invention has following characteristics:
(1) adopt the tetrakis hydroxymetyl phosphonium sulfuric of Ytterbium trichloride and pentoxyverine modification, reduce the reactive behavior of tetrakis hydroxymetyl phosphonium sulfuric;
(2) tetrakis hydroxymetyl phosphonium sulfuric, Graphene, phosphide is adopted to improve the flame retardant resistance of urethane;
(3) catalyzer of sodium glucoheptonate to remnants is fixed, and reduces the toxicity of catalyzer;
embodimentthe present invention is further illustrated below in conjunction with example.
example one
(1) be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, add the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20%, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, be that 20% sodium hydroxide solution regulator solution pH value is to 7 ~ 8 with massfraction again, 3h is stirred at 20 DEG C, after reaction terminates, filter, dry, be crushed to more than 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) above-mentioned (1) ytterbium phosphorus fire retardant 60g and hexamethylene diisocyanate 30g is installed to stirring arm, thermometer, prolong 500ml four-hole boiling flask in, under dibutyl tin laurate 0.18g existent condition, 2h is reacted at 70 DEG C, add sodium glucoheptonate 0.1g again, react 30min at 70 DEG C, obtain base polyurethane prepolymer for use as 90.1g;
(3) in base polyurethane prepolymer for use as, 4-acetaminosalicylic acid 2.34g and butanone 4.5g is added, under 70 DEG C of conditions, react 1 h, add triethylamine 4.5g, 70 DEG C are carried out neutralization reaction 30 min, the 120g that adds water carries out 70 DEG C of emulsification 1h, and forming a kind of solid content is 38.5% Hdyrophilic polyurethane 219g;
(4) in 100g water, add 20g Graphene and 2-naphthylamines-3,6-disulfonic acid sodium salt 6g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) by graphene dispersing solution 8.4g and 3 in (4), 5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate 16.8g joins in (3) Hdyrophilic polyurethane, 40 DEG C, pH is 7,600rpm down cut stirs 60min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
example two
(1) be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, add the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20%, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, be that 20% sodium hydrate regulator solution pH value is to 7 ~ 8 with massfraction again, 3h is stirred at 30 DEG C, after reaction terminates, filter, dry, be crushed to more than 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) above-mentioned (1) ytterbium phosphorus fire retardant 60g and hexamethylene diisocyanate 15g is installed to stirring arm, thermometer, prolong 500ml four-hole boiling flask in, under dibutyl tin laurate 0.53g existent condition, 3h is reacted at 90 DEG C, add sodium glucoheptonate 0.15g again, react 30min at 90 DEG C, obtain base polyurethane prepolymer for use as 75.1g;
(3) in base polyurethane prepolymer for use as, norepinephrine 2.4g and butanone 18.8g is added, under 80 DEG C of conditions, react 3h, add triethylamine 5.3g, 80 DEG C are carried out neutralization reaction 60 min, the 120g that adds water carries out 80 DEG C of emulsification 1h, and forming a kind of solid content is 36.5% Hdyrophilic polyurethane 216g;
(4) in 100g water, add 20g Graphene and Sodium sulfanilate 8g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) by graphene dispersing solution 15.8g in (4) and O-ethyl-S-sec-butyl-2-oxo-1,3-thiazolidine-3-base Thiophosphonate 31.6g joins in (3) Hdyrophilic polyurethane, 30 DEG C, pH is 7,1100rpm down cut stirs 90min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
example three
(1) be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, add the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20%, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, be that 20% sodium hydroxide solution regulator solution pH value is to 7 ~ 8 with massfraction again, 3h is stirred at 25 DEG C, after reaction terminates, filter, dry, be crushed to 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) above-mentioned (1) ytterbium phosphorus fire retardant 60g and hexamethylene diisocyanate 20g is installed to stirring arm, thermometer, prolong 500ml four-hole boiling flask in, under dibutyl tin laurate 0.36g existent condition, 2.5h is reacted at 80 DEG C, add sodium glucoheptonate 0.12g again, react 45min at 80 DEG C, obtain base polyurethane prepolymer for use as 80.2g;
(3) in base polyurethane prepolymer for use as, O-(4-hydroxyl-3 is added, 5-diiodo-phenyl)-3,5-bis-iodo-TYR 2.3g and butanone 14.8g, 2h is reacted under 75 DEG C of conditions, add triethylamine 4.8g and carry out 75 DEG C of neutralization reaction 45 min, add water 120g, and 75 DEG C are carried out emulsification 1h, and forming a kind of solid content is 37.5% Hdyrophilic polyurethane 218g;
(4) in 100g water, add 20g Graphene and succinate sodium 2-ethylhexyl 7g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) graphene dispersing solution 12.3g and two (p-nitrophenyl) azide phosphonate 24.6g in (4) is joined in (3) Hdyrophilic polyurethane, 45 DEG C, pH is 7,850rpm down cut stirs 75min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
example four
(1) be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, add the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20%, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, be that the sodium hydroxide solution regulator solution pH value of 20% is to 7 ~ 8 with massfraction again, 3h is stirred at 20 DEG C, after reaction terminates, filter, dry, be crushed to 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) above-mentioned (1) ytterbium phosphorus fire retardant 60g and hexamethylene diisocyanate 30g is installed to stirring arm, thermometer, prolong 500ml four-hole boiling flask in, under dibutyl tin laurate 0.18g existent condition, 2h is reacted at 70 DEG C, add sodium glucoheptonate 0.1g again, react 30min at 70 DEG C, obtain base polyurethane prepolymer for use as 90.1g;
(3) in base polyurethane prepolymer for use as, O-(4-hydroxyl-3 is added, 5-diiodo-phenyl)-3,5-bis-iodo-TYR 2.34g and butanone 4.5g, 1 h is reacted under 70 DEG C of conditions, add triethylamine 4.5g and carry out neutralization reaction 30 min at 70 DEG C, the 120g that adds water carries out emulsification 1h at 70 DEG C, and forming a kind of solid content is 38.5% Hdyrophilic polyurethane 219g;
(4) in 100g water, add 20g Graphene and 2-phosphonobutane-1,2,4-tricarboxylic acid sodium salt 6g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) by graphene dispersing solution 8.4g, four (2 in (4), 3-dibromopropyl) ethylene glycol bis phosphonic acid ester 16.8g and N, N-bis-(carboxymethyl) glycine tripotassium salt 1.2g joins in above-mentioned (3) Hdyrophilic polyurethane, temperature 30 DEG C, pH be 7,600rpm down cut stirs 60min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
example five
(1) be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, add the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20%, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, be that 20% sodium hydroxide solution regulator solution pH value is to 7 ~ 8 with massfraction again, 3h is stirred at 30 DEG C, after reaction terminates, filter, dry, be crushed to more than 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) above-mentioned (1) ytterbium phosphorus fire retardant 60g and hexamethylene diisocyanate 15g is installed to stirring arm, thermometer, prolong 500ml four-hole boiling flask in, under dibutyl tin laurate 0.53g existent condition, 3h is reacted at 90 DEG C, adding sodium glucoheptonate 0.15g, react 30min at 90 DEG C, obtain base polyurethane prepolymer for use as 75.1g;
(3) in base polyurethane prepolymer for use as, 4-acetaminosalicylic acid 2.4g and butanone 18.8g is added, 3h is reacted under 80 DEG C of conditions, add triethylamine 5.3g and carry out neutralization reaction 60 min at 80 DEG C, the 120g that adds water carries out emulsification 1h at 80 DEG C, and forming a kind of solid content is 36.5% Hdyrophilic polyurethane 216g;
(4) in 100g water, add 20g Graphene, 3-(4-isobutyl phenenyl)-2,3-epoxy Sodium propanecarboxylate 8g and mono-methyl terephthalic acid sylvite 1.6g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) by graphene dispersing solution 15.8g, O-ethyl-S-sec-butyl-2-oxo-1 in (4), 3-thiazolidine-3-base Thiophosphonate 31.6g and 2,2-dimethyl-1,3-dioxolane-4-carboxylic acid potassium 2.1g joins in (3) Hdyrophilic polyurethane, temperature 30 DEG C, pH be 7,1100rpm down cut stirs 90min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
Beneficial effect of the present invention is further illustrated below by relevant experimental data:
Table one Graphene and rare earth modified aqueous polyurethane coating and sizing agent institute film forming properties
| Experimental group | Example one | Example two | Example three | Example four | Example five | PU-1 |
| Hardness | B | B | B | B | B | B |
| Sticking power/level | 3 | 3 | 3 | 3 | 3 | 2 |
| Snappiness/mm | 2 | 3 | 2 | 2 | 3 | 2 |
Can find from table one, from hardness, sticking power, flexibility better performances, wherein the rank of hardness is followed successively by C, B, A from low to high, and the rank of sticking power is 1,2,3,4 from low to high, snappiness is followed successively by 1 from low to high, 2,3,4.
The mechanical property of table two Graphene and rare earth modified aqueous polyurethane coating and sizing agent gained film
| Experimental group | Example one | Example two | Example three | Example four | Example five | PU-1 |
| Elongation at break/% | 143 | 158 | 129 | 176 | 162 | 122 |
| Tensile strength/MPa | 6.8 | 6.8 | 6.8 | 5.4 | 5.7 | 5.2 |
| Abrasion resisting/level | 4.7 | 4 | 3.7 | 4.7 | 4.7 | 3,8 |
The reference of table two middle finger object detection method (Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999), coating gained film elongation at break of the present invention, tensile strength, wear-resistant all performances are better.
Flame retardant resistance is weighed by smoke density method (maximum smoke density, reach the maximum smoke density time), oxygen index, vertical combustion index (flaming combustion time, glowing time), and elongation at break characterizes its mechanical property.
The flame retardant resistance of table three Graphene and rare earth modified aqueous polyurethane coating and sizing agent gained film
| Example one | Example two | Example three | Example four | Example five | Market PU-1 | |
| Maximum smoke density | 25 | 27 | 29 | 13 | 9 | 42 |
| Reach maximum smoke density time/s | 165 | 165 | 180 | 215 | 210 | 120 |
| Oxygen index | 27.6 | 25.7 | 25.8 | 25.8 | 26.8 | 21 |
| Flaming combustion time/s | 21.4 | 21.4 | 12.3 | 11.8 | 11.6 | 68 |
| Glowing time/s | 0 | 0 | 0 | 0 | 0 | 0 |
The detection of table three indices is respectively according to following standard: smoke density measures according to GB8323-2008, and oxygen index adopts GB/T5454-1997 " textile combustion performance test-oxygen index method " to measure; Flaming combustion time and glowing time are measured by GB/T 5455-1997 " textile combustion energy test-normal beam technique ".
as shown in Table 3, when Graphene of the present invention and rare earth modified aqueous polyurethane coating and sizing agent gained film burn, maximum smoke density significantly reduces, and reach maximum smoke density time significant prolongation, oxygen index significantly improves, and combustion time obviously shortens.
Claims (5)
1. the preparation method of Graphene and rare earth modified aqueous polyurethane coating and sizing agent, is characterized in that:
(1) the aqueous sodium hydroxide solution 44g that 92g tetrakis hydroxymetyl phosphonium sulfuric and massfraction are 20% is added in the reactor, 2h is reacted at 80 DEG C, then Ytterbium trichloride aqueous solution 272g and pentoxyverine 2g that massfraction is 20% is added, use sodium hydroxide solution regulator solution pH value to 7 ~ 8 again, at 20 ~ 30 DEG C, stir 3h, after reaction terminates, filter, dry, be crushed to more than 3000 orders, ytterbium phosphorus fire retardant 96.2g can be obtained;
(2) under dibutyltin dilaurate catalyst existent condition, be 2:1 ~ 4 by weight: 1, ytterbium phosphorus fire retardant is mixed with hexamethylene diisocyanate, 2 ~ 3h is reacted at 70 ~ 90 DEG C, add sodium glucoheptonate again, react 30min at 70 ~ 90 DEG C, obtain base polyurethane prepolymer for use as; Described catalyst levels is 0.2 ~ 0.7% of ytterbium phosphorus fire retardant and hexamethylene diisocyanate gross weight, sodium glucoheptonate be ytterbium phosphorus fire retardant, hexamethylene diisocyanate, total catalyst weight 0.1 ~ 0.2%;
(3) in base polyurethane prepolymer for use as, add the hydrophilic chain extender of base polyurethane prepolymer for use as gross weight 2.6 ~ 3.2% and the butanone solvent of base polyurethane prepolymer for use as gross weight 12 ~ 25%, 1 ~ 3h is reacted under 70 ~ 80 DEG C of conditions, the triethylamine adding polyurethane prepolymer body weight 5 ~ 7% carries out neutralization reaction 30 ~ 60min, add water and carry out emulsification, form a kind of hydrophilic urethane for subsequent use;
(4) in 100g water, add 20g Graphene and dispersion agent 6 ~ 8g, temperature be 30 DEG C, under pH is the condition of 7, ultrasonication 20min, obtains graphene dispersing solution for subsequent use;
(5) phosphide of the graphene dispersing solution of Hdyrophilic polyurethane solid content 10 ~ 20% and hydrophilic urethane solid content 20 ~ 40% is joined in urethane, the condition down cut being 7 at pH stirs 60 ~ 90min, obtains Graphene and rare earth modified aqueous polyurethane coating and sizing agent.
2. the preparation method of a kind of Graphene as claimed in claim 1 and rare earth modified aqueous polyurethane coating and sizing agent, it is characterized in that: chainextender is 4-acetaminosalicylic acid, norepinephrine, O-(4-hydroxyl-3,5-diiodo-phenyl) any one in-3,5-bis-iodo-TYRs.
3. the preparation method of a kind of Graphene as claimed in claim 1 and rare earth modified aqueous polyurethane coating and sizing agent, it is characterized in that: the dispersion agent of graphene solution is 2-naphthylamines-3,6-disulfonic acid sodium salt, Sodium sulfanilate, succinate sodium 2-ethylhexyl, 2-phosphonobutane-1,2, any one of 4-tricarboxylic acid sodium salt, 3-(4-isobutyl phenenyl)-2,3-epoxy Sodium propanecarboxylate.
4. the preparation method of Graphene as claimed in claim 1 and rare earth modified aqueous polyurethane coating and sizing agent, it is characterized in that: phosphide is 3,5-di-tert-butyl-4-hydroxyl benzyl diethyl phosphonate, O-ethyl-S-sec-butyl-2-oxo-1, any one in 3-thiazolidine-3-base Thiophosphonate, two (p-nitrophenyl) azide phosphonate, four (2,3-dibromopropyl) ethylene glycol bis phosphonic acid ester.
5. the preparation method of Graphene as claimed in claim 1 and rare earth modified aqueous polyurethane coating and sizing agent, is characterized in that: shear agitation speed is 600 ~ 1100rpm.
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| CN105131679A (en) * | 2015-10-26 | 2015-12-09 | 王秋芹 | Graphene anticorrosive paint and preparation method thereof |
| CN105820791A (en) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | Graphene modified polyurethane composition, polyurethane adhesive prepared from composition, preparation method of adhesive, and aerostat |
| CN105838229A (en) * | 2016-04-29 | 2016-08-10 | 李强 | Waterborne flame retardant polyurethane paint and preparing method thereof |
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| CN103897495A (en) * | 2014-04-21 | 2014-07-02 | 烟台大学 | Preparation method of flame-retardant and light-resistant coating |
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| CN102898936A (en) * | 2012-10-13 | 2013-01-30 | 段宝荣 | Method for preparing fire-retarding aqueous polyurethane |
| CN103897495A (en) * | 2014-04-21 | 2014-07-02 | 烟台大学 | Preparation method of flame-retardant and light-resistant coating |
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| CN105820791A (en) * | 2016-02-29 | 2016-08-03 | 洛阳尖端技术研究院 | Graphene modified polyurethane composition, polyurethane adhesive prepared from composition, preparation method of adhesive, and aerostat |
| CN105820791B (en) * | 2016-02-29 | 2018-12-21 | 洛阳尖端技术研究院 | Graphene modified polyurethane composition, using its preparation polyurethane binder, the adhesive preparation method |
| CN105838229A (en) * | 2016-04-29 | 2016-08-10 | 李强 | Waterborne flame retardant polyurethane paint and preparing method thereof |
| CN105970760A (en) * | 2016-06-15 | 2016-09-28 | 东南大学 | Interface bonding method for polyurethane interspace elastic mixtures and bituminous mixtures |
| CN105970760B (en) * | 2016-06-15 | 2018-05-04 | 东南大学 | The interfacial adhesion method of polyurethane gap elasticity mixture and asphalt |
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| CN107974231A (en) * | 2016-10-24 | 2018-05-01 | 深圳光启空间技术有限公司 | Adhesive, its preparation method and envelop materials |
| CN107974231B (en) * | 2016-10-24 | 2021-10-15 | 青岛中塑高新材料有限公司 | Adhesive, preparation method thereof and capsule material |
| CN110204962A (en) * | 2019-05-27 | 2019-09-06 | 华侨大学 | A kind of Graphene conductive ink and preparation method thereof |
| WO2020239143A1 (en) * | 2019-05-27 | 2020-12-03 | 华侨大学 | Graphene conductive ink and preparation method therefor |
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