CN116004110A - Wear-resistant polyurethane floor coating with self-lubricating function and preparation method thereof - Google Patents
Wear-resistant polyurethane floor coating with self-lubricating function and preparation method thereof Download PDFInfo
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- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 14
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- Paints Or Removers (AREA)
Abstract
The application relates to the field of floor coatings, and particularly discloses a wear-resistant polyurethane floor coating with a self-lubricating effect and a preparation method thereof. The wear-resistant polyurethane floor coating with the self-lubricating effect comprises a component A and a component B, wherein the weight ratio of the component A to the component B is (1-3) 1; the component A comprises the following components in parts by weight: 60-80 parts of polyalcohol; 0-10 parts of castor oil; 80-100 parts of isocyanate; the component B comprises the following components in parts by weight: 25-40 parts of modified calcium carbonate; 20-30 parts of chlorinated paraffin; 8-14 parts of chain extender; 10-15 parts of a solvent; 0.3-0.5 part of catalyst; 0.5-3 parts of additive; the preparation method of the modified calcium carbonate comprises the following steps: adding chitin into 40-70wt% silk fibroin aqueous solution, stirring and mixing to obtain a mixture A; adding calcium carbonate into the mixture A, stirring, mixing, freeze drying, pulverizing, and sieving. The wear-resistant polyurethane floor coating with the self-lubricating function has the characteristics that a lubricating layer is formed on the friction surface, and the wear resistance is excellent.
Description
Technical Field
The application relates to the field of coatings, in particular to a wear-resistant polyurethane floor coating with a self-lubricating function and a preparation method thereof.
Background
The floor paint is also called floor paint, which is mainly prepared from film forming substances such as resin and the like as main agents, and pigment, solvent, curing agent and the like as auxiliary materials, and has the effects of protecting the ground, dust prevention, wear resistance and moisture prevention, so that the floor paint is widely applied to modern industrial ground, commercial ground, garage ground and the like.
The floor coating comprises the following raw materials: epoxy resin floor paint, polyurethane floor paint, acrylic resin floor paint and the like are continuously perfected along with the production process and construction technology, and the production and application of polyurethane paint are strongly promoted.
There is a polyurethane floor coating at present, comprising a component A and a component B, wherein the component A comprises 2,4 '-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate and polytetrahydrofuran ether glycol; the component B comprises polytetrahydrofuran ether glycol, polyether resin and diethyl toluene diamine, and the abrasion of the coating is 45/mg.
However, in the above coating, although the fluorine modified resin and the abrasion resistant filler are added to the coating components to reduce the friction coefficient of the coating surface and improve the abrasion resistance level of the coating, the abrasion is still higher, and the abrasion resistance of the coating needs to be further improved.
Disclosure of Invention
In order to reduce abrasion of the coating and improve the abrasion resistance of the coating, the application provides the abrasion-resistant polyurethane floor coating with a self-lubricating effect and a preparation method thereof.
The wear-resistant polyurethane floor coating and the preparation method thereof adopt the following technical scheme:
in a first aspect, the present application provides a wear-resistant polyurethane floor coating with a self-lubricating effect, which adopts the following technical scheme: a wear-resistant polyurethane floor coating with a self-lubricating effect comprises a component A and a component B, wherein the weight ratio of the component A to the component B is (1-3) 1;
the component A comprises the following components in parts by weight: 60-80 parts of polyalcohol; 0-10 parts of castor oil; 80-100 parts of isocyanate; the component B comprises the following components in parts by weight: 25-40 parts of modified calcium carbonate; 20-30 parts of chlorinated paraffin; 8-14 parts of chain extender; 10-15 parts of a solvent; 0.3-0.5 part of catalyst; 0.5-3 parts of additive;
the preparation method of the modified calcium carbonate comprises the following steps: adding chitin into 40-70wt% silk fibroin aqueous solution, stirring and mixing to obtain a mixture A; adding calcium carbonate into the mixture A, stirring, mixing, freeze drying, pulverizing, and sieving.
Through adopting above-mentioned technical scheme, carry out performance testing to the terrace coating that this application was made, owing to use modified calcium carbonate in the coating, the wearing and tearing when making its 1000r are only 17/mg, and the coating wearing and tearing of not using modified calcium carbonate are up to 30/mg, indicate because of adding modified calcium carbonate, make the terrace coating made possess excellent wear resistance, and analysis its reason probably lies in: during friction, the acting force of friction and extrusion transfers the silk fibroin or chitin to the friction interface, and forms an organic film lubrication friction interface, so that the surface of the coating is protected from abrasion. Meanwhile, the heat generated by friction heats the friction interface, so that the silk fibroin or the chitin is pyrolyzed to form tar-like substances and some gases such as CO and the like, the tar-like substances lubricate the friction interface, and the gases form an air cushion, so that abrasion is slowed down, and the wear resistance of the coating is improved;
on the other hand, the chitin is deeply penetrated into the pores of the calcium carbonate to support and increase the hardness of the calcium carbonate, and the calcium carbonate carries the chitin so as to be uniformly dispersed in the paint; the chitin and the calcium carbonate are adhered together by the slurry formed by the silk fibroin to prepare the calcium carbonate with higher hardness; and by virtue of the hydrophilic and oleophilic characteristics of the silk fibroin, the compatibility between calcium carbonate and other components such as polymers, castor oil and the like is improved, the hardness of the coating after curing is improved, and the wear resistance of the coating is further improved.
Preferably, the concentration of the aqueous silk fibroin solution is 50-60wt%.
By adopting the technical scheme, when the concentration of the aqueous solution of the silk fibroin is in the range, on one hand, the silk fibroin macromolecules are gathered, entangled and interpenetrated to form a compact network structure, and the strength of the modified calcium carbonate is improved by filling and supporting the calcium carbonate; on the other hand, the modified effect of the silk fibroin aqueous solution on the modified calcium carbonate is improved, so that the hardness of the coating is improved, and the wear resistance of the coating is further improved.
Preferably, the weight ratio of the silk fibroin aqueous solution to the chitin to the calcium carbonate is (1.5-3): 0.3-0.4): 1.
Preferably, the weight ratio of the aqueous silk fibroin solution to the calcium carbonate is 2.2:1.
Preferably, the chitin is also pretreated before being added into the silk fibroin aqueous solution, and the pretreatment method is as follows:
adding chitin into the mixed solution of sodium hydroxide and urea, stirring, mixing, swelling, adding into the mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid, stirring, refluxing, ultrasonic treating, standing, and freeze drying.
By adopting the technical scheme, after the chitin is swelled, the acid breaks the polymer chain to degrade the chitin, so that the chitin is uniformly dispersed in the silk fibroin aqueous solution and is not agglomerated while the particle size of the chitin is reduced, and the modification effect of the modified calcium carbonate is improved. The performance of the floor coating prepared by the application is detected, the abrasion of the coating which is not pretreated with the chitin is 17/mg, the abrasion of the coating which is pretreated with the chitin is reduced to 11/mg, and the abrasion resistance of the coating is obviously improved.
Preferably, the specific method of freeze drying is as follows: freeze drying at-10deg.C to-20deg.C for 3 hr, and freeze drying at-40deg.C to-60deg.C for 18 hr.
By adopting the technical scheme, when the modified calcium carbonate is frozen rapidly at the temperature of minus 50 ℃, a large number of pores are generated on the surface of the modified calcium carbonate, the water absorption of the modified calcium carbonate is improved, and by pre-freezing at the temperature of minus 20 ℃, the temperature difference is reduced, the porosity is reduced, the water absorption of the modified calcium carbonate is reduced, and the anti-permeability performance of the coating is improved.
Preferably, the polyol is a mixture of polyether glycol and polyester triol, and the weight ratio of the polyether glycol to the polyester triol is 1 (0.2-0.4).
By adopting the technical scheme, the polyester triol and the polyether diol are compounded, and the ester group is introduced, so that the acting force among molecules in a polyurethane chain is increased, the hydrogen bonding effect is enhanced, a physical crosslinking network is thickened, the tensile strength and the hardness of the coating are improved, and the wear resistance of the coating is further improved.
Compared with the floor coating prepared by using polyether glycol alone, the floor coating prepared by the method has the advantages that the abrasion is 17/mg, the abrasion of the coating using polyester triol and polyether glycol is 14-15/mg, and the abrasion resistance of the coating is improved.
Preferably, the chain extender is a mixture of hydrazine hydrate and MOCA; the weight ratio of hydrazine hydrate to MOCA is (1.2-1.5): 1.
By adopting the technical scheme, compared with the use of MOCA only in the coating, the hydrazine hydrate increases the rigidity of the coating, and the prepared coating has high rigidity and good wear resistance.
In a second aspect, the present application provides a method for preparing a self-lubricating wear-resistant polyurethane floor coating, which adopts the following technical scheme:
a preparation method of wear-resistant polyurethane floor coating with a self-lubricating effect comprises the following steps:
s1, dehydrating polyalcohol and castor oil in vacuum, cooling to 55-65 ℃, adding isocyanate, heating to 85-95 ℃ for continuous reaction, cooling, degassing and discharging to obtain a component A;
s2, adding a chain extender, a catalyst and an additive into chlorinated paraffin, dehydrating at 105-115 ℃, cooling to 55-65 ℃, adding a solvent and modified calcium carbonate, stirring, degassing, and discharging to obtain a component B;
and S3, stirring and mixing the component A and the component B, and discharging to obtain the composite material.
By adopting the technical scheme, the steps are fewer, the process is concise and efficient, the industrial amplified production of the floor coating is facilitated, and the prepared floor coating has excellent wear resistance and higher adhesive force.
In summary, the present application has the following beneficial effects:
1. the application adopts chitin to fill micropores of calcium carbonate, adopts silk fibroin aqueous solution to coat the calcium carbonate, prepares modified calcium carbonate with high strength, and directly improves the wear resistance of the coating; meanwhile, in the friction process, silk fibroin or chitin can migrate to a friction interface of the floor coating to form a lubricating layer, so that a self-lubricating effect is achieved; or pyrolyzing to generate an air cushion at a friction interface, so that the abrasion of the coating is reduced, and the abrasion resistance of the coating is improved;
2. in the application, the concentration of the silk fibroin aqueous solution is controlled, so that the silk fibroin forms a compact network structure, the modifying effect on calcium carbonate is improved, and the wear resistance of the prepared coating is better;
3. according to the preparation method, the chitin is pretreated, degraded and thinned, the chitin is not easy to agglomerate, the modification effect on calcium carbonate is improved, the chitin is fully dispersed in the coating, and the wear resistance of the prepared coating is better.
Detailed Description
The present application is further described in detail below with reference to examples, wherein MOCA is 4,4' -methylenebis (2-chloroaniline), abbreviated herein as MOCA only.
Preparation example
Preparation example 1
The modified calcium carbonate comprises the following components in parts by weight as shown in table 1:
adding 2.5kg of chitin into 35kg of 40wt% silk fibroin aqueous solution (prepared by conventionally mixing silk fibroin with water), stirring and mixing for 20min to obtain a mixture A; adding 10kg of calcium carbonate into the mixture A, stirring and mixing for 1h at 25 ℃, freeze-drying for 18h at minus 50 ℃, grinding and crushing, and sieving with a 150-mesh sieve to obtain the calcium carbonate.
Chitin was obtained from shandong duckweed poly biotechnology limited;
calcium carbonate, 77% porosity, 800 mesh particle size.
PREPARATION EXAMPLES 2 to 5
The modified calcium carbonate differs from preparation example 1 in the concentration of the aqueous silk fibroin solution as follows:
preparation example 1, concentration of silk fibroin aqueous solution 40wt%;
preparation 2, aqueous silk fibroin solution concentration was 50wt%.
Preparation example 3, aqueous silk fibroin solution concentration was 55wt%.
Preparation 4, aqueous silk fibroin solution concentration was 60wt%.
Preparation 5, aqueous silk fibroin solution concentration was 70wt%.
Preparation examples 6 to 8
The difference between the modified calcium carbonate and the preparation example 1 is that the amounts of the aqueous silk fibroin solution and the chitin are different, as follows:
the weight ratio of the silk fibroin aqueous solution, the chitin and the calcium carbonate in preparation example 1 is 3.5:0.25:1.
Preparation example 6, silk fibroin aqueous solution, chitin and calcium carbonate in a weight ratio of 1.5:0.3:1.
Preparation example 7, silk fibroin aqueous solution, chitin and calcium carbonate in a weight ratio of 2.2:0.35:1.
Preparation example 8, silk fibroin aqueous solution, chitin and calcium carbonate in a weight ratio of 3:0.4:1.
Preparation example 9
The modified calcium carbonate is different from the preparation example 1 in that the chitin is also pretreated before being added into the aqueous solution of silk fibroin, and the pretreatment method is as follows:
100g of chitin is added into a mixed solution consisting of 6L of sodium hydroxide aqueous solution (mass fraction 10%), 7L of urea aqueous solution (concentration 15 wt%) and stirred and mixed, swelled for 5h, added into a mixed solution consisting of 2L of concentrated hydrochloric acid (mass fraction 37%), 4L of concentrated hydrochloric acid (mass fraction 98%), stirred and refluxed at 110 ℃ for 2h, sonicated for 2h, then repeatedly refluxed and sonicated for three times respectively, and then left stand and dried by nitrogen.
Preparation example 10
The modified calcium carbonate differs from preparation example 9 in that the conditions for freeze-drying are different, and the specific method for freeze-drying is as follows: freeze-drying at-10deg.C for 3 hr, and freeze-drying at-40deg.C for 18 hr.
PREPARATION EXAMPLE 11
The modified calcium carbonate differs from preparation example 9 in that the conditions for freeze-drying are different, and the specific method for freeze-drying is as follows: freeze-drying at-15deg.C for 3 hr, and freeze-drying at-50deg.C for 18 hr.
Preparation example 12
The modified calcium carbonate differs from preparation example 9 in that the conditions for freeze-drying are different, and the specific method for freeze-drying is as follows: freeze-drying at-20deg.C for 3 hr, and freeze-drying at-60deg.C for 18 hr.
Comparative preparation example 1
A modified calcium carbonate differing from preparation example 1 in that an equal amount of aqueous soy protein solution (40 wt% concentration) was used instead of the aqueous silk fibroin solution in the preparation of the modified calcium carbonate;
the aqueous solution of soybean protein is obtained by adding soybean protein powder into water, stirring at 50deg.C until completely dissolved, and the particle size of soybean protein powder is 80 mesh.
Comparative preparation example 2
The difference between the modified calcium carbonate and the preparation example 1 is that the chitosan is used to replace the chitin with the same amount in the preparation process of the modified calcium carbonate;
chitosan was obtained from Hebei Jiuyu biotechnology Co.
Examples
Example 1
The wear-resistant polyurethane floor coating with the self-lubricating effect comprises a component A and a component B, wherein the components and the corresponding weights of the components are shown in a table 1, and the wear-resistant polyurethane floor coating is prepared by the following steps:
s1, dehydrating polyol (polyether N-210) and castor oil in vacuum at 110 ℃, cooling to 60 ℃, adding isocyanate (MDI), heating to 90 ℃ for reaction for 3 hours, cooling, degassing and discharging to obtain a component A;
s2, adding a chain extender (MOCA), a catalyst (triethylenediamine) and an additive (BYK 204, BYK 161) into chlorinated paraffin, dehydrating for 3 hours at 110 ℃, cooling to 60 ℃, adding a solvent (No. 260 solvent oil) and modified calcium carbonate (obtained by preparation example 1), stirring and degassing for 1 hour, and discharging to obtain a component B;
wherein, the chlorinated paraffin is industrial grade chlorinated paraffin No. 52;
s3, taking 100kg of the component A and 100kg of the component B, stirring and mixing for 5min, and discharging to obtain the composite material.
Comparative examples 1 to 2
A polyurethane floor coating differs from example 3 in the amounts of the components used, see Table 1.
TABLE 1 Each of the components in examples 1-5, comparative examples 1-2 and weights (kg)
The polyurethane floor coating differs from example 3 in the use of modified calcium carbonate as follows: comparative example 3, using an equivalent amount of calcium carbonate instead of modified calcium carbonate; calcium carbonate, 77% porosity, 800 mesh particle size.
Comparative example 4 modified calcium carbonate was prepared from comparative preparation example 1.
Comparative example 5 modified calcium carbonate was prepared from comparative preparation 2.
Examples 6 to 7
The wear-resistant polyurethane floor coating with the self-lubricating effect is different from the example 1 in that the weight ratio of the component A to the component B is different as follows:
the weight ratio of the component A to the component B in the embodiment 1 is 1:1.
The weight ratio of the component A to the component B in the example 6 is 2:1.
The weight ratio of the component A to the component B in the embodiment 7 is 3:1.
Comparative examples 6 to 7
The polyurethane floor coating is different from the example 1 in that the weight ratio of the component A to the component B is different as follows: the weight ratio of the comparative example 6 to the components A and B is 0.8:1.
The weight ratio of the component A to the component B in example 7 is 3.5:1.
Examples 8 to 18
The difference between the self-lubricating wear-resistant polyurethane floor coating and the example 1 is that the modified calcium carbonate is used in the conditions shown in Table 2.
TABLE 2 usage of modified calcium carbonate in examples 8-18
| Examples | 1 | 8 | 9 | 10 | 11 | 12 |
| Preparation example of modified calcium carbonate | 1 | 2 | 3 | 4 | 5 | 6 |
| Examples | 13 | 14 | 15 | 16 | 17 | 18 |
| Preparation example of modified calcium carbonate | 7 | 8 | 9 | 10 | 11 | 12 |
Examples 19 to 21
A self-lubricating wear-resistant polyurethane floor coating is different from example 1 in that a mixture of equal amounts of polyether glycol (polyether N-210) and polyester triol (polycaprolactone triol) in the following weight ratio is used to replace polyether N-210; the weight ratio of example 19, polyether N-210, polycaprolactone triol was 1:0.2.
Example 20, polyether N-210, polycaprolactone triol in a weight ratio of 1:0.25.
The weight ratio of example 21, polyether N-210, polycaprolactone triol was 1:0.3.
Examples 22 to 24
The self-lubricating wear-resistant polyurethane floor coating is different from example 1 in that the same amount of hydrazine hydrate and MOCA are used for replacing MOCA according to the following weight ratio:
the weight ratio of example 22, hydrazine hydrate, MOCA was 1.2:1.
The weight ratio of example 23, hydrazine hydrate, MOCA was 1.35:1.
The weight ratio of example 24, hydrazine hydrate, MOCA was 1.5:1.
Performance detection
The floor coatings prepared in examples and comparative examples were subjected to the following performance tests, and the test results are recorded in table 3.
Detection method
1. Wear resistance: according to the standard GB/T1768-2006, an ASR-5612 type Taber abrasion instrument is adopted, a sample is polished under the test conditions of 750g load, 1000 revolutions and CS10# abrasion grinding wheel, the abrasion of the paint is recorded, and the lower the abrasion is, the better the abrasion resistance of the paint is shown.
Sample preparation: preparing the coating into a coating film sheet with the thickness of (1.5+/-0.2) mm by using a coating machine, curing for 96 hours under the conditions of the temperature of (25+/-2) DEG C and the relative humidity of (50+/-10)%, demoulding, turning over and continuing curing for 72 hours to obtain the coating film.
2. Paint adhesion rating: drawing 10X 10 small grids with the length of 1mm X1 mm on the surface of a sample, drawing a deep coating layer, firmly adhering the tested small grids by using 3M No. 600 gummed paper, holding one end of the gummed paper, rapidly tearing off the gummed paper in the vertical direction (90 ℃) and repeating the test twice at the same position, and grading according to the following standard:
5B, the scribing edge is smooth, and no paint falls off at the scribing edge and the crossing point;
4B, small pieces of paint fall off at the scribing intersection points, wherein the total falling area is less than 5%;
3B, small pieces of paint fall off at the scribing edges and the crossing points, wherein the falling area is between 5 and 15 percent; 2B, the scribing edges and the crossing points are provided with flake paint falling off, and the falling-off area is 15% -35%; 1B, the scribing edges and the crossing points are provided with flake paint falling off, and the falling-off area is between 35 and 65 percent; 0B, the scribing edges and the crossing points are provided with flake paint falling off, and the falling-off area is more than 65%;5B indicates the optimum paint adhesion, and 0B indicates the worst paint adhesion.
Sample preparation: prepared according to standard GB/T1727-79.
TABLE 3 Performance test results
As is clear from Table 3, in example 1, the abrasion of the floor coating produced was only 17/mg by using the modified calcium carbonate produced in preparation example 1, whereas in comparative example 3, the abrasion of the coating produced was as high as 30/mg by not using the modified calcium carbonate, indicating that the use of the modified calcium carbonate greatly reduced the abrasion of the coating, greatly improved the abrasion resistance of the coating, and the reason for analysis was probably:
during friction, silk fibroin or chitin can be transferred to the friction interface, and an organic film is formed at the friction interface to lubricate the friction interface and protect the surface of the paint from abrasion. Meanwhile, the heat generated by friction is heated to cause the friction interface, silk fibroin or chitin to be pyrolyzed at the friction interface to form tar-like substances and some gases such as CO and the like, the tar-like substances lubricate the friction interface, and the gases form an air cushion, so that the abrasion of the friction interface on the surface of the coating can be slowed down, and the abrasion resistance of the coating is improved.
Secondly, silk fibroin improves the compatibility between calcium carbonate and other components of the coating, so that modified calcium carbonate is uniformly dispersed in the coating, chitin is deeply penetrated into the calcium carbonate, the strength of the calcium carbonate is improved, the hardness of the coating after solidification is directly improved, the wear resistance is improved, and on the other hand, the adhesive force of the coating is improved, and the adhesive force grade of the floor coating prepared by the application is as high as 5B and is optimal through detection.
As can be seen from the results of Table 3, example 1, comparative example 4 and comparative example 5, silk fibroin and chitin are selected specifically, and other substances cannot be used instead. Comparative example 4 differs from example 1 in that soy protein was used instead of silk fibroin, comparative example 4 in which the coating abrasion was 28/mg, which is significantly higher than in example 1 using silk fibroin, comparative example 5 in which chitosan was used instead of chitin, and coating abrasion was 27/mg, which is significantly higher than in example 1 using chitin, indicating that the abrasion resistance of the coating was significantly reduced when soy protein, chitosan, were used, and in the technical scheme of the present application, only silk fibroin and chitin could be used.
Examples 1 to 5 differ from comparative examples 1 to 2 in that the amounts of the respective components used are different, and the abrasion in examples 1 to 5 is 12 to 17/mg, and the abrasion of the coating is low and the abrasion resistance is excellent; in comparative example 1, the amount of modified calcium carbonate used was reduced compared with example 3, the abrasion of the paint was significantly increased to 25/mg, and it can be seen from the combination of example 3 and comparative example 1 that the abrasion resistance of the paint was improved by increasing the amount of modified calcium carbonate used, but when the amount of modified calcium carbonate was further increased to comparative example 2, the abrasion of the paint did not change significantly compared with example 3, indicating that the excessive amount of modified calcium carbonate did not further improve the abrasion resistance of the paint, the combination cost and other factors, the amount of modified calcium carbonate used should be in the range of examples 1 to 5.
Examples 6 to 7 and comparative examples 6 to 7 are different from example 1 in that the weight ratio of the first component to the second component is different, and each performance of the coating in examples 6 to 7 is better than that of comparative examples 6 and 7, which indicates that the performance of the coating is better when the amounts of the first component and the second component used are within the ranges of examples 1, 6 and 7.
Examples 8 to 11 are different from example 1 in that the concentration of the aqueous silk fibroin solution is different, and as can be seen from Table 3, the abrasion of the paint is lower when the concentration of the aqueous silk fibroin solution is 40wt% to 70wt%, wherein the abrasion is further reduced when the concentration of the aqueous silk fibroin solution is 50wt% to 60wt%, and the abrasion resistance of the paint is optimal.
Examples 12-14 differ from example 1 in that the weight ratio of the aqueous silk fibroin solution, the chitin and the calcium carbonate is different, and it can be seen from Table 3, examples 1 and 12-14 that a certain compounding effect exists among the aqueous silk fibroin solution, the chitin and the calcium carbonate.
Example 15 differs from example 1 in that the chitin is further pretreated before being added into the aqueous silk fibroin solution, the abrasion of the coating is obviously reduced from 17/mg before pretreatment to 11/mg, and the abrasion resistance of the coating is improved;
the reason for this analysis may be: the pretreatment refines the chitin, the chitin is not agglomerated, and is uniformly dispersed in the silk fibroin aqueous solution, so that the modification effect on calcium carbonate is improved, and the chitin is uniformly dispersed in the paint, so that the effect of full lubrication in friction is achieved.
Examples 16-18 differ from example 15 in that the freeze-drying conditions differ, and the modified calcium carbonate under the conditions of examples 16-18 has better properties and the resulting coating has better properties.
In the preparation method of the coating, the temperature after temperature reduction in the step S1 can be selected within the range of 55-65 ℃ and the temperature after temperature rise can be selected within the range of 85-95 ℃; the dehydration temperature of step S2 can be selected within the range of 105-115 ℃ and the temperature after cooling down can be selected within the range of 55-65 ℃, and the above selection does not have a great influence on the performance of the floor coating, in this application, only the steps of cooling down to 50 ℃ and heating up to 90 ℃ in step S1 and dehydrating and cooling down to 60 ℃ at 110 ℃ in step S2 are briefly introduced.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (9)
1. The wear-resistant polyurethane floor coating with the self-lubricating effect is characterized by comprising a component A and a component B, wherein the weight ratio of the component A to the component B is (1-3) 1;
the component A comprises the following components in parts by weight: 60-80 parts of polyalcohol; 0-10 parts of castor oil; 80-100 parts of isocyanate;
the component B comprises the following components in parts by weight: 25-40 parts of modified calcium carbonate; 20-30 parts of chlorinated paraffin; 8-14 parts of chain extender; 10-15 parts of a solvent; 0.3-0.5 part of catalyst; 0.5-3 parts of additive;
the preparation method of the modified calcium carbonate comprises the following steps: adding chitin into 40-70wt% silk fibroin aqueous solution, stirring and mixing to obtain a mixture A; adding calcium carbonate into the mixture A, stirring, mixing, freeze drying, pulverizing, and sieving.
2. The self-lubricating wear-resistant polyurethane floor coating disclosed in claim 1, wherein: the concentration of the aqueous silk fibroin solution is 50-60wt%.
3. The self-lubricating wear-resistant polyurethane floor coating disclosed in claim 1, wherein: the weight ratio of the silk fibroin aqueous solution, the chitin and the calcium carbonate is (1.5-3) (0.3-0.4) 1.
4. A self-lubricating wear-resistant polyurethane floor coating as claimed in claim 3, wherein: the weight ratio of the silk fibroin aqueous solution to the calcium carbonate is 2.2:1.
5. The self-lubricating wear-resistant polyurethane floor coating disclosed in claim 1, wherein: before adding the chitin into the silk fibroin aqueous solution, the chitin is also pretreated, and the pretreatment method comprises the following steps:
adding chitin into the mixed solution of sodium hydroxide and urea, stirring, mixing, swelling, adding into the mixed solution of concentrated sulfuric acid and concentrated hydrochloric acid, stirring, refluxing, ultrasonic treating, standing, and freeze drying.
6. The self-lubricating wear-resistant polyurethane floor coating disclosed by claim 5, wherein the self-lubricating wear-resistant polyurethane floor coating is characterized by comprising the following components in percentage by weight: the freeze drying method comprises the following specific steps: freeze drying at-10deg.C to-20deg.C for 3 hr, and freeze drying at-40deg.C to-60deg.C for 18 hr.
7. The self-lubricating wear-resistant polyurethane floor coating disclosed in claim 1, wherein: the polyol is a mixture of polyether glycol and polyester triol, and the weight ratio of the polyether glycol to the polyester triol is 1 (0.2-0.4).
8. The self-lubricating wear-resistant polyurethane floor coating disclosed in claim 1, wherein: the chain extender is a mixture of hydrazine hydrate and MOCA; the weight ratio of hydrazine hydrate to MOCA is (1.2-1.5): 1.
9. A method for preparing the self-lubricating wear-resistant polyurethane floor coating as claimed in any one of claims 1 to 8, comprising the following steps:
s1, dehydrating polyalcohol and castor oil in vacuum, cooling to 55-65 ℃, adding isocyanate, heating to 85-95 ℃ for continuous reaction, cooling, degassing and discharging to obtain a component A;
s2, adding a chain extender, a catalyst and an additive into chlorinated paraffin, dehydrating at 105-115 ℃, cooling to 55-65 ℃, adding a solvent and modified calcium carbonate, stirring, degassing, and discharging to obtain a component B;
and S3, stirring and mixing the component A and the component B, and discharging to obtain the composite material.
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