CN113122175B - Preparation method of elastic polyaspartic ester pouring sealant and product thereof - Google Patents
Preparation method of elastic polyaspartic ester pouring sealant and product thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The application provides a preparation method of an elastic polyaspartic ester pouring sealant, which comprises the following steps: mixing the component A and the component B according to the mass ratio of (0.6-2.5) to (0.53-1.7); the component B is a curing agent, and the component A comprises polyether polyol modified polyaspartic acid ester resin; the preparation method of the polyether polyol modified polyaspartic acid ester resin comprises the following steps: carrying out vacuum reaction on polyether polyol and polyaspartic acid ester under the action of an ester exchange catalyst, adding a hydrochloric acid aqueous solution after the reaction is finished, uniformly stirring, stopping the reaction, and removing the ester exchange catalyst to obtain polyether polyol modified polyaspartic acid ester resin; the polyaspartate is F420 or F524. The preparation method of the elastic polyaspartic ester pouring sealant provided by the application has the advantages of no defects caused by a catalyst, long room temperature operation time and high drying speed.
Description
Technical Field
The application relates to the field of pouring sealant product processing, in particular to a preparation method of an elastic polyaspartic ester pouring sealant and a product thereof.
Background
The pouring sealant is a glue used for bonding, sealing, encapsulating and coating protection of electronic components. The pouring sealant is liquid before being cured and has fluidity. The pouring sealant can realize the use value after being completely cured, and can play the roles of water resistance, moisture resistance, dust prevention, insulation, heat conduction, confidentiality, corrosion resistance, temperature resistance and shock resistance after being cured.
The traditional pouring sealant mainly comprises polyurethane pouring sealant, organic silicon pouring sealant and epoxy pouring sealant. Wherein, the epoxy pouring sealant is rigid pouring sealant, is difficult to be made into elastic pouring sealant, and promotes reaction by adding catalysts such as tertiary ammonia, imidazole and the like; the organic silicon pouring sealant has good elasticity, high and low temperature resistance and excellent electrical insulation, but the organic silicon pouring sealant has poor adhesion to a base material and low material strength, the condensed organic silicon pouring sealant can be completely cured by an organic tin catalyst, and the addition type organic silicon pouring sealant needs to be added with a platinum catalyst to promote the addition reaction of a silicon-hydrogen bond and an unsaturated double bond. The polyurethane pouring sealant has good cohesiveness to a base material, but the early reaction releases heat, the viscosity is increased quickly, and the later curing speed is slow. Polyurethane and water can cause foaming under the action of organic metal or amine catalysts, and organic lead, organic mercury and organic tin catalysts are commonly used in polyurethane pouring sealant, for example, the patent with the publication number of CN103724592B discloses a preparation method of a polyurethane elastomer composition for electronic encapsulation, wherein the organic mercury or organic lead catalysts are adopted to catalyze the reaction of polyurethane and polyether polyol, although the reaction selectivity of polyurethane and hydroxyl is high, and the reaction catalytic capability of isocyanate and water is weak. However, catalysts such as organic mercury, organic lead, organic tin and the like belong to toxic and harmful substances, and the catalysts are remained in the polyurethane pouring sealant material, so that the environmental pollution is caused, the body of a user is injured, and the special groups such as pregnant women, infants and the like are particularly injured.
Because the catalyst is needed to be used or contained in the component A when the component A and the component B are mixed in the preparation process of the polyurethane pouring sealant at present, the defects caused by the use of the catalyst can be overcome. Therefore, the application provides a preparation method of the elastic polyaspartic ester pouring sealant, wherein a catalyst is not used in the mixing process of the component A and the component B, and the catalyst is not contained in the component A.
Disclosure of Invention
In order to overcome the defects caused by the use of a catalyst in the preparation process of the elastic polyaspartic ester pouring sealant and improve the operation time of the elastic polyaspartic ester pouring sealant, the application provides a preparation method of the elastic polyaspartic ester pouring sealant and a product thereof.
In a first aspect, the application provides a preparation method of an elastic polyaspartic ester pouring sealant, which is realized by adopting the following technical scheme:
a preparation method of elastic polyaspartic ester pouring sealant comprises the following steps: mixing the component A and the component B according to the mass ratio of (0.6-2.5) to (0.53-1.7); the component B is a curing agent, and the component A comprises polyether polyol modified polyaspartic acid ester resin;
the preparation method of the polyether polyol modified polyaspartic acid ester resin comprises the following steps:
carrying out vacuum reaction on polyether polyol and polyaspartic acid ester under the action of an ester exchange catalyst, adding a hydrochloric acid aqueous solution after the reaction is finished, uniformly stirring, stopping the reaction, and removing the ester exchange catalyst to obtain polyether polyol modified polyaspartic acid ester resin;
the polyaspartate is F420 or F524.
By adopting the technical scheme, under the action of an ester exchange catalyst, the polyether polyol modified polyaspartic acid ester F420 or polyaspartic acid ester F524 is added with hydrochloric acid aqueous solution for termination reaction to prepare the polyether polyol modified polyaspartic acid ester resin, the hydrochloric acid aqueous solution not only has the effect of termination reaction, but also can remove the ester exchange catalyst, so that the polyether polyol modified polyaspartic acid ester resin and a curing agent do not participate in the reaction of the catalyst, the defects brought by the catalyst can be overcome, the environmental pollution caused by the residue of catalysts such as organic mercury, organic lead and organic tin is avoided, and the room temperature operation time of the elastic polyaspartic acid ester pouring sealant is prolonged.
Preferably, the mass ratio of the polyether polyol to the polyaspartic acid ester is (1-4): 1.
By adopting the technical scheme, the mass ratio of the polyether polyol to the polyaspartic acid ester is (1-4) to 1, so that the polyether polyol has better elasticity and hardness and short drying time; the mass ratio of the polyether polyol to the polyaspartic acid ester is too low, and although glue can be generated to a certain extent, the elasticity of the elastic polyaspartic acid ester pouring sealant can be reduced; and the mass ratio of the polyether polyol to the polyaspartic acid ester is too high, so that the hardness of the generated elastic polyaspartic acid ester pouring sealant can be reduced, the drying performance is poor, and the drying time is long.
Preferably, the polyether polyol is selected from one or more of PPG 1000, PPG 2000, PPG 3000 and PPG 5000.
By adopting the technical scheme, the polyether polyols PPG 1000, PPG 2000, PPG 3000 and PPG 5000 modified polyaspartic acid ester have the advantages of high reaction speed, excellent mechanical property, good elasticity, proper hardness and long operation time.
Preferably, the concentration of the hydrochloric acid aqueous solution is 0.15-0.25 mol/L.
By adopting the technical scheme, the hydrochloric acid aqueous solution with the concentration of 0.15-0.25mol/L has a good effect of terminating the ester exchange reaction of polyether polyol and polyaspartic acid ester, can avoid the phenomenon that the polymerization degree of the elastic polyaspartic acid ester pouring sealant is too high, influences the bonding property and elasticity of the elastic polyaspartic acid ester pouring sealant, can effectively remove an ester exchange catalyst, and simultaneously can not react with amino to form salt.
Preferably, the mass ratio of the aqueous hydrochloric acid solution to the transesterification catalyst is 1:1.
By adopting the technical scheme, when the mass ratio of the hydrochloric acid aqueous solution to the ester exchange catalyst is 1:1, the removal effect of the hydrochloric acid aqueous solution on the ester exchange catalyst is the best, so that the performance of the elastic polyaspartic acid ester pouring sealant can be improved.
Preferably, the component A also comprises an antifoaming agent, and the mass ratio of the polyether polyol modified polyaspartic acid ester resin to the antifoaming agent is (99.3-99.7): (0.3-0.7); more preferably, the mass ratio of the polyether polyol modified polyaspartic acid ester resin to the defoaming agent is 99.5: 0.5.
By adopting the technical scheme, the addition of the defoaming agent can effectively remove small bubbles generated in the preparation process of the elastic polyaspartic ester pouring sealant. When the mass ratio of the polyether polyol modified polyaspartic acid ester resin to the defoaming agent is 99.5:0.5, the defoaming effect of the elastic polyaspartic acid ester pouring sealant is good, and the transparency of the elastic polyaspartic acid ester pouring sealant can be improved. When the content of the defoaming agent is high, although no bubbles are formed, slight turbidity occurs, and when the content of the defoaming agent is reduced, the defoaming effect is poor.
Preferably, the antifoaming agent is selected from one or more of BYK1790, BYK-085 and BYK-024.
By adopting the technical scheme, the defoaming agents BYK1790, BYK-085 and BYK-024 can reduce bubbles of the component A. Wherein BYK-024 is a modified polydimethylsiloxane solution and is easy to float upwards to cause oil floating on the surface of the material; BYK1790 does not contain organic silicon, and the transparency of the corresponding elastic polyaspartic ester pouring sealant is better; BYK-085 is an organic silicon type defoaming agent, and the defoaming agent has poor compatibility with a pouring sealant system, so that the transparency of the system is reduced.
Preferably, the amine value of the A component is 41.4-173.3mg KOH/g.
By adopting the technical scheme, the amino group of the component A corresponds to the NCO group of the component B according to the mol ratio of 1:1.05, the elastic polyaspartic ester pouring sealant prepared has high elastic recovery rate, and the rest performances of the elastic polyaspartic ester pouring sealant are excellent.
In a second aspect, the present application provides an elastic polyaspartic ester pouring sealant, which adopts the following technical scheme:
an elastic polyaspartic acid ester pouring sealant prepared by the preparation method.
By adopting the technical scheme, the elastic polyaspartic ester pouring sealant prepared by the preparation method has the advantages of high elastic recovery rate, long room-temperature operation time and high drying speed.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, under the action of an ester exchange catalyst, the polyether polyol modified polyaspartic acid ester F420 or polyaspartic acid ester F524 is added with hydrochloric acid aqueous solution to terminate the reaction, so that the reaction of the polyether polyol modified polyaspartic acid ester resin and a curing agent is not involved with the catalyst, the defects brought by the catalyst can be overcome, the environmental pollution caused by the residue of catalysts such as organic mercury, organic lead and organic tin is avoided, and the room-temperature operation time of the elastic polyaspartic acid ester pouring sealant is prolonged.
2. The mass ratio of the polyether polyol to the polyaspartic acid ester is (1-4): 1, has better elasticity and hardness and short drying time.
3. This application adopts the hydrochloric acid aqueous solution that concentration is 0.15-0.25mol/L, and it is better to the transesterification termination effect of polyether polyol and polyaspartic acid ester, can avoid elasticity polyaspartic acid ester casting glue's polymerization degree too high, influences elasticity polyaspartic acid ester casting glue's adhesive property and elasticity, and can effectively get rid of the ester exchange catalyst, can not react salifying with the amino simultaneously.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the present application are commercially available, and those not mentioned in the present application are purchased from national pharmaceutical group chemical agents limited, unless otherwise specified.
Examples
Examples 1-17 provide a method for preparing an elastomeric polyaspartic ester potting adhesive, and are described below with reference to example 1.
The preparation method of the elastic polyaspartic ester pouring sealant provided by the embodiment 1 comprises the following preparation steps:
s1, synthesizing polyether polyol modified polyaspartic acid ester resin: mixing 70g of polyether polyol PPG 2000 and 30g of polyaspartic acid ester F420, carrying out vacuum reaction for 4h at 110 ℃ and the vacuum degree of 100Pa under the catalysis of 0.5g of aluminum triisopropoxide, adding 0.5g of 0.2mol/L hydrochloric acid aqueous solution, uniformly stirring, and cooling to 40 ℃ to obtain polyether polyol modified polyaspartic acid ester resin;
s2, synthesizing a component A: adding 0.5g of BYK1790 defoaming agent into the polyether polyol modified polyaspartic acid ester resin to obtain a component A, wherein the NH value is 62.8mg KOH/g;
s3, synthesizing a component B: and (2) dehydrating 65.6g of polyether polyol PPG 3000 at 120 ℃ and 99Pa for 2h, cooling to 70 ℃, adding 34.4g of HMDI prepolymer, and stirring until the reaction is complete to obtain a polyurethane curing agent (component B), wherein the NCO value of a finished product is as follows: 8.26g/100 g;
s4, synthesizing elastic polyaspartic acid ester pouring sealant: mixing the component A and the component B according to the mass ratio of 1.7: 1, mixing, stirring uniformly, and defoaming for 5min to obtain an elastic polyaspartic ester pouring sealant;
wherein the polyether polyol PPG 2000 is purchased from eastern Lanxingdong;
the polyaspartic ester F420 is purchased from New Material Ltd of Zhuhai Feiyang, and has an amine value of 202mg KOH/g;
the CAS number of the aluminum triisopropoxide is 555-31-7;
the BYK1790 defoamer was purchased from Pico;
the polyether polyol PPG 3000 is purchased from eastern bluestar;
the HMDI prepolymer is available under the trade designation HA262, purchased from Wanhua Chemicals.
Example 2, the same as example 1, except that:
s1, synthesizing polyether polyol modified polyaspartic acid ester resin: mixing 50g of polyether polyol PPG 3000 and 50g of polyaspartic acid ester F420, carrying out vacuum reaction for 4h at 110 ℃ and the vacuum degree of 100Pa under the catalysis of 0.5g of triisopropanolamine aluminum, adding 0.5g of 0.2mol/L hydrochloric acid aqueous solution, uniformly stirring, and cooling to 40 ℃ to obtain polyether polyol modified polyaspartic acid ester resin;
s2, synthesizing a component A: adding 0.5g of BYK1790 defoaming agent into polyether polyol modified polyaspartic acid ester resin to obtain a component A, wherein the NH value is 103.65mg KOH/g;
s3, synthesizing a component B: dehydrating 83.6g of polyether polyol PPG 4000 at 120 ℃ and 99Pa for 2h, cooling to 70 ℃, adding 16.4g of HMDI prepolymer, stirring until the reaction is completed, adding 6.4g of HDI trimer TPA-100 to obtain a polyurethane curing agent (component B), wherein the NCO value of a finished product is as follows: 4.7g/100 g;
s4, synthesizing elastic polyaspartic acid ester pouring sealant: mixing the component A and the component B according to the mass ratio of 1: 1.7, stirring uniformly, and defoaming for 5min to obtain the elastic polyaspartic ester pouring sealant;
wherein the polyether polyol PPG 4000 is purchased from Dow of Lanxingdong;
the HDI trimer TPA-100 was purchased from Asahi chemical Co.
Example 3, the same as example 1, except that:
s1, synthesizing polyether polyol modified polyaspartic acid ester resin: mixing 80g of polyether polyol PPG 5000 and 20g of polyaspartic acid ester F420, carrying out vacuum reaction for 4h at 110 ℃ and the vacuum degree of 100Pa under the catalysis of 0.5g of aluminum triisopropoxide, adding 0.5g of 0.2mol/L hydrochloric acid aqueous solution, uniformly stirring, and cooling to 40 ℃ to obtain polyether polyol modified polyaspartic acid ester resin;
s2, synthesizing a component A: adding 0.5g of BYK1790 defoaming agent into the polyether polyol modified polyaspartic acid ester resin to obtain a component A, wherein the NH value is 41.4mg KOH/g;
s3, synthesizing a component B: and (2) dehydrating 71.8g of polyether polyol PPG 2000 at 120 ℃ and-99 Pa for 2h, cooling to 70 ℃, adding 28.2g of HMDI prepolymer, and stirring until the reaction is complete to obtain a polyurethane curing agent (component B), wherein the NCO value of a finished product is as follows: 6.03g/100 g;
s4, synthesizing elastic polyaspartic acid ester pouring sealant: mixing the component A and the component B according to the mass ratio of 1: 0.53, stirring uniformly, and defoaming for 5min to obtain the elastic polyaspartic ester pouring sealant;
wherein the polyether polyol PPG 5000 is purchased from eastern Lanxingdong.
Example 4, like example 1, differs only in that: the polyaspartic acid ester F524 is replaced by the polyaspartic acid ester F420 with the same mass, the amine value of the polyaspartic acid ester F524 is 243.9mg KOH/g, and the polyaspartic acid ester F524 is purchased from New Material GmbH of Zhuhai Feiyang.
Example 5, which differs from example 1 only in that: the equal mass of the polyether polyol PPG 2000 is replaced by polyether polyol PPG 1000, and the polyether polyol PPG 1000 is purchased from east Lanxingdao.
Example 6, which differs from example 1 only in that: and the polyether polyol PPG 2000 and other components are replaced by polyether polyol PPG 5000.
Example 7 differs from example 1 only in that: the aluminum triisopropoxide is replaced by isopropyl titanate with the same mass, the CAS number of the isopropyl titanate is 546-68-9, and the isopropyl titanate is purchased from Nayao chemical Co.
Example 8, which differs from example 1 only in that: the aluminum triisopropoxide is replaced by titanium tetrachloride with the same quality, the CAS number of the titanium tetrachloride is 7550-45-0, and the titanium tetrachloride is purchased from the advanced chemical technology of Wuhan limited company.
Example 9, which differs from example 1 only in that: the concentration of the hydrochloric acid aqueous solution is changed from 0.2mol/L to 0.25 mol/L.
Example 10, which differs from example 1 only in that: the concentration of the hydrochloric acid aqueous solution is changed from 0.2mol/L to 0.15 mol/L.
Example 11, which differs from example 1 only in that: the mass of aluminum triisopropoxide was changed from 0.5g to 0.8 g.
Example 12, which differs from example 1 only in that: the mass of the BYK1790 antifoaming agent is changed from 0.5g to 0.3 g.
Example 13, which differs from example 1 only in that: the mass of the BYK1790 antifoaming agent is changed from 0.5g to 0.7 g.
Example 14, which differs from example 1 only in that: and the BYK1790 defoaming agent and the like are replaced by a BYK-024 defoaming agent.
Example 15, which differs from example 1 only in that: and the BYK1790 defoaming agent and the like are replaced by BYK-085 defoaming agent.
Example 16, which differs from example 1 only in that: the mass of the polyether polyol PPG 2000 was replaced by 15g from 70 g.
Example 17, which differs from example 1 only in that: the mass of the polyether polyol PPG 2000 was replaced by 120g from 70 g.
In examples 1, 4 to 17 of the present application, the amine number of the A component, and the mass ratio of the A component and the B component are shown in Table 1.
TABLE 1 amine number of A-component, mass ratio of A-component and B-component in examples 1, 4 to 17
| Examples | Amine number of component A (mg KOH/g) | The mass ratio of the component A to the component B |
| Example 1 | 62.8 | 1.7:1 |
| Example 4 | 52.7 | 2:1 |
| Example 5 | 64.9 | 1.6:1 |
| Example 6 | 61.6 | 1.7:1 |
| Example 7 | 62.8 | 1.7:1 |
| Example 8 | 62.8 | 1.7:1 |
| Example 9 | 62.8 | 1.7:1 |
| Example 10 | 62.8 | 1.7:1 |
| Example 11 | 62.8 | 1.7:1 |
| Example 12 | 62.8 | 1.7:1 |
| Example 13 | 62.8 | 1.7:1 |
| Example 14 | 62.8 | 1.7:1 |
| Example 15 | 62.8 | 1.7:1 |
| Example 16 | 173.3 | 0.6:1 |
| Example 17 | 42.0 | 2.5:1 |
Comparative example
Comparative example 1, which differs from example 4 only in that: the polyaspartic acid ester F524 and the like are replaced by polyaspartic acid ester F520, the amine value of the polyaspartic acid ester F520 is 202.5mg KOH/g, and the polyaspartic acid ester is purchased from New Material Ltd of Zhuhai Feiyang.
Comparative example 2, which differs from example 4 only in that: the polyaspartic acid ester F524 is replaced by polyaspartic acid ester F220 in equal mass, the amine value of the polyaspartic acid ester F220 is 170mg KOH/g, and the polyaspartic acid ester F220 is purchased from New Material Ltd of Zhuhai Feiyang.
In comparative examples 1 to 2 of the present application, the amine number of the A component, and the mass ratio of the A component and the B component are shown in Table 2.
TABLE 2 amine number of component A, mass ratio of component A and component B in comparative examples 1 to 2
| Comparative example | Amine number of component A (mg KOH/g) | The mass ratio of the component A to the component B |
| Comparative example 1 | 60.0 | 1.8:1 |
| Comparative example 2 | 75.6 | 1.4:1 |
Comparative example 3 provides a polyurethane potting adhesive, which comprises the following preparation steps:
s1, dehydrating 35g of polyether glycol PPG 400, 25g of polyether glycol PPG 750 and 40g of polyether glycol PPG 3000 at 120 ℃ and 99Pa for 2h, cooling to 30 ℃, adding 0.4g of phenylmercuric acetate, stirring uniformly, packaging and discharging to obtain a component A, wherein the OH value is 177mg KOH/g;
56g of trifunctional polyether polyol 330N resin is dehydrated for 2 hours at 120 ℃ and-99 Pa, then the temperature is reduced to 70 ℃, 44g of HMDI is added and stirred until the reaction is completed, a curing agent component B is obtained, and the NCO value of the finished product is as follows: 12.69g/100 g;
mixing the component A and the component B according to the mass ratio of 1:1, mixing, stirring uniformly, and defoaming for 5min to obtain a polyurethane pouring sealant;
wherein the polyether polyol PPG 400 is purchased from eastern Lanxingdong;
the polyether polyol PPG 750 is purchased from eastern Lanxingdong;
the number of the phenylmercuric acetate CAS is 62-38-4, and the phenylmercuric acetate is purchased from chemical technology Co., Ltd of Ke chemical engineering (Beijing);
the trifunctional polyether polyol 330N resin was purchased from the eastern bluestar.
Performance test
The following performance tests were performed on the potting adhesives provided in examples 1 to 17 and comparative examples 1 to 3 of the present application.
1. Elasticity: pouring the pouring sealant described in the embodiments 1-17 and the comparative examples 1-3 into a tetrafluoroethylene mold with the length of 165mm, the width of 19mm and the height of 10mm to prepare a rubber strip of a sample, selecting 60mm in the middle of the rubber strip, using a mark line to mark, using a universal stretcher to stretch directionally to 100% of elongation, maintaining the directional stretching for 5min, resetting and taking down a sample strip, immediately measuring the length of the mark line to obtain a numerical value a, and then obtaining an elastic recovery rate R calculation formula as follows:
R=（2-a/60）×100%
the results of the test of the elastic recovery R are shown in Table 3.
2. Shore hardness: the Shore hardness of the potting compounds described in examples 1 to 17 and comparative examples 1 to 3 was tested with reference to the GB/T2411-2008 standard, and the test results are shown in Table 3.
3. Run time, cure time, final dry time, final appearance: the potting compounds described in examples 1 to 17 and comparative examples 1 to 3 were potted in small disks 4cm in diameter and 1cm in height, and the pot life, curing time, final drying time and final appearance were observed, with the test results shown in Table 3.
Table 3 performance test data
| Pouring sealant | Elastic recovery rate R (%) | Shore hardness | Operating time (min) | Curing time (min) | Final drying time (h) | Final appearance |
| Example 1 | 100 | Shore A67 | 70 | 240 | 48 | Transparent bubble-free |
| Example 2 | 100 | Shore A73 | 40 | 110 | 30 | Transparent bubble-free |
| Example 3 | 100 | Shore A50 | 60 | 180 | 36 | Transparent bubble-free |
| Example 4 | 100 | Shore A62 | 110 | 330 | 60 | Transparent bubble-free |
| Example 5 | 100 | Shore A72 | 35 | 110 | 36 | Transparent bubble-free |
| Example 6 | 100 | Shore A60 | 90 | 290 | 55 | Transparent bubble-free |
| Example 7 | 100 | Shore A67 | 64 | 220 | 48 | Transparent bubble-free |
| Example 8 | 100 | Shore A67 | 50 | 160 | 48 | Transparent bubble-free |
| Example 9 | 100 | Shore A67 | 61 | 200 | 48 | Transparent bubble-free |
| Example 10 | 100 | Shore A67 | 59 | 190 | 48 | Transparent bubble-free |
| Example 11 | 100 | Shore A67 | 60 | 200 | 48 | Transparent bubble-free |
| Example 12 | 100 | Shore A67 | 67 | 236 | 48 | Transparent and containing a small amount of bubbles |
| Example 13 | 100 | Shore A67 | 66 | 235 | 48 | Slight turbidity without bubbles |
| Example 14 | 100 | Shore A67 | 64 | 232 | 48 | Turbidity without bubbles |
| Example 15 | 100 | Shore A67 | 68 | 237 | 48 | Transparent and containing a small amount of bubbles |
| Example 16 | 83 | Shore A87 | 90 | 330 | 48 | Transparent bubble-free |
| Example 17 | 100 | Shore A55 | 77 | 280 | 66 | Transparent bubble-free |
| Comparative example 1 | 100 | Shore A55 | 25 | 600 | 72 | Transparent bubble-free |
| Comparative example 2 | 100 | Non-drying | - | - | - | - |
| Comparative example 3 | 100 | Shore A26 | 2 | 6 | 12 | Transparent bubble-free |
The present application is described in detail below with reference to the test data provided in table 3.
As can be seen from examples 1-3 and comparative example 1, the component A and the component B are mixed without using a catalyst, and the component A is removed of the ester exchange catalyst, so that the environmental pollution caused by the residue of catalysts such as organic mercury, organic lead and organic tin is avoided, the operation time of the pouring sealant can be prolonged, and the curing time and the drying time of the pouring sealant can be shortened.
As can be seen from examples 1 and 4 and comparative examples 2 to 3, the kind of polyaspartic ester has a great influence on the shore hardness, the operation time, the curing time and the final drying time of the elastic polyaspartic ester potting adhesive, wherein the shore hardness corresponding to polyaspartic ester F420 is higher than the shore hardness corresponding to polyaspartic ester F524, and the operation time, the curing time and the final drying time corresponding to polyaspartic ester F420 are lower than the operation time, the curing time and the final drying time corresponding to polyaspartic ester F524; the elastic polyaspartic ester pouring sealant prepared by the polyaspartic ester F520 is not dry; polyaspartic acid ester F220 has a low Shore hardness, short operation time, short curing time, and short final drying time. Comprehensively considered, the elastic polyaspartic ester pouring sealant corresponding to the polyaspartic ester F420 has better performance.
As can be seen from examples 1 and 5 to 6 of the present application, the elastic polyaspartic acid ester pouring sealant corresponding to the polyether polyol PPG 1000, the PPG 2000, and the PPG 5000 modified polyaspartic acid ester F420 has excellent performance, wherein the shore hardness corresponding to the PPG 1000 is high, the operation time, the curing time, and the final drying time corresponding to the PPG 5000 are long, and the shore hardness, the operation time, the curing time, and the final drying time of the PPG 2000 are moderate.
From examples 1 and 7 to 8 of the present application, it can be seen that the kind of the transesterification catalyst has an influence on the operation time and the curing time of the elastic polyaspartic ester potting adhesive, wherein the operation time and the curing time corresponding to aluminum triisopropoxide are longer, the operation time and the curing time corresponding to titanium tetrachloride are shorter, and the operation time and the curing time corresponding to isopropyl titanate are moderate.
From the examples 1 and 9-10, the concentration of the hydrochloric acid aqueous solution has an influence on the operation time and the curing time of the elastic polyaspartic ester pouring sealant, wherein the operation time and the curing time are longer for 0.2mol/L, shorter for 0.25mol/L, and moderate for 0.15 mol/L.
From examples 1 and 11 of the present application, it can be seen that when the amount of transesterification catalyst is increased from 0.5g to 0.8g, the operating time and curing time of the elastomeric polyaspartic ester potting compound are correspondingly reduced.
As is clear from examples 1 and 12 to 13 of the present application, slight clouding occurred when the mass of the defoaming agent was large, and a small amount of bubbles occurred when the mass of the defoaming agent was small. And when the mass ratio of the polyether polyol modified polyaspartic acid ester resin to the defoaming agent is 99.5:0.5, the polyether polyol modified polyaspartic acid ester resin is transparent and free of bubbles, and the operation time and the curing time are high.
From examples 1 and 14 to 15 of the present application, it is understood that the kind of the defoaming agent has a large influence on the defoaming effect and the transparency, and has a corresponding influence on the operation time and the curing time of the elastic polyaspartic ester potting adhesive. Wherein, the performance of BYK1790 is better than BYK-024, and better than BYK-085.
From examples 1 and 16 to 17 of the present application, it can be seen that the mass ratio of the polyether polyol to the polyaspartic acid ester has a greater influence on the elasticity, hardness and drying properties of the elastic polyaspartic acid ester potting compound. Wherein, the mass ratio of the polyether polyol to the polyaspartic acid ester is too low, and the elasticity of the elastic polyaspartic acid ester pouring sealant is obviously reduced; the mass ratio of the polyether polyol to the polyaspartic acid ester is too high, the hardness of the generated elastic polyaspartic acid ester pouring sealant can be reduced, the drying performance is poor, and the drying time is long.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The preparation method of the elastic polyaspartic ester pouring sealant is characterized by comprising the following steps:
mixing the component A and the component B according to the mass ratio of (0.6-2.5) to (0.53-1.7), and uniformly stirring to obtain the elastic polyaspartic ester pouring sealant;
the component B is a curing agent, and the component A comprises polyether polyol modified polyaspartic acid ester resin;
the preparation method of the polyether polyol modified polyaspartic acid ester resin comprises the following steps:
carrying out vacuum reaction on polyether polyol and polyaspartic acid ester under the action of an ester exchange catalyst, adding a hydrochloric acid aqueous solution after the reaction is finished, uniformly stirring, stopping the reaction, and removing the ester exchange catalyst to obtain polyether polyol modified polyaspartic acid ester resin;
the polyaspartate is F420 or F524.
2. The method for preparing the elastic polyaspartic ester pouring sealant as claimed in claim 1, wherein the mass ratio of the polyether polyol to the polyaspartic ester is (1-4): 1.
3. The method of claim 1, wherein the polyether polyol is selected from one or more of PPG 1000, PPG 2000, PPG 3000, and PPG 5000.
4. The method as claimed in claim 1, wherein the concentration of the aqueous solution of hydrochloric acid is 0.15-0.25 mol/L.
5. The method for preparing the elastic polyaspartic ester pouring sealant as claimed in claim 4, wherein the mass ratio of the hydrochloric acid aqueous solution to the ester exchange catalyst is 1:1.
6. The method for preparing the elastic polyaspartic ester pouring sealant as claimed in any one of claims 1-5, wherein the component A further comprises an antifoaming agent, and the mass ratio of the polyether polyol modified polyaspartic ester resin to the antifoaming agent is (99.3-99.7): (0.3-0.7).
7. The method of claim 6, wherein the defoaming agent is selected from one or more of BYK1790, BYK-085 and BYK-024.
8. The method of claim 6, wherein the amine value of the A component is 41.4-173.3mg KOH/g.
9. An article of manufacture obtained by the method of making an elastomeric polyaspartate pouring sealant of any of claims 1-8.
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| CN115505360B (en) * | 2022-10-25 | 2023-04-14 | 深圳市彩田化工有限公司 | Quick-drying rock plate adhesive and preparation method thereof |
| CN115651153A (en) * | 2022-12-06 | 2023-01-31 | 上海东大化学有限公司 | Flame-retardant bi-component polyurethane grouting material and preparation method thereof |
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