阅读说明：本技术 一种有机硅改性的pae树脂、制备方法及其a类阻燃涂料 (Organic silicon modified PAE resin, preparation method and A-type flame-retardant coating thereof ) 是由 卢鹏飞 朱银邦 赵军子 姜山 方雪 李林 于 2020-12-30 设计创作，主要内容包括：本发明公开了一种有机硅改性的PAE树脂、制备方法及其A类阻燃涂料,利用马来酸二甲酯与聚硅硼氧烷的酯交换反应获得马来酸聚硅硼氧烷酯,再与氨基双封端的四甲基二硅氧烷衍生物通过迈克尔加成反应获得有机硅改性的PAE树脂。该树脂可用于复配PAE聚脲树脂,具备优秀的防滑、耐磨、耐污特性之外,还具备优异的耐火性能,在防火性能测试中的防火等级被评定为A级。(The invention discloses an organic silicon modified PAE resin, a preparation method and an A-type flame retardant coating thereof. The resin can be used for compounding PAE polyurea resin, has excellent anti-skid, wear-resisting and stain-resisting characteristics and excellent fire resistance, and the fire-proof grade in the fire-proof performance test is A grade.)

1. A preparation method of organic silicon modified PAE resin is characterized by comprising the following steps:

(1) adding a catalyst into a dimethylbenzene solution of dimethyl maleate and polyborosiloxane for ester exchange reaction, heating and refluxing, and removing a dimethylbenzene solvent in vacuum to obtain polyborosiloxane maleate;

(2) the organosilicon modified PAE resin is obtained by Michael addition reaction of polysiloxane maleate and amino double-end-capped tetramethyl disiloxane derivative.

2. The method of preparing a silicone-modified PAE resin according to claim 1, wherein: the described polyborosiloxane is a polymer synthesized by using tetramethoxysilane or ethyl orthosilicate and boric acid and water alcoholic solution under the catalytic reaction; the molar ratio of tetramethoxysilane or tetraethoxysilane to boric acid is (2-3): 1.

3. The method of preparing a silicone-modified PAE resin according to claim 2, characterized in that: the molar ratio of the dimethyl maleate to the polyborosiloxane is 1 (2-2.4).

4. The method of preparing a silicone-modified PAE resin according to claim 3, wherein: the catalyst in the step (1) is selected from any one or combination of more of sodium methoxide, triethylamine and p-toluenesulfonic acid; the input amount of the catalyst is 0.01-0.1 wt%.

5. The process for the preparation of a silicone-modified PAE resin according to any one of claims 1 to 4, characterized in that: and (3) in the step (2), the Michael addition reaction is carried out at the temperature of 60-80 ℃ and nitrogen is introduced for reaction for 16-30 hours.

6. The method of preparing a silicone-modified PAE resin according to claim 5, wherein: the molar ratio of the poly (borosiloxane maleate) to the amino di-terminated tetramethyl disiloxane derivative is (2-2.4): 1.

7. The silicone-modified PAE resin obtained by the process of claim 1.

8. A class A flame retardant coating comprising a component A and a component B, wherein:

the component A comprises the following components in percentage by mass

B component

Phosphatized phenyl isocyanate;

the mass ratio of the component A to the component B is 1-3: 1.

9. The class a flame retardant coating of claim 8, wherein: the metallic aluminum filler is selected from any one or combination of aluminum borate, aluminum oxide and aluminum hydroxide.

10. The class a flame retardant coating of claim 8, wherein: the auxiliary agent comprises any one or combination of more of a leveling agent, color paste, a defoaming agent, titanium dioxide and silicon dioxide.

Technical Field

The invention relates to the field of high molecular polymer chemistry, in particular to organic silicon modified PAE resin, a preparation method and an A-type flame retardant coating thereof.

Background

The existing antiskid, wear-resistant, stain-resistant and heat-insulating organic floor is not high in fireproof grade, easy to burn and generate dense smoke, the use of materials is limited, and the floor is required to have stain-resistant, antiskid, fireproof and nontoxic characteristics in scenes such as hospitals, schools and laboratories. Especially, most polyaspartic acid ester polyurea terraces can not reach the grade A fire-proof grade.

The ministry of public security of the people's republic of China and the ministry of housing and urban and rural construction have made relevant standard specifications for external thermal insulation systems of buildings, and are stipulated in the second article of "temporary regulations on external thermal insulation systems and external wall decoration fire prevention" (official general word [2009] 46) ": the combustion performance of the external heat-insulating material for civil buildings is preferably A grade and should not be lower than B2 grade. According to the relevant regulations of the national GB 8624-2006 classification of the combustion performance of building materials and products, the A-grade paving material simultaneously meets GB/T5464-2010 incombustibility test (delta T is less than or equal to 30 ℃, delta m is less than or equal to 50 percent, tf is 0s) and GB/T14402-2007 combustion heat value test (PSC is less than or equal to 2.0 MJ/kg).

Chinese patent CN105602424A discloses a weather-resistant halogen-free flame-retardant insulating polyurea coating, wherein weather-resistant polyaspartic acid resin is adopted, has secondary amino groups which can react with isocyanic acid to form resin with a polyurea structure, but the flame-retardant effect of the coating is not good; other technologies are mostly started from the aspect of isocyanate modification, and the flame retardant effect of the obtained product is limited.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a preparation method of organic silicon modified PAE resin synthesized by dimethyl maleate and the PAE resin prepared by the method; it is a further object of the present invention to provide a class A flame retardant coating composition for use in the preparation of the aforementioned resins.

The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing a silicone-modified PAE resin, comprising the steps of:

(1) adding a catalyst into a dimethylbenzene solution of dimethyl maleate and polyborosiloxane for ester exchange reaction, heating and refluxing, and removing a dimethylbenzene solvent in vacuum to obtain polyborosiloxane maleate;

(2) the organosilicon modified PAE resin is obtained by Michael addition reaction of polysiloxane maleate and amino double-end-capped tetramethyl disiloxane derivative.

The poly-silicon boron Siloxane (SiOB) is a polymer synthesized by tetramethoxysilane or tetraethoxysilane and boric acid and water alcoholic solution under the catalytic reaction. The preparation method of the polyborosiloxane and the related synthetic theory refer to' residual boron and the like, the synthesis and performance research of the polyborosiloxane modified epoxy resin [ D ], the combined fertilizer: university of fertilizer industry, 2011 ". In the present invention, the catalytic reaction is carried out at 60 to 80 ℃ for 2 to 3 hours. The alcohol in the alcohol solution is from any one or combination of ethanol, propanol and isopropanol. In order to ensure that colorless and transparent micromolecule monohydroxy polyborosiloxane is obtained, the molar ratio of tetramethoxysilane or tetraethoxysilane to boric acid is adjusted to be (2-3) to 1 during synthesis, and the molar number of water added is equal to the molar number of tetramethoxysilane/tetraethoxysilane/2-boric acid. When the molar ratio of tetramethoxysilane/ethyl orthosilicate to boric acid is 2: 1, the addition amount of water is 0.01-0.1% of the total weight of the raw materials. If the content of boric acid is increased, the polymerization degree of the polyborosiloxane is greatly increased, and a polyhydroxy high molecular substance is generated, so that the subsequent ester exchange reaction with dimethyl maleate is not facilitated.

The amino-bis-terminated tetramethyldisiloxane derivative is selected from any one of the group consisting of, but not limited to, 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane polymers. The amino-bis-blocked tetramethyldisiloxane derivative has an average molecular weight of 200-2000, preferably 200-500.

Further, the molar ratio of the dimethyl maleate to the polyborosiloxane is 1 to (2-2.4); more preferably, the aforementioned molar ratio is 1: 2.1, thereby ensuring that the methyl ester groups of dimethyl maleate are adequately substituted in the transesterification.

Further, the reflux temperature in the step (1) is preferably 140-160 ℃, and the reflux reaction is performed for 3-10 hours. Preferably, the reflux reaction time is 6 hours.

Further, the catalyst in step (1) is selected from the group consisting of but not limited to sodium methoxide, triethylamine, p-toluenesulfonic acid, and any one or more of the combination thereof; among them, p-toluenesulfonic acid is preferably used as a catalyst, has better solubility in xylene and has excellent catalytic rate; the input amount of the catalyst is 0.01-0.1 wt%.

Further, in the step (2), the Michael addition reaction is carried out at the temperature of 60-80 ℃ and nitrogen is introduced for reaction for 16-30 hours. Preferably, the reaction temperature of the Michael addition reaction is 70 ℃ and the reaction time of introducing nitrogen is 24 hours.

The molar ratio of the poly (borosiloxane maleate) to the amino-di-terminated tetramethyl disiloxane derivative is (2-2.4) to 1, so that primary amine is completely converted into secondary amine, and the polyurea reaction time is prolonged.

The silicone-modified PAE resin obtained was prepared as described above as a yellow slightly transparent liquid with a viscosity of 1000-.

The invention also provides a flame-retardant PAE polyurea composition, which comprises a component A and a component B, wherein:

the component A comprises the following components in percentage by mass

B component

Phosphatized phenyl isocyanate;

the mass ratio of the component A to the component B is 1-3: 1.

Wherein the aluminum borate is mainly used for enhancing the strength of the composition, and the preferred addition amount is 0.5 wt%.

Further, the metallic aluminum filler is selected from any one or combination of aluminum oxide and aluminum hydroxide. Preferably, the metallic aluminum filler is a nano-scale powdery filler.

Further, the auxiliary agent is selected from any one or combination of more of leveling agent, color paste, defoaming agent, titanium dioxide and silicon dioxide, and can be selectively used or replaced based on the prior art by the skilled person.

Has the advantages that: the organic silicon modified PAE resin provided by the invention fully considers the influence of molecular weight on ester exchange reaction and Michael addition reaction during preparation, and after the obtained organic silicon modified PAE resin is compounded into a two-component flame-retardant PAE polyurea coating composition, the coating composition has the characteristics of skid resistance, heat preservation and wear resistance, and particularly improves the fire-proof grade to A grade, so that the fire-proof effect is difficult to realize by the existing organic resin coating. Meanwhile, the coating still has good service performance, and the hardness and the elongation rate of the coating reach the standards of the existing floor coating.

Detailed Description

The present invention is further illustrated by the following specific examples.

Example 1

A preparation method of organic silicon modified PAE resin comprises the following steps:

(1) adding tetraethoxysilane, boric acid and water into an ethanol solution, heating to 60-80 ℃, reacting for 2-3 hours under a catalyst (dilute hydrochloric acid), preserving heat, distilling under reduced pressure, removing water and ethanol, and drying in vacuum to obtain colorless and transparent polyborosiloxane.

(2) Adding a catalyst into a xylene solution of dimethyl maleate and polyborosiloxane for ester exchange reaction, wherein the molar ratio of the dimethyl maleate to the polyborosiloxane is 1: 2-2.4, heating and refluxing for 3-10 hours, and then removing a xylene solvent in vacuum to obtain the polyborosiloxane maleate; the catalyst in the step is selected from any one or combination of more of sodium methoxide, triethylamine and p-toluenesulfonic acid, and the input amount of the catalyst is 0.01-0.1 wt%.

(3) Introducing nitrogen into polysiloxane boron alkyl maleate and amino double-terminated tetramethyl disiloxane derivatives at 60-80 ℃ through Michael addition reaction for reacting for 16-30 hours to obtain organic silicon modified PAE resin;

the amino-bis-terminated tetramethyldisiloxane derivative of this step may be 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane or a polymer of 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane (D4), having an average molecular weight of 200-. The molar ratio of the poly (borosiloxane maleate) to the amino-bis-terminated tetramethyl disiloxane derivative is (2-2.4) to 1.

The silicone-modified PAE resin prepared by the above steps (1) - (3) is a yellow slightly transparent liquid with a viscosity of 1000-.

Example 2

(1) Adding ethyl orthosilicate, boric acid (the molar ratio is 3: 1) and water into an ethanol solution, heating to 60-80 ℃, reacting for 2-3 hours under a catalyst (dilute hydrochloric acid), preserving heat, distilling under reduced pressure, removing water and ethanol, and drying in vacuum to obtain colorless and transparent polyborosiloxane.

(2) Adding 0.05 wt% of p-toluenesulfonic acid catalyst into a xylene solution of dimethyl maleate and polyborosiloxane according to the molar ratio of 1: 2.1 for transesterification reaction, heating and refluxing at the reaction temperature of 140 ℃ and 160 ℃ for 6 hours, and then removing the xylene solvent in vacuum to obtain the polyborosiloxane maleate.

(3) The polysiloxane maleate and 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane (average molecular weight 220) are mixed according to the molar ratio of 2.2: 1, and nitrogen is introduced at 70 ℃ for reaction for 24 hours to obtain the organic silicon modified PAE resin.

Example 3

(1) Adding ethyl orthosilicate, boric acid (the molar ratio is 2.5: 1) and water into an ethanol solution, heating to 70-80 ℃, reacting for 2-3 hours under a catalyst (dilute hydrochloric acid), preserving heat, distilling under reduced pressure, removing water and ethanol, and drying in vacuum to obtain colorless and transparent polyborosiloxane.

(2) Adding 0.05 wt% of p-toluenesulfonic acid catalyst into a xylene solution of dimethyl maleate and polyborosiloxane according to the molar ratio of 1: 2.3 for transesterification reaction, heating and refluxing at the reaction temperature of 140 ℃ and 160 ℃ for 6 hours, and then removing the xylene solvent in vacuum to obtain the polyborosiloxane maleate.

(3) Taking a polymer (with the average molecular weight of 300) of 1, 3-bis (3-aminopropyl) -1, 1, 3, 3-tetramethyldisiloxane and octamethylcyclotetrasiloxane, mixing the polymer with polyborosiloxane maleate and reacting the mixture with nitrogen at 70 ℃ for 24 hours according to the molar ratio of 1: 2.1, and obtaining the organic silicon modified PAE resin.

Example 4

A halogen-free flame-retardant PAE polyurea coating comprises a component A and a component B, wherein:

the component A comprises the following components in percentage by mass

B component

100% Anhui Cyseifu of phosphated phenyl isocyanate

The mass ratio of the component A to the component B is 2: 1. Uniformly mixing the component A and the component B in proportion, and rolling and coating a paint film with the thickness of 60-200um by using a roller.

Example 5

A halogen-free flame-retardant PAE polyurea coating comprises a component A and a component B, wherein:

component A

B component

100% Anhui Cyseifu of phosphated phenyl isocyanate

The mass ratio of the component A to the component B is 2: 1. Uniformly mixing the component A and the component B in proportion, and rolling and coating a paint film with the thickness of 60-200um by using a roller.

Example 6

A halogen-free flame-retardant PAE polyurea coating comprises a component A and a component B, wherein:

component A

B component

100% Anhui Cyseifu of phosphated phenyl isocyanate

The mass ratio of the component A to the component B is 2: 1. Uniformly mixing the component A and the component B in proportion, and rolling and coating a paint film with the thickness of 60-200um by using a roller.

Comparative example

A halogen-free flame-retardant PAE polyurea coating comprises a component A and a component B, wherein:

component A

B component

100% Anhui Cyseifu of phosphated phenyl isocyanate

The mass ratio of the component A to the component B is 2: 1. Uniformly mixing the component A and the component B in proportion, and rolling and coating a paint film with the thickness of 60-200um by using a roller.

Test examples

According to the national standard GB/T14402-2007 determination of combustion performance and combustion heat value of building materials and products, the coatings of the above examples and comparative examples are subjected to fire prevention and performance tests, test objects are paint films with the thickness of 60-200um which are obtained by coating the coatings by using a roller coating method, and a detection test is carried out after 72 hours.

TABLE 1 Combustion Performance test

As shown in Table 1, the combustion performance of the coating provided by the invention reaches the A-grade standard and obviously exceeds the requirement of GB/T14402 on A-grade fire prevention. The flame value of a paint film coated with a commercial PAE resin mixed with the same curing agent and metallic aluminum filler under the combustion performance test is far beyond the paint described in the embodiment of the invention.

The service performance is detected according to GB/T22374 plus 2008 floor coating standards, and the heat preservation performance is tested according to a test method of GB/T10294 plus 2008 ' determination of the steady-state thermal resistance and related characteristics of the heat-insulating material ' protective hot plate method '. The test results are shown in table 2:

TABLE 2 terrace paint usability and insulation Performance test

As can be seen from Table 2, the floor coating prepared based on the organosilicon modified PAE resin ensures the basic service performance of the floor, and the elasticity, the wear resistance and the skid resistance of the final coating can be adaptively changed by adjusting the content of the A component PAE resin by the technical personnel in the field so as to meet the actual construction requirement.