阅读说明：本技术 一种光固化阻燃地板涂料及其制备方法 (Photocuring flame-retardant floor coating and preparation method thereof ) 是由 成伟 刘晓亚 李晓杰 杨鹏飞 王道清 于 2021-09-09 设计创作，主要内容包括：本发明涉及一种光固化阻燃地板涂料的组成及其制备方法。所述地板涂料的基体树脂结构中含有Cl、P、Si改性丙烯酸酯低聚物,具有紫外光固化的特性,可以极大提高紫外光固化涂料的阻燃性能。本发明方法实践性高、可行性好,是解决紫外光固化阻燃特性的一种优良阻燃剂,是绿色环保的紫外光固化涂料。(The invention relates to a composition of a photocuring flame-retardant floor coating and a preparation method thereof. The base resin structure of the floor coating contains Cl, P and Si modified acrylate oligomer, has the characteristic of ultraviolet curing, and can greatly improve the flame retardant property of the ultraviolet curing coating. The method has high practicability and good feasibility, is an excellent flame retardant for solving the problem of ultraviolet curing flame retardant property, and is an environment-friendly ultraviolet curing coating.)

1. The photocuring flame-retardant floor coating is characterized by comprising the following raw materials in parts by weight:

wherein the Cl, P and Si modified acrylate resin is a reaction product of the following substances in percentage by mass: the amount of the hydroxyethyl acrylate is 10-20% of the total amount of the reaction, the amount of the epichlorohydrin is 10-15% of the total amount of the reaction, the amount of the phosphorus pentoxide is 10-20% of the total amount of the reaction, the amount of the 3-glycidyl ether oxypropyl methyldiethoxysilane is 10-15% of the total amount of the reaction, the catalyst is boron trifluoride ethyl ether solution, the amount of the catalyst is 0.2-0.4% of the total amount of the reaction, and the balance is tetrahydrofuran solvent.

2. The light-cured flame-retardant floor coating of claim 1, wherein the 6-functional polyurethane acrylate is a synthetic product of a hydroxyl-terminated polyester polyol and IPDI pre-branched reaction, and then end-capped with PETA.

3. The light-curable flame-retardant floor coating according to claim 1, wherein the reactive diluent is one or more of tripropylene glycol diacrylate, trihydroxymethane triacrylate, 1, 6-hexanediol diacrylate, pentaerythritol triacrylate.

4. The photo-curable flame retardant floor coating according to claim 1, wherein the photo-initiator is one or more of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, benzophenone, and methyl o-benzoylbenzoate.

5. The photo-curable flame-retardant floor coating according to claim 1, wherein the matting agent is one or more of Woodford OK500, OK520 and OK 412.

6. The photo-curing flame-retardant floor coating according to claim 1, wherein the wear-resistant powder is one or more of nano silica and nano alumina.

7. The light-cured flame-retardant floor coating according to claim 1, wherein the auxiliary agent is one or more of BYK2009, BYK2008, BYK2013 and BYK 025.

8. The method for preparing the photocuring flame-retardant floor coating as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:

the first step is as follows: synthesizing Cl, P and Si modified acrylate resin:

the reaction is carried out under the protection of nitrogen, firstly, hydroxyethyl acrylate is added into a reaction bottle containing a dried tetrahydrofuran solvent, then epoxy chloropropane is added into the reaction bottle for reaction, boron trifluoride diethyl etherate solution is slowly added, and the reaction is carried out for 3 hours at the temperature of 45 ℃; slowly adding phosphorus pentoxide, reacting at room temperature for 3h, adding 3-glycidyl ether oxypropyl methyldiethoxysilane into a reaction bottle, reacting at 100 ℃ for 4-6 h to obtain Cl, P and Si modified acrylate resin;

the second step is that: and (5) synthesizing the coating.

Technical Field

The invention belongs to the technical field of coatings, relates to an Ultraviolet (UV) curing coating, and relates to a composition of a photocuring flame-retardant floor coating and a preparation method thereof

Background

The ultraviolet curing is one of radiation curing, is an environment-friendly curing mode, can greatly reduce the curing energy consumption, has high energy utilization rate, and has the advantages of no pollution, high curing speed, high coating quality, suitability for continuous large-scale production and the like; as a new rapidly developed green technology, the ultraviolet curing coating becomes an important floor coating and is widely applied. With the intensive research on ultraviolet curing coatings, people have higher and higher requirements on the performance and the function of the ultraviolet curing coatings, and the ultraviolet curing flame-retardant floor coatings are typical of the ultraviolet curing flame-retardant floor coatings;

in order to improve the flame retardance of the ultraviolet curing material, the ultraviolet curing material has become a special requirement on material characteristics in recent years, particularly in the fields of furniture and building materials in the field of coatings, the ultraviolet curing coating is expected to have flame retardance, and in order to improve the flame retardance, cold-splicing inorganic flame retardant is a common practice in the composition, but excessive addition of the ultraviolet curing coating affects the film forming performance, the addition amount of the ultraviolet curing coating is small, the flame retardance is insufficient, the definition of a coating is greatly affected, and the texture of wood cannot be displayed; othera minor et al, 201910670511.7, "A oligomer of acrylate containing chlorine and phosphorus and its preparation method", only mention the synthesis of acrylate modified with Cl and phosphate, no silicon element, no organic synthesis of these three elements into an oligomer, silicon element can stabilize carbon layer after burning, and cooperate with P, N to prevent fire from spreading; in order to improve the flame retardant property of the floor coating, it is very important to synthesize the coating which can participate in ultraviolet curing crosslinking and has the flame retardant property.

By combining the two properties, the modified acrylate resin containing Cl, P and Si with flame retardance is developed to prepare the photocuring flame-retardant floor coating, and the photocuring flame-retardant floor coating has the characteristics of good flame retardance and high definition and has very important practical significance.

Disclosure of Invention

In order to overcome the technical problem of insufficient flame retardance of the existing floor coating, the invention aims to synthesize a modified acrylate resin containing Cl, P and Si and a polyurethane resin, and prepare a photocuring flame-retardant floor coating by utilizing a synergistic flame-retardant mechanism of P, N and Si elements, wherein the adopted curing mode is photocuring and accords with the trends of green, environmental protection and energy conservation.

The purpose of the invention is realized by the following technical scheme: the light-cured flame-retardant floor coating comprises the following raw materials in parts by weight:

wherein the Cl, P and Si modified acrylate resin is a reaction product of the following substances in percentage by mass: the amount of the hydroxyethyl acrylate is 10-20% of the total amount of the reaction, the amount of the epichlorohydrin is 10-15% of the total amount of the reaction, the amount of the phosphorus pentoxide is 10-20% of the total amount of the reaction, the amount of the 3-glycidyl ether oxypropyl methyldiethoxysilane is 10-15% of the total amount of the reaction, the catalyst is boron trifluoride ethyl ether solution, the amount of the catalyst is 0.2-0.4% of the total amount of the reaction, and the balance is tetrahydrofuran solvent.

The 6-functional polyurethane acrylate is a synthetic product which is prepared by carrying out a pre-grafting reaction on hydroxyl-terminated polyester polyol and IPDI (isophorone diisocyanate) and then capping with PETA (polyethylene terephthalate A).

The active diluent is one or more of tripropylene glycol diacrylate, trihydroxymethane triacrylate, 1, 6-hexanediol diacrylate and pentaerythritol triacrylate.

The photoinitiator is one or more of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, benzophenone and methyl o-benzoylbenzoate.

The matting agent is one or more of winning wound OK500, OK520 and OK 412.

The wear-resistant powder is one or more of nano silicon dioxide and nano aluminum oxide.

The auxiliary agent is one or more of BYK2009, BYK2008, BYK2013 and BYK 025.

The preparation method of the photocuring flame-retardant floor coating comprises the following steps: the first step is as follows: synthesizing Cl, P and Si modified acrylate resin:

the reaction is carried out under the protection of nitrogen, firstly, hydroxyethyl acrylate is added into a reaction bottle containing a dried tetrahydrofuran solvent, then epoxy chloropropane is added into the reaction bottle for reaction, boron trifluoride diethyl etherate solution is slowly added, and the reaction is carried out for 3 hours at the temperature of 45 ℃; slowly adding phosphorus pentoxide, reacting at room temperature for 3h, adding 3-glycidyl ether oxypropyl methyldiethoxysilane into a reaction bottle, reacting at 100 ℃ for 4-6 h to obtain Cl, P and Si modified acrylate resin;

the second step is that: and (5) synthesizing the coating.

Has the advantages that:

the photocuring flame-retardant floor coating prepared by the invention has the characteristics of good flame-retardant property, high curing speed, environmental protection and energy conservation. When the coating is coated on the wood floor, the coating weight reaches 300g/m²And the flame retardance of the light-cured flame-retardant floor coating composition reaches the highest flame-retardant grade B1B according to the test of GB 8624-2012.

Detailed Description

The preparation used in the invention is not limited to manufacturers as long as the preparation is qualified industrial products, and is a conventional product sold in the market.

Throughout the application, the following terms have the indicated meanings:

code number or term	Name of Chinese
		PAM	Cl, P, Si modified acrylate resin, self-made
PUA	6-functional urethane acrylates from Insemann AgiSyn
		PETA	Pentaerythritol triacrylate, available from Changxing chemical company, Taiwan (Taiwan corporation)
TMPTA	Trimethylolpropane triacrylate, obtained from Sartomer
		OK500	Silicon dioxide matting agent, Yingchuang
BKY2009	Matte powder dispersant from birk
		TEGO451	Levelling agents, Woods
TEGO920	Antifoams, self-healing wound
		Wear-resistant powder	Alumina wear-resistant powder obtained from Hangzhou Wanjing new material
TPO	2,4, 6-trimethylbenzoyl-diphenylphosphine oxide from Tianjin Jieshi chemical
		1173	2-hydroxy-2-methyl-1-phenyl-1-propanone from Tianjin Jiu chemical industry

The photocuring flame-retardant floor coating is characterized by being prepared from the following components in parts by weight:

wherein the Cl, P and Si modified acrylate resin is a reaction product of: hydroxyethyl acrylate, 20-30% of the total amount of the reaction, epichlorohydrin, 20-30% of the total amount of the reaction, phosphorus pentoxide, 10-20% of the total amount of the reaction, 3-glycidyl ether oxypropyl methyldiethoxysilane, 10-20% of the total amount of the reaction, and boron trifluoride diethyl etherate, 0.2-0.4% of the total amount of the reaction;

wherein the Cl, P and Si modified acrylate resin is synthesized as follows:

the reaction is carried out under the protection of nitrogen, firstly, hydroxyethyl acrylate is added into a reaction bottle containing a dried tetrahydrofuran solvent, then epoxy chloropropane is added into the reaction bottle for reaction, boron trifluoride diethyl etherate solution is slowly added, and the reaction is carried out for 3 hours at the temperature of 45 ℃; slowly adding phosphorus pentoxide, reacting at room temperature for 3h, adding 3-glycidyl ether oxypropyl methyldiethoxysilane into a reaction bottle, reacting at 100 ℃ for 4-6 h to obtain Cl, P and Si modified acrylate resin;

the reaction formula of the Cl, P and Si modified acrylate resin is as follows

The content of Cl, P and Si modified acrylate resin is 30-45 wt%;

wherein the 6-functional polyurethane acrylate is a synthetic product which is prepared by pre-branching reaction of hydroxyl-terminated polyalcohol and isophorone diisocyanate (IPDI) and end capping with pentaerythritol triacrylate (PETA); the active diluent is one or more of tripropylene glycol diacrylate, trihydroxymethane triacrylate, 1, 6-hexanediol diacrylate and pentaerythritol triacrylate; the photoinitiator is one or more of 2-hydroxy-2-methyl propiophenone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, benzophenone and methyl o-benzoylbenzoate; the matting agent is one or more of Wojian OK500, OK520, AT3600 and AT 3300; the wear-resistant powder is one or more of nano silicon dioxide and nano aluminum oxide; the auxiliary agent is one or more of BYK2009, BYK2008, BYK2013 and BYK 025.

Example 1 Cl, P, Si modified acrylate resin PAM

Synthesis of Cl, P, Si modified acrylate resin was carried out in accordance with the 3 sets of data listed in Table 1

EXAMPLE 1 synthetic resin

The reaction is carried out under the protection of nitrogen, firstly, hydroxyethyl acrylate is added into a reaction bottle containing a dried tetrahydrofuran solvent, then epoxy chloropropane is added into the reaction bottle for reaction, boron trifluoride diethyl etherate solution is slowly added, and the reaction is carried out for 3 hours at the temperature of 45 ℃; slowly adding phosphorus pentoxide, reacting at room temperature for 3h, adding 3-glycidyl ether oxypropyl methyldiethoxysilane into a reaction bottle, reacting at 100 ℃ for 4-6 h to obtain Cl, P and Si modified acrylate resin;

example 2 preparation of photo-curable flame retardant floor coating

The coatings were formulated according to the 4-set data recipe of Table 3 below.

The components are prepared into a coating, and relevant indexes are controlled; fineness:<30 um; curing speed: greater than 400mj/cm²(degree of cure RAU 85%).

Example 3 preparation of photo-curable flame retardant floor coating

The coatings were formulated according to the 3-set data recipe of Table 4 below.

The components are prepared into a coating, and relevant indexes are controlled; fineness:<30 um; curing speed: greater than 400mj/cm²(degree of cure RAU 85%).

EXAMPLE 4 preparation of photo-curable flame retardant floor coating

The coatings were formulated according to the 3-set data recipe of Table 5 below.

The components are prepared into a coating, and relevant indexes are controlled; fineness:<30 um; curing speed: greater than 400mj/cm²(degree of cure RAU 85%).

Example 5 test method for flame retardancy:

1, general Condition determination

The environmental temperature is 20-25 ℃; the relative humidity of the environment is 40-60%; ambient pressure 1.013 x 10⁵5% pa; the laboratory cleanliness meets the GB50073-2001 requirement, and the dust content of the ten-thousand-level cleanliness is not less than 0.5um and not more than 350 particles/L.

2 preparation of paint samples

Treating 100 oak wood multi-layer solid wood floors of 120 x 900cm by 400-mesh sand paper, uniformly stirring the samples, and coating the samples by a three-roller machine to obtain 30.0g/m²Semi-curing by using ultraviolet light, coating the next procedure for 10 times, and finally completely curing by using 3 lamps. Marking the painted floor by using an oily marker pen, and detecting according to GB8624-2012Standard detection, the flame retardant grade is judged according to the critical radiation flux, and the judgment grade is shown in Table 6

TABLE 6

Table 7 shows the flame retardant performance tests of the above 2, 3, 4 and three sets of experiments

The data show that the ultraviolet curing coating added with the Cl, P and Si modified acrylate resin is coated on the wood floor, has good protection effect on the combustion of wood, delays the combustion of the wood, mainly comes from the Cl, P and Si modified acrylate resin and the polyurethane acrylic resin added in the combustion process, Cl element can prevent the free radical reaction of the combustion, HCL is generated, oxygen in air is diluted, P-N element forms a stable carbon layer in high-temperature combustion, oxygen in the air contacted by the wood is isolated, the temperature of the surface of the wood is reduced, and N is released₂Diluting oxygen in the air; si forms a compact barrier layer in high-temperature combustion, the stability of the carbon layer is improved, the flame retardant purpose is achieved through the synergistic flame retardant effect of Cl, P, N and Si, and the flame retardant property is continuously increased along with the increase of the addition amount of the P element; contains light-curable double bonds, participates in the cross-linking reaction of the coating, and the adhesive force is improved along with the addition of Cl, P and Si modified acrylate resin.