CN106432332A - Preparation method of phosphorus and nitrogen contained acrylate and copolymer core-shell particles of phosphorus and nitrogen contained acrylate - Google Patents

Abstract

The invention discloses a preparation method of phosphorus and nitrogen contained acrylate and copolymer core-shell particles of the phosphorus and nitrogen contained acrylate. Phenylphosphonic dichloride, hydroxyethyl acrylate and diethylamine which are taken as raw materials react with trimethylamine as an acid binding agent in tetrahydrofuran at 0-5 DEG C, and phosphorus and nitrogen contained acrylate is prepared. The synthesis method is simple, and the cost is low. The phosphorus and nitrogen contained acrylate can be subjected to free-radical copolymerization with other acrylate monomers. The core-shell particles of the phosphorus and nitrogen contained acrylate are prepared with a core-shell emulsion polymerization method, the core-shell particles have the advantages of adjustable structure and composition, have certain flame retardancy on the premise that the structure of a core-shell impact modifier is not changed and are expected to be used for toughening flame retardant materials.

Description

A kind of preparation method of phosphorus nitrogen-containing acrylate and its copolymer core-shell particles

technical field

The invention relates to a preparation method of phosphorus nitrogen-containing acrylate and its copolymer core-shell particles, belonging to the technical field of polymer chemistry and polymer technology.

Background technique

In recent years, with the continuous improvement of awareness of environmental protection and safety protection, halogen-free flame retardants have become a hot spot in the field of flame retardant development. However, halogen-free flame retardants have disadvantages such as low flame retardant efficiency and poor mechanical properties of materials after flame retardancy. Solving the contradiction between "improving flame retardancy and maintaining mechanical properties" has become an important issue. Combining "structural modification with functional modification" is a new way to solve this problem. Acrylate copolymer particles with a core-shell structure are impact modifiers for many polymer materials, but there is no report on the flame-retardant functionalization of such core-shell impact modifier particles. The main content of the invention is to combine the flame retardant elements with the structure of the core-shell impact modifier to prepare a novel flame retardant functional impact modifier.

Phosphorus-containing acrylates can be used to prepare intrinsic phosphorus-containing resins, coatings, adhesives, etc. by free radical copolymerization, and can also be copolymerized with other flame-retardant monomers to prepare polymeric flame retardants. Chinese patent 200910116317.0 discloses a bifunctional phosphorus-containing acrylate (1), and prepares a flame-retardant coating with a hyperbranched structure with a trifunctional amine compound. The hyperbranched structure is beneficial to improving the toughness of the coating. Chinese patent 201510810594.7 discloses the preparation method of a new phosphorus-containing acrylate monomer (2) that can be used for free radical polymerization. The monomer can be added to polymer materials as a reactive flame retardant to play a flame-retardant role. Chinese patent ZL201110128125.9 discloses a phosphorus nitrogen-containing acrylate monomer (3), which is used to prepare polyacrylate emulsions, reducing the amount of flame retardants used. Chinese patents ZL201410096997.5 and ZL201410096979.7 respectively disclose the copolymerization of phosphorus-containing acrylate (4,5) and silicon-containing acrylate to prepare polymeric flame retardants, which can be used for flame-retardant modification of polystyrene and other materials. There is no report on the preparation of core-shell impact modifiers. There are two main methods for the preparation of phosphorus-containing acrylates: one is obtained by reacting acryloyl chloride with epoxy or hydroxyl groups. This method is expensive to synthesize and is not suitable for industrialization, such as US Patent US5399733A and Chinese Patents ZL201410096997.5 and ZL201410096979 .7; The other is the reaction of monohydroxy acrylic acid with phosphorus (phosphine) chloride. Because phosphorus (phosphine) chloride is cheap and widely available, it is more suitable for industrialization, such as Chinese patent ZL200910116317.0.

The feature of the invention is that the phosphorus-nitrogen-containing acrylate is introduced into the structure of the core-shell impact modifier as a comonomer, and the flame-retardant functionalization is carried out on the impact modifier. The synthesis method of the phosphorus nitrogen-containing acrylate in the invention is simple, low in cost, suitable for industrial production, and can be copolymerized with other acrylate monomers through free radicals. Core-shell particles are prepared by the core-shell emulsion polymerization method, which has the advantages of adjustable structure and composition; Under the premise of the structure of the stabilizer, the particles themselves have a certain flame retardancy, and are expected to be used for toughening flame-retardant materials.

Contents of the invention

The purpose of the present invention is to provide a preparation method of phosphorus nitrogen-containing acrylate and its copolymer core-shell particles.

Phosphorous nitrogen-containing acrylate in the present invention has structural characteristics as shown in formula (I):

(I).

Phosphorous nitrogen-containing acrylate in the present invention, its preparation method is characterized in that:

Add phenylphosphoryl dichloride (PDCP) to triethylamine (TEA) in a molar ratio of 1:2.2 to 1:3 and solvent tetrahydrofuran (THF) into a three-necked flask equipped with a stirrer and cool to -5- 0°C, dropwise add hydroxyethyl acrylate (HEA) which is equimolar to phenylphosphoryl dichloride (PDCP), react at 0-5°C for 2-4 hours, then dropwise add phenylphosphoryl dichloride (PDCP) ) equimolar diethylamine, react at 0-5°C for 2-4 hours, then warm up to room temperature and react for 2-6 hours, the reaction mixture is filtered to remove triethylamine hydrochloride, and the obtained filtrate removes solvent and unreacted The light yellow viscous liquid is obtained after triethylamine, which is the phosphorous nitrogen-containing acrylate monomer; the reaction formula is as formula (II):

(II).

The preparation method of the copolymer core-shell particle containing phosphorus nitrogen acrylate in the present invention, its formula and process are as follows:

First add 80g of distilled water, 0.4g of sodium bicarbonate (NaHCO ₃ ) and emulsifier 2.5g of sodium dodecyl sulfate (SDS), 1.5g of OP-10 into a 250ml four-necked flask, and add the initiator after it dissolves Potassium persulfate (KPS) 0.1g, heat up to 60°C, add 30%-50% of inner core monomer (monomer mixture with phosphorus nitrogen-containing acrylate and butyl acrylate in a mass ratio of 1:4 to 4:1) , raise the temperature to 70-75°C to initiate polymerization, and then drop the remaining inner core monomer (a monomer mixture with a mass ratio of phosphorus nitrogen-containing acrylate to butyl acrylate of 1:4 to 4:1), and react for 1-3 hours ; Add 0.1g KPS, add dropwise shell monomer (methyl methacrylate), reaction temperature 75-80°C, react for 2-6 hours after dropwise addition, to obtain polymer core-shell emulsion; wherein, core monomer and The mass ratio of shell monomers is 5:5 to 7:3; the mass ratio of total monomers to distilled water is 4:6 to 6:4. After the emulsion is demulsified, it is filtered, washed and dried to obtain the copolymer core-shell particles.

The benefit of the present invention lies in that the core-shell particles of phosphorus nitrogen-containing acrylate are prepared by the core-shell emulsion polymerization method, which has the advantages of adjustable structure and composition. Without changing the structure of the core-shell impact modifier, the particles themselves have Certain flame retardancy is expected to be used for toughening flame retardant materials.

Description of drawings

Figure 1 H NMR spectrum of phosphorus nitrogen-containing acrylate in Example 1.

Fig. 2 Infrared spectrum of phosphorus-nitrogen-containing acrylate in Example 1.

Fig. 3 Particle size distribution curves of copolymer core-shell particles in Example 2 and Example 3.

Fig. 4 Combustion heat release curves of the copolymer core-shell particles in Example 2 and Example 3.

detailed description

The preparation method of the phosphorus-nitrogen-containing acrylate and its copolymer core-shell particles of the present invention, as well as the thermal decomposition and combustion heat release properties of the particles will be further described in detail below through examples.

Example 1

Add 19.5g (0.1mol) of phenylphosphoryl dichloride (PDCP), 25.3g (0.25mol) of triethylamine (TEA) and 80mL of solvent tetrahydrofuran (THF) into a three-necked flask equipped with a stirrer and cool down to -5 -0°C, add 11.6g (0.1mol) of hydroxyethyl acrylate (HEA) dropwise, react at 0-5°C for 3 hours, add 7.3g (0.1mol) of diethylamine (DEA) dropwise, After reacting at ℃ for 2 hours, raise the temperature to room temperature and react for 4 hours. The reaction mixture is filtered to remove triethylamine hydrochloride, and the obtained filtrate removes the solvent and unreacted triethylamine to obtain a crude product; the product is mobile with ethyl acetate. The phase was purified by neutral silica gel column chromatography, and the light yellow viscous liquid was obtained after removing ethyl acetate, which was phosphorus-nitrogen-containing acrylate.

Example 2

First add 80ml of distilled water to a 250ml four-neck flask equipped with an electric stirrer, a thermometer, and a reflux condenser, then turn on the stirring device, add 0.4gNaHCO3, 2.5gSDS and 1.5gOP-10 to make it stir slowly. After it dissolves, add 0.1g KPS and start to heat up. After the temperature rises to about 60°C, add 20g of inner core monomer (a mixture of 15g of phosphorus nitrogen-containing acrylate and 10g of butyl acrylate), raise the temperature to 70-75°C, initiate polymerization, and then add dropwise The remaining 36g of inner core monomer (a mixture of 10g of phosphorus nitrogen-containing acrylate and 26g of butyl acrylate) was reacted for 2 hours, and 0.1g of KPS was added, and 21g of methyl methacrylate, a shell monomer, was added dropwise, and the reaction was continued for 3 hours. After the emulsion is demulsified, copolymer core-shell particles with particle diameters ranging from 0.05 to 0.16 microns are obtained.

Example 3

First add 80ml of distilled water to a 250ml four-neck flask equipped with an electric stirrer, a thermometer, and a reflux condenser, then turn on the stirring device, add 0.4gNaHCO3, 2.5gSDS and 1.5gOP-10 to make it stir slowly. After it dissolves, add 0.1g KPS and start to heat up. After the temperature rises to about 60°C, add 20g of inner core monomer (a mixture of 16g of phosphorus-nitrogen acrylate and 4g of butyl acrylate), raise the temperature to 70-75°C, initiate polymerization, and then add dropwise The remaining 30g of inner core monomer (a mixture of 24g of phosphorus-nitrogen acrylate and 6g of butyl acrylate) was reacted for 2 hours, and 0.1g of KPS was added, and 25g of methyl methacrylate, a shell monomer, was added dropwise, and the reaction was continued for 3 hours. After the emulsion is demulsified, copolymer core-shell particles with a particle size of 0.05-0.23 microns are obtained.

Claims (7)

1. a kind of phosphorus-nitrogen containing acrylate, its architectural feature such as formula（I）Shown：

（I）.

2. a kind of phosphorus-nitrogen containing acrylate according to claim 1, its preparation method is characterised by：

By diphenylphosphoryl dichloro (PDCP) and triethylamine (TEA) in molar ratio 1:2.2 to 1:3 ratio and solvents tetrahydrofurane (THF) add and be furnished with the there-necked flask of agitator and -5-0 DEG C is cooled to, Deca and diphenylphosphoryl dichloro (PDCP) equimolar 2-(Acryloyloxy)ethanol（HEA）, after reacting 2-4 hour at 0-5 DEG C, Deca and diphenylphosphoryl dichloro (PDCP) equimolar two Ethamine, after reacting 2-4 hour, is warming up to room temperature reaction 2-6 hour at 0-5 DEG C, and reactant mixture is through filtering off except triethylamine Hydrochlorate, the filtrate for obtaining obtains pale yellow viscous liquid, as phosphorus-nitrogen containing propylene after removing solvent and unreacted triethylamine Acid ester monomer；Reaction equation such as formula（II）：

（II）.

3. the copolymer core-shell particles for being prepared using phosphorus-nitrogen containing acrylate as claimed in claim 1, it is characterised in that：With formula （I）Shown phosphorus-nitrogen containing acrylate and butyl acrylate are interior nuclear monomer, with methyl methacrylate as shell monomers, to pass through Prepared by core-shell emulsion polymerization reaction.

4. the preparation method of copolymer core-shell particles according to claim 3, it is characterised in that be prepared as follows：

First by 80g distilled water, 0.4g sodium bicarbonate（NaHCO₃）With emulsifying agent 2.5g sodium lauryl sulphate（SDS）、1.5gOP- 10, it is added in the four-hole boiling flask of 250ml, after its dissolving, adds initiator potassium persulfate（KPS）0.1g, is warming up to 60 DEG C, Add the interior nuclear monomer of 30%-50%（Phosphorus-nitrogen containing acrylate and the mixture of butyl acrylate）, it is warming up to 70-75 DEG C of initiation poly- The remaining interior nuclear monomer of Deca after conjunction, after reaction 1-3 hour；Add 0.1gKPS, Deca shell monomers（Methyl methacrylate Ester）, reaction temperature 75-80 DEG C, 2-6 hour being reacted after completion of dropping, obtains polyalcohol nucleocapsid emulsion；This emulsion after breakdown of emulsion, Filter, washing, dry, obtain copolymer core-shell particles.

5. copolymer core-shell particles according to claim 3 or 4, it is characterised in that phosphorus-nitrogen containing third in described interior nuclear monomer Olefin(e) acid ester with the mass ratio of butyl acrylate is：1:4 to 4:1.

6. copolymer core-shell particles according to claim 3 or 4, it is characterised in that interior nuclear monomer and shell monomers mass ratio For 5:5 to 7:3.

7. the preparation method of copolymer core-shell particles according to claim 4, it is characterised in that total monomer and distilled water Mass ratio is 4:6 to 6:4.