KR100841927B1 - Triphenyl phosphate-grafted polymer resin having butadiene moiety and preparing process thereof - Google Patents

Abstract

A method for preparing a polymer resin grafted with triphenyl phosphate is provided to solve the problem related to the complicated conventional process, and to simplify the extrusion and injection processes of a polymer resin blend using triphenyl phosphate. A method for preparing a polymer resin grafted with triphenyl phosphate comprises the steps of: dissolving a polymer resin having butadiene residues and triphenyl phosphate in an organic solvent; and introducing a radical reaction catalyst thereto to allow grafting of triphenyl phosphate to the butadiene residues. The polymer resin having butadiene residues includes at least one resin selected from a butadiene resin, acrylonitrile-butadiene-styrene resin and high-impact polystyrene resin.

Description

Triphenyl phosphate-grafted polymer resin manufacturing method and polymer resin composition produced by the same {Triphenyl Phosphate-Grafted Polymer Resin having Butadiene Moiety and Preparing Process Thereof}

1 is a schematic diagram of triphenylphosphate graft reaction for butadiene residues

Figure 2 is the FT-IR absorbance spectrum of the butadiene resin grafted triphenylphosphate

Figure 3 is the FT-IR absorption spectrum of acrylonitrile-butadiene-styrene copolymer resin grafted with triphenylphosphate

The present invention relates to a method for preparing a polymer resin and a polymer resin composition prepared by the same, and more particularly, triphenyl phosphate by radical reaction to a single or copolymer containing butadiene (BD) residues. , TPP) is grafted with triphenylphosphate that can increase the convenience in extrusion and injection processes while maintaining the impact strength reinforcement effect of butadiene when blending with resins such as polycarbonate (PC). It relates to a method for producing a polymer resin and a polymer resin composition produced thereby.

In general, phenyl phosphate compounds are used as a representative phosphate flame retardant, and in particular, the importance of the halogen-based flame retardant in relation to environmental regulations has increased in importance. However, phosphate-based flame retardants have a high flame retardant requirement to be added to the resin composition in order to add sufficient phosphorus content, and physical property degradation and process complexity due to excessive addition of monomolecular materials are likely to occur.

Triphenylphosphate (TPP) is applied to polycarbonate (PC) / acrylonitrile-butadiene-styrene (ABS) (PC / ABS) blends and the like to produce flame-retardant polymer resin molded articles. It is used. However, due to the low melting point of the triphenyl phosphate (TPP) and volatility in the liquid phase, there are many difficulties in manufacturing and process, such as having to provide a separate cooler or an independent input device in the extrusion and injection molding process.

In order to solve this problem, in recent years, various angles have been studied. For example, a variety of phenyl-based epoxy resins including novolac types may be reported by using branded together to improve processability. (K. Lee, et al., Polymer , 43 , 2249-2253, 2002.)

In addition, in the case of resorcinol bis (diphenyl phosphate), RDP and phenyl phosphate flame retardants such as triphenyl phosphate (TPP) and bisphenol A bis (diphenyl phosphate, BDP) PC) and acrylonitrile-butadiene-styrene (ABS) have been reported to have better flame retardancy and process stability (V. Sergei, et al., Journal of Vinyl & Additive Technology , 6). , 123, 2000; V. Sergei, et al., Journal of Vinyl & Additive Technology , 7 , 98, 2001.), which are very costly to manufacture and are very unsuitable for application in the mass production stage.

On the other hand, the synthesis of phosphorus-containing monomers and the polymerized polymer was reacted with an epoxy resin using an amine end to be applied as a curing agent and toughening agent (Young-ran Park et al., Polymer (Korea) , 22 , 901, 1998.) Although also reported, butadiene (BD) containing a polymer resin had a problem that can not be applied.

Some researchers have grafted high molecular weight unsaturated carboxylic acids to butadiene residues in ABS resins (ZF Zhuo, et al., Journal of Polymer Science, Part A: Polymer Chemistry , 39 , 486, 2001; ZF Zhuo, et al., Journal of Applied Polymer Science , 83 , 1934, 2002.) and studies on the efficiency of initiators on the butadiene moieties of styrene-butadiene-styrene resins and graft polymerization of maleic acid Z. Aimin, et al., European Polymer Journal , 39 , 1291, 2003.), but all of the above studies have been limited to graft polymerization of polymers having unsaturated carboxylic acids.

Accordingly, the present invention has been made in view of the above problems, and by dissolving the polymer resin having butadiene residue and triphenylphosphate (TPP) in a suitable organic solvent and introducing a radical reaction catalyst to break the double bond of butadiene residue By giving activity, and by grafting the phosphorus of triphenylphosphate (TPP) as a binding atom to the activated butadiene (BD) residue, triphenylphosphate is solved by solving the complexity of the process caused by conventional triphenylphosphate (TPP) It is an object to make it possible to simplify the process in the extrusion and injection process of the polymer resin mixture (TPP) is applied.

The present invention relates to a method for producing a polymer resin grafted with triphenyl phosphate, and a polymer resin composition prepared by the present invention, comprising polycarbonate by grafting triphenyl phosphate by radical reaction to a single or copolymer containing butadiene residues When blending with a resin, such as butadiene has the characteristic that can increase the convenience in the extrusion and injection process while maintaining the impact strength reinforcement effect.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

Figure 1 shows a schematic diagram of the triphenyl phosphate (TPP) graft reaction to the butadiene (BD) residues of the present invention, as shown, is activated by treating the radical reaction catalyst for the double bond of the butadiene residues As the phosphorus atom of triphenylphosphate (TPP) binds to the activated butadiene moiety, the double bond with oxygen is dissociated and the oxygen atom becomes active.

The oxygen atom having the activity desorbs the hydrogen of the next carbon atom of the butadiene residue, and the double bond positions of the butadiene residues are shifted one by one to create a new double bond by chain transfer. .

While another triphenyl phosphate (TPP) is reacted to a new active site generated by the transfer of the double bond, a polymer resin in which triphenyl phosphate (TPP) is grafted by a chain reaction is obtained.

After the reaction is completed, the polymer solution is immersed in the cooled metalol to obtain a precipitate, and then repeatedly dissolved and precipitated in an organic solvent and methanol to be purified, and then the polymer resin is dried.

Examples of the polymer resin having the butadiene (BD) residue include butadiene (BD), high impact styrene resin (HI Impact), and acrylonitrile-butadiene-styrene (ABS). It is possible to use individually or in mixture of 2 or more from the group which comprises, Preferably it is preferable to select from butadiene (BD) and ABS, and to use.

The organic solvent to be used is preferably selected from toluene and tetrahydrofuran (THF), and in the case of butadiene (BD) resin, toluene is advantageous because it can proceed a homogeneous reaction, and ABS and impact styrene are advantageous. In the case of resin (HIPS), the use of tetrahydrofuran (THF) is advantageous because it can proceed a homogeneous reaction.

The radical reaction catalyst may be any one selected from diazo and peroxide.

Preferably, it is preferable to use peroxide-based benzoyl peroxide (BPO). When using azobisisobutyronitrile (AIBN), which is a diazo-based reaction catalyst, the graft reaction is performed at a lower temperature. Although it is possible to proceed, it is preferable to use benzoyl peroxide (BPO) because a lower graft rate is obtained than using benzoyl peroxide (BPO).

Hereinafter, the present invention will be described in detail with reference to the following Examples.

Example 1

In a three-necked flask equipped with a nitrogen purge tube, a reflux tube, an anchor teflon stirrer and an electric stirrer, 5.4 g of butadiene (BD) resin and 32.6 g of triphenylphosphate (TPP) were mixed. The mixture was stirred for 1 hour at 85 ° C. under a nitrogen stream from which oxygen and water were removed and completely dissolved.

Then, 24.2 g of benzoyl peroxide (BPO), a peroxide-based reaction catalyst, was added to the solution, followed by reaction for 4 hours, and when the reaction was completed, it was put in cooled methanol to obtain a precipitate, dissolved and precipitated in toluene and methanol. After repeating three times, and dried under vacuum at 60 ℃ for 1 day to obtain a white powdery resin.

From the FT-IR absorption spectra shown in FIG. 2, the peaks of the hydroxyl groups which were not present in butadiene (BD) and triphenylphosphate (TPP) were prominent at around 3,500 cm −1. As the P = O bond was broken, the graft reaction proceeded and at the same time, it was confirmed that a hydroxyl group existed for phosphorus of triphenylphosphate (TPP).

From the H1 NMR and C13 NMR measurements on the dried samples it can be seen that the triphenylphosphate (TPP) was grafted at a graft rate of 0.74 mol / molBD for the butadiene (BD) residue.

Example 2

75 ml of tetrahydrofuran (THF) was added to a mixture of butadiene (BD) resin and triphenylphosphate (TPP) prepared as in Example 1, and passed through a pyrogarol trap to remove oxygen and water at 85 ° C. under a nitrogen stream. Stir for 1 hour to dissolve completely.

After 24.2 g of benzoyl peroxide (BPO) was added to the solution and reacted for 1 hour, the reaction proceeded very rapidly, and white powder was precipitated within minutes after the catalyst was added, and the precipitate was separated by filtering. Purification was performed several times with hot methanol.

The purified result was dried under vacuum at 45 ° C. for 1 day to obtain a white resin powder.

Solid phase H1 NMR and solid C13 NMR measurements on the dried sample showed that triphenylphosphate (TPP) was grafted at a graft rate of 0.34 mol / molBD for the butadiene (BD) residue.

Example 3

24 g of ABS resin, 65.3 g of triphenylphosphate (TPP) and 150 ml of tetrahydrofuran (THF) were added to the same device as in Example 1, and passed through a pyrogarol trap to remove oxygen and moisture at 85 ° C. Stir for hours to dissolve completely.

24.2 g of benzoyl peroxide (BPO) was added to the solution, followed by reaction for 4 hours. Upon completion of the reaction, the mixture was put in cooled methanol to obtain a precipitate. The solution was dissolved in tetrahydrofuran (THF) and methanol and precipitated three times. Then, it dried under vacuum at 60 degreeC for 1 day, and obtained the white powdery resin powder.

FT-IR measurements on the dried sample shown in FIG. 3 confirmed that triphenylphosphate (TPP) was effectively grafted.

From the H1 NMR measurement on the dried sample, it was confirmed that triphenylphosphate (TPP) corresponding to 0.58 mol / molBD of butadiene residue was grafted to the ABS resin having 45 mol% butadiene residue.

Examples 4 to 17

Triphenyl phosphate (TPP) graft on a butadiene residue-containing polymer resin was carried out by variously adjusting the conditions, using the same device as in Example 1, and detailed conditions and triphenyl phosphate on butadiene residues of the resin. The substitution rate of (TPP) is shown in the following table. All experimental conditions not mentioned otherwise were performed in the same manner as in Example 1.

In all cases, the grafted resin was obtained as a white powder after drying.

 Polymer resin  Reaction catalyst BD residue: TTP: Catalyst molar ratio  Organic solvent  Reaction temperature (℃)  Response time (hr)  Graft Rate (mol / molBD)  Example 4  BD  BPO  2: 2: 1  toluene  85  4  0.72  Example 5  BD  BPO  100: 100: 1  toluene  85  4  0.12  Example 6  BD  BPO  100: 100: 1  toluene  85  24  0.52  Example 7  BD  BPO  100: 100: 1  THF  85  2  0.06  Example 8  BD  AIBN  1: 1: 1  toluene  45  4  0.32  Example 9  ABS  BPO  2: 2: 1  THF  85  4  0.69  Example 10  ABS  BPO  100: 100: 1  THF  85  4  0.08  Example 11  ABS  BPO  100: 100: 1  THF  85  36  0.32  Example 12  ABS  AIBN  1: 1: 1  THF  45  4  0.26  Example 13  HIPS  BPO  1: 1: 1  THF  85  4  0.84  Example 14  HIPS  BPO  2: 2: 1  THF  85  4  0.79  Example 15  HIPS  BPO  100: 100: 1  THF  85  4  0.23  Example 16  HIPS  BPO  100: 100: 1  THF  85  36  0.58  Example 17  HIPS  AIBN  1: 1: 1  THF  45  4  0.49

The present invention is not limited to the above embodiments, but various modifications can be made within the scope of the claims of the present invention, which is to be understood that they fall within the scope of the present invention.

The present invention configured as described above, by dissolving the polymer resin having a butadiene residue and triphenyl phosphate (TPP) in a suitable organic solvent and adding a radical reaction catalyst to break the double bond of the butadiene residue to impart activity, thereby A polymer to which triphenylphosphate (TPP) is applied to solve the complexity of the process caused by conventional triphenylphosphate (TPP) by grafting phosphorus of phenylphosphate (TPP) to a butadiene (BD) residue activated as a binding atom. There is an effect that can simplify the process in the extrusion and injection process of the resin mixture.

Claims (4)

A triphenyl phosphate-grafted polymer resin characterized in that a triphenyl phosphate is grafted to a butadiene residue by dissolving a polymer resin having a butadiene residue and a triphenyl phosphate under an organic solvent and adding a radical reaction catalyst. Manufacturing method. The method of claim 1, A polymer resin having a butadiene residue comprises at least one of a butadiene resin, an ABS resin, and a HIPS resin. The method of claim 1, The organic solvent is any one selected from toluene and tetrahydrofuran. The method for producing a polymer resin grafted with triphenylphosphate. In a solvent which is any one selected from toluene and tetrahydrofuran, Dissolves triphenylphosphate and is made of at least one of butadiene resin, ABS resin and HIPS resin, Triphenyl phosphate is composed of a polymer resin in which triphenyl phosphate is grafted to a butadiene residue by adding a radical reaction catalyst, and a graft ratio of triphenyl phosphate to butadiene is 0.06 mol / molBD to 0.84 mol / molBD. Grafted Polymer Resin.

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