Patent Application
20210371591
The present invention relates to novel phosphorus containing oligomers and polymers, to methods or preparing the same and to a phosphorus containing hydrogel or organogel.
Polyamides (notably polyamide 6 or “PA6”) and Polyesters (PET) are commonly used in manufacturing textile fibers. Such polymers need to be flame retarded for fire safe application. The flame-retardancy of such polymers is either achieved by incorporating a flame-retardant moiety in the backbone of the polymer (copolymerization) or by incorporating a non-reactive additive during their thermal processing. Incorporation of an additive in the polymer during polymer processing offers the advantage of flexibility and simplicity. However, such non-reactive additives will leach out during their subsequent wet processing, especially during dyeing of textile fibers at temperatures greater than 100° C. Two possible ways to avoid such issues would be to either graft the reactive additive to the back bone of the polymer chain during thermal processing or to create non-leaching macromolecular additives during thermal processing of the polymer. Chemically grafting of additives to the polymer backbone would prevent their leaching during their subsequent wet treatments, whereas additives in macromolecular form will entangle with the polymer chain and thus will be prevented from migrating out of the polymer during subsequent after treatments. These two ways to render polymers flame retardant are rather novel and not much is known in the literature. Only limited knowledge exists regarding reactive extrusion of PA6 for improving its flame retardancy and thermal stability.
Reactive hindered phenols are efficient thermal stabilizers which could trap RO and ROO radicals to suppress aging process by donating hydrogen atoms and forming stable free radicals. Such phenols might be grafted onto the backbones of PA6 in a reactive extrusion process with high grafting efficiency in order to improve thermal oxidative stability [1]. In situ preparation of melamine cyanurate-PA6 nanocomposite from reaction of melamine and cyanuric acid in the extrusion process [2] is an efficient and innovative method to improve the flame retardancy of the polymer; however, such polymer formulations cannot be spun into textile fibers. Melamine cyanurate thus formed in situ will agglomerate to form large particles which could get clogged in a normal spinning process.
Reactive extrusion in form of chain extension has been widely used for the modification of polymers such as PA-6 and PET, and it is possible to increase the molecular weight of these polymers by reactive extrusion adding a chain extender to the extrusion process. The most commonly used chain extenders are 1,1′isophthaloyl-bis-caprolactam and 2,2′-bis(2-oxazoline) for PA-6 [3, 4], and pyromellitic dianhydride and triglycidyl isocyanurate for PET [5]. In these cases, however, no flame retardancy has been achieved.
Recently, water-insoluble and water-swellable gels are attracting an increasing interest in a wide range of biomedical applications such as in the pharmaceutical field as carriers for delivery of various drugs, peptides, and proteins. Their reversible swelling ability enables them to modulate the release behavior according to the external stimuli such as pH, temperature, ionic strength, electric field, or specific analyte concentration gradients.[6-10]. A number of methods have been developed for preparation of cross-linked polymeric gels, such as radicals initiation generated via thermal energy [11] or the photo-cleavage of initiator molecules [12], and “Click” chemistry [13], but the applications of above methods are limited because of the toxicity of used catalyst or initiator and the complicated chemical synthesis makes them still a significant challenge.
The inventors have discovered that reactive organophosphorus compounds containing unsaturated vinyl groups can be used in a flexible and highly controlled manner to prepare various macromolecular derivatives either via radical reactions or via Michael addition with suitable nucleophiles. Based on the fact that secondary amine groups on the one hand and vinyl groups on the other hand can work as mutual linking sites, an arsenal of novel and useful addition products can be built up. As will be appreciated from the various aspects outlined below, selecting the number of secondary amine sites and vinyl sites of the participating reaction partners allows one to generate very different addition products. In particular, one can form either linear chain type macromolecules (i.e. linear oligomers or polymers) or highly crosslinked network polymers.
Therefore, according to one aspect of the invention, there is provided a phosphorus containing linear oligomer or polymer with general formula (A)
wherein
n is at least 2;
R1 is selected from the group consisting of phenyl, substituted phenyl, benzyl, substituted benzyl, a linear or branched alkyl group with up to 5 carbon atoms, and a linear or branched alkoxy group with up to 5 carbon atoms;
—X—R′—X— is selected from the group consisting of
or —X—R′—X— is —NR2—R′″—NR2— wherein
R2 is a methyl or alkyl group and
R′″ is selected from the group consisting of:
According to another aspect of the invention, a method of preparing a phosphorus containing oligomer or polymer (A) as defined above, comprises an addition reaction of a divinyl posphine oxide (B)
and an amine compound (C) containing two secondary amine groups according to
H—X—R′—X—H (C).
wherein —X—R′—X— is as defined just hereinabove.
According to a further aspect of the invention, there is provided a phosphorus containing cross-linked network polymer of general formula (D)
wherein R is selected from the group consisting of
According to a still further aspect of the invention, a method of preparing a cross-linked network polymer (D) as defined above comprises an addition reaction of trivinyl posphine oxide (E)
and an amine compound (F) containing two secondary amine groups according to
H—N—R—N—H (F)
wherein —N—R—N— is selected from the group consisting of
According to a still further aspect of the invention, there is provided a phosphorus containing cross-linked network polymer of general formula (G)
wherein R is selected from the group consisting of
According to yet another aspect of the invention, a method of preparing a cross-linked network polymer (G) as defined above comprises an addition reaction of trivinyl posphine oxide (E)
and an amine compound (H) containing three secondary amine groups according to
—HN—R(NH—)—NH— (H)
wherein —N—R(N—)—N— is selected from the group consisting of
According to yet a further aspect of the invention, there is provided a phosphorus containing cross-linked network polymer of general formula (J)
wherein R is selected from the group consisting of
and wherein R1 is selected from the group consisting of
a linear or branched alkyl group with up to 5 carbon atoms, and
a linear or branched alkoxy group with up to 5 carbon atoms.
According to another aspect of the invention, a method of preparing a cross-linked network polymer (J) as defined above comprises an addition reaction of a divinyl posphine oxide (K)
wherein R1 is as defined above for (J),
and an amine compound (H) containing three secondary amine groups according to
—HN—R(NH—)—NH— (H)
wherein —N—R(N—)—N— is selected from the group consisting of
According to a further aspect of the invention, there is provided a phosphorus containing hydrogel or organogel comprising a cross-linked network polymer as defined above in water or in an organic solvent.
In advantageous embodiments, the above defined methods are carried out during thermal processing of a blend comprising a thermoplastic base polymer and an admixture of:
Advantageously, the thermoplastic base polymer is a polyamide, polyolefin, polyester or polycarbonate.
According to another aspect of the invention, there is provided a method of forming a phosphorous containing polymer, the method comprising the following steps:
According to an advantageous embodiment, the base polymer is a polyamide or a polyester.
As known in principle, there are different ways to achieve radical initiation. According to one embodiment, the radical formation is effected by thermal activation, i.e. heating. The process can be self-catalyzing or it can be promoted by addition of a free radical initiator. According to another embodiment, the radical formation is effected by ultraviolet irradiation or by electron beam irradiation, which generally requires providing the reaction mixture in the form of a thin layer or fiber.
According to a further aspect, a phosphorus containing oligomer or polymer as defined above is used as flame retardant composition.
According to yet another aspect, there is provided a polymeric material with improved flame resistance, comprising a phosphorus containing oligomer or polymer as defined above admixed in a melt processable polymer,
The above mentioned and other features and objects of this invention and the manner of achieving them will become more apparent and this invention itself will be better understood by reference to the following description of various embodiments of this invention taken in conjunction with the accompanying drawings, wherein are shown:
An overview of functional additives playing an important role in the present work is given in the following Table 1:
As shown schematically in
The gels can be prepared by reacting either divinyl or trivinyl phosphorus compounds with appropriate nucleophiles (see Scheme 1) via a Michael addition reaction in water suitable organic solvents.
The general structures of gels made from trivinyl phosphorus derivatives (TVPO) are shown in Scheme 2:
The general structure of gels made from divinyl phosphorus derivatives are shown in Scheme 3:
All phosphorus-based additives used in this work contain one or more vinyl groups that can react with the methylene groups (—CH2-) of PA6 and PET by radical reaction. Table 2 summarizes the list of processing trials performed on the reactive phosphorus additives. In order to promote the radical reaction, a radical initiator was added in some experiments.
The kneading trials were performed at 240° C. for PA-6 and 260° C. for PET and 30 rpm using a Brabender-mixer. The polymer was fed first and the additives were fed after two minutes, the total mixing time was 10 minutes.
The vinyl groups of the phosphorus additives used in this work can react with the amino groups (—NH—) of PA-6 and/or Piperazine by Michael addition reaction. Table 3 explicates the trial performed on the reactive phosphorus additives. The trial was performed at 240° C. and 30 rpm using a Brabender-mixer.
The third approach consists of physical mixing of the flame-retardant additive and the polymer by kneading and subsequently e-beam treatment to crosslink the additive to the polymer backbone. This physical mixing is not considered reactive extrusion; however, we cannot avoid reaction of some vinyl groups of the phosphorus additives with the polymer, even in absence of any radical initiator. Some of the materials obtained via approach 1 and 2 were used in the post crosslinking experiments; the list is shown in Table 4.
Plates (150*50*0.5 mm) of the above materials have been made by compression molding at 260° C. for PA6 and 290° C. for PET. The plates were subsequently exposed to electron irradiation. The energy supplied through the electron beams allows the reaction between the vinyl groups present in the additives and the polymer chains.
The plates were treated on both sides (the penetration of the electron beam is 200-250 μm) in N2-atmosphere at 200 kV with a speed of 6 m/min. In order to evaluate the amount of reacted additive as a function of the energy supplied doses of 50, 100 and 200 kGy were used.
Table 5 summarizes the thermal data of all polymer formulations obtained by Approach 1 and Approach 2. From the thermal gravimetric analysis (TGA) performed, it is clear that additives lower the decomposition temperature of the PA in air and nitrogen and this effect is more evident in the materials processed with DCP. No significant differences in melting and crystallization temperature were detected from differential scanning calorimetry analysis (DSC).
The extruded polymers were then grinded and extracted with chloroform. The P-analysis using ICP instrument was done for each sample before and after extraction to calculate the flame retardant retained. The various formulations were evaluated for % P content using ICP-OES method. To estimate the % P retention the polymer formulations were extracted with chloroform at 100° C. for 1 hour and then estimated for % P retention. Table 6 presents the phosphorus content and its retention after solvent extraction.
The trial PA6/DV/PIP has showed promising processability characteristics as well as higher phosphorus retention, which led to the production of compound (PA6/DV/PIP-Comp) in kilogram quantity and subsequent fibers (PA6/DV/PIP-FB) with the same concentration of additives. The virgin PA-6 was previously dried in a vacuum oven at 100° C. for 12 hrs and then physically premixed with the additives for 30 mins. This compound was obtained using a corotating twin screws (16 mm) compounder; the processing temperature and the temperature of the die were respectively 265° C. and 251° C. at 110 rpm. The output rate of the compounder was 500 g/hr. The same compound was used to produce fibers; the processing temperature and the temperature of the spin pack were 275° C. and 245° C. respectively and the output rate was 360 cm3/hr. The resulting filament was drawn up to a draw ratio of 4 which led to final fiber diameter of 70 μm.
As shown in Table 7, compounding and kneading (PA6/DV/PIP-Comp and PA6/DV/PIP) gave similar results in terms of phosphorus retention. Instead, the % P retention significantly increased for the fibers, it is probably due to the longer processing of the material, which leads to a higher reaction yields (Michael Addition).
The mechanical properties of the fibers were investigated; they are summarized in Table 8 and data presented are the average over 20 measurements.
The e-beam treated plates were then grinded and extracted with chloroform. The P-analysis using ICP instrument was done for each sample before and after extraction to calculate the flame retardant retained. The various formulations were evaluated for % P content using ICP-OES method. To estimate the % P retention the polymer formulations were extracted with chloroform at 100° C. for 1 hour and then estimated for % P retention. Table 9 summarizes the various polymer formulations, e-beam treatments intensity and their % P content and retention.
#The “gray” (Gy) is defined as the absorption of one joule of radiation energy per kilogram of matter.
As shown in Table 9, even with low e-beam irradiation, phosphorus retention higher than 90% was achieved for all the PA6-based materials. Thus, this procedures offer a novel way of permanently immobilizing FR additives in the polymer. For PET-based material, after the e-beam irradiation, the phosphorus retention increased significantly but the values are still low.
Small-scale fire tests were performed on various formulations to evaluate their fire behavior. Limiting oxygen index (LOI) test and vertical burning test (BKZ— Swiss standard) were performed on plates of PA6-MB and PA6/DV/PIP-Comp. For both tests, plates (150*50*0.5 mm) of the above materials have been made by compression molding at 260° C.
The LOI is the minimum concentration of oxygen, expressed as a percentage, which will support combustion of a polymer; it is measured by flowing a mixture of oxygen and nitrogen over a burning specimen, the test is repeated reducing the oxygen concentration until the flame does not propagate.
The test consists in putting in contact the lower edge of the samples with a propane gas flame (40±2 mm in length) for 15 s. The burner is inclined by 45° relative to the vertical line. The damaged length and the afterglow time are measured.
□ The values are the average of 3 tests.
Thus, it is clear such flame-retardant modifications improve the fire protections of polyamide 6 remarkably.
TVPO (64.02 mg, 0.50 mmol) and piperazine (64.60 mg, 0.75 mmol) were added to water (2.5 ml). The resulting mixture was stirred at 90° C. for 0.5 h and a colorless transparent gel was obtained. The solvents were evaporated by freeze-drying.
TVPO (64.02 mg, 0.50 mmol), piperazine (64.60 mg, 0.75 mmol) Polyethylene glycol (20K) (12.80 mg, 10%) were added to water (2.5 ml). The resulting mixture was stirred at 90° C. for 0.5 h. The solvents were evaporated by freeze-drying.
TVPO (64.02 mg, 0.50 mmol), piperazine (64.60 mg, 0.75 mmol) Polyethylene glycol (200K) (6.40 mg, 5%) were added to water (2.5 ml). The resulting mixture was stirred at 90° C. for 0.5 h. The solvents were evaporated by freeze-drying.
TVPO (64.02 mg, 0.50 mmol), piperazine (64.60 mg, 0.75 mmol) Polyethylene glycol (300 K) (6.90 mg, 5%) were added to water (2.5 ml). The resulting mixture was stirred at 90° C. for 0.5 h. The solvents were evaporated by freeze-drying.
TVPO (128 mg, 1 mmol) and DPP (157.7 mg, 0.75 mmol) were added to Ethanol (2.5 ml). The resulting mixture was stirred at 80° C. for 1.5 h. The solvents were evaporated by freeze-drying.
TVPO (64.02 mg, 0.50 mmol) and 1,10-di(piperazin-1-yl)decane (232.89 mg, 0.75 mmol) were added to ethanol (5 ml). The resulting mixture was stirred at 85° C. for 8 h and a colorless transparent gel was obtained. The solvents were evaporated by freeze-drying.
TVPO (64.02 mg, 0.50 mmol) and 2,4,6-tri(piperazin-1-yl)-1,3,5-triazine (166.72 mg, 0.50 mmol) were added to ethanol (5 ml). The resulting mixture was stirred at 85° C. for 1 h and a colorless transparent gel was obtained. The solvents were evaporated by freeze-drying.
DVPO (133.54 mg, 0.75 mmol) and 2,4,6-tri(piperazin-1-yl)-1,3,5-triazine (166.72 mg, 0.50 mmol) were added to ethanol (5 ml). The resulting mixture was stirred at 85° C. for 8 h and a colorless transparent gel was obtained. The solvents were evaporated by freeze-drying.
Swelling ratio of cross-linked gels was measured by soaking the gel in a particular solvent till to reach equilibrium swelling. Then, the swelled gel was taken out by spatula on a butter paper carefully, blotted quickly with a moist tissue paper (in respective solvent) and weighed. The solvent uptake ratio (swelling ratio, SR) of swelled gel was determined following the formula:
Where, Ws and Wd represent the weight of swelled and dry crosslinked gels respectively. The swelling behavior of synthesized gels have been investigated in solvents having different polarities and results are summarized in Table 11.
2. pH-Responsiveness of Hydrogels
pH responsive properties of hydrogels were performed at room temperature in the range of pH 2 to 7.4. pH of the aqueous media was adjusted by 0.1 N NaOH or 0.1 N HCl solution. A measured amount of gel was soaked at a particular pH till equilibrium swelling was achieved, then, taken out, blotted quickly with a moist tissue paper and weighted. Swelling ratio was calculated as mentioned earlier.
The release behavior of a gel describes the release of certain substances trapped in the gel matrix. This can be influenced by different factors such as pH, temperature, ionic strength, electric field or specific analyte concentration gradients. Depending on the factor, the gels are suitable for different application areas. Healthy human skin is slightly acidic due to secretion of lactic acid and sebum and has a pH of about 5. In certain injuries, the pH changes to neutral or basic 10 (blood pH=˜7.4). Such stimuli can be utilized to trigger the release of active ingredients. Once the skin has regenerated, the pH drops and the release is inhibited or stopped altogether. Gels that are pH-sensitive can be applied to wounds.
To study the drug release behavior, Methylene blue and Acid Blue 80 were chosen as the model molecules. The model molecule was initially dissolved in water (1 mg/1 ml) at room temperature and then gels were soaked in it. After 4 h the gels were removed from the solution and washed with water repeatedly till colorless water was obtained. As qualitative estimation for gel A as an example, the release of Acid Blue 80 was estimated visually. The figure (
Similarly, the qualitative estimation of release behavior of gel A containing methylene blue (model basic drug) was also recorded. The figure (
| Number | Date | Country | Kind |
|---|---|---|---|
| 18173380.9 | May 2018 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2019/063001 | 5/20/2019 | WO | 00 |
