MECHANICALLY REINFORCED, TRANSPARENT, ANTI-BIOFOULING THERMOPLASTIC RESIN COMPOSITION AND MANUFACTURING METHOD THEREOF
20200115534 ยท 2020-04-16
Inventors
Cpc classification
C08L23/0815
CHEMISTRY; METALLURGY
C08L2205/05
CHEMISTRY; METALLURGY
B29B9/12
PERFORMING OPERATIONS; TRANSPORTING
B29B7/88
PERFORMING OPERATIONS; TRANSPORTING
C08L2201/08
CHEMISTRY; METALLURGY
C08L2205/06
CHEMISTRY; METALLURGY
B29B9/06
PERFORMING OPERATIONS; TRANSPORTING
B29C41/003
PERFORMING OPERATIONS; TRANSPORTING
B29C48/40
PERFORMING OPERATIONS; TRANSPORTING
B29C49/0005
PERFORMING OPERATIONS; TRANSPORTING
C08L33/12
CHEMISTRY; METALLURGY
B29K2105/0005
PERFORMING OPERATIONS; TRANSPORTING
C08L23/0815
CHEMISTRY; METALLURGY
B29C48/919
PERFORMING OPERATIONS; TRANSPORTING
B29C48/022
PERFORMING OPERATIONS; TRANSPORTING
C08L2201/10
CHEMISTRY; METALLURGY
International classification
B29C48/40
PERFORMING OPERATIONS; TRANSPORTING
B29B9/12
PERFORMING OPERATIONS; TRANSPORTING
B29C41/00
PERFORMING OPERATIONS; TRANSPORTING
B29C48/88
PERFORMING OPERATIONS; TRANSPORTING
C08L33/12
CHEMISTRY; METALLURGY
B29C48/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
This invention discloses a transparent standalone resin or masterbatch concentrate composition and manufacturing method of transforming commercial transparent grade base thermoplastics into anti-biofouling resins through extrusion or any similar hot melt mixing processes. The re-compound solids enable a number of product reforming processes, including but not limited to thermoforming, profile extrusion, injection molding, blow molding, blow filming, film casting, and spinning into articles of different shapes and geometries or overmolding on plastic substrates that can resist surface adsorption of microbes, mammalian cells, proteins, peptides, nucleic acids, steroids and other cellular constituents after solidification. The articles formed thereof additionally exhibit mechanical reinforcement and no leaching while retain the optical clarity of the base thermoplastics in the same product form as quantified in terms of the light transmittance and haze.
Claims
1. A composition for forming a functional polymer or a masterbatch concentrate resin comprising a transparent grade base thermoplastics at 70-99 wt %, impact modifiers at 0.1-30 wt %, chemical modifiers at 0.5-10 wt %, and other additives at 0.1-6 wt %, wherein said chemical modifiers comprise non-fouling modifiers in 0.1-5 wt %; and wherein said other additives comprise one or more of initiators, cross-linking agents, nucleators, anti-oxidants, and/or auxiliary additives in 0.1-6 wt %.
2. The composition of claim 1, wherein said transparent grade base thermoplastics comprise homopolymers, copolymers and blends of polyolefins, cyclic polyolefins, acrylics, acetates, styrenics, polyesters, polyimides, polyaryletherketones, polycarbonates, polyurethanes and thermoplastic elastomers.
3. The composition of claim 1, wherein said transparent grade base thermoplastics comprises poly(methyl methacrylate) (PMMA), polystyrene (PS), polyethylene terephthalate (PET), polycarbonate (PC), polymethylpentene (PMP), polysulfone, polyamide (PA), polyvinyl chloride (PVC), styrene acrylonitrile (SAN), styrene-methacrylate based copolymer, polypropylene based copolymer, acrylonitrile butadiene styrene (ABS), polyimide (PI) cellulosic resins, methyl methacrylate butadiene styrene (MBS), and styrene ethylene butylene styrene block thermoplastic elastomer (SEBS).
4. The composition of claim 3, wherein said polypropylene based copolymer comprises polypropylene random copolymer (PPR), impact-modified polypropylene compound (PPM) and polypropylene homopolymer (PPH).
5. The composition of claim 1, wherein said non-fouling modifiers comprise one or more of linear and/or multi-armed structures of non-ionic surfactants and are in a concentration from 0.5 wt % to 10 wt %.
6. The composition of claim 5, wherein said non-ionic surfactants comprise fatty alcohol polyoxyalkylene ethers, polyoxyalkylene sorbitan/sorbitol fatty acid esters, polyoxyalkylene alkyl amines, polyether glycols, fatty acid alkanolamides and their derivatives.
7. The composition of claim 5, wherein said non-ionic surfactants comprise polyethylene glycol (PEG) sorbitol hexaoleate, AEO-5 and polyetheramine.
8. The composition of claim 7, wherein said PEG sorbitol hexaoleate has an average molecular weight from 2000 to 20,000 Da.
9. The composition of claim 7 wherein said polyetheramine has a molecular weight from 200 to 6,000 Da.
10. The composition of claim 1, wherein said impact modifiers comprise polyolefin elastomers (POE) and thermoplastic polyurethane (TPU).
11. The composition of claim 1, wherein said initiators comprise an acid or base catalyst and exist in either standalone form or is supported on filler particles with a weight percentage from 0.01 to 0.2 wt %.
12. The composition of claim 1, wherein said initiators comprise tosylic acid, tetramethylammonium hydroxide, or an organic peroxide and exist in either standalone form or is supported on filler particles with a weight percentage from 0.01 to 0.2 wt %.
13. The composition of claim 12, wherein said organic peroxide comprises dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, benzoyl peroxide.
14. The composition of claim 1, wherein said cross-linking agents comprise triallyl isocyanurate, N,N-m-phenylene dismaleimide or sulfur and are in a concentration from 0.01 to 0.2 wt %.
15. The composition of claim 1, wherein said nucleators comprise MILLAD NX8000, MILLAD 3988, ADK STAB NA-18 or ADK STAB NA-25 in a concentration from 0.1 to 3 wt %.
16. The composition of claim 1, wherein said anti-oxidants comprise butylated hydroxytoluene, IRGANOX 1010, Irganox 1076, Irganox 1098, Irgafos 168 or Irganox B 225, and are in a concentration from 0.1 to 2 wt %.
17. The composition of claim 1, wherein said auxiliary additives comprise alumina nanoparticles and are in a concentration from 0.1 to 4 wt %.
18. The composition of claim 7, wherein said polyetheramine comprise JEFFAMINE D-230 or T-5000.
19. The composition of claim 17, wherein said alumina nanoparticles are AEROXIDE Alu C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION OF THE INVENTION
[0025] References in the specification to one embodiment, an embodiment, an example embodiment, etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
[0026] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of about 0.1% to about 5% should be interpreted to include not only the explicitly recited concentration of about 0.1 wt. % to about 5 wt. %, but also the individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, and 3.3% to 4.4%) within the indicated range.
[0027] As described herein, the terms a or an are used to include one or more than one and the term or is used to refer to a nonexclusive or unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.
[0028] In the methods of manufacturing described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Recitation in a claim to the effect that first a step is performed, and then several other steps are subsequently performed, shall be taken to mean that the first step is performed before any of the other steps, but the other steps can be performed in any suitable sequence, unless a sequence is further recited within the other steps. For example, claim elements that recite Step A, Step B, Step C, Step D, and Step E shall be construed to mean step A is carried out first, step E is carried out last, and steps B, C, and D can be carried out in any sequence between steps A and E, and that the sequence still falls within the literal scope of the claimed process. A given step or sub-set of steps can also be repeated.
[0029] Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.
Definitions
[0030] The singular forms a, an and the can include plural referents unless the context clearly dictates otherwise.
[0031] The term about can allow for a degree of variability in a value or range, for example, within 10%, or within 5% of a stated value or of a stated limit of a range.
[0032] The term independently selected from refers to referenced groups being the same, different, or a mixture thereof, unless the context clearly indicates otherwise. Thus, under this definition, the phrase X1, X2, and X3 are independently selected from noble gases would include the scenario where, for example, X1, X2, and X3 are all the same, where X1, X2, and X3 are all different, where X1 and X2 are the same but X3 is different, and other analogous permutations.
DETAILED DESCRIPTIONS OF PREFERRED EMBODIMENTS
[0033] The present invention is not to be limited in scope by any of the following descriptions. The following examples or embodiments are presented for exemplification only.
[0034] The modification of the transparent grade base thermoplastics according to the present invention can be processed in either one-step or two-step method (
[0035] One or more of linear and/or multi-armed structures of non-ionic surfactants is/are selected as the non-fouling modifiers. The non-ionic surfactants are chosen from fatty alcohol polyoxyalkylene ethers, polyoxyalkylene sorbitan/sorbitol fatty acid esters, polyoxyalkylene alkyl amines, polyether glycols, fatty acid alkanolamides and their derivatives. Polyethylene glycol (PEG) sorbitol hexaoleate, AEO-5 and polyetheramine (JEFFAMINE D-230 or T-5000) are preferred non-fouling modifiers. Proper ratio and combination of functional modifiers is key to the anti-biofouling performance and retention of transparency of the transparent grade base thermoplastic materials. Typical ratio is adjusted from 0.5 to 10% on a weight basis with respect to the total weight of the composition. In a specific embodiment, thePEG sorbitol hexaoleate has a molecular weight ranging from 2,000 to 20,000 Da (or 2 to 20 kDa). In another specific embodiment, said polyetheramine has a molecular weight ranging from 200 to 6,000 Da.
[0036] Elastomers, such as polyolefin elastomer (POE) and thermoplastic polyurethane (TPU), are chosen as impact modifiers for modifying different transparent grade base thermoplastics. VISTAMAXX and ENGAGE series POE and ELASTOLLAN series TPU are preferably suggested in this case. The suggested ratio ranges from 0.1 to 30% by weight with respect to the total weight of the composition in order to augment the impact strength. Initiators and additives including tosylic acid, tetramethylammonium hydroxide, and/or an organic peroxide, such as dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane and benzoyl peroxide, in a weight percentage from 0.01% to 0.2% with respect to the total weight of the composition are added to initiate covalent grafting of the non-fouling modifiers onto the base polymers and/or impact modifiers.
[0037] Other additives, such as anti-oxidant, cross-linking agent, optical brightener, color masterbatch, odor absorbent, etc. are chosen to control the appearance and the scent of the articles. The anti-oxidant is preferred to be selected from butylated hydroxytoluene, IRGANOX 1010, IRGANOX 1076, IRGANOX 1098, IRGAFOS 168 or IRGANOX B 225 with a weight percentage to the total weight of the composition from 0.1 to 2 wt %. The cross-linking agent is preferred to be selected from triallyl isocyanurate, N,N-m-phenylene dismaleimide or sulfur with a weight percentage to the total weight of the composition from 0 to 1 wt %. The initiator is preferred to be selected from dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene or benzoyl peroxide with a weight percentage to the total weight of the composition from 0.01 to 0.2 wt %. The nucleator is preferred to be selected from MILLAD NX8000, MILLAD 3988, ADK STAB NA-18 or ADK STAB NA-25 with a weight percentage to the total weight of the composition from 0 to 3 wt %. An auxiliary additive is preferred to be alumina nanoparticles (AEROXIDE Alu C) for enhancement of the heat deflection temperature of base polymers with suggested weight percentage to the total weight of the composition from 0.1 to 4 wt %.
[0038] During injection molding, the cycle time typically ranges from a few seconds to 5 minutes for extremely thick-wall parts per shot. On average, the injection falls in the range between 20 and 60 seconds for a well-designed mold and with a proper barrel and mold temperature control. For instance, samples of dogbone tensile test bars (Type I, ASTM D638), Izod impact test bars (ASTM D256), flat circular plates with thickness of 1.5 mm and diameter of 60 mm for optical haze/transmittance (ASTM D1003) and yellowness index (ASTM E313) measurement and rectangular strips for heat deflection temperature measurement (ISO 75) were produced on a 150-ton injection molding machine in one single shot from the mold cavity. Extrusive compounding was performed on a co-rotating twin-screw extruder. The extruder had a screw diameter of 26 mm, a screw length-to-diameter (L/D) ratio of 42:1 and an adjustable speed of 50-500 rpm. Its barrel was divided into 7 temperature zones, one of which was located at the die orifice. The extruder was equipped with a volumetric feeder composed of two separate compartments that can feed two different types of raw materials at an equivalent ratio.
[0039] Protein repellent assay procedures are herein described as follows:
(a) 0.5 ml bovine serum albumin (BSA)/0.01 M phosphate-buffered saline (0.1 g/ml, pH 7.4) protein solution is wetted on a flat surface of a molded circular plate sample;
(b) The protein solution is placed at room temperature for half an hour for adsorption;
(c) The protein solution is withdrawn by aspiration;
(d) Bradford reagent (Cat. no. B6916, Sigma) of the same volume is deposited on the affected area to stain the potentially protein-fouled sample surface;
(e) Color change of the Bradford reagent (from brown to blue) qualitatively indicates the presence of adsorbed proteins.
[0040] The incubation protocol for microbial adsorption tests on the molded circular plate samples is herein described by the schematic diagram in
EXAMPLES
[0041] The embodiments of the present invention can be better understood by reference to the following examples which are offered by way of illustration. The present invention is not limited to the examples given herein.
Example 1
[0042] The modification of MBS, a highly transparent methyl methacrylate butadiene styrene plastic compound, was rendered by extrusive compounding of 94% MBS resin with 1% IRGANOX B 225 and 5% AEO-5, a fatty alcohol ethoxylate, on a weight basis with a processing temperature ranging from 180 C. to 210 C. to obtain functional resin directly. The modified formulation was re-pelletized as standalone resin (herein annotated as MBS-M) that could be fed into an injection molding machine (with processing temperature of 210 C.) to obtain plastic samples dictated by the mold tooling design.
TABLE-US-00001 TABLE 1 Izod % reduction % reduction Impact Elongation Mechanical of E. coli of S. aureus Transparency Haze Strength HDT at break Strength adsorption adsorption Sample (%) (%) (KJ/m.sup.2) ( C.) (%) (N/mm.sup.2) (%) (%) MBS 88.4 7.3 24.42 83.5 89.2 28.04 (Control) MBS-M 89.6 6.5 47.11 79.8 82.6 24.37 99% 96%
Example 2
[0043] The modification of PPR, a transparent polypropylene random copolymer, was rendered by extrusive compounding of PPR resin with 30% polyolefin elastomer (VISTAMAXX 6202, ExxonMobil), 2% JEFFAMINE D-230, 2% poly(ethylene glycol) sorbitol hexaoleate, 3.75% alumina nanoparticles, 0.1% dicumyl peroxide, 0.05% triallyl isocyanurate and 0.01% CBS-127, an optical brightener, on a weight basis with processing temperature ranging from 170 C. to 190 C. to obtain a functional masterbatch concentrate (herein, annotated as PPR-M) after pelletization. The masterbatch was dry blended at a ratio of 1:1.5 w:w PPR with 0.1% overall by weight of NX8000 and subsequently fed into an injection molding machine (with processing temperature of 190 C.) to obtain plastic samples. The characterization results are summarized in Table 2. Alumina nanoparticles helped to minimize the reduction of heat deflection temperature (HDT) by counteracting the influence of addition of polyolefin elastomer.
TABLE-US-00002 TABLE 2 Izod % reduction of % reduction Impact E. coli of S. aureus Transparency Haze Strength HDT Yellowness Protein adsorption adsorption Sample (%) (%) (KJ/m.sup.2) ( C.) Index repellency (%) (%) PPR 84.1 26.4 7.21 78.1 10.6 No (Control) PPR-M 82.5 28.2 15.42 77.6 11.9 Yes >99% >99%
Example 3
[0044] The modification of PPM, an impact-modified polypropylene compound, was rendered by extrusive compounding of PPM resin with 2% JEFFAMINE D-230, 2% AEO-5, 1% MILLAD NX8000, 0.1% dicumyl peroxide and 0.05% triallyl isocyanurate with processing temperature ranging from 170 C. to 190 C. to obtain a functional masterbatch concentrate (herein, annotated as PPM-M) after pelletization. The masterbatch was dry blended at a ratio of 1:1.5 w:w PPM with 0.1% overall by weight of IRGANOX 1010 and 0.1% overall by weight of IRGAFOS 168 for injection molding with processing temperature of 190 C.
TABLE-US-00003 TABLE 3 Izod % reduction of Impact Repellency E. coli % reduction of Transparency Haze Strength HDT towards adsorption S. aureus adsorption Sample (%) (%) (KJ/m.sup.2) ( C.) Protein (%) (%) PPM 81.9 23.7 44.55 71.8 No NA NA (Control) PPM-M 82.6 20.3 47.46 73.1 Yes >99% >99%
Example 4
[0045] The modification of PPH, a transparent polypropylene homopolymer, was rendered by extrusive compounding of PPH resins with 30% VISTAMAXX 3980FL, 2% JEFFAMINE D-230, 2% poly(ethylene glycol) sorbitol hexaoleate, 0.1% dicumyl peroxide, 0.05% triallyl isocyanurate and 3.75% alumina nanoparticles with processing temperature ranging from 180 C. to 200 C. The reformulated pellets were then directly subjected to injection molding (with processing temperature of 200 C.) to get molded samples. The characterization results are summarized in the table below. The impact strength increased significantly by more than 120% with respect to the base PPH plastic. Alumina nanoparticles were added to keep the heat deflection temperature (HDT) of PPH as high as about 80 C. for warm water contacting applications. Characterization results are summarized in Table 4.
TABLE-US-00004 TABLE 4 % Izod % reduction reduction Impact Repellency of E. coli of S. aureus Yellowness Transparency Haze Strength HDT towards adsorption adsorption Sample Index (%) (%) (KJ/m.sup.2) ( C.) Protein (%) (%) PPH 10.06 83.9 17.0 4.49 98.9 No NA NA (Control) PPH-M 15.83 81.6 29.5 9.94 79.2 Yes >99% >99%
Example 5
[0046] The modification of SEBS, a styrene ethylene butylene styrene block thermoplastic elastomer, was rendered by extrusive compounding of SEBS resins with 0.1% tosylic acid, 2.5% polyethylene glycol (average molecular weight of 10,000) and 2.5% AEO-5 on a weight basis with processing temperature ranging from 170 C. to 220 C. The reformulated pellets were directly subjected to injection molding (with a processing temperature of 210 C.) to obtain molded samples. Characterization results are summarized in Table 5
TABLE-US-00005 TABLE 5 % reduction % reduction Repellency of E. coli of S. aureus Yellowness Transparency Elongation at towards adsorption adsorption Sample Index (%) Haze (%) break (%) Protein (%) (%) SEBS 8.12 82.5 20.2 420% No NA NA (Control) SEBS-M 10.03 79.2 26.4 400% Yes >99% >98%