Fiber And Blended Polymers In Composite With Modulus, Heat Resistance, and Impact Strength

Abstract

The claimed material relates to a composite of an interfacial modified fiber and mixed or combined polymer composite having enhanced impact, and modulus properties.

Claims

1. A thermoplastic composite masterbatch comprising a fiber phase and a polymer phase: (a) the fiber phase comprising greater than 50 wt. % a glass fiber with a length greater than about 1 mm, a diameter greater than about 0.8 microns and an aspect ratio greater than about 10, the fiber having about 0.1 to 5 wt. % of an exterior coating comprising a mixture of organo metallic interfacial modifiers, the wt. % based on the fiber phase and; (b) the polymer phase comprising a thermoplastic polymer comprising vinyl chloride and a chlorinated polyethylene (CPE) at a weight ratio of about 0.1 to 10 parts by weight of polymer per part of CPE; wherein the master batch and a composite there\from has a COTE (D6341) of 0.5 to 1.5 in/in/ F., a room temperature impact resistance of about 200 to 1000 ft-lb-in.sup.1 (ASTM D256), a flexural modulus (ASTM D790) of about 0.4 to 3 Mpsi and a heat distortion of less than about 50 hrs. at 143 F.

2. The masterbatch of claim 1 comprising about 55 to 70 wt. % fiber phase dispersed in a about to 60 wt. % of a polymer phase.

3. The masterbatch of claim 1 comprising a glass fiber having a length of 1 to 20 mm, a diameter of 1-15-0 microns and an aspect ratio greater than 90.

4. The masterbatch of claim 1 comprising a PVC polymer.

5. The masterbatch of claim 4 comprising a PVC homo polymer.

6. The masterbatch of claim 1 comprising a CPE with 25 to 45 wt. chlorine.

7. The composite of claim 1 comprising fiber having about 0.5 to 3 wt. % of an exterior coating comprising a mixture of mixed interfacial modifiers, the wt. % based on the fiber phase.

8. A fence rail comprising a composite of the masterbatch of claim 1 comprising 3 to 10 wt. % CPE and 5 to 10 wt. % glass and a mixed organo metallic interfacial modifiers.

9. A fence rail comprising a composite of the masterbatch of claim 1 comprising 3 to 7 wt. % CPE and 3 to 7 wt. % glass and a mixed organo metallic interfacial modifiers.

10. A thermoplastic composite member comprising a fiber phase and a polymer phase: (a) the fiber phase comprising about 1 to 20 wt. % of a glass fiber with a length greater than about 1 mm, a diameter greater than about 0.8 microns and an aspect ratio greater than about 10, the fiber having about 0.1 to 5 wt. % of an exterior coating comprising a mixture of organo metallic interfacial modifiers, the wt. % based on the fiber phase; and; (b) the polymer phase comprising 80 to 99 wt. % of a thermoplastic polymer comprising vinyl chloride and a chlorinated polyethylene (CPE) at a weight ratio of about 0.1 to 50 parts by weight of CPE per 100 part of polymer; wherein the composite has a COTE (D6341) of 1.0 to 3.010.sup.5 in/in/ F., a room temperature impact resistance of about 100 to 500 ft-lb-in.sup.1 (ASTM D256), a flexural modulus (ASTM D790) of about 0.4-0.5 Mpsi and a heat distortion of more than 50 hours at 143 F.

11. The member of claim 10 comprising about 2 to 10 wt. % fiber phase dispersed in a about 90 to 98 wt. % of a polymer phase

12. The member of claim 10 comprising a glass fiber having a length of 1 to 20 mm, a diameter of 1-15-0 microns and an aspect ratio greater than 90.

13. The member of claim 10 comprising a PVC polymer.

14. The member of claim 12 comprising a PVC homo polymer.

15. The member of claim 10 comprising a CPE with 25 to 40 wt. chlorine.

16. The member of claim 10 comprising fiber having about 0.5 to 3 wt. % of an exterior coating comprising a mixed interfacial modifier, the wt. % based on the fiber phase.

17. The member of claim 10 comprising fiber having about 1 to 1.5 wt. % of an exterior coating comprising an interfacial modifier, the wt. % based on the fiber phase.

18. The member of claim 10 comprising an organo metallic interfacial modifier.

19. The member of claim 10 comprising a profile.

Description

BRIEF DESCRIPTION OF THE FIGURE

[0016] FIG. 1 shows a cross section of a typical structural member of the disclosure.

DETAILED DISCUSSION

[0017] Novel composites can be made by a combination of CPE and PVC polymers with an interfacial modified fiber to achieve novel physical and process properties including impact, heat stability, and modulus. A combination of a thermoplastic polymer and a chlorinated polyethylene (CPE) can be used.

[0018] Chlorinated polyethylene (CPE) is made by chlorinating polyethylene polymer materials. The chlorinated polyethylene polymer properties depend on the properties of the starting polymer material and the amount of, and distribution of the chlorination produced. In the chlorination of polyethylene, a chlorine atom is substituted randomly for a hydrogen atom on the polymer chain accompanied by the formation of hydrochloric acid (HCl). This occurs in a free radical mechanism, usually catalyzed by UV light or other high energy initiators. The chlorination process of the polymer chain involves solvent based and solvent-less or anhydrous processing. Commercial chlorinated polyethylene has a chlorine content that can range from 20 to 50%. Higher molecular weight and linear polyethylene yields a chlorinated polyethylene with a higher viscosity and tensile properties. The chlorine content can influence tensile properties, flexibility, et cetera.

[0019] Chlorinated polyethylene (CPE) is different from polyvinyl chloride (PVC and C-PVC). PVC is polymerized typically from mostly vinyl chloride monomers yielding polymer blocks of a regular but alternating array of chlorine atoms on a polymer backbone. Most commercial PVC materials are vinyl chloride homopolymers. Chlorinating PVC can make C-PVC. CPE is made from a polyethylene polymer (PE) containing mostly ethylene monomers. CPE is randomly chlorinated to form random chlorine atom substitutions replacing hydrogen atoms on the polymer backbone.

[0020] A large variety of thermoplastic homopolymer and copolymer materials can be combined with the chlorinated polyethylene (CPE) used in the composite materials. We have found that polymer materials useful in the composite include both condensation polymeric materials and addition or vinyl polymeric materials. Vinyl polymers are typically manufactured by the polymerization of monomers having an ethylenically unsaturated olefinic group. Condensation polymers are typically prepared by a condensation polymerization reaction which is typically considered to be a stepwise chemical reaction in which two or more molecules combined, often but not necessarily accompanied by the separation of water or some other simple, typically volatile substance. Such polymers can be formed in a process called polycondensation. The typical polymer has a density of at least 0.85 gm-cm.sup.3, however, polymers having a density of greater than 0.96 are useful to enhance overall product density. A density is often up to 1.7 or up to 2 gm-cm.sup.3 or can be about 1.5 to 1.95 gm-cm.sup.3.

[0021] Vinyl polymers include polyacrylonitrile; polymer of alpha-olefins such as ethylene, propylene, etc.; polymers of chlorinated monomers such as vinyl chloride, vinylidene chloride, can be used to make PVC, C-PVC; polymers form acrylate monomers such as acrylic acid, methyl acrylate, methyl methacrylate, acrylamide, hydroxyethyl acrylate, and others; styrenic monomers such as styrene, alpha-methyl styrene, vinyl toluene, etc.; vinyl acetate; and other commonly available ethylenically unsaturated monomer compositions. Examples include polyethylene, polypropylene, polybutylene, acrylonitrile-butadiene-styrene (ABS), polybutylene copolymers, polyacetal resins, polyacrylic resins, homopolymers or copolymers comprising vinyl chloride, vinylidene chloride, fluorocarbon copolymers, such as PVC and C-PVC etc.

[0022] Commercial exterior weathering compounded PVC compound are formed by the incorporation of additives (but not necessarily all of the following) such as heat stabilizers, UV stabilizers, plasticizers, processing aids, impact modifiers, thermal modifiers, fillers, flame retardants, biocides, blowing agents and smoke suppressors, and pigments. The choice of additives used for the PVC finished product is controlled by the cost performance requirements of the end use specification (underground pipe, window frames, intravenous tubing and flooring all have quite different ingredients to suit their environmental performance requirements).

[0023] Condensation polymers include nylon, phenoxy resins, polyarylether such as polyphenylether, polyphenylsulfide materials; polycarbonate materials, chlorinated polyether resins, polyethersulfones resins, polyphenylene oxide resins, polysulfone resins, polyimide resins, thermoplastic urethane elastomers and many other resin materials. Condensation polymers that can be used in the composite materials include polyamides, polyamide-imide polymers, polyarylsulfones, polycarbonate, polybutylene terephthalate, polybutylene naphthalate, polyetherimides, polyether sulfones, polyethylene terephthalate, thermoplastic polyamides, polyphenylene ether blends, polyphenylene sulfide, polysulfones, thermoplastic polyurethanes and others. Preferred condensation engineering polymers include polycarbonate materials, polyphenylene oxide materials, and polyester materials including polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polybutylene naphthalate materials.

[0024] Useful fiber includes both natural and synthetic fibers. Claimed composites are free of particulate such as inorganic fillers. Natural fiber includes those of animal or plant origin. Plant based examples include cellulosic materials such as wood fiber, cotton, flax, jute, cellulose acetate etc.; animal-based materials made of protein include wool, silk etc. Synthetic fibers include polymer materials such as acrylic, aramid, amide-imide, nylon, polyolefin, polyester, polyurethane, carbon, etc.

[0025] Other types include glass, metal, or ceramic fibers. Metallic fibers are manufactured fibers of metal, metal coated plastic, or a core completely covered by metal. Non-limiting examples of such metal fibers include gold, silver, aluminum, stainless steel, and copper. The metal fibers may be used alone or in combinations. The determinant for the selection metal fiber is dependent on the properties desired in the composite material or the shaped article made therefrom.

[0026] One useful fiber comprises a glass fiber known by the designations: A, C, D, E, Zero Boron E, ECR, AR, R, S, S-2, N, and the like. Generally, any glass that can be made into fibers either by drawing processes used for making reinforcement fibers or spinning processes used for making thermal insulation fibers. Such fiber is typically used as a length of about 0.8-100 mm often about 2-100 mm, a diameter about 0.8-100 microns and an aspect ratio (length divided by diameter) greater than 90 or about 100 to 1500.

[0027] These commercially available fibers are often combined with a sizing coating. Such coatings cause the otherwise ionically neutral glass fibers to form and remain in bundles or fiber aggregates. Sizing coatings are applied during manufacture before gathering. The sizing minimizes filament degradation caused by filament-to-filament abrasion. A commercial sizing is not an interfacial modifier and can be lubricants, protective, or reactive couplers but do not contribute to the properties of a composite using an interfacial modifier coating on the fiber surface.

[0028] The fiber is typically coated with an interfacial surface chemical treatment also called an interfacial modifier (IM) or mixtures thereof. An IM supports or enhances the final properties of the composite such as modulus, impact strength, heat stability, viscoelasticity, rheology, high packing fraction, and fiber surface inertness. These properties are not present in commercial contemporary composite materials.

[0029] An interfacial modifier is an organo-metallic material, or mixture thereof, provides an exterior coating on the fiber promoting the close association, but not attachment or bonding, of polymer to fiber and fiber to fiber. An interfacial moodier is a compound with a central atom and a set of ligands surrounding the atom. The composite properties arise from the intimate association of the polymer, CPE and fiber obtained by use of careful processing and manufacture. An interfacial modifier is in part an organic material, in some examples an organo-atomic or organo-metallic material, that provides an exterior coating on the fiber to provide a surface that can associate, but does not react, with the polymer promoting the close association of polymer and fiber but with no reactive bonding, such as covalent bonding for example, of polymer to fiber, fiber to fiber, or fiber to a different particulate, such as a glass fiber. In one embodiment, the coating of interfacial modifier at least partially covers the surface of the fiber. In another embodiment, the coating of interfacial modifier continuously and uniformly covers the surface of the fiber, in a continuous coating phase layer

[0030] Interfacial modifiers used in the application fall into broad categories of organo metallic compounds including, for example, titanate compounds, zirconate compounds, hafnium compounds, samarium compounds, strontium compounds, neodymium compounds, yttrium compounds. Useful IM ligands contain from about 1 to about 4 ligands. A variety of ligand on the central atom can be used. Ligand Alkyl or alkyl groups as means a branched or unbranched saturated hydrocarbon group of 1 to 100 carbon atoms, preferably 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isohutyl, t-butyl, octyl, letradecyl, hexaderyt, eicosyl, letracosyl and the like, as well as cycloalkyt groups such as cyclopentyl, cyclohexyl and the like. Optionally, an alkyl can contain 1 to 6 linkages selected from the group consisting of O, S, -M- and NR where R is hydrogen, or C.sub.1-C.sub.8 alkyl or lower alkenyl. In addition to the alkyl groups identified herein, other possible alkyl groups can be used in the practice of the described methods.

[0031] Various organic ligands can be used. Acidic and basic compounds can be used. Oxoacids can be used. Oxoacid means an acid that includes oxygen, at least one element other than oxygen, at least one hydrogen atom bound to oxygen, and forms an ion upon loss of one or more protons. Examples include carboxylic acids, sulfuric acid, nitric acid, phosphoric acid, and halogen-containing oxoacids, such as hypochlorous acid, chlorous acid, chloric acid, perchloric acid, etc. Others, for example, are P(OH).sub.3, RC(O)OH, HOSOH, HOCl, HONO, (HO).sub.2SO.sub.2, R(O)(OH).sub.2. Others can lose a positive hydrogen ion(s) and become mildly basic. Other acids include conjugate bases, salts, or esters. Others include n-allyl cadmium phosphonate, n all yl zinc phosphonate, n-alkyl cadmium carboxylate, n-alkyl zinc carboxylate and the like. In some embodiments, the n-alkyl portion of the phosphonate can be any hydrocarbon compound (e.g., alkanes, alkenes, and alkynes of which any can be linear, branched, or cyclic). Esters thereof are useful that include at least one hydroxyl group that has been replaced by an alkyl (alkoxy) group. Exemplary phosphonic acid compounds include alkyl phosphonic acid compounds, such as, for example, C.sub.1-C20 alkyl phosphonic acid compounds, where the alkyl group can be linear or branched (e.g., tetradecyl phosphonic acid, methyl phosphonic acid, ethyl phosphonic acid, butyl phosphonic acid, hexyl phosphonic acid, octyl phosphonic acid, and the like).

[0032] Other suitable alkoxy groups can include a RO group. Suitable ligands include C.sub.1-C.sub.20 groups, where the alkyl group can be linear or branched (e.g., lauric, myristic palmitic and stearic acetic, propionic, butyric, hexanoic, and octanoic). In some embodiments, a mixture of at least one C.sub.4-C.sub.12 group and at least one C.sub.1-C.sub.10 group can be used. In certain embodiments, a mixture of two alkyl group compounds is used. For example, a first alkyloxy compound can be selected from C.sub.1-C.sub.10 alkoxy compounds and a second carboxylic acid compound can be selected from C.sub.10-C.sub.20 alkyl carboxylic acid compounds

[0033] Ligands comprising hydrocarbyl phosphate esters and/or hydrocarbyl sulfonate esters and about 1 to 4 hydrocarbyl oxy acids or alkoxy groups ligands which may further contain unsaturation and heteroatoms such as oxygen, nitrogen, and sulfur. The specific type of organo-titanate, organo-aluminates, organo-strontium, organo-neodymium, organo-yttrium, organo-zirconates which can be used, and which be referred to as organo-metallic compounds in an embodiment can have at least one hydrolysable group, at least one organic moiety, or a hetero organic moiety with P, S or N atoms. Mixtures or blends of the organo-metallic interfacial modifiers materials can be used. The mixture of the interfacial modifiers may be applied inter- or intra-fiber, which means at least one of the fibers can have more than one interfacial modifier coating the surface (intra), or more than one interfacial modifier coating may be applied to different fibers or fiber size distributions. Minimal amounts of the modifier can be used including about 0.005 to 8 wt.-%, about 0.02 to 6.0, wt. %, about 0.02 to 3.0 wt. %, about 0.02 to 4.0 wt. % or about 0.02 to 5.0 wt. %.

TABLE-US-00001 TABLE 1 Typical Formulations Component Useful wt. % Useful wt. % Chlorinate Polyethylene 10 to 35 15 to 25 Polymer 35 to 75 50 to 70 Fiber 35 to 75 50 to 70 Interfacial modifier 0.1 to 5 1 to 4 based on fiber

TABLE-US-00002 TABLE 2 Typical Formulations Component Useful wt. % Useful wt. % Chlorinate Polyethylene 10 to 35 15 to 25 PVC Polymer 35 to 75 50 to 70 Fiber 35 to 75 50 to 70 Interfacial modifier 0.1 to 5 1 to 4 based on fiber

TABLE-US-00003 TABLE 3 Typical Formulations Component Useful wt. % Useful wt. % Chlorinate Polyethylene Balance Balance Polymer 3 to 10 4 to 8 Glass Fiber 5 to 10 6 to 9 Interfacial modifier 0.1 to 5 0.2 to 3 (based on fiber)

TABLE-US-00004 TABLE 4 Typical Formulations Component Useful wt. % Useful wt. % Chlorinated Polyethylene Balance Balance PVC Polymer 3 to 10 4 to 8 Glass Fiber 5 to 10 6 to 9 Interfacial modifier 0.1 to 5 0.2 to 3 (based on fiber)

TABLE-US-00005 TABLE 5 Composite Typical Properties Useful Workable value @ 20 wt. Value @ 6 wt. Property Method % Glass Fiber % Glass Fiber Units Flexural D790 >0.5 >0.4 Mpsi Modulus Heat As >250 >50 Hours @ Deflection described 143 F. Room ASTM >100 >300 in-lb.-in.sup.1 Temp D4226 Impact COTE D6341 <2.0 10.sup.5 <3.0 10.sup.5 in/in/ F.

EXPERIMENTAL SECTION

Examples 1 to 3

[0034] An amount of an exterior weathering compounded PVC including 3.5 phr of an acrylic shell and a core impact modifier was fed to a twin screw extruder, with a 60 wt. % glass fiber/20 w. % PVC/20 Wt. % CPE masterbatch. The glass fiber coated with 1.48 wt. % of a mixed organometallic interfacial modifier. The ratios PVC to masterbatch was controlled to achieve a design amount in 0, 6, 7, and 12 wt. % glass fiber in examples 1 to 3 of the composite final. product. The blend was extruded into the fence rail profile like that of FIG. 1 at 190 C. and 500 lb./hr. with a cap of 0.015 in. of an external PVC. The extruded profile properties. Test samples were obtained and evaluated as shown below:

TABLE-US-00006 TABLE 6 Test Composites Component Ex. 1 Wt. % Ex. 2 Wt. % Ex. 4 Wt. % PVC Balance Balance Balance CPE 0 wt. % 2 wt. % 4 wt. % Glass fiber 0 wt. % 6 wt. % 12 wt. % Interfacial n/a 1.48 wt. % 1.48 wt. % Modifier on glass

Testing Methods:

[0035] Testing methods are indicated in the tables of data for all tests except the heat distortion test that is done as follows:

[0036] In the heat distortion test, a length of extruded profile is placed in a thermostatically controlled chamber at a temperature of about 143 F. the length is supported at each end leaving an unsupported length of about 8 feet. Directly under the center of the supports profile is a laser inferometer that can measure the heat deflection of the profile in thousands of an inch over a fixed period typically 10-500 hours. The data is reported in hours needed to result in a deflection due to heat equal to the unsupported span length divided by 120.

TABLE-US-00007 TABLE 7 Composite Test Protocols Test Metric Method Ex. 1 Ex. 2 Ex. 4 COTE In/in/ F. D6341 3.2 10.sup.5 2.2 10.sup.5 1.7 10.sup.5 Room In-lb-In.sup.1 D4226 50 69 158 Temp. Impact Flex Mpsi D790 39 40 40 Modulus Heat hrs. As 13 345 70 Distortion described

Detailed Discussion of FIG. 1

[0037] In FIG. 1 there is a drawing of a cross section of a horizontal rail support used in an external fencing system. In FIG. 1, there is a profile cross section 10 including a composite exterior wall of the profile comprising the composite as disclosed herein. Further in FIG. 1 is shown a series of walls within the composite profile. In profile 10 there is a reinforcing walls 14 a-c that cooperate with voids 11 a-c, providing structural integrity to the base portion 16 of the profile 10. Further, there is reinforcing walls 11 d-e further providing horizontal structural integrity to the profile. Further in FIG. 1 there are reinforcing walls 11 f and voids 12 a-b within the profile that cooperates and defines an insertion locus 15 for the vertical members in a wall fence system. Further in the FIG. 1 there is an internal void space 13 and 13a providing space defining the structural members of the structural members 11b-c of the profile. Reinforced base 16 comprises walls 11 a-c and voids 14 a-c

TABLE-US-00008 TABLE 8 FIG. 1 - Reference Numbers Reference number Component Description 10 Composite profile Fence rail profile member 11 Outside wall of Defines the dimensional parameters profile of the profile 11 a-e Reinforcing walls Reinforces the outside walls of the of profile profile 11 f Reinforcing walls Reinforces the slot of the profile of profile 12 a-b Internal voids Voids cooperates with walls 11f to provide structural integrity to slot 13 13a Internal voids Voids cooperates with walls to provide structural integrity to profile 14 a-c Base voids Voids cooperates with walls 11 a-c to provide structural integrity to profile 15 Inset space Insert slot support for upright fencing member 16 Base structure Base of member defined by walls 11 a-c and voids 14 a-c

[0038] The claims may suitably comprise, consist of, or consist essentially of, or be substantially free or free of any of the disclosed or recited elements. The claimed technology is illustratively disclosed herein can also be suitably practiced in the absence of any element which is not specifically disclosed herein. The various embodiments described above are provided by way of illustration only and should not be construed to limit the claims attached hereto. Various modifications and changes may be made without following the example embodiments and applications illustrated and described herein, and without departing from the true spirit and scope of the following claims.

[0039] The specification shows an enabling disclosure of the composite technology, other embodiments may be made with the claimed materials. Accordingly, the invention is embodied solely in the claims hereinafter appended. The claims may suitably comprise, consist of, or consist essentially of, or be substantially free or free of any of the disclosed or recited elements. The claimed technology is illustratively disclosed herein can also be suitably practiced in the absence of any element which is not specifically disclosed herein. The various embodiments described above are provided by way of illustration only and should not be construed to limit the claims attached hereto. Various modifications and changes may be made without following the example embodiments and applications illustrated and described herein, and without departing from the true spirit and scope of the following claims.

[0040] The specification shows an enabling disclosure of the composite technology, other embodiments may be made with the claimed materials.