Flame retardant poly(vinyl chloride) compounds

Information

  • Patent Grant
  • 11339233
  • Patent Number
    11,339,233
  • Date Filed
    Tuesday, September 11, 2018
    5 years ago
  • Date Issued
    Tuesday, May 24, 2022
    2 years ago
  • Inventors
  • Original Assignees
    • GEON Performance Solutions, LLC (Westlake, OH, US)
  • Examiners
    • Huhn; Richard A
    Agents
    • Wolf, Greenfield & Sacks, P.C.
Abstract
Disclosed herein are plasticized poly(vinyl chloride) compounds. One aspect relates to a flame retardant poly(vinyl chloride) compound, comprising a mixture of poly(vinyl chloride); and a plasticizer comprising polymeric plasticizer, and/or alkyl aryl fire retardant plasticizer, wherein the mixture has a Limiting Oxygen Index of greater than 50% according to ASTM D2863; an Elongation at Break of at least 10% according to ASTM D638 (Type IV); and a Modulus of Elasticity of less than about 15,000 psi according to ASTM 638 (Type IV).
Description
FIELD OF THE INVENTION

This invention concerns use of plasticized poly(vinyl chloride) compounds for such purposes as a flexible, flame retardant, polymeric, building and construction product.


BACKGROUND OF THE INVENTION

People benefit from plastic articles. From their invention in the mid-20th Century until the present, thermoplastic polymers have become the composition of many consumer products. Such products are relatively lightweight, sturdy, and corrosion resistant.


Plasticized poly(vinyl chloride), invented by Waldo Semon of B.F. Goodrich, has been a top performing plastic resin for decades. Billions of kilograms of poly(vinyl chloride) (also known as “PVC”) resin are molded and extruded each year into countless products. With conventional additives, poly(vinyl chloride) provides unparalleled durability, flame resistance, chemical resistance, weatherability, electrical properties, and clarity to name a few.


Wire and cable manufacturers often use plasticized PVC for insulation and sheathing in building and construction environments. Performance of plasticized PVC compound at various temperatures is predicted based on accelerated oven aging tests. A cable rated at 60° C. by Underwriters' Laboratories (UL) is tested at 100° C. for seven days, whereas a cable rated at 75° C. is tested at 100° C. for ten days. Some plasticizers conventionally used are phthalates, citrates, soyates, and trimellitates.


For other types of materials used in building and construction environments, ASTM International (www.astm.org) has established a strict standard for testing the surface burning characteristics of building materials: “ASTM E84-15a Standard Test Method for Surface Burning Characteristics of Building Materials.” This E84 test concerns the fire-test-response standard for the comparative surface burning behavior of building materials applicable to exposed surfaces such as walls and ceilings. The E84 test is conducted with the specimen in the ceiling position with the surface to be evaluated exposed face down to the ignition source. To satisfy the requirements of the E84 test, the material, product, or assembly shall be capable of being mounted in the test position during the test. Thus, the specimen shall either be self-supporting by its own structural quality, held in place by added supports along the test surface, or secured from the back side.


SUMMARY OF THE INVENTION

What is needed in the art is a plasticized PVC compound that is flexible and can pass the E84 test identified above. The more rigid the poly(vinyl chloride) compound, the easier it is to pass the E84 test. But if one reformulates for flexibility as is desired in this instance, then the E84 test is more difficult to pass.


Therefore, plasticized PVC compounds need a careful balance of ingredients, to be flame retardant and flexible.


One aspect of the present invention is a flame retardant poly(vinyl chloride) compound, comprising: a mixture of (a) poly(vinyl chloride); (b) a plasticizer selected from the group consisting of (1) polymeric plasticizer, (2) alkyl aryl fire retardant plasticizer, and combinations thereof and optionally (c) functional additives, wherein the mixture has a Limiting Oxygen Index of greater than 50% according to ASTM D2863; an Elongation at Break of at least 10% according to ASTM D638 (Type IV); and a Modulus of Elasticity of less than about 15,000 psi according to ASTM 638 (Type IV).


Another aspect of the present invention is a building and construction article made from the poly(vinyl chloride) compound identified above.





BRIEF DESCRIPTION OF DRAWING


FIG. 1 is a photograph of a test plaque of Example 4.





EMBODIMENTS OF THE INVENTION

Poly(Vinyl Chloride) Resins


Polyvinyl chloride polymers are widely available throughout the world. Polyvinyl chloride resin as referred to in this specification includes polyvinyl chloride homopolymers, vinyl chloride copolymers, graft copolymers, and vinyl chloride polymers polymerized in the presence of any other polymer such as a HDT distortion temperature enhancing polymer, impact toughener, barrier polymer, chain transfer agent, stabilizer, plasticizer or flow modifier.


For example a combination of modifications may be made with the PVC polymer by overpolymerizing a low viscosity, high glass transition temperature (Tg) enhancing agent such as SAN resin, or an imidized polymethacrylate in the presence of a chain transfer agent.


In another alternative, vinyl chloride may be polymerized in the presence of said Tg enhancing agent, the agent having been formed prior to or during the vinyl chloride polymerization. However, only those resins possessing the specified average particle size and degree of friability exhibit the advantages applicable to the practice of the present invention.


In the practice of the invention, there may be used polyvinyl chloride homopolymers or copolymers of polyvinyl chloride comprising one or more comonomers copolymerizable therewith. Suitable comonomers for vinyl chloride include acrylic and methacrylic acids; esters of acrylic and methacrylic acid, wherein the ester portion has from 1 to 12 carbon atoms, for example methyl, ethyl, butyl and ethylhexyl acrylates and the like; methyl, ethyl and butyl methacrylates and the like; hydroxyalkyl esters of acrylic and methacrylic acid, for example hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate and the like; glycidyl esters of acrylic and methacrylic acid, for example glycidyl acrylate, glycidyl methacrylate and the like; alpha, beta unsaturated dicarboxylic acids and their anhydrides, for example maleic acid, fumaric acid, itaconic acid and acid anhydrides of these, and the like; acrylamide and methacrylamide; acrylonitrile and methacrylonitrile; maleimides, for example, N-cyclohexyl maleimide; olefin, for example ethylene, propylene, isobutylene, hexene, and the like; vinylidene chloride, for example, vinylidene chloride; vinyl ester, for example vinyl acetate; vinyl ether, for example methyl vinyl ether, allyl glycidyl ether, n-butyl vinyl ether and the like; crosslinking monomers, for example diallyl phthalate, ethylene glycol dimethacrylate, methylene bis-acrylamide, tracrylyl triazine, divinyl ether, allyl silanes and the like; and including mixtures of any of the above comonomers.


The present invention can also use chlorinated polyvinyl chloride (CPVC), wherein PVC containing approximately 57% chlorine is further reacted with chlorine radicals produced from chlorine gas dispersed in water and irradiated to generate chlorine radicals dissolved in water to produce CPVC, a polymer with a higher glass transition temperature (Tg) and heat distortion temperature. Commercial CPVC typically contains by weight from about 58% to about 70% and preferably from about 63% to about 68% chlorine. CPVC copolymers can be obtained by chlorinating such PVC copolymers using conventional methods such as that described in U.S. Pat. No. 2,996,489, which is incorporated herein by reference. Commercial sources of CPVC include Lubrizol Corporation.


The preferred composition is a polyvinyl chloride homopolymer.


Commercially available sources of polyvinyl chloride polymers include OxyVinyls LP of Dallas, Tex. and Shintech USA of Freeport, Tex.


PVC Compounds


Flexible PVC resin compounds typically contain a variety of additives selected according to the performance requirements of the article produced therefrom well within the understanding of one skilled in the art without the necessity of undue experimentation.


Plasticizers


Non-limiting examples of plasticizers conventionally used with poly(vinyl chloride) are phthalates, citrates, soyates, and trimellitates. In this instance two specific plasticizers are currently preferred.


One currently preferred plasticizer is Palamoll™ 654 medium viscosity polymeric plasticizer, which is a mixture of hexanedioic acid, polymer with 1,4-butanediol and 2,2-dimethyl-1,3-propanediol, isononyl ester sold by BASF. The plasticizer is non-phthalate, a consideration in current market conditions and is registered as CAS No. 208945-12-4.


The other currently preferred plasticizer is Santicizer™ 2148 plasticizer, which is r sold by Valtris and is registered as CAS No. 27460-02-2.


Either the polymeric plasticizer or the alkyl aryl plasticizer can be used as the only plasticizer for the flame retardant PVC compound. Alternatively, the two plasticizers can be combined in any ratio between above.


Whether alone or combined, the parts by weight of the currently preferred plasticizer(s) range(s) from about 115 to 130 parts per 100 parts of the PVC polymer.


Other Functional Additives


The PVC compounds used herein can contain effective amounts of additives according to the experimental results identified in the Examples.


The poly(vinyl chloride) compound disclosed here as suitable for building and construction environments requiring passage of the E84 test include:


Calcium-zinc heat stabilizers, if present, in the amount of from about 1 to about 4 parts per 100 parts of PVC;


Alumina trihydrate flame retardant, if present, in the amount of from about 320 to about 380 parts per 100 parts of PVC;


Zinc borate flame retardant, if present, in the amount of from about 20 to 30 parts per 100 parts of PVC;


Smoke suppressant, if present, comprising a Basic Zinc Molybdate Complex on Mg(OH)2 in the amount of from 3 to 8 parts per 100 parts of PVC;


Calcium carbonate functional filler, if present, in the amount of from about 150 to about 300 parts per 100 parts of PVC;


Stearic acid lubricant, if present, in the amount of from about 0.25 to about 0.75 parts per 100 parts of PVC; and


Carbon black pigment, if present, in the amount of from about 2 to about 5 parts per 100 parts of PVC.


The compound disclosed here can include other conventional plastics additives in an amount that is sufficient to obtain a desired processing or performance property for the compound. The amount should not be wasteful of the additive nor detrimental to the processing or performance of the compound. Those skilled in the art of thermoplastics compounding, without undue experimentation but with reference to such treatises as Plastics Additives Database (2004) from Plastics Design Library (www.elsevier.com), can select from many different types of additives for inclusion into the compounds of the present invention.


Non-limiting examples of other optional additives include adhesion promoters; biocides (antibacterials, fungicides, and mildewcides); anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppressants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them.


Processing


The preparation of compounds of the present invention is as follows. The compound of the present can be made in batch or continuous operations from a powder blend which is typically prepared in a batch-wise operation.


Such powder blending in a batch process typically occurs in a powder mixer such as a Henschel or Littleford mixer, or a ribbon blender that physically mixes all the additives including liquid plasticizers with PVC resin without bringing the polymer matrix to a melting temperature. The mixing speeds range from 60 to 3000 rpm and temperature of mixing can be ambient up to 250° F. (121° C.). The output from the mixer is a well blended powder product that can flow into a machine that can bring up the blend temperature to induce melting of some ingredients including the PVC resin.


Mixing in a batch process typically occurs in a Banbury mixer that is also elevated to a temperature that is sufficient to melt the polymer matrix to permit addition of the solid ingredient additives of any optional additive. The mixing speeds range from 60 to 3000 rpm and temperature of mixing ranges from 250° F. to 430° F. (120° C. to 220° C.), typically 325° F. (163° C.). Then, the melted mixture is put on to a two roll mill at 320° F./345° F. (160-174° C.). The material is milled for about four minutes and then the milled, compounded strip is then cubed for later extrusion or molding into polymeric articles. Alternatively, for experimental evaluation, the compounded strip can be formed into a plaque by compression molding for physical testing purposes.


Compounds can be formed into powder, cubes, or pellets for further extrusion into profile or sheet form, with or without subsequent molding, into polymeric components and parts.


Extrusion and molding techniques are well known to those skilled in the art of thermoplastics polymer engineering. Without undue experimentation but with such references as “Extrusion, The Definitive Processing Guide and Handbook” “Specialized Molding Techniques” and “Handbook of Mold, Tool and Die Repair Welding” published by Plastics Design Library (www.elesevier.com), one can make articles of any conceivable shape and appearance using compounds of the present invention. Non-limiting examples are reshaping in the melt form into extruded, molded, thermoformed, calendered, or 3D printed polymer articles.


For the E84 test, calendered, thermoformed, or other high aspect ratio polymer articles can be made.


USEFULNESS OF THE INVENTION

Building and construction markets can benefit from the PVC compounds disclosed herein. With a combination of flame retardance sufficient to pass the E84 test and also have sufficient flexibility to be useful as a building or construction material, occupied spaces can utilize these compounds in a variety of shapes. For example, profile extruded parts can complement high aspect ratio parts, both from the same or similar compounds disclosed herein. Also, post-shaping of films, sheets, panels, etc. can be used in both ceiling and wall construction.


As stated previously, rigid poly(vinyl chloride) can pass the E84 test. But rigidity is not preferred in building and construction. Increasing the flexibility of the poly(vinyl chloride) increases the usefulness of the PVC compound in building and construction but decreases its chances of passing the E84 test. As the Example and Comparative Examples demonstrate, finding that rare balance of ingredients can yield a successful candidate for flexible, flame retardant building and construction products.


Examples

Table 2 shows the sources of ingredients for the Examples and all Comparative Examples. Table 3 shows the processing conditions for making all experimental samples.












TABLE 2





Ingredient
Chemical Name
Purpose
Company







PVC RESIN OXY
PVC Homopolymer
PVC Resin
OxyVinyls


240
Resin


PLASTISTAB 2581
CaZn Heat
Stabilizer
AM



Stabilizer

Stabilizers


PALAMOLL 654
Polymeric
Plasticizer
BASF


CAS No. 208945-
Plasticizer


12-4


SANTICIZER 2148
Aryl Phosphate
Flame
Valtris


CAS No. 27460-02-

Retardant


2

Plasticizer


ALUMINA
Alumina Trihydrate
Flame
Various


TRIHYDRATE

Retardant


CHARMAX FS-
Basic Zinc
Smoke
Polymer


BZMA
Molybdate
Suppressant
Additives



Complex on

Group



Mg(OH)2


CALCIUM
Calcium Carbonate
Filler
GLG


CARBONATE


Minerals


GLC-1012D


STEARIC ACID
Stearic Acid
Lubricant
Various


N550 CARBON
Carbon Black
Pigment
Columbian


BLACK
















TABLE 3





Processing Instructions


#1 Roll Mill















Weigh All Ingredients Together in One Container


Mix Well and then Mill at 320-335° F. (160-168° C.) for 4 Minutes


Compression Press at 345° F. (174° C.) to


form plaques for physical testing




















TABLE 4






Testing
Test




Test Name
Authority
No.
Variations
Units







Specific Gravity*
ASTM
D792




Durometer Hardness, A,
ASTM
D2240
Shore A



Instant**


Durometer Hardness, A,
ASTM
D2240
Shore A



15 sec delay**


Durometer Hardness, D,
ASTM
D2240
Shore D



Instant**


Durometer Hardness, D,
ASTM
D2240
Shore D



15 sec delay**


Flexible Tensile***
ASTM
D638
type IV
psi


100% Modulus***
ASTM
D638
type IV
psi


Elongation***
ASTM
D638
type IV
%


Flame: LOI Oxygen
ASTM
D2863

%


Index****



Oxygen





*0.63 cm thick sample


**5.08 cm × 508 cm × 0.63 cm sample


***15.2 cm × 15.2 cm × 1.9 cm sample


****15.2 cm × 15.2 cm × 0.32 cm sample






Table 5 shows the formulations and physical properties of the Examples and the Comparative Examples.









TABLE 5







Formulations and Test Results

















Example












(Parts by Weight)
A
B
1
2
3
C
4
D
5
6




















PVC RESIN OXY 240
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00


PLASTISTAB 2581
1.76
1.76
1.76
1.76
1.76
1.76
1.76
1.76
1.76
1.76


PALAMOLL 654
115.00
115.00
127.00
127.00
85.00
85.00
64.00
64.00
115.00
0.00


SANTICIZER 2148
0.00
0.00
0.00
0.00
42.00
42.00
63.00
63.00
0.00
115.00


ALUMINA
360.00
270.00
360.00
300.00
360.00
300.00
360.00
300.00
360.00
360.00


TRIHYDRATE












FR ZINC BORATE
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00
25.00


(FB467)












CHARMAX FS-BZMA
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00
5.00


CALCIUM
175.00
270.00
175.00
250.00
175.00
250.00
175.00
250.00
175.00
175.00


CARBONATE GLC-












1012D












STEARIC ACID
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.50
0.31
0.31


N55O CARBON BLACK
3.52
3.52
3.52
3.52
3.52
3.52
3.52
3.52
3.52
3.52


Total Parts:
785.78
790.78
797.78
812.78
797.78
812.78
797.78
812.78
785.59
785.59


Specific Gravity
1.93
1.98
1.90
1.93
1.89
1.91
1.89
1.91
1.93
1.92


Durometer Hardness, A,
98
98
97
96
93
92
92
92
98
95


Instantaneous












Durometer Hardness, A,
97
96
95
94
89
88
88
88




15 sec delay












Durometer Hardness, D,
60
60
54
52
42
38
41
40




Instantaneous












Durometer Hardness, D,
49
49
44
42
33
29
32
30




15 sec delay












Tensile Strength at break
728
738
754
530
433
334
368
280
916
553


(psi)












Modulus of Elasticity
13,000
16,000
10,000
11,500
5,700
6,300
5,700
5,400
14,700
8,500


(psi)












Elongation (%)
9
9
16
14
15
26
31
43
12.7
10


Flame: LOI
82
77
70
66
60
49
57
47
78
54


Oxygen Index









Of the ten formulations, six were able to satisfy the conditions of flexibility and flame retardance.


All ten formulations had the same amounts of PVC polymer, heat stabilizer, zinc borate flame retardant, smoke suppressant, and carbon black. Thus, the plasticizer content, the alumina trihydrate flame retardant, stearic acid, and the calcium carbonate filler were varied.


For Comparative Examples A-B and Examples 1, 2, and 5, no Santicizer 2148 Aryl Phosphate Flame Retardant Plasticizer was used. One difference between Examples 1 and 2 and Comparative Examples A and B was the higher parts of Palamoll 654 polymeric plasticizer which caused a slight reduction in Limiting Oxygen Index but higher (and acceptable) percent Elongation. The difference between Comparative Example A and Example 5 was the amount of lubricant, which caused a significant difference in Elongation results even though Moduli of Elasticity were both within the acceptable range of less than 15,000 psi.


The total plasticizer content for Comparative Examples A and B and Examples 5 and 6 was 115 parts vs. Examples 1-4 and Comparative Examples all having 127 total parts of plasticizer present. Satisfaction of the three criteria of Moduli of Elasticity, Elongation, and Limiting Oxygen Index caused separation of Examples 1-6 from Comparative Examples A-D.


The use of either the Palamoll 654 plasticizer or the Santicizer 2148 plasticizer (also having flame retardant properties) or both also provided differentiation within Examples 1-6. Examples 1, 2, and 5 used only the former, while Example 6 used only the latter.


Comparative Examples C-D and Examples 3 and 4 tested the ratio of Paramoll™ 254 plasticizer to Santicizer 2148 plasticizer at 67:33 (2:1) and 50:50 (1:1) ratios. The comparison of Comparative Example C to Example 3 and the comparison of Comparative Example D to Example 4 were consistent at both ratios tested by Examples 3 and 4 providing slightly higher Moduli of Elasticity results but also significantly higher percent Elongation. The differentiation between the two pairs was the 20% larger amount of alumina trihydrate flame retardant present in Examples 3 and 4 vs Comparative Examples C and D, respectively.


As between Example 3 and Comparative Example D, both having a 1:1 ratio of the two types of plasticizer, the Limiting Oxygen Index (LOI) test, a predictor for passing the E84 test, provided the basis of differentiating between the two sets of physical properties. The LOI results for Example 3 were 20% better than the LOI results for Comparative Example D.


While it is true that all but two of the Comparative Examples A and B have a higher LOI than any of the Examples, it is the balance of physical properties which must be established for a successful building and construction polymer article envisioned in this disclosure.


Only the formulations of Examples 1-6 satisfy the following criteria (with current preferences for the criteria within Examples 1-6):


a Limiting Oxygen Index of greater 50% according to ASTM D2863 (and with a current preference for greater than 55%);


an Elongation at Break of at least 10% according to ASTM D638 (Type IV) (and with a current preference for at least 20%); and


a Modulus of Elasticity of less than about 15,000 according to ASTM 638 (Type IV) (and with a current preference for less than about 10,000.)


Operating within all three of the criteria at their current preference, Example 4 is presently preferred. FIG. 1 shows a photo of the flexibility of Example 4 with opposing edges touching as a result of restraint by a metallic binder clip.


Other of the physical properties can be adjusted according to commercial or manufacturing preferences. For example, use of additional calcium carbonate filler or use of additional different fillers, such as copper or tungsten metal particles, or both, can increase specific gravity.


Without undue experimentation and with use of the experimental results, a person having ordinary skill in the art will be able to construct formulations suitable for achieving physical properties for flame retardant, flexible PVC compounds within the acceptable and preferred criteria, respectively.


The invention is not limited to the above embodiments. The claims follow.

Claims
  • 1. A flame retardant poly(vinyl chloride) compound, comprising: a mixture of: poly(vinyl chloride); anda plasticizer comprising: polymeric plasticizer, and/oralkyl aryl fire retardant plasticizer;wherein the mixture has: a Limiting Oxygen Index of greater than 50% according to ASTM D2863;an Elongation at Break of at least 10% according to ASTM D638 (Type IV); anda Modulus of Elasticity of less than about 15,000 psi according to ASTM 638 (Type IV).
  • 2. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises a polymeric plasticizer.
  • 3. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises a polymeric plasticizer of a mixture of hexanedioic acid, polymer with 1,4-butanediol and 2,2-dimethyl-1,3-propanediol, isononyl ester.
  • 4. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises a polymeric plasticizer registered as CAS No. 208945-12-4.
  • 5. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises an alkyl aryl fire retardant plasticizer.
  • 6. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises a non-halogen alkyl aryl fire retardant plasticizer.
  • 7. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises an aryl phosphate registered as CAS No. 27460-02-2.
  • 8. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises a polymeric plasticizer and an alkyl aryl fire retardant plasticizer.
  • 9. The flame retardant poly(vinyl chloride) compound of claim 8, wherein the plasticizer comprises a polymeric plasticizer of a mixture of hexanedioic acid, polymer with 1,4-butanediol and 2,2-dimethyl-1,3-propanediol, isononyl ester.
  • 10. The flame retardant poly(vinyl chloride) compound of claim 8, wherein the mixture has: a Limiting Oxygen Index of greater than 50% and less than or equal to 82% according to ASTM D2863;an Elongation at Break of at least 10% and less than or equal to 43% according to ASTM D638 (Type IV); anda Modulus of Elasticity of at least 5,400 psi and less than about 15,000 psi according to ASTM 638 (Type IV).
  • 11. The flame retardant poly(vinyl chloride) compound of claim 8, wherein the poly(vinyl chloride) comprises poly(vinyl chloride) homopolymer.
  • 12. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises both a plasticizer registered as CAS No. 208945-12-4 and a plasticizer registered as CAS No. 27460-02-2, wherein the two plasticizers are combined in a ratio of from 99:1 to 1:99 of CAS No. 208945-12-4 to CAS No. 27460-02-2.
  • 13. The flame retardant poly(vinyl chloride) compound of claim 12, wherein the two plasticizers are combined in a ratio of from 75:25 to 25:75 of CAS No. 208945-12-4 to CAS No. 27460-02-2.
  • 14. The flame retardant poly(vinyl chloride) compound of claim 12, wherein the two plasticizers are combined in a ratio of from 67:33 to 33:67 of CAS No. 208945-12-4 to CAS No. 27460-02-2.
  • 15. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the total amount of any plasticizer with CAS No. 208945-12-4 and any plasticizer with CAS No. 27460-02-2 present in the mixture is from about 115 to about 130 parts per 100 parts of the poly(vinyl chloride), by weight.
  • 16. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the plasticizer comprises both plasticizer with CAS No. 208945-12-4 and plasticizer with CAS No. 27460-02 2, and the total amount of plasticizer with CAS No. 208945-12-4 and plasticizer with CAS No. 27460-02-2 present in the mixture is from about 115 to about 130 parts per 100 parts of the poly(vinyl chloride), by weight.
  • 17. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has a Limiting Oxygen Index of greater than 55% according to ASTM D2863.
  • 18. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has a Limiting Oxygen Index of less than or equal to 82% according to ASTM D2863.
  • 19. The flame retardant poly(vinyl chloride) compound of claim 18, wherein the mixture has a Modulus of Elasticity of at least 5,400 psi according to ASTM 638 (Type IV).
  • 20. The flame retardant poly(vinyl chloride) compound of claim 18, wherein the mixture has an Elongation at Break of less than or equal to 43% according to ASTM D638 (Type IV).
  • 21. The flame retardant poly(vinyl chloride) compound of claim 20, wherein the mixture has a Modulus of Elasticity of at least 5,400 psi according to ASTM 638 (Type IV).
  • 22. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has an Elongation at Break of at least 20% according to ASTM D638 (Type IV).
  • 23. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has an Elongation at Break of less than or equal to 43% according to ASTM D638 (Type IV).
  • 24. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has a Modulus of Elasticity of less than 10,000 psi according to ASTM 638 (Type IV).
  • 25. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture has a Modulus of Elasticity of at least 5,400 psi according to ASTM 638 (Type IV).
  • 26. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the poly(vinyl chloride) comprises poly(vinyl chloride) homopolymer.
  • 27. The flame retardant poly(vinyl chloride) compound of claim 1, wherein the mixture further comprises a functional additive selected from the group consisting of calcium-zinc heat stabilizers, alumina trihydrate flame retardant, zinc borate flame retardant, basic zinc molybdate complex on magnesium hydroxide smoke suppressant, calcium carbonate density modifying filler, metallic particles density modifying filler, stearic acid lubricant, carbon black pigment, and any combination of the additives so listed.
  • 28. A polymer article comprising the flame retardant poly(vinyl chloride) compound of claim 1.
CLAIM OF PRIORITY

This application is a national stage filing under 35 U.S.C. § 371 of International Patent Application No. PCT/US2018/050498, filed Sep. 11, 2018, which claims the benefit of U.S. Provisional Patent Application Ser. No. 62/559,252 filed on Sep. 15, 2017, each of which is hereby incorporated by reference in its entirety.

PCT Information
Filing Document Filing Date Country Kind
PCT/US2018/050498 9/11/2018 WO 00
Publishing Document Publishing Date Country Kind
WO2019/055426 3/21/2019 WO A
US Referenced Citations (150)
Number Name Date Kind
2753595 Dulmage Jul 1956 A
2996489 Dannis et al. Aug 1961 A
3476627 Squires Nov 1969 A
3486193 Christensen et al. Dec 1969 A
3655850 Woodham et al. Apr 1972 A
3670056 Heiberger et al. Jun 1972 A
3674812 Gibbons Jul 1972 A
3712594 Schippers et al. Jan 1973 A
3712776 Woodham et al. Jan 1973 A
3714315 Minton et al. Jan 1973 A
3819577 McRowe Jun 1974 A
3868341 Sauer Feb 1975 A
3880802 Dickens, Jr. Apr 1975 A
3901850 Kurtz Aug 1975 A
3926881 Kracklauer Dec 1975 A
3926883 Touval Dec 1975 A
3929933 Gallagher Dec 1975 A
3941908 Valia Mar 1976 A
3953650 Sauer Apr 1976 A
3957723 Lawson May 1976 A
3985706 Kay Oct 1976 A
3988393 Gallagher Oct 1976 A
3992500 Kruder et al. Nov 1976 A
3993607 Florence Nov 1976 A
4001172 Steinkamp et al. Jan 1977 A
4003874 Ide et al. Jan 1977 A
4004405 Darchuk Jan 1977 A
4015832 Kruder Apr 1977 A
4035324 Lawson Jul 1977 A
4046719 Stanaback Sep 1977 A
4049747 Jin Sep 1977 A
4079036 Ohmori Mar 1978 A
4100325 Summers et al. Jul 1978 A
4102106 Golder et al. Jul 1978 A
4111882 Deatcher Sep 1978 A
4111885 Abu-Isa Sep 1978 A
4123585 Sparzak Oct 1978 A
4147636 Drake Apr 1979 A
4154922 Donohue May 1979 A
4207224 Randell Jun 1980 A
4213487 Funk et al. Jul 1980 A
4272427 Davis Jun 1981 A
4288588 Donohue Sep 1981 A
4308198 Vroomans Dec 1981 A
4341881 Kracklauer Jul 1982 A
4403056 Giolito Sep 1983 A
4423960 Anders Jan 1984 A
4459387 Parker Jul 1984 A
4491553 Yamada et al. Jan 1985 A
4496692 Riew et al. Jan 1985 A
4514449 Budich et al. Apr 1985 A
4536360 Rahrig Aug 1985 A
4560618 Goswami Dec 1985 A
4573799 Anders Mar 1986 A
4593060 Gupta Jun 1986 A
4616989 Mewes et al. Oct 1986 A
4680334 Wallace Jul 1987 A
4702961 Chung Oct 1987 A
4708623 Aoki et al. Nov 1987 A
4710533 Neuman Dec 1987 A
4711921 Lehr Dec 1987 A
4801627 Rahrig et al. Jan 1989 A
4820750 Lehr et al. Apr 1989 A
4820763 Yang Apr 1989 A
4868247 Lehr et al. Sep 1989 A
4870126 Kinson et al. Sep 1989 A
4874858 Magistro Oct 1989 A
4888148 Hartitz Dec 1989 A
4965309 Batdorf Oct 1990 A
4977193 Croce et al. Dec 1990 A
5008145 Kinson et al. Apr 1991 A
5026582 Hartitz Jun 1991 A
5059261 Condo et al. Oct 1991 A
5059476 Steiniger et al. Oct 1991 A
5064293 Nakamura Nov 1991 A
5080968 Riew et al. Jan 1992 A
5100946 Hung et al. Mar 1992 A
5102465 Lamond Apr 1992 A
5141042 Schwaegerle Aug 1992 A
5141426 Capelle Aug 1992 A
5194498 Stevenson et al. Mar 1993 A
5221504 Capelle Jun 1993 A
5268424 Lawson Dec 1993 A
5274043 Greenlee et al. Dec 1993 A
5281379 Noguchi et al. Jan 1994 A
5358024 Schwaegerle Oct 1994 A
5380786 Greenlee et al. Jan 1995 A
5494718 Adams et al. Feb 1996 A
5497594 Giuseppe et al. Mar 1996 A
5591497 Hartitz Jan 1997 A
5603998 Hartitz Feb 1997 A
5604278 Hartitz Feb 1997 A
5735599 Ishibashi et al. Apr 1998 A
5769128 Auvil et al. Jun 1998 A
5775378 Auvil et al. Jul 1998 A
5858522 Turk et al. Jan 1999 A
5880177 Higgs et al. Mar 1999 A
5882564 Puppin Mar 1999 A
5948492 Cargile Sep 1999 A
5969045 Schmitz et al. Oct 1999 A
6015611 Deaner et al. Jan 2000 A
6043312 Fagher Mar 2000 A
6054538 Thulliez Apr 2000 A
6062719 Busby et al. May 2000 A
6093359 Gauchel et al. Jul 2000 A
6114425 Day Sep 2000 A
6132076 Jana et al. Oct 2000 A
6136246 Rauwendaal et al. Oct 2000 A
6190581 Duffin, Jr. et al. Feb 2001 B1
6210616 Suwanda Apr 2001 B1
6216608 Woods et al. Apr 2001 B1
6328919 Pham et al. Dec 2001 B1
6352039 Woods et al. Mar 2002 B1
6365710 Wang et al. Apr 2002 B1
6428728 Sakai et al. Aug 2002 B1
6464913 Korney, Jr. Oct 2002 B1
6513963 Derezinski Feb 2003 B2
6531526 Detterman Mar 2003 B1
6565784 Esseghir et al. May 2003 B1
6590041 Eguchi et al. Jul 2003 B1
6593403 Simon et al. Jul 2003 B1
6682814 Hendrickson et al. Jan 2004 B2
6821599 Kuroda et al. Nov 2004 B1
7030179 Patterson et al. Apr 2006 B2
7144952 Court et al. Dec 2006 B1
7198840 Lee et al. Apr 2007 B2
7238739 Hawrylko et al. Jul 2007 B2
7858008 Lee et al. Dec 2010 B2
7943691 Shakir et al. May 2011 B2
20010044487 Day Nov 2001 A1
20020188077 Kumaki et al. Dec 2002 A1
20030157321 Dalal et al. Aug 2003 A1
20030195279 Shah Oct 2003 A1
20050182167 Goodson Aug 2005 A1
20050234155 Bacaloglu Oct 2005 A1
20060111495 Tabla et al. May 2006 A1
20060194904 Moy Aug 2006 A1
20090075539 Dimanshteyn et al. Mar 2009 A1
20100012906 Layman, Jr. Jan 2010 A1
20100311855 Quante Dec 2010 A1
20110198108 Abu-Ali Aug 2011 A1
20120142839 Day Jun 2012 A1
20140116749 Shoemaker May 2014 A1
20150353711 Zucchelli Dec 2015 A1
20160075866 Kahn Mar 2016 A1
20160122471 Bae May 2016 A1
20160237297 Kuwahara et al. Aug 2016 A1
20170121456 Bae May 2017 A1
20170121514 Chaudhary May 2017 A1
20170335197 Abu-Ali Nov 2017 A1
Foreign Referenced Citations (15)
Number Date Country
1296514 May 2001 CN
101497727 Aug 2009 CN
107141659 Sep 2017 CN
0 107 063 May 1984 EP
1 564 087 Apr 1980 GB
H03-195754 Aug 1991 JP
H08-188652 Jul 1996 JP
2004-107520 Apr 2004 JP
WO 0036009 Jun 2000 WO
WO-0036009 Jun 2000 WO
WO 2008154153 Dec 2008 WO
WO 2014070355 May 2014 WO
WO 2017201130 Nov 2017 WO
WO 2019055426 Mar 2019 WO
WO 2020086455 Apr 2020 WO
Non-Patent Literature Citations (21)
Entry
International Search Report and Written Opinion for International Application No. PCT/US2018/050498 dated Feb. 18, 2019.
International Preliminary Report on Patentability for International Application No. PCT/US2018/050498 dated Mar. 26, 2020.
Office Communication for U.S. Appl. No. 16/283,322 dated Jun. 1, 2020.
[No Author Listed], Chlorinated Polyethylene (CPE) Website. Zijiang Chemical. In existence prior to Oct. 21, 2019 at <http://www.zijiangchem.com/products_detail_en/id/19.html>. 4 pages.
[No Author Listed], CPE/CM Chlorinated Polyethylene: The Technical Specification. In existence prior to Oct. 21, 2019 at <http://dhard.ucp-is.com/docs/specs/rubber/CSPE/CPE.gen.spec.pdf>. 1 page.
[No Author Listed], Extruding Cubes of Rigid Geon® Vinyls into Profiles. Technical Service Report No. 13. PolyOne Corporation. 1992:4 pages.
[No Author Listed], Extrusion of Geon® Rigid Cellular Vinyl. Technical Service Report No. 7. PolyOne Corporation. Apr. 1993:6 pages.
[No Author Listed], Fiberloc® 97510 Vinyl Compound Technical Data Sheet. PolyOne Corporation. May 16, 2001:1 page.
[No Author Listed], Fiberloc® 97520 Vinyl Compound Technical Data Sheet. PolyOne Corporation. May 16, 2001:1 page.
[No Author Listed], Fiberloc® 97530 Vinyl Compound Technical Data Sheet. PolyOne Corporation. May 16, 2001:1 page.
[No Author Listed], Sheet Extrusion of Geon® Rigid PVC Compounds. Technical Service Report No. 1. PolyOne Corporation. Mar. 1995:4 pages.
[No Author Listed], Weipren CPE 6335 Technical Data Sheet. Lianda. Jan. 2012:1 page.
Gibbons et al., Extrusion. Mod Plast Encycl. 1986: 220-34.
Jia et al., Properties of poly(vinyl chloride) incorporated with a novel soybean oil based secondary plasticizer containing a flame retardant group. J Appl Poly Sci. Mar. 2015;132(25): 9 pages.
Meijer et al., The Modeling of Continuous Mixers. Part I: The Corotating Twin-Screw Extruder. Polymer Engineering and Science. Mar. 1988;28(5):282-4.
Rauwendaal, Polymer Extrusion. 1986: 458-76.
Summers et al., The Chemical Mechanisms of Outdoor Weathering in Polyvinyl Chloride. J Vin Tech 1983;5(3):91-5.
Weil et al., Flame and Smoke Retardants in Vinyl Chloride Polymers—Commercial Usage and Current Developments. J Fire Sci. May 2006; 24: 211-36. Epub Apr. 27, 2006.
Office Action for CN Application No. 201880067605.9 dated Aug. 11, 2021.
Feng et al., Synthesis of a novel phosphorus-containing plasticizer based on castor oil and its application for flame retardancy of polyvinyl chloride. Korean J Chem Eng. Jun. 30, 2015;32(6):1201-6. Abstract only.
Jia, Synthesis and Performance of Castor Oil-Based Flame Retardant Plastic Plasticizers. China Doctoral Dissertations Full-text Database Science-Engineering. Jan. 15, 2017;l:B016-6. Abstract only.
Related Publications (1)
Number Date Country
20200216586 A1 Jul 2020 US
Provisional Applications (1)
Number Date Country
62559252 Sep 2017 US