JPH03500900A - Polyamide composition resistant to fluorocarbon and hydrocarbon permeation - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Fluorocarbon and hydrocarbon permeation BoI amide of Background technology The present invention relates to polyamide compositions, and more particularly to fluorocarbon and hydrocarbon compositions. The present invention relates to polyamide compositions that are resistant to permeation.

Currently, manufacturing of products resistant to fluorocarbon penetration, such as hoses and tubing, The use of nitrile rubber-based compositions is known. Nitrile rubber is Butaje It is a J/lz copolymer. These are flexible It is known to be gas permeable and oil resistant. Babbi The Vanderb iltRubber Handbook Arti Vanderbilt (RTV anderbilt) (1978) describes typical nitrates useful in hose manufacturing. (on page 720). Such compositions are formulated with polyamides may be useful for producing fluorocarbon permeable products; There are certain limitations to the processing of such compositions. An important issue is processing polyamide At the temperatures required to lonitrile monomer is formed. Both of these substances are preferred do not have. Therefore, it is resistant to fluorocarbon permeation and hydrocarbon permeation. Processes that are controllable in terms of flexibility and are typically used in nylon processing conditions, i.e. 425-625°F (218-329°C). There is a technological need for polyamide compositions that can be processed without releasing harmful decomposition compounds. It is considered essential.

Leopard The present invention is resistant to fluorocarbon and hydrocarbon permeation and is controllable at the same time. It is a polyamide composition with flexible properties. Polyamide composition of the present invention The composition has a rubbery phase that flexibilizes, which is not woody but naturally flexible. Resistant to permeation of fluorocarbons and hydrocarbons, typically about 425-62 At high processing temperatures for polyamides that are within the range of 5"F (218-329"C) It can be processed by This rubber is made of selective polyethylene functionalized by polar groups. When incorporated into a phase, it also has tensile-type physical properties while maintaining a low flexural modulus. , a composition is obtained that is resistant to the permeation of fluorocarbons and hydrocarbons. child As such, the compositions of the present invention contain about 50-90% by weight polyamide, about 425-625% °F (218-329°C) without significant decomposition. and about 5-40% by weight of a polar polyethylene.

The above composition includes about 0-15% by weight plasticizer and about 0-10% by weight polyamide chain extender. can have. These last two components make the polyamide even more flexible. Balancing flexibility and physical properties, fluorocarbon resistance It can be used to fine-tune the properties and hydrocarbon resistance without disturbing them.

The present invention also provides a method for permeating fluorocarbons and hydrocarbons produced from the above compositions. Also includes products that are resistant to Particularly important products are refrigerants for refrigerators and air conditioning systems. Pipes and hoses commonly used as flow channels for fluorocarbons. be.

Kyousangtan U real ship scorching Ω theory The present invention comprises polyamide, a rubber phase, polyethylene functionalized with polar groups and any A polyamide composition consisting essentially of a plasticizer and a polyamide chain extender.

The polyamide component of the composition of the invention is the main component. The weight percent range for this component is Preferably about 50-90% by weight of the entire composition, more preferably about 60-90% by weight %, more preferably about 70-80% by weight. Poria suitable for use here Mido has repeating amide units as part of the polymer backbone and is suitable for end group titrations. Therefore, it is preferable to have a number average molecular weight of about 15,000 to 40,000 as measured. Contains desirable long chain polymer amides. The polyamide suitable for use here is technology and It can be manufactured by known conventional methods.

Non-limiting examples of such polyamides include (a) lactams, preferably ε-carbons; Polyamide (nylon 6) i(b) di produced by polymerization of prolactam Condensation of an amine and a dibasic acid, preferably hexamethylene diamine and adipic acid Condensation of nylon 6.6L hexamethylenediamine and sebacic acid (nylon 6.6L) Polyamide and polytetramethylene adipamide manufactured by Ron 6.10) Self-condensation of de(nylon 4.6)i and (C) amino acids, preferably 11- Polyamide produced by self-condensation of aminodecanoic acid (nylon 11), or or random, block or graph consisting of two or more of these polyamides. There are interpolymers. Polymer obtained by polymerization of ε-caprolactam Amides are preferred. Copolymer of caprolactam and hexamethylene adipamide (N6.66) is most preferred.

Polyamides such as nylon 6, or nylon 6.6, contain a variety of terminal functional groups. Such functional groups include (a) Carboxyl group; a) A carboxyl group bonded to one end of the polyamide chain and a carboxyl group bonded to the other end. The combined amide group ([capped J end) (polycaprolacta (C) Amino groups bonded to both ends of the polyamide chain; and (d) Polyamide A carboxyl group bonded to one end of the lyamide chain and an amine group bonded to the other end (polycarbonate). prolactam).

If polycaprolactam is not washed, the weight of polycaprolactam is used as the standard. up to 15% by weight, typically 0.5-12% by weight of caprolactam monomer. or may contain water-extractable caprolactam oligomers. At N6.66, The amount of caprolactam corresponds to the amount of caprolactam in the N6.66 polymer.

The composition contains a polar or non-polar rubber phase and can withstand temperatures between 425 and 625 without significant decomposition. (218-329°C). non-nitrile type rubber It is preferable to use The polar rubber phase used here refers to a glass transition temperature of less than 0°C. acids, esters, ethers, aldehydes, Low modulus flexible polymers containing polar monomers of ketones, alcohols and halides. means rimmer. Polar rubber contains anhydride (anh) to react with nylon. ydride).

In some cases, the rubber phase may also be non-polar. This is the glass transition temperature 0'C, preferably less than -25°C, e.g. Inelastic modulus including nonpolar monomers such as alpha-olefins such as pyrene, butylene, etc. Contains flexible polymers. Anhydride for non-polar rubber to react with nylon It may also contain anhydricle groups.

However, if the rubber phase is non-polar, the third component of the composition of the invention (detailed below) ) to obtain favorable resistance to fluorocarbons and hydrocarbons. It should be adjusted accordingly. Related to non-polar rubbers, grafted onto ethylene copolymers ethylene and other than ethylene, such as α-olefins, which have reactive components such as copolymers with monomers are preferred. Ethylene and α-olefin are ethylene and , at least one C,-C, preferably C3-C,α-olefin. Preferably, it is a copolymer with an α-olefin. Propylene is a copolymer. The preferred monomer is selected as a C3-C,α-olefin. example Other C3-C,α-ols such as 1-butene, 1-pentene, 1-hexene Use of lefins in place of or in addition to propylene in copolymers be able to. Ethylene/propylene diene polymers are also preferred for use in the present invention. stomach.

Other preferred embodiments include functionalizing polar or non-polar rubbers. Ru. For example, a carboxyl or carboxylate functional group can be converted into ethylene/CI Cba α-olefin copolymer is an α,β-ethylenically unsaturated C,-C,radical. reaction with an unsaturated reactive graft component selected from the group consisting of bonic acids or derivatives thereof. It can be supplied by making it correspond. Such derivatives include dicarboxylic There are acid anhydrides. Specific examples of such acids and derivatives include maleic acid, maleic anhydride, metal salts of maleic acid, maleic acid monoethyl ester, maleic acid monoethyl ester , fumaric acid, fumaric acid monoethyl ester, itaconic acid, vinylbenzoic acid, vinyl Luphthalic acid, metal salts of fumaric acid monoethyl ester, maleic acid or fumaric acid acid or itaconic acid with methyl, propyl, isopropyl, butyl, isobutyl , hexyl, cyclohexyl, octyl, 2-ethylhexyl, decyl, stair Lyle, methoxyethyl, ethoxyethyl, hydroxy or ethyl alcohol etc. There is a monoester of The reactive component is a well-known grafting product to the ethylene monomer. It can be grafted by a process.

Useful reactive copolymers of ethylene and alpha-olefins are based on ethylene. It contains 30-60% by weight, preferably 40-45% by weight of α-olefins. this The copolymer also contains 0.1-9% by weight, preferably 0.1-4% by weight, more preferably or 0.3 to 2.0% by weight of grafting moiety ) is also included. The graft copolymer has a molecular weight of 2,000 to 100,000, preferably 2,000 to 100,000, preferably 2, 000 to 65,000, more preferably 5,000 to 35,000, most preferably has a number average molecular weight of s, ooo to 20.000. Reduced solution viscosity (RSV) Typical values for are between 0.5 and 3.5. An RSV of 2.8 has a number average molecular weight of approximately 80. OOO2 is equivalent, and 2.0 no I'lSV is equivalent to a number average molecular weight of about 35,000, RSV1. O corresponds to a number average molecular weight of about 12,000. RSV is 110°C Measurements are based on a 0.1% solution in xylene.

A good guideline for the selection of rubber phase components can be found in rubber solubility parameters. It can be obtained by looking at Easily soluble substances have relatively high molten carbon parameters. However, it is considered to be polar in nature. The opposite is true for relatively nonpolar substances. do.

The solubility parameters used for permeation resistance were discussed in U.S. Patent No. 4,26L473. ing. Solubility parameters used in this patent for use in the present invention is the square of the cohesive energy density (calories/c+n 3. (AL/cc)) Defined as a root, a polymer hand such as Branclrup Book (Polymer) Iandbook) Chapter 4 [John Willie John Wiley & 5ons.

Inc., published in 1967]. typical fluorocar Bon's solubility parameter is approximately 5.5. The solubility parameters of various substances are For ease of reference, it is summarized in Table 1 below: 1-11 Search ljn standing nine: Shio- (cal/cc) Fluorocarbon 5゜5 Polyethylene 8゜0 Polypropylene 7.9 EPR' Nitrile rubber (B/AN) 80/20 8.7 70/309.4 60/40 10.5 0/100 12.8 Polyvinyl acetate 9.4 Polyvinyl alcohol 12.6 Polylauryllactam (NI2) 9.5 Polyundecaneamide (Nl+) 9 ．． 9 Polycaprolactam (N,) 12.7 Polyhexaneethylene-sebamide (N6,1°, 12.5 Polyhexamethylene adipamide (N6.6) 13.6 Cabrolactam/hexamethylene diammonium 12.8 adipate copolymer -(N6.6) M-ethyl o,p-)luenesulfonamide 11.9 Thus, the rubber phase component If a non-polar rubber is selected as the Polar rubber about O-40%, preferably 10-30%, more preferably about 5-20% It will be understood by those skilled in the art that it is desirable to use rubber like this can be used to stretch polyamide compositions without substantially affecting the tensile properties of the polymer. It has been found that this makes it even more flexible. As mentioned above, these non-polar The polymer can be used as described above so long as the total solubility parameter of the polymer is less than about 9.0. May include polymers and copolymers having the same monomer units as the polar polymer . These non-polar rubbers do not need to contain groups that react with the end groups of the polyamide, but The terminal groups of the polyamide bond to the reactive groups of the non-polar rubber to form a network graft structure. It is preferable to contain a small amount of reactive groups so as to The invention combines with theory Although one does not wish to This is one of the reasons why it helps maintain physical properties while imparting properties.

Ethylene-ethyl acrylate, ethylene-vinyl acetate and ethylene-vinyl acrylate Ethylene polymers such as alcohol, and ethylene/propylene copolymers -, ethylene/propylene/diene copolymer, ethylene/butylene copolymer Ethylene copolymers such as stomach.

The inventors of the present invention have discovered that hydrocarbon resistance can be achieved without reducing the overall mechanical properties of the composition. The addition of functionalized polyethylene is included in the compositions of the present invention to impart character. 6 Therefore, the composition of the present invention also contains polyethylene having functional groups. It contains about 5-40%, preferably about 10-35%. The polyethylene has a polyethylene of about 9.0 or more. about 425-625°F without exhibiting significant decomposition, with solubility parameters above (218-329°C). of the present invention The polyethylene preferably has an overall copolymer solubility parameter of greater than 9.0. Graft along the backbone, i.e. into the backbone, to make it larger. be an ethylene-based polymer with sufficient polar groups attached or otherwise attached. is preferable. This polar group is attached to a terminal group such as an acid or amino group on the polyamide. It may be reactive or non-reactive.

Preferred polyethylenes for the present invention contain ethylene monomer units, e.g. dolide, acid groups and their salts, ester groups, aldehydes, ketones, ethers, hydroxy Polyethylene consisting of polar monomer units such as sil groups, halogen groups, salts, etc. It's Ren. For example, salts of zinc, sodium, potassium, calcium, copper, lead, etc. Metal salts such as; esters, alcohols, acids, etc. are particularly preferred. to ionomer A full description of the same can be found in U.S. Pat. No. 4,404,325. relatively low Ionomers having higher molecular weights, such as from about 1500 to 3500, are also useful. Ru.

The composition may also include a plasticizer suitable for plasticizing the polyamide component of the composition. Ru. The flexibility of the entire composition of the present invention is increased by the addition of such plasticizers. Even greater improvements can be made. The preferred amount of plasticizer is about 2-20% by weight, especially The preferred amount is from about 5 to about 20% by weight. Such plasticizers are very diverse. For example, but not limited to, cabrolactum and lauryllactam. lactams such as o, p-)luenesulfonamide, n-ethyl o, p-tolu Sulfonamides such as en-sulfonamide and n-butylbenzenesulfonamide May contain mido. Other plasticizers include phthalate plasticizers, adipate plasticizers, and phosphorus plasticizers. Phate plasticizers, glycolate plasticizers and the above sulfonamide plasticizers, - selected from the group consisting of melitate plasticizers and polymer type permanent plasticizers There are plasticizers.

When using large amounts of plasticizer to obtain greater flexibility of the overall composition , high molecular weight species (sp. Optionally, a polyamide chain extender can be added as a fifth component to obtain Both have been found to be desirable. High molecular weight species are not leached from the composition Possesses high levels of plasticizers.

A polyamide chain extender is a polyamide chain extender that reacts with both amines and acids to form amide bonds. It means a compound that can increase the molecular weight. For example, U.S. Pat. No. 433,116, No. 4,417,031 and No. 4,417,032 are appropriate. It describes a chain extender. A suitable amount is about 0-10% by weight, preferably 0-5% by weight. % by weight, most preferably within the range of about 0.1 to about 3% by weight.

To increase resistance to fluorocarbon or hydrocarbon permeation, the composition Other polar materials such as polyvinyl acetate, inorganic salts, etc. may also be included.

The compositions of the present invention may contain one or more conventional additives that do not substantially affect the impact properties of the composition. conventional additives, such as stabilizers and inhibitors against oxidative, thermal and ultraviolet degradation; Lubricants and release agents, colorants (including dyes and pigments), flame retardants, fibrous or granular fillers It may contain a filler, a reinforcing agent, a nucleating agent, etc. These additives are usually added during the mixing process. It will be done.

Typical oxidative and thermal stabilizers that may be present in the blends of the invention include, for example: Halides of Group 1 metals such as sodium, potassium, and lithium ;Copperous compounds such as chloride, bromide, and jodide Halides: Hindered phenols, hydroquinones, aromatic amines and their groups There are a variety of replacement elements and combinations thereof.

Typical UV stabilizers include various substituted resorcinols, salicylates, and benzenes. These include triazole and benzophenone.

Typical lubricants and mold release agents include stearic acid, stearyl alcohol, and stearyl alcohol. There is mido. A typical organic dye is nigrosine, and a typical pigment is carbon dioxide. Titanium, cadmium sulfide, cadmium selenide, phthalocyanine, ultramarine carbon blue, carbon black, etc.

Typical flame retardants include organic halogens such as decabromodiphenyl ether, etc. There are oxidized compounds.

The composition of the present invention comprises a polyamide and at least one polymer, either uniaxially or biaxially. Melt compounding into a homogeneous mixture in a ring screw extruder or other melt compounding equipment It can be manufactured by

The composition can be molded by conventional molding methods used in the manufacture of thermoplastic products. Parts such as tubes, films, sheets, fibers and oriented fibers A wide range of products are available as extrusion products such as fiber, laminates and wire coatings. It can be processed into products for use. "Molding" means blending. It means forming a product by deforming it in a hot plastic state.

The compositions of the present invention can be used in pumps, including reservoir tubes and hoses, for conveying fluorocarbon fluids. It is particularly useful for producing extruded bodies. This composition is suitable for a variety of these types of tubes and base; extruded nylon tubes, hoses and pipes; nylon and other polymers - Useful in the production of coextruded products with materials and coatings.

Real-l-± Several examples are set forth below to illustrate the nature of the invention and how it may be practiced.

However, the invention should not be considered limited to these details. with all departments Percentages are by weight unless otherwise indicated. The raw materials used are as follows. two envoys XPN-1576 Nine 6/66 (85/15), approximately 7-8% Caprola (Caproamide/hexamethylenediamine adipate (85/1) 5) Also called.

Liver Nylon 6° containing 9-11% unextracted caprolactam EPM-g-M^ Ethylene with 0.45% maleic anhydride grafted Propylene rubber, ethylene content is 45%.

E/EA/MA Ethylene/ethyl acrylate containing 1% maleic anhydride (6 6/33) Copolymer.

EAA ethylene/acrylic acid copolymer (93,5/6.5, Dow Chemical Company) (From Doll Chemical Co.)].

] S-9721 Zinc ionomer from DuPont, i.e. -Ethylene/methacrylic acid/chemically called Surlyn 9721 Zinc methacrylate (90/4/6) terpolymer.

0PTSA o, p-) luenesulfonamide, nylon plasticizer.

U, C, BK Black 40 with 60% or more ethylene vinyl acetate carrier Universal carbon black dispersion as %.

EVOH ethylene vinyl alcohol copolymer, especially ethylene/vinyl alcohol (vinyl acetate) (80/19/1) terpolymer.

The compositions in the examples below are generally prepared by first dry compounding the ingredients and L/D 25: 1 conventional screw and equipped with a Maddock mixing head. Approximately 500°F (260° C) by melt-extrusion molding. extruded strands He was quickly given a water bath. The strands were passed through a pellet machine and the pellets were collected. . Test specimens were molded at a temperature slightly above the polyamide melting point. The melting temperature is approximately 1 Maintained at 60-180°F (71-82°C). The molding cycle is 10 in front of the ram. -30 seconds, residence for 10-25 seconds.

Melt index was measured according to ASYM D-1238 Condition Q.

The impact value is 1/8' (0,32 cm) or 1/4' (0,64 cm) as mentioned above. c+n) Using the test piece, test according to ASTM D=256 notched Izot. I tried it.

Tensile strength and elongation were tested according to ASTM D-638, and flexural modulus was tested according to ASTM Tested according to D-790.

In the examples, the following materials were used. The polyamide contains 92 mol% of caprolactam and hex. Nylon 6/66 copolymer containing 8 mol% of sameethylene adipamide It's Rimmer. If this copolymer is not washed, the caprolactam monomer 7 It contained ~9%. The copolymer has a fora+ic acid viscosity (fora+ic acid vis cosity) 70. Formic acid viscosity is 50% formic acid (90% concentration). Dissolve 5.5g of Ron and measure.

The fluorocarbon permeation test is conducted using the Springbo Inspection Association method. rn　Testing　In5titute　procedure) provided.

Test methods generally involve manufacturing assemblies (including cells, pressure cups, specimens, and screens). Tare the sample; Clamp the specimen; Bring the assembly below 0°C. dichlorodifluoromethane [Refrigerant (Refrig. erant) 12) Charge 60g; Seal the charged cell with a pressure cup. Condition in a 100°C oven for 2 hours; Cool to ambient temperature. However, it was necessary to measure the initial weight (to 0.01 g).

The specimens were exposed to 100°C for 3 days, cooled and weighed. repeated weight checks . Weight loss was reported during sequential data times.

■12i Examples 1-6 provide a detailed description of the invention based on the nylon 6766 copolymer described above.

These examples illustrate various combinations of rubber phase, polar ethylene copolymer and plasticizer. do. The rubber phase is an ethylene propylene copolymer grafted with maleic anhydride. It consisted of ma. Ethylene propylene maleic anhydride graph) (E PMA) is 45% ethylene, 55% propylene, and grafted maleic anhydride. Contained 0.45% of acid. It had a reduced solution viscosity of 1.6. Converted solution viscosity The temperature was measured in a 1% solution in xylene at 110°C.

The polar polyethylene is Surlyn 9721 ionomer sold by DuPont. there were. This material contains approximately 10% methacrylic acid that is 60% neutralized with zinc. It has been suggested that it is a ren methacrylic acid copolymer. This material is a meltindicator. 1.0. The plasticizer is manufactured by Monsand Corporation (Monsand Corporation). .

0, P-toluenesul currently sold by Corpora Lion) Santicizer 9, which is a honamide, is plasticizer and resin modifier (Plasticizer sand Re5in Modifi ERS) State to the Mont Sandy's newsletter in the title J -IC / PL -361 It is.

劃-”- Example 1 provides a detailed description of the invention. This composition includes caprolactam and N-ethyl o, p-) 85 mol% luenesulfonamide and 15 mol% hexamethyleneadipamide A composition based on a nylon 6.66 copolymer having This copolymer contains 7-9% caprolactam monomer when not washed. This composition Furthermore, ethylene propylene copolymer grafted with maleic anhydride (hereinafter referred to as Below, EPMA) is included. EPMA is a 45:55 weight percent ethylene to propylene Including Ren. Maleic anhydride grafted onto ethylene propylene copolymer 0.66% by weight is present. This copolymer has a reduced solution viscosity of 1.5 and a weight of was calculated to be 10,000 to 12,000. The converted solution viscosity is 110°C Measurements are made using a 0.1% solution in Lens. EPMA has a solubility parameter greater than 9.0. It is a non-polar rubber containing insufficient maleic anhydride to have a EPMA The solubility parameter of is calculated to be approximately 8.0.

The composition additionally contains an ethylene acrylic acid copolymer. ethylene acrylic acid co The polymer (hereinafter referred to as EAA) is commercially available from Dow Chemical as Dow AA Resin 455. has been done. It has a melt index of 5.5g/10 minutes and an acrylic acid content of 6. ．． 5% by weight and an ethylene content of 93.5% by weight.

The physical properties of the composition are summarized in Table 2 below: MFR: Melt flow rate comp, comparative example FIMod: Flexural modulus EX, example YIELD ST: Yield strength YIELD EL: Yield elongation u, r, sr: ultimate tensile strength U, EL: Ultimate elongation Melt flow ratio is ASTM test, kD-123 Measured according to 8. All compositions had zero melt flow under these test conditions. . Examining Comparative Examples 1 and 2 and Example 1, it can be seen that 10% substitution of polar HA^ rubber It can be seen that when compared to No. 2, maintenance of physical properties occurs. The corresponding equivalent non- The flexural modulus is somewhat higher than when polar rubber is used. However, considering Comparative Example 1 As you can see, the flexural modulus is still quite low. 50% each of nylon and reactive rubber The composition of Comparative Example 3 containing levels had too much physical properties to be flexible. This indicates that it can cause deterioration in sexual performance.

solitude 21 Examples 2 to 5 are the type of nylon 6/66 used in Example 1, EP? IA and HEAA are different. A composition comprising an amount of Composition and physical properties results are summarized in Table 3 below. Ru: Rai-Lord-1 EX2 EX3 EX4 EX5 Examination of Table 5 shows that the amount of polar polyethylene and rubber phase provides sufficient tensile properties. It can be seen that the flexural modulus varies widely while maintaining a relatively low flexural modulus. . The results show that using only rubber at the 50% level results in a substantial decrease in flexural modulus. Reference is made to the comparative examples in Table 2 which suggest this. However, the physical properties deteriorate.

Considering Examples 2-4, when combining polar polyethylene and rubber phase at 50% level, , the flexural modulus is still relatively low, but it is not very low when only non-polar rubber is used. , it was found that the benefits obtained with varying amounts of polar polyethylene were still obtained. Ru. More importantly, when considering the physical properties of each of Examples 2 to 5, only the rubber phase appears. It can be seen that the tensile strength is greater than when using .

Therefore, the combination of polar polyethylene and rubber phase allows a reduction in the flexural modulus, while maintaining higher tensile strength than would be possible without polar polyethylene. At the same time, the flexural modulus is similar to that obtained when only polar polyethylene is used. , had a low flexural modulus.

Table 3 shows that flexible compositions resistant to fluorocarbons and hydrocarbons are ionomers. or by the introduction of an ionic copolymer (S 9721). show. This salt-containing copolymer is believed to yield very high levels of permeation resistance. . The introduction of 0PTSA (o,Po-toluenesulfonamide) plasticizer Xible 12 to 17 are the original products containing only polar rubber, regardless of the presence or absence of nylon plasticizer. The polymer used was ethylene in a molar ratio of 66:33:1; It is a terpolymer of ethyl acrylate and maleic anhydride. This is the converted viscosity 1 ．． 4, with a calculated solubility parameter of 8.4. The compositions evaluated were o , p-toluenesulfonamide (OPTSA). is an ethylene vinyl acetate copolymer containing 40% carbon black. Also includes some universal carbon blacks.

The composition and physical properties are summarized in Table 4 below: EX12 l EX14 EX15 】-”-Yo [1hiro] The above example shows that a flexible composition with excellent mechanical properties is Describe the benefits obtained from semi-polar rubber, which contributes to its resistance to carbon and hydrocarbons. Ru. It should be noted that relatively good flexibility is obtained.

The compositions evaluated in Table 5 illustrate polyamide compositions containing polar rubbers of the present invention. . This composition also contains various amounts of 0PTSA plasticizer, - Also evaluate the use of black masterbatch.

These examples show that flexible highly polar blends can be easily made without deteriorating properties. Also explain that it is colored. For example, the highly polar flexible The compound exhibits very favorable mechanical properties and has a measured fluorocarbon resistance. Demonstrate functionality.

Table 5 below has a combination of resistance to fluorocarbon permeation and good mechanical properties. Indicates a heat stabilized compound.

Bud-”L-table Fluorocarbon test: 0.25 gtN loss after 13 days, 0.31 g loss after 19 days loss In the above examples (19 and 20), when the composition is the same, polar ethylene acrylic acid is Replacement with polar salt ionomers (high solubility parameters) results in remarkable fluorophobic resistance. This shows that carbon permeability occurs. When a part of the ionomer is replaced with a plasticizer, In case (EX.

21), flexibility increases, but fluorocarbon resistance slightly deteriorates. .

Part of Kaya I Fluorocarbon ≦Grade Fluorocarbon resist: 39A tested, 48A tested (Springbow) ) After 19 days O in 7 days; 21 g loss 0.31 g loss 0 in 14 days ．． 35g loss 0.44g loss in 21 days The above example was created by increasing the ionomer content and using low modulus nylon 6766. This means that even non-polar rubbers like EPM-g-MA have a high level of fluorocarbon resistance. Explain that sex can be obtained.

A man's part Fluorocarbon-compatible flexible comparator containing low levels of polar rubber. Sound CompD: MP 55χ 0ETSA 5χ EX, 24 EX, 25 EX, 26 EX, 27 This table shows the replacement with ionomer Even if the non-polar rubber is further degraded by Indicates that it is manufactured. At about 8% by weight, the flexural modulus is 100Kpsi (6 90 MPa).

The following table shows the permeability, measured in hexane, of the various ingredients used in the compositions of the invention. Report excessive data.

Other useful guidance on the generation of flexible polyamide compositions is provided in Table 8. It is a measurement of the permeability of the individual polymer components themselves, such as:

厘lj■11L:l '. Hexane EvOHA fluorocarbon compound EX, 28 plates 9 plates 0 Dish 1 Concave 2 The fluorocarbon resistance advantage of using EVOH is that hexane permeation Proven by testing. These examples show that while still maintaining a low modulus, the Explained that EVOH can be introduced to provide resistance to Ron flexible grades. I will clarify. Regarding the elastic modulus of 76K psi (525MPa), it is flexible. Only 8% by weight of non-polar rubber was required for this purpose.

Bo 3A Countersink Nail 刹　■　” A set of ionomeric polymers as shown in Example 33 vs. Example 34 and Example 35 vs. Example 36. Coordination can be used to tune mechanical properties.

international search report -””””””””””””PCT/US88103688

Claims (10)

[Claims] 1. The following ingredients: About 50-90% by weight of polyamide; with a solubility parameter of less than about 9.0 and a significant fraction at about 218-329°C. about 5-40% by weight of a functionalized rubber phase that can be melt processed without decomposition; and About 5-40% by weight polyethylene with a solubility parameter of about 9.0 or higher A composition consisting of. 2. The composition of claim 1 also comprising about 5-15% by weight of plasticizer based on the polyamide. . 3. 3. The composition of claim 2 which also includes about 1-10% by weight of a polyamide chain extender. 4. The polyamide component is present in an amount ranging from about 60% to about 90% by weight of the total composition. The composition according to claim 1, wherein the composition comprises: 5. The polyamide component is present in an amount within the range of about 70 to about 80% by weight of the total composition. 5. The composition according to claim 4, wherein the composition comprises: 6. the rubber is functionalized with carboxyl or carboxylate functional groups; 6. The composition according to claim 5. 7. The rubber phase is ethylene ethyl acrylate, ethylene vinyl acetate, tyrene vinyl alcohol, ethylene propylene copolymer, ethylene propylene selected from the group consisting of dienecoupolymer and ethylene butylene copolymer 6. The composition according to claim 5. 8. The rubber phase component is present in an amount of about 5-20% by weight based on the total weight of the composition. 8. The composition according to claim 7. 9. The polyethylene has ethylene monomer units, anhydride, acid groups and their salts. , ester groups, hydroxyl groups, halogen groups, aldehydes, ketones and ethers and a polar monomer group selected from the group consisting of: Compositions as described. 10. Approximately 5 to 20% by weight of a plasticizer suitable for plasticizing the polyamide component of the composition. The composition according to claim 9, comprising: