JPH01500272A - Reducing moisture in polyamide compositions - 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] Reducing moisture in polyamide compositions Technical field The present invention relates to novel polyamide compositions with low water absorption.

More specifically, the present invention can reduce the sensitivity of polyamide to water. The present invention relates to a polyamide composition into which dihydric phenol is introduced.

Background technology Polyamide, also known as nylon, is well known and has been a huge commercial success.

Most polyamides are used in the production of fibers and/or bristles, but even newer and/or the modified polyamide can be parted through a molding process, e.g. injection molding. Its use and demand for manufacturing products is increasing. In addition, polyamide, rubber heavy The development of polymers and copolymers as well as blends with other thermoplastics This greatly expands the property distribution and therefore the potential end uses for polyamides. It was.

However, despite advances in polyamide technology and development, polyamides are Its use is still limited by its extreme susceptibility. polyamide is the result of direct immersion or exposure to water vapor itself, e.g. due to high temperatures. , tend to increase in weight and swell or swell. As a result, weight and More importantly, dimensional stability is necessary and important! & Holly For use, Poria Blends of mid and polyamides still cannot be used.

The present invention provides polyamide compositions and polyamide blends with significantly reduced water absorption. Enables the production of compositions. Therefore, these compositions maintain the dimensional specifications of the parts. It can be used for any important end use.

Disclosure of invention The present invention provides at least one type of polyamide and a method for reducing water absorption of the polyamide. an amount of at least if oligomeric or polymeric phenol sufficient to and/or thermoplastic polyamide compositions containing dihydric or polyhydric phenols. Ru. In particular, oligomeric and polymeric phenols such as polyvinyl fluoride phenol and phenol formaldehyde resins, and the following formula: from about 0.5 to about 30% by weight, based on the polyamide, of dihydric and polyhydric phenols of was found to significantly improve dimensional stability and reduce water absorption when mixed in an amount of did. where n is 2 or 3, m is 3 or 4, and (n+m)=6; p is 1 or 2, each r is independently 0.1 or 2, each S is independently 0 as appropriate ．． 1.2.3 or 4; t is 0.1.2, 3; is 4, each R independently Hydrogen; halogen, such as bromine, chlorine, fluorine; C1-C16 alkyl, C -C aryl or C7-C2o arylalkyl group (any of these 01 ~Can be substituted with a C12 alkyl group or a halogen atom, and an aryl group is present. When present, the aryl group is 10-1C1-C3 alkylene or alkylidene. , or -802- bridging group); or hydroxy an aryl or alkylhydroxyaryl group; and each R' is independently Carbon-carbon direct bond or divalent alkyl, aryl, arylalkyl, hydrogen Droxyaryl or alkylhydroxyaryl groups (halogens of each of these groups) (containing substituted derivatives) - divalent ester and amide groups; b) selected from the group consisting of a member of the crosslinking group selected from the group consisting of crosslinking groups containing b); Ta Dashi has two adjacent alkyl groups on the phenolic ring with a third carbon atom. There are no phenolic hydroxy groups present.

detailed description Polyamides suitable for use in the practice of this invention are well known and widely commercially available. It is. Basically, polyamide has two or more groups between the amino group and the carboxylic acid group. Polymerize monoamino-monocarboxylic acids or their lactams with carbon atoms ; Diamine and diamine containing two or more carbon atoms between amino groups in substantially equal molecular proportions; Polymerize with carboxylic acid; monoaminocarboxylic acid or its lactam as mentioned above , by polymerization with substantially equal molecular proportions of diamine and dicarboxylic acid. Obtainable. Dicarboxylic acids can be used as their functional derivatives, such as esters or Can be used in the form of acid chlorides.

The term "substantially equal" proportions (of diamine and dicarboxylic acid) refers to strictly equal Molecular proportions and conventional techniques for stabilizing the viscosity of the resulting polyamide In order to include both cases that slightly deviate from the strict equimolecular ratio shown in the technique, It is what you use.

Monoamino-monocarboxylic acids or their lactams as described above useful in the production of polyamides Examples of compounds include compounds containing 2 to 16 carbon atoms between the amino group and the carboxylic acid group. In the case of lactams, the above carbon atoms form a ring with the -Co-NH group. . Specific examples of aminocarboxylic acids and lactams include 6-aminocaproic acid , butyrolactam, vivalolactam, caprolactam, capryllactam, ena tractam, undecanolactam, dodecanolactam, and 3- and 4- Mention may be made of aminobenzoic acid.

Diamines suitable for use in making polyamides include alkyl, amines, There are lyl and alkyl-aryl diamines. As this type of diamine, For example, the general formula: %formula% (in the formula, n is an integer of 2 to 16), such as trimethylenediamine Tetramethylenediamine, Pentamethylenediamine, Octamethylenediamine and especially hexamethylene diamine, as well as trimethylhexamethylene diamine. Examples include amine, m-phenylenediamine, and m-xylylenediamine.

Dicarboxylic acids can also be aromatic, such as isophthalic acid and terephthalic acid. , can also be aliphatic. Among them, aliphatic dicarboxylic acids have the following formula: %formula% and Y in the formula represents a divalent aliphatic group containing two or more carbon atoms, and such Examples of uric acids include sebacic acid, octadecanedioic acid, superic acid, glutaric acid, and pimelic acid. There are phosphoric and adipic acids.

Typical examples of polyamide, i.e. nylon, include: Polypyrrolidone (nylon 4) Polycaprolactam (nylon 6) Polycapryllactam (Nylon 8) Polyhexamethylene adipamide (Nylon 8) Nylon 6.6) Polyundecanolactam (Nylon 11) Polycaprolactam (nylon 12) polyhexamethylene azelainamide (nylon 6.9) poly Hexamethylene diamine (nylon 6.10) polyhexamethylene Isophthalimide (nylon 6, ■) polyhexamethylene Terephthalamide (nylon 6, T) hexamethylene diamine and n-dodecanedioic acid Polyamide (nylon 6.12) and terephthalic acid and/or isophthalic acid and trimethylhexamethyl Polyamide obtained from 1/2 diamine, adipic acid and m-xylylene diamine Polyamides obtained from amines, adipic acid, azelaic acid and 2,2-bis- Polyamide obtained from (p-aminocyclohexyl)propane and tereph Polya obtained from tarric acid and 4,4'-diamino-dicyclohexylmethane There is mido.

Copolymers of the above polyamides or prepolymers thereof may also be used when carrying out the present invention. suitable for use. This type of copolyamide includes the following copolymers:

Hexamethylene adipamide/caprolactam (nylon 6.6/6) Hexamethylene adipamide/hexamethylene isophthalamide (nylon 6. 6/6. I) Hexamethylene adipamide/hexamethylene terephthalamide ( Nylon 6.6/6. T) Hexamethyleneadipamide/Hexamethylene 1/Nazela Inamide (nylon 6.6/6.9) hexamethyleneadipamide/hexame Tylene azelainamide/caprolactam (nylon 6.6/6.9/6) A mixture and/or combination of two or more of the above polyamides or prepolymers thereof Each polymer is also within the scope of this invention.

The polyamides mentioned above may be oligomeric or polymeric phenolics or dihydric or By introducing polyhydric phenol, it is said to be more dimensionally stable and resistant to water absorption. Less sensitive.

Oligomeric and polymeric phenols are have free (i.e., unreacted) phenolic hydroxy groups, but oligomeric or a pendant phenol group attached to the polymer chain.

These usually have a number average molecular weight of 40,000 or less, preferably about 400 to 30,000 It is 00. Examples of suitable polymeric phenols include polyvinylphenol and and phenol-formaldehyde resins (e.g. novolak and resol resins) fat).

Suitable phenols are dihydric or polyhydric phenols, especially bisphenols. child The species of phenol generally has the following formula: % formula % (n+m)=6; p is 1 or 2, each r is independently 0.1 or 2, Each S is independently 0.1, 2°3 or 4 as appropriate; t is 0, 1, 2.3 or 4. Each R is independently hydrogen; halogen, such as bromine, chlorine, fluorine, etc.; C1-C16 alkyl, CB=C18 aryl or C7-C2o arylal Kyl group (all of these are substituted with a C1-12 alkyl group or a halogen atom) and when an aryl group is present, the aryl group is 10-1C, ~C a Can be linked by alkylene or alkylidene, or -802- bridging group or a hydroxyaryl or alkylhydroxyaryl group; and each R' is independently a carbon-carbon direct bond, divalent alkyl, ali aryl, arylalkyl, hydroxyaryl or alkylhydroxyaryl (including halogen-substituted derivatives of each of these groups) - divalent esters and amides do group; and A group consisting of a member of the cross-linking group selected from the group consisting of hetero-containing cross-linking groups, including with two adjacent atoms on the phenolic ring with a tertiary alpha carbon atom. There are no phenolic hydroxy groups with alkyl groups.

Examples of phenols corresponding to the above formula include resorcinol, hydroquinone, 1.2.4-benzenetriol, phloroglucinol, 2.2-bis(4-hyron) Droxyphenyl)propane, bis(4-hydroxyphenyl)methane, 2.2 -bis(4-hydroxyphenyl)hebutane, 2゜2-bis(3-chloro-4- hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydro) xyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl) 4.4'-(p-phenylenediisopropylidene)-bis -(2,6-xylenol), 4.4'-(p-phenylene diisopropylide ) Bisphenol, methylene bisphenol, biphenol, naphthalene dioxide 4.4'-cyclohexylidene bisphenol, α, α', α'-bis (4-hydroxyphenol)-1,3,5-1-lyisopropylbenzene, 2 ゜2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis( 3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,2-bis(4-hydroxyphenyl) Droxyphenyl) sulfone, 2,2-(2,4-dihydroxyphenyl) sulfone There are some examples.

The amount of polymeric phenol or bisphenol used in practicing this invention is , an amount capable of imparting dimensional stability to the polyamide and reducing its water absorption; or an amount that provides an improvement of at least 10% compared to unmodified polyamide. . Generally, the amount of phenol is based on the total weight of phenol and polyamide, approximately 0.5 to about 30%, preferably about 2 to about 25% by weight.

The present invention further comprises a second thermoplastic polymer and/or a rubbery impact modifier. It can also be applied to polyamide compositions containing the same. Second thermoplastic polymer pair The weight ratio of the polyamide depends essentially on the desired properties of the final blend composition. Although it can be practically used at any weight ratio, for example, 1-99:99-1, rubber Blends containing impact modifiers preferably contain up to 50% by weight based on the total composition. Preferably it should contain from about 5 to about 35% by weight.

Suitable thermoplastic polymers that can be included in the blends contemplated by the present invention Polyimide, polyamideimide, polyetherimide, polyalkylene ester ether, polyphenylene ether, polyarylate, polyester amide, polyester There are also lyesters. All of these thermoplastic polymers are well known and widely commercially available. ing.

Suitable rubbery impact modifiers are also well known and widely commercially available. Included within the scope of the invention Examples of many rubbery impact modifiers include polyolefins and copolymers. Lefins, such as polyethylene, polypropylene, ethylene-propylene copolymer Ethylene, such as copolymers of ethylene and acrylic acid and alkyl acrylic acid. -propylene-diene monomer rubber (EPDM); diene rubber and copolymer; For example, polybutadiene, polyisoprene, styrene-butadiene copolymer, Styrene-butadiene-styrene block copolymers, etc.; nitrile rubber and copolymers combinations, e.g. styrene-acrylonitrile, acrylonitrile-butadiene- Examples include styrene type copolymers. This kind of suitable rubbery impact resistance Modifiers are described, inter alia, in U.S. Pat. , No. 3.000,866, No. 3,093,620, No. 3.093,621 , No. 3,063,973, No. 3.147.230, No. 3,154.528 , No. 3.260,708, and Silatiig cs ztttg) “Stere Ogomu and other elastonic methods (S tere.

Rubber and 0ther Elastonic Process) J, Noyes Development Co., Ltd. tCorporatlon), Park Ridge, New Chassis, USA. K Rldge, NJ), 1967, all of which are These are listed as references for the present invention.

A preferred group of rubbery impact modifiers includes the rubbery impact modifiers described above, as well as polycarbonate. Chemically (e.g., bonding) or physically interacts with the polyamide to modify its impact strength. (unreacted) functional pendant groups that can be further increased than the functionalized rubber, e.g. carbonyl, carboxy, carboxylic acid anhydride, epoxy, ether, ester , amine, amide, etc., copolymerized or grafted. be.

This type of functionalized rubbery impact modifier and its blends with polyamides are commercially available. No. 4,174.358, US Pat. No. 4,474.927, among others. No. 4.346,194, No. 4,251,644, No. 3.884,882 No. 4,147,740, No. 3.388.186, and No. 3.465. No. 059, and [epoxy-modified polyethylene] by G. allucci et al. P reparation and Reactlon sorE poy, y-Modlrled P olyethylene)J , Journal of Applied Polymer Science (J, A pl), Poly, S cl,) , Vol. 27, pp. 425-437 (1982). These are listed as references for the present invention.

Optionally, the compositions of the invention also contain one or more fillers and/or reinforcements. can do. Examples of fillers and/or reinforcements of this type include glass Fibers, carbon fibers, glass spheres, inorganic fillers such as mica and silica, carb There are blacks, etc. When using this type of filler and/or reinforcement is less than about 50% by weight of the composition, preferably from about 5 to about 30% by weight, based on the total composition. % should be included.

Finally, the compositions of the invention may contain other ingredients such as flame retardants, colorants, nucleating agents, anti-drip agents, etc. Agents, stabilizers, etc. may also be used in effective amounts known in the art according to the purposes for which they are normally used. can contain.

The compositions of the present invention can be made by any known melt blending method.

For example, ingredients can be triblended,7 extruded or milled, and then powdered. Alternatively, it can be manufactured by extrusion compounding. suitable for this kind of method Equipment includes extruders, Banbury mixers, rollers, kneaders, etc. Matako These compositions can be manufactured by continuous or batch processing.

The following examples are provided to enable those skilled in the art to better understand how to carry out the invention. This is shown below. These examples are given for illustrative purposes only and are The invention is not limited to these. All compositions are parts by weight unless otherwise specified. Indicated by

All blends are manufactured in single- or twin-screw extruders from 250 to Manufactured by extrusion at 300°C. Mix all ingredients and feed together Ta. After drying, the blend composition was injection molded to produce test parts.

Water uptake and swelling are typically measured in samples soaked in deionized water at 75°C for approximately 40 hours. and measured it. Samples were cooled to room temperature for testing. In some cases, The amount of water absorbed was measured for the sample immersed in water at room temperature for 3 weeks.

The two methods gave similar results.

Examples 1-7, Comparative Examples A-F A series of polyamides were prepared to demonstrate the applicability of the present invention to various polyamide compositions. and polyamide blend compositions were produced. In these examples, we used Bisphenol is 2,2-bis(4-hydroxyphenyl)propane (bisphenol). Nord A). The composition of the specific examples and the results obtained in each example are It was as shown in Table 1.

As can be seen from each example in Table 1, bisphenol A alone water absorption, and even its blends with other thermoplastic polymers. Importantly, moisture swelling was significantly reduced. Add bisphenol A It has also been observed that the processability of the composition increases with consequent increase in spiral flow. It was.

Examples 8 to 10, Comparative Example G A second series of blends to demonstrate the effectiveness of bisphenols at various loadings. Manufactured. The specific composition of each blend and the results obtained are shown in Table 2. It was.

Table 2 G 8 9 10 Polyamide 50 50 50 50 Polyetherimide a50505050 bisphenol A-2511 Weight, addition rate, %* 4.2 3.7 3.3 2.4 expansion*, mil/inch 9.08.3 7.2 3.9 (8,) (20) (57) a. Reference notes to Table 1 *Soaked in water at 75℃ for 40 hours Examples 11 to 16, Comparative Example H In order to demonstrate the effect of reducing water absorption of various bisphenol polyamide compositions, A series of compositions were prepared. The specific composition and physical properties of each composition are shown in Table 3. It was as shown. Each composition in Table 3 contains 45 parts of polyphenylene ether, 45 parts polyamide 6.6; 10 parts styrene-hydrogenated butadiene-styrene Riblock copolymer; 0.7 parts of citric acid-hydrate and the bisphene shown in the table. Contains nol. The weight gain rate was determined by immersing the sample in water for 21 days at room temperature. was tested.

〉　I Examples 17-18, Comparative Example 1 In order to demonstrate the effect of the polymeric phenol used in carrying out the present invention, A final series of compositions was produced.

These compositions and their physical properties are as shown in Table 4. all groups The composition consists of 45 parts polyphenylene oxide, 45 parts polyamide, 6.6.10 parts styrene-hydrogenated butadiene-styrene triblock copolymer, and 0.35 of maleic anhydride. The expansion and weight gain rate was 40 at 75°C. Measurements were made on samples immersed in water for an hour. The improvement rate is shown in parentheses.

Table 4 Examples Additive substance amount (parts) Weight increase Expansion rate (%) (mil/inch) 1 - 2.82 7.0 17 Polyvinylphenol A 3.0 2.12 (25) 5.0 (29) a , polyvinylphenol, number average molecular ffi 1,500-7,000b, polyvinylphenol, Vinylphenol, number average molecule E130,000 This invention is based on the above teachings. Further modifications and variations are of course possible. Therefore the above book The particular embodiments of the invention may vary within the full scope defined by the appended claims. It should be understood that changes can be made.

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Claims (1)

[Claims] 1. a) at least one polyamide; and b) capable of providing the improvements described below. (i) at least two unreacted phenolic hydroxy groups along the chain; oligomeric and polymeric phenols, characterized in that they have ii) The following formula: (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and (II) ▲ Mathematical formulas, chemical formulas, tables, etc. There are dihydric and polyhydric phenols represented by ▼ [n in the formula is 2 or 3, m is 3 or 4, and (n+m)=6; p is 1 or 2, each r is independent 0, 1 or 2, each s is independently 0, 1, 2, 3 or 4 as appropriate; t is 0 , 1, 2, 3 or 4; each R is independently hydrogen; halogen; C1 to C16 atom; C6-C18 aryl or C7-C20 arylalkyl group (these Any of these can be substituted with a C1-C12 alkyl group or a halogen atom, When an aryl group is present, it is -O-, C1-C3 alkylene or can be bonded by alkylidene, or -SO2- bridging group); or or hydroxyaryl or alkylhydroxyaryl group; and each R' is each independently a carbon-carbon direct bond, or a divalent alkyl, aryl, aryl alkyl, hydroxyaryl or alkylhydroxyaryl groups (these (including halogen-substituted derivatives of each group); divalent ester and amide groups; and -O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -S-,▲There are mathematical formulas, chemical formulas, tables, etc. From hetero-containing cross-linking groups, including ▼, ▲mathematical formulas, chemical formulas, tables, etc. selected from the group consisting of a member of the crosslinking group selected from the group consisting of at least one phenolic additive (with the exception of phenolic additives with tertiary alpha carbon atoms) A phenolic hydroxy group with two adjacent alkyl groups on the phenol ring is (absent), reduces water absorption and improves swelling resistance when exposed to moisture. A novel polyamide composition.