TW546350B - Nucleation of polyamides in the presence of hypophosphite - Google Patents

Abstract

The present invention provides polyamide compositions comprising a polyamide, nylon 2, 2, and a phosphorous-containing whitening agent having formula I, wherein R is hydrogen, an alkyl group with 1 to 6 carbons, a cycloalkyl group with 5 to 6 carbons, or a phenyl or methylphenyl aromatic group, and M is hydrogen or a metal. In a preferred embodiment, the polyamide is nylon 6, 6(polyhexamethylene adipamide) and the phosphorous-containing whitening agent is a hypophosphorous acid or a metal hypophosphite. Sodium hypophosphite is especially preferred. The polyamide compositions of the present invention have improved molding cycle times, and are tough, white and color-stable.

Description

546350 V. Description of the invention (1) Background of the invention 1. Field of the invention ... The present invention relates to the preparation of a synthetic polyamide composition having a high degree of whiteness and color stability and improving the molding cycle time. 2. Description of Related Techniques The polymerization of suitable diamines and dicarboxylic acids to form polyfluorene is a well-known technique and is of considerable commercial importance. Polyamines have a variety of uses. An important commercial use is resins for molded articles, especially those requiring toughness and heat resistance.

Nuc leants are often used to improve the molding cycle time or crystallinity of polyamides. For example, U.S. Patent No. 3, 0 0 0, 3 4 5 discloses the use of, for example, sodium phenylphosphonate, sodium isobutylphosphonate, oxidation ballast, desertification, vaporized mercury, cadmium acetate, acetate or phenol. (Nuc 1 eating agent). U.S. Patent Nos. 3,585,264 and 4,866,115 also disclose the use of nucleating agents to improve the crystallinity of polyamides. Hypophosphite compounds have been used as catalysts for the polymerization of polyamides, for example, in U.S. Patent Nos. 3, 8 6 0, 5 5 8; 3, 1 73, 8 98; and 3, 691, 131. In U.S. Patent Nos. 3,860,558 and 3,691,131,

Metal hypokarates are used with hindered phenol compounds as antioxidants. In U.S. Patent No. 3, 1 73, 8 98, a small concentration of a secondary metal salt of a specific metal is used. The use of hypophosphite in the polymerization process also gives polyamide a greater degree of whiteness and color stability. 2 One problem with polyamines is that most nucleating agents are less effective in the presence of hypophosphite. Therefore, the polyamine composition and manufacturing method

546350 V. Description of the invention (2) In a demand, it will convey several advantages through the use of nuclear agents, such as reducing the molding cycle time when the use of hypophosphite is allowed. SUMMARY OF THE INVENTION An object of the present invention is a polyamidoamine composition comprising (a) polyamidoamine resistant to 2,2, and (b) a phosphorus-containing whitening agent having formula I: Formula I: Η

I R *-Prr ~ 〇

L wherein R is hydrogen, an alkyl group having 1 to 6 carbons, a cycloalkyl group having 5 to 6 carbons, or a phenyl or tolyl aromatic group and M is hydrogen or a metal, and (c) Nylon 2 The amount of 2, can effectively cause the nucleat ion of polyamide outside Nylon 2, 2. The polyamide of (a) is preferably resistant to dragon 6, 6, and the phosphorus-containing whitening agent of (b) is preferably selected from the group consisting of hypophosphorous acid and metal salts thereof. More preferably, the phosphorus-containing whitening agent is a metal hypophosphite in which the metal is selected from the group of groups I a, I I a, or I I b of the periodic table. Particularly preferred is sodium hypophosphite. In a particular embodiment, the composition includes a whitening agent® between about 5 ppm and 500 ppm of phosphorus by weight, and more preferably between about 20 ppm and 80 ppm. Dish by weight. Nylon 2, 2 is preferably present in an amount between about 2 ppm and 2000 ppm by weight, and more preferably between about 5 p p m and 50 p p m by weight.

Another object of the present invention is a method for making nuclearized polyamines

546350 V. Description of the invention (3) (nucleated Pollyamide), including polyammonium amines outside Phosphate albino-graft resistant Nylon 2,2 and Nylon 2,2 ^ nucleation of amidine in the lower cold part . In addition, the composition of the present invention exhibits commercial color stability, and also improves the whiteness and color of the molding meter. The phase a:% time. The polyamidamine group of the present invention exhibits toughness due to recrystallization at the temperature of Ayase. The higher re-crystallization time is from the upper to the lower final cooling from melting, because when smelting from y improves the molding cycle time and increases production and production. Zhuo's premature sclerosis. This is an example of a description of specific embodiments. The polyamines of the present invention are formed by condensing polymers, polyamines formed by polycondensation via amino groups, and polyamines obtained by polycondensation =-mixtures of amines and acids obtained by polycondensation. One of the preferred amines is carboxyl and " I. A particularly good polyamine is polyhexamethylene which is generally known as the brother τ hexamethylene diamine diamine, She Shao 6'6. The present invention is useful for all forms of polyamines, and is used as a pair: the useful forms include mixed, alloys, and polyamines, and the useful ones are Nylon U and Nylon 6, Nylon 6IA, and Nylon 6T; ; Car == copolymer The phosphorus whitening agent of the present invention is preferably sub-brand / water. Acid or metal hypophosphite, all of which belong to: two =, 舁 is more preferably hypophosphite 1 belongs to Chevron or Period I or b group. For example, the metal may be lithium, ′,, a calcium, aluminum, or zinc. It is also possible to use transition gold, '. , Potassium, barium, magnesium, and salt are sodium hypophosphite.乂 仏, metal dysprosium acid, Nylon 2, 2 and phosphorus-containing whitening agent can be mixed in eight mouths to the amine polycondensation step

546350 V. Description of the invention (4) Before, during or after. Preferably, the phosphorus-containing whitening agent is added during the polycondensation step to form a white polymer. The yellowing of the polymer is due to the oxidation during the polycondensation. The subsequent addition of the phosphorus-containing whitening agent cannot reverse it; however, the phosphorus-containing whitening agent shows a color stabilizer in subsequent melting and polymer melting steps. efficacy. Therefore, Nylon 2, 2 and the phosphorus-containing whitening agent can be added to the polymer before or during the polycondensation step to form a batch, and the reaction is completed by heating. The Nylon 2,2 can also be added to the polyamide which has been formed by adding it to the molten polyamide. Preferably, Nylon 2,2 can be mixed with solid polyamide. Optionally, the solid polyamide is in the form of a block, pellet, or sheet which can be coated or sprinkled with ingredients and then melted. Preferably, Nylon 2, 2 can be mixed into one group of polyamide pills, but a phosphorus-containing whitening agent can be mixed into a second group of polyamide pills. The two sets of polyamide pellets were then mixed and melted. In another specific embodiment, one group of polyamide pills contains Nailong 2,2, and is mixed with the phosphorus-containing whitening agent and a second group of phosphorus-containing whitening agent-containing polyamide pills and melted together. The polyamide composition of the present invention may further include conventional polymer additives well-known in the prior art including fillers, reinforcing agents, stabilizers, dyes, flame retardants, mold release agents, plasticizers, pigments, Ultraviolet absorbers, antistatic agents, lubricants, etc. can be added in effective amounts without adversely affecting the composition of the present invention. The following examples include specific embodiments describing the invention. It should be appreciated that those techniques in the prior art, which are disclosed in the examples, the techniques discovered by the present inventors after the existing ones make the application of the present invention work well, and then

546350 V. Description of the invention (5) " '---- 2: Apply it carefully to form a better model. However, those prior art techniques according to the disclosure of the present invention "perceive many of their changes that can cause their disclosure in specific embodiments and still obtain similar or similar results without affecting the spirit and objectives of the present invention. Comparison Example 1 contains a phosphorus-containing whitening agent, in particular sodium hypophosphite, and a resistant composition of Nylon 6,6. It is compared with the result of adding talc (known nucleating agent); The result of slippery 5. A controlled composition is formed from solutia Inc. ^ is VYDYNE compared to the traditional Nylon 6,6 pellets for commercial use. The addition of sub-% acid sodium is 70 ppm by weight. Phosphorus thus controls the composition. This control composition 4 is referred to herein as Composition 1. The concentrate of the two parent mixtures is sprinkled with 5% Cimpact 6 9 9 or Mistron Superfrost (various commercial uses from Luzenac) Talc) to V yd YNE pellets as described above. The formulations of each sprayed pellet are then placed in a ZSK-40 twin screw extruder in a bucket & dish at 2 7 5 C. Combination 1 pill is processed-mixed (pr occess-b 1 end) to mold the object and mix the matrix The pellets are added to an injection molding machine. The percentage of the parent mixture pellets added to the processing mix formulation is 0% of the control formulation or 2 / of each type of parent mix to make two talc-containing formulations. , Each with a final talc concentration of 0.1%. The tensile strength of the articles molded from the control and two talc-containing formulations, the elongation to failure, and the recrystallization temperature were determined by previously known techniques. Measure. The results are shown in Table 1.

Page 10

546350 V. Description of the invention (6) Table% masterbatch mixture / talc-type talc concentration (° / 〇) tensile strength ISO 527 (MPa) to the degree of failure ISO 527 (%)-~ 5〇 ~~ (° 〇-- -r -—__ 21 QQ 0 ° / 〇0 2% / Cimpact 699 0 · 1 92.7 231 ^ U. 11 2% / Mistron Superfrost 0.1 9Γ3 ~ 22.3 ~ '230.6 ----- As shown in the table! Add Talc as a nucleating agent improves the recrystallization without adding a nucleating agent to the control group. As a result, the molding cycle time can be reduced again. However, in the presence of sodium hypophosphite, the changes of six and six will cause dragon 6,6 The elongation reduced to failure is more than 50% relative to the second control °. The elongation reduced to failure has a significant requirement for maintaining physical properties: the use of the product is unacceptable. Commercial use examples $ at 0!) _ To 22 ppm In the presence of Nylon 2,2, a pair of dragon molding resin composition is prepared. Spread 50. The weight of ppm is two weights: two of m contains Nailong 2,2 powder (the chaos of Bruggemann is on the νγ testicle as described above to form the parent mixture. The :; the person): · 81 cm Π 1/2 British She, 24/1 length / diameter ratio early pump extruder and "丨 nifer-type / 28〇 ^ 2 85 tT"-〇 group ΪΓ :, pill / Λ system is the composition of 1 pill With the mother mixture into the forming machine through the method-mixing to complete. Adding People to the Method-Blend

Page 11 546350 V. Description of the invention (7) The range of the parent mixture pill of the formulation is from 0% to 5%, and the result is a concentration of 0 to 22 ppm β.... At 0.001 to 22 ppm, the Nylon 2 2 formulation was measured for tensile strength, elongation to failure, and recrystallization temperature. For example, the recrystallization temperature is DSC ~ 7 (Perkin Elmer), and the exothermic spike is measured at 50 ° C after 1 minute at 20 ° C per minute. 〇Heating from 50 ° C to 285 ° C at 285 ° C and cooling at 2 ° C per minute from 285 ° C to 5 ° C. See Table 2 for its seabass. / 'N ° Table 2% Concentration (ppm) of the masterbatch mixture Nylon 2, 2 Tensile strength ISO 527 (MPa) to failure elongation ISO 527 (%) Recrystallization temperature (° C) 0 0 81.2 48.9 217.3 1 4.4 83.7 51.7 225.3 2 8X 84.3 46.1 225.6 3 13.2 84.9 41.4 225.9 5 22 85.5 40.6 226.3

In all cases, the addition of Nylon 2, 2 increased the recrystallization temperature by at least 8 · 0 C. However, unlike the comparative example, the use of Nylon 2 in the presence of scale-containing albino agents (especially sodium hyposcale acid), 2 between 4 · 4 ppm and 2 2 ppm did not lead to unacceptable Reducing the percentage elongation at failure For all four test formulations, the percentage elongation at failure is between 83% and 106% of the corresponding control formulation. The tensile strength is similar. It will not be changed in the presence of sodium hypophosphite by using Nylon 2, 2 as a nucleating agent.

Page 12 546350 Fifth, the description of the invention (8) changes. All the specific implementation variations made according to the present disclosure can be used in the composition and method. In general, the agents and methods as described in the description and substitutes and improvements can be achieved and implemented without performing improper experiments. . When the compositions and methods of the present invention are described in a preferred example, those prior art will clearly show the steps described herein or the subsequent steps to apply the group without disturbing the concept, spirit and aims. More specifically, it is shown that specific chemically related agents can replace the same or similar results achieved here. All of these similar alternatives clearly show that those skills are regarded as being within the concept, spirit, and goal of a patented invention.

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Claims (1)

546350 Case No. 88108914 Amendment date 7, filed for patent application 8. If you apply for a special spear] the composition of the first item in the scope, wherein Nylon 2, 2 is present in an amount between 5 ppm and 50 ppm, by weight Count it. 9. A composition comprising Nylon 6,6;-a scale-containing whitening agent having formula I: Formula 1: R-wherein R is hydrogen, an alkyl group having 1 to 6 carbons, having 5 to 6 A cycloalkyl group of carbon, or a phenyl or tolyl aromatic group, and M is hydrogen or a metal; and the amount of Nylon 2,2 is effective to cause the nucleation of Nylon 6,6 (nuc 1 ea ti. η) The method of amine polymerization of amine polymerization is only 2 pairs of dragon-making system. vUml 7 mJUJ species are uniformly cooled down and white.-I 10 in addition to phosphorus-type storage of amine polymerization polymerization in addition to ingredients The formula has the following Η R -P:: 〇M where R is hydrogen, an alkyl group having 1 to 6 carbons, a cycloalkyl group having 5 to 6 carbons, or a phenyl or Tolyl aromatic group, and M is hydrogen or metal; and (b) Nylon 2, 2 in an amount effective to cause nucleation of polyamide O: \ 58 \ 58731.ptc Page 2 2000.12.11.015 546350 h Case No. 88108914 Amendment 6. Those applying for patent (nucleation). 11. The method as claimed in item 10 of the patent application, wherein the polyamine is Nailong 6,6. 12. The method of claim 10, wherein the phosphorus-containing whitening agent is a metal hypophosphite, and the metal of the metal hypophosphite is selected from the group consisting of the la, Ila, or lib groups of the periodic table. 13. The method according to item 12 of the patent application, wherein the metal hypophosphite is sodium hypophosphite. 14. The method according to item 13 of the scope of patent application, wherein the metal hypophosphite is present in an amount between 5 p p m and 50 p p m, by weight. 15. The method according to item 13 of the scope of patent application, wherein the metal hypophosphite salt is present in an amount between 20 ppm and 80 ppm, by weight. 16. The method according to item 10 of the scope of patent application, wherein Nylon 2, 2 is present in an amount between 2 ppm and 2000 ppm, by weight. 17. The method according to item 10 of the scope of patent application, wherein Nylon 2, 2 is present in an amount between 5 ppm and 50 ppm, by weight. 18. A method for manufacturing nuclearized Nylon 6,6, which includes cooling and melting Nylon 6,6 and Nylon 2,2 in the presence of a metal hypophosphite, and the amount of Nylon 6,2 can be effectively induced to cause Nylon 6,6 Nucleation (nuc 1 eati〇η). O: \ 58 \ 5873l.ptc Page 3, 2000.12.11.016 546350 _M Case No. 88108914 VI. Patent Application Scope Dagger --- 1. A polyamine composition comprising (a) —Polyurethane except 2, 2 Amidine, (b) a filler-containing whitening agent having the formula I: Η Formula I R- -P: 00M where R is hydrogen, an alkyl group having 1 to 6 carbons, and a cycloalkyl group having 5 to 6 carbons , Or a phenyl or fluorenyl aromatic group and M is hydrogen or a metal, and (c) and Long 2,2, the amount of which can effectively cause the nucleation of polyamines other than Nailong 2,2 (Nucleation) 〇 2. The composition according to item 1 of the scope of patent application, wherein the polyamidoamine (a) is puppet 6,6. 3. The composition according to item 1 of the patent application scope, wherein the phosphorus-containing whitening agent is a metal hypophosphite, and the metal of the metal hypophosphite is selected from the bases of the la, IIa or lib group of the periodic table. Among them, metal hypophosphite, among which metal hypophosphonate, is by weight. Among them, metal hypophosphite is by weight. Among them, Nylon 2, 2 is present. If the composition in the scope of patent application No. 3 is sodium hypophosphite '5. If the composition in the scope of patent application No. 4 is present, the amount is between 5 ppm and 500 ppm Interstitial 6. If the composition in the scope of the patent application is under item 4, the amount is between 20 ppm and 80 ppm. 7. If the composition in the scope of the patent application is under item 1, the amount is between 2 ppm and 2000 ppm. By weight O: \ 58 \ 58731.ptc Page 1 2003.06.26.015